(meth)acryloyl group-containing compound and method for producing the same

专利摘要:
PURPOSE: Provided are a (meth)acryloyl group-containing compound suitable for various uses and a method for producing the compound with ease under a mild condition. CONSTITUTION: The (meth)acryloyl group-containing compound is prepared by the method comprising the step of reacting a compound having both (meth)acryloyl group and vinyl ether group with a compound having two or more functional groups reactive in the addition reaction with the vinyl ether group. The functional groups are selected from hydroxy group, carboxy group and thiol group.
公开号:KR20030038394A
申请号:KR1020020066776
申请日:2002-10-31
公开日:2003-05-16
发明作者:후까다아끼히꼬；유루기게이지；아와지도시오；오쯔끼노부아끼
申请人:가부시키가이샤 닛폰 쇼쿠바이；
IPC主号:

专利说明:

Compound containing (meth) acryloyl group and preparation method thereof {(METH) ACRYLOYL GROUP-CONTAINING COMPOUND AND METHOD FOR PRODUCING THE SAME}
[17] The present invention relates to a compound comprising a (meth) acryloyl group, a method for producing the same, and also a photocurable composition and an aqueous photocurable composition containing the compound containing the (meth) acryloyl group.
[18] Compounds containing a (meth) acryloyl group are radically polymerizable and thus are useful compounds in various industrial applications. Among them, the compound having two or more (meth) acryloyl groups has a high glass transition temperature (Tg) due to the improved crosslinking property upon curing, thereby forming a cured material having excellent physical properties such as heat resistance. Compounds having two or more such (meth) acryloyl groups include a housing; Construction and architecture; Electricity, electronics and information; Multifunctional crosslinkers, crosslinkable oligomers or crosslinks for a variety of applications such as matrices for composite materials, casting materials, inks, coatings, paints, adhesives, printing plates, various resist materials associated with electronic components, and the like Used as a sex polymer. Therefore, compounds having two or more (meth) acryloyl groups require various performances according to their respective applications.
[19] Method for producing a compound having two or more (meth) acryloyl groups, for example, (1) a method comprising incorporating an alcoholic hydroxyl group and (meth) acrylic acid by dehydration reaction, (2) alcoholic A method comprising incorporating a hydroxyl group and a (meth) acryloyl chloride by dehydrochlorination, (3) reacting an alcoholic hydroxyl group with an isocyanate compound having a (meth) acryloyl group Various methods are well known, including the method of the same, and (4) adding glycidyl (meth) acrylate to the phenolic hydroxyl group, carboxyl group or thiol group by ring opening addition.
[20] However, in the conventional method, such a condition is difficult because some (meth) acryloyl groups disappear by polymerization and a colored product is produced. In addition, the toxicity of the raw materials to be used is likewise a problem. Therefore, there is room for devising a compound having two or more (meth) acryloyl groups to be suitably used for various applications and a method for preparing the compound simply and effectively under mild conditions.
[21] In addition, a technique for using a compound having two or more (meth) acryloyl groups as described above is a non-aqueous or non-aqueous or used to reduce environmental damage as a means for curing or forming images and patterns Aqueous photocurable compositions are included. The photocurable resin composition for image formation can be precisely processed by applying the principle of photolithography, and can be used to form an image by providing a cured material having excellent physical properties by photocuring, and thus related to electronic components and printing plates. It is used in various resist materials. When photolithography is used, such a photocurable resin composition for image formation requires tack-free after film formation, photosensitivity during exposure, and developability after exposure. Moreover, when the photocurable resin composition for image formation is used for an electronic component as a resist material, it is required to improve the water resistance and moisture resistance of a hardened | cured material, and also to reduce the dielectric constant of a hardened | cured material for improving transmittance | permeability.
[22] As a photocurable resin composition for image formation of this kind, for example, a carboxyl group-containing epoxy (meth) compounded with a carboxyl group by reacting an epoxy (meth) acrylate obtained by reacting an epoxy resin with a (meth) acrylate with an acid anhydride. Acrylate is used as disclosed in Japanese Laid-Open Publication No. 61-243869 and Japanese Laid-Open Publication No. 63-258975.
[23] However, in these techniques, hydroxyl groups in the polar groups are generated in the reaction of the epoxy compound as a raw material and (meth) acrylic acid, which limits the water resistance of the cured material and makes it difficult to lower the dielectric constant of the cured material. Therefore, there has been a need for an image forming photocurable resin composition having excellent balance of satisfactory mutual properties such as non-tackiness, light sensitivity and developability as well as improvement of important properties such as water resistance and electrical properties. The photocurable compositions can also form patterns and moldings made of inorganic materials. As a method for forming an accurate pattern from an inorganic material, an inorganic powder such as a metal powder, a metal oxide powder, a fluorescent powder, or an organic frit is additionally mixed with a binder resin to prepare a paste-like composition, and photographed. There is a commonly well known method which includes forming a pattern from the composition by a plate method or the like, and then forming the pattern by baking and thermally decomposing the organic material.
[24] As a technique for using a photocurable binder resin, for example, Japanese Unexamined Patent Publication No. 2000-298336 includes (A) an inorganic powder, (B) a cellulose carboxylic acid-modified photocurable binder resin, (C) a photoreactive monomer, and ( D) An alkali developable photocurable composition containing a photopolymerization initiator is disclosed. Also, JP-A-10-306101 discloses a photopolymerizable resin composition containing (a) a modified cellulose compound, (b) a photopolymerization initiator, (c) an ethylene compound, and (d) an inorganic and / or metallic powder. have.
[25] However, in these techniques, in order to completely remove the binder resin by thermal decomposition, it was required to calcine the composition under relatively high temperature conditions for a long time, and the organic material derived from the binder is due to incomplete thermal decomposition, resulting in a calcined organic material. It is easy to remain in the inorganic pattern or inorganic molding formed by decomposition of the. Thus, there is room for further improvement in this respect. In addition, in the formation of the pattern using the photo-plating method, it was also required that the binder resin be sufficiently photocured in order for the pattern to be sufficiently divided.
[26] In addition, aqueous photocurable compositions have many different paints, thanks to little damage to the environment due to the use of water as a diluent solvent, and the excellent curability of the (meth) acryloyl group containing compounds due to (meth) acryloyl groups. It is expected to be widely used in adhesives, resists, printing inks and the like.
[27] As these aqueous photocurable compositions having curability, for application in the field of ink jet, U.S. Patent No. 5623001 (columns 7 to 8) discloses an ink jet ink composition containing 20 to 75 mass% of water, a water-soluble ultraviolet polymerizable material, a photopolymerization initiator and a colorant, and which can be cured by ultraviolet rays. In addition, U.S. Patent 3204407 (one side) discloses an ink jet printer ink containing at least water, a water-soluble photocurable resin prepolymer, a photopolymerization initiator, and a water-soluble dye. Further, Japanese Laid-Open Patent Publication No. 2000-186242 (pages 2 to 22) discloses an ink containing a coloring material, a polymerizable oligomer, water, and a photopolymerization initiator having solubility in water of at least 3 mass% and used for ink jet recording. It is.
[28] In these techniques, it is described that poly (meth) acrylate compounds of polyethylene glycol are used. However, when pigments or dyes are mixed in water with a (meth) acrylate compound of polyethylene glycol, aggregation occurs or sedimentation is caused rapidly depending on the type of pigment or dye, and sometimes the stability of the composition is significantly brittle. do. Therefore, there was room for further improvement in this regard.
[29] Further, as a thermosetting composition, Patent No. 3021755 includes acetal groups or ketal groups which are homopolymers or copolymers of adducts of vinyloxyalkyl (meth) acrylates and alcohols or ortho acid esters on pages 1, 2, 6, and 7. It is disclosed that inclusion compounds can be used as constituents. In such acetal group-containing or ketal group-containing compositions, the adducts are those used as intermediates for the formation of homopolymers or copolymers, but for the use of such adducts for various paints, adhesives, resists, print inks and the like. There is no disclosure concerning. Furthermore, neither setting the number of functional groups in the alcohol or ortho acid ester used in the synthesis of the adducts nor setting the number of (meth) acryloyl groups in the adduct is disclosed.
[30] In view of the above industry situation, the present invention provides a compound having a (meth) acryloyl group suitably used in various applications, a method for simply preparing the compound under mild conditions, and a useful photocurable composition containing the compound. And an aqueous photocurable composition.
[31] The present inventors have a compound having two or more functional groups capable of adding a compound having both a (meth) acryloyl group and a vinyl ether group to the vinyl ether group (in particular, the functional group of the compound consists of a hydroxyl group, a carboxyl group and a thiol group And low molecular weight compounds, oligomers and polymers having (meth) acryloyl groups are produced under mild conditions without the product being colored or polymerizing some (meth) acryloyl groups. It was. In addition, the present inventors also found that a low molecular weight compound, an oligomer and a polymer having a (meth) acryloyl group obtained by the housing; Construction and architecture; Electricity, electronics and information; As a multifunctional crosslinking agent, crosslinkable oligomer or crosslinkable polymer for various applications such as matrix for composite materials, casting materials, inks, coatings, paints, adhesives, printing plates, various resist materials related to electronic components, etc. It has been found that the compound is a useful compound with excellent physical properties. And with this finding, this means that the problem described above can be solved.
[32] A composition containing both a compound having a (meth) acryloyl group and a photopolymerization initiator is found to be a photocurable composition capable of precise image formation since it can form a high resolution pattern when photolithography is used. In addition, both the developability and tackiness of the film are excellent, and in addition, the water resistance and moisture resistance of the cured material can be improved, and a lower dielectric constant can be obtained. In addition, compositions containing inorganic powders are found to be photocurable compositions useful for a variety of applications, such as electronic components, because of their excellent thermal degradability during firing, and inorganic materials can be used to form moldings and accurate patterns. In addition, when containing water, the composition has excellent curability and water resistance after curing due to the reactivity of the (meth) acryloyl group, and suppresses a decrease in dissolution stability and dispersion stability even when colorants such as dyes and pigments coexist. It can be an aqueous composition. In addition, since the composition is an aqueous composition, it may be an aqueous photocurable composition useful for various applications.
[33] These findings have led to the completion of the present invention.
[1] 1 shows an IR spectral diagram of the reaction product obtained in the example.
[2] 2 shows an IR spectral diagram of the reaction product obtained in the example.
[3] 3 shows an IR spectral diagram of the reaction product obtained in the example.
[4] 4 shows an IR spectral diagram of the reaction product obtained in the example.
[5] 5 shows an IR spectral diagram of the reaction product obtained in the example.
[6] 6 shows an IR spectral diagram of the reaction product obtained in the example.
[7] 7 shows the IR spectral diagram of the reaction product obtained in the example.
[8] 8 shows an IR spectral diagram of the reaction product obtained in the example.
[9] 9 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[10] 10 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[11] 11 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[12] 12 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[13] 13 is a ¹ H-NMR diagram of the reaction product obtained in the example.
[14] 14 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[15] 15 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[16] 16 is a ¹ H-NMR diagram of the reaction product obtained in the Example.
[34] Accordingly, the present invention provides a compound having a (meth) acryloyl group, which comprises reacting a compound having both a (meth) acryloyl group and a vinyl ether group with a compound having at least two functional groups capable of addition reaction with the vinyl ether group. Provide a method.
[35] The present invention also provides a photocurable composition containing both a compound having a (meth) acryloyl group and a photopolymerization initiator.
[36] The present invention also provides an aqueous photocurable composition containing a compound having a (meth) acryloyl group and water.
[37] In the following, the present invention is described in detail.
[38] The method for producing a compound having a (meth) acryloyl group of the present invention includes a reaction of a compound having both a (meth) acryloyl group and a vinyl ether group, and a compound having at least two functional groups capable of addition reaction with the vinyl ether group. do. As the compound having a (meth) acryloyl group produced by the present invention, a compound having two or more (meth) acryloyl groups is preferable.
[39] In the present invention, a compound having both a (meth) acryloyl group and a vinyl ether group, and a compound having two or more functional groups capable of addition reaction with the vinyl ether group (hereinafter also referred to as a compound having two or more functional groups) alone Or a combination of two or more species.
[40] As a compound which has both a (meth) acryloyl group and a vinyl ether group, the (meth) acrylate represented by following formula (3) suitably is included, for example;
[41]
[42] (Wherein R ⁷ represents a hydrogen atom or a methyl group, R ⁸ represents an organic moiety, and R ⁹ represents a hydrogen atom or an organic moiety).
[43] Suitable for use as the organic moiety represented by R ⁸ are linear, branched or cyclic alkylene groups of 2 to 18 carbon atoms, alkoxyalkylene groups of 2 to 20 carbon atoms, halogenation of 2 to 8 carbon atoms (e.g. Brominated or fluorinated) alkylene groups, polyethylene glycol structures excluding terminal hydroxyl groups, polypropylene glycol structures excluding terminal hydroxyl groups, polybutylene glycol structures excluding terminal hydroxyl groups, and aryl groups. Among these, a polyethylene glycol structure having a degree of polymerization of 1 to 10,000, a polypropylene glycol structure and a polybutylene glycol structure, and an alkylene group having 2 to 4 carbon atoms are suitable. More preferred are polyethylene glycol structures having a degree of polymerization of 1 to 100, polypropylene glycol structures and polybutylene glycol structures, alkylene groups having 2 carbon atoms (-CH ₂ CH _2- ), and alkylene groups having 3 carbon atoms (-CH ₂ CH). ₂ CH _2- ). Most preferable are the polyethylene glycol structure, the polypropylene glycol structure, and the polybutylene glycol structure whose polymerization degree is 1-15.
[44] Suitable for use as the organic moiety represented by R ⁹ are linear, branched or cyclic alkyl groups of 1 to 10 carbon atoms, and aromatic groups of 6 to 11 carbon atoms which may be substituted. Among these, an alkyl group having 1 to 2 carbon atoms and an aromatic group having 6 to 8 carbon atoms are suitable.
[45] Specifically, the compound represented by the formula (3) suitably includes the following chemical species: 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyl Oxyethyl (meth) acrylate, 2-vinyloxypropyl (meth) acrylate, 4-vinyloxybutyl (meth) acrylate, 1-methyl-3-vinyloxypropyl (meth) acrylate, 1-vinyloxymethyl Propyl (meth) acrylate, 2-methyl-3-vinyloxypropyl (meth) acrylate, 1,1-dimethyl-2-vinyloxyethyl (meth) acrylate, 3-vinyloxybutyl (meth) acrylate, 1-methyl-2-vinyloxypropyl (meth) acrylate, 2-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, 4 -Vinyloxymethylcyclohexylmethyl (meth) acrylate, 3-vinyloxymethylcyclohexyl Methyl (meth) acrylate, 2-vinyloxymethylcyclohexylmethyl (meth) acrylate, p-vinyloxymethylphenylmethyl (meth) acrylate, m-vinyloxymethylphenylmethyl (meth) acrylate, o-vinyloxymethylphenyl Methyl (meth) acrylate, 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxy) propyl (meth) Acrylate, 2- (vinyloxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxy) isopropyl (meth) acrylic Rate, 2- (vinyloxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) ethyl ( Meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) ethyl (meth) acrylic Nitrate, 2- (vinyloxyethoxyethoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) propyl ( Meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) propyl (meth) acrylate, 2- (vinyloxyethoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyiso Propoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy) isopropyl (meth) acrylate, 2- (vinyloxyisopropoxyisopropoxy) isopropyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxy ) Ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxyethoxy) ethyl (meth) acrylic 2- (vinyloxyisopropoxyethoxyethoxy) ethyl (meth) acrylate, 2- (vinyloxyisopropoxyethoxyethoxyethoxyethoxy) ethyl (meth) acrylate, polyethylene glycol Monovinyl ether (meth) acrylates, polypropylene glycol monovinyl ether (meth) acrylates, and polybutylene glycol monovinyl ether (meth) acrylates.
[46] The aforementioned compounds having two or more functional groups capable of addition reaction with vinyl ether groups may be low molecular weight compounds, oligomers or polymers. Functional groups capable of addition reaction with vinyl ether groups preferably include hydroxyl groups, carboxyl groups and thiol groups. In other words, suitable for use as the compound having two or more functional groups are compounds having two or more functional groups selected from the group consisting of hydroxyl groups, carboxyl groups and thiol groups. In this way, the (meth) acryloyl group is produced under mild conditions by the reaction of a compound having both (meth) acryloyl group and vinyl ether group and a compound having at least two functional groups selected from the group consisting of hydroxyl, carboxyl and thiol groups. Can be incorporated. Thus, a compound having a (meth) acryloyl group is simply prepared under mild conditions without coloration of the product.
[47] The above-mentioned compound having two or more functional groups, and among these compounds, the compound selected from the group consisting of hydroxyl groups, carboxyl groups and thiol groups, suitably include the chemical species described in the following (1) to (6) :
[48] (1) Compounds having hydroxyl groups: polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, 1,3-propanediol, 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1, 4-butanediol, neopentyl glycol, xylylene glycol, hexanediol, glycerin, polyglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, alkylene oxide adducts of bisphenol A, polyethylene glycol, Polypropylene glycol, unsaturated polyesters, saturated polyesters, epoxyacrylates, phenoxy resins, polymers containing hydroxyl groups and epoxy resins; Polycondensation compounds of phenols such as bisphenol, hydroquinone, resorcinol, pyrogallol and phenol resins; p-hydroxyphenethyl alcohol; Saponified compounds of poly (vinyl alcohol) resins; cellulose; Sugars such as glucose, fructose, mannite, starch, sorbitol and dextran.
[49] (2) Compounds having carboxyl groups: oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimeric acid, trimellitic acid, fatigue Mellitic acid, butanetetracarboxylic acid, unsaturated polyesters, saturated polyesters, reaction products of epoxy resins and dibasic acids, reaction products of epoxyacrylates and dibasic acids and polymers containing carboxyl groups.
[50] (3) Compound having a thiol group: 2,3-butanediol, dipentenedithiol, ethylcyclohexyldithiol, 1,6-hexanedithiol, trimethylolpropanetris- (thioglycolate), pentaerythritol tetrakis- (Thioglycolate), 1,4-butanedioldi (β-thiopropionate), trimethylolpropanetris (β-thiopropionate) and pentaerythritol tetrakis- (β-thiopropionate).
[51] (4) compounds having hydroxyl and carboxyl groups: hydroxy acids such as hydroxyacetic acid, lactic acid, glyceric acid, tartaric acid and citric acid; Hydroxybenzoic acid, hydroxynaphthoic acid, unsaturated polyesters, saturated polyesters, and polymers having both carboxyl and hydroxyl groups.
[52] (5) A compound having a hydroxyl group and a thiol group: mercaptoethanol.
[53] (6) A compound having a carboxyl group and a thiol group: mercaptopropionic acid. Among these, an epoxy acrylate, unsaturated polyester, a phenol resin, an epoxy resin, a phenoxy resin, and a hydroxyl group containing polymer are suitable.
[54] As the above-mentioned epoxy acrylate, an epoxy acrylate having a (meth) acryloyl group can be obtained by the addition reaction of (meth) acrylic acid with an epoxy resin such as bisphenol form and novolak form. Epoxyacrylates can be obtained by the addition reaction of an epoxy resin with an unsaturated monobasic acid by ring opening. Unsaturated monobasic acids suitably include the unsaturated monobasic acids mentioned later, and one or more species may be used. Moreover, if desired, saturated monobasic acids and / or polybasic acids may be used in combination with unsaturated monobasic acids.
[55] Any well known epoxy resin having two or more epoxy groups in one molecule may be used as the epoxy resin to form the epoxyacrylate. Suitable for use as the epoxy resin include bisphenol type epoxy resins; Biphenyl type epoxy resins; Alicyclic epoxy resins; Polyfunctional glycidylamine resins such as tetraglycidyldiaminodiphenylmethane; Polyfunctional glycidyl ether resins such as tetraglycidyl tetraphenyl ethane; Phenol novolac type epoxy resins and cresol novolac type epoxy resins; Reaction products of epichlorohydrin and polyphenol compounds obtained by condensation of phenol compounds such as phenol, o-cresol, m-cresol and naphthol with aromatic aldehydes having phenolic hydroxyl groups; Reaction products of epichlorohydrin and polyphenol compounds obtained by addition reaction of phenolic compounds with diolefin compounds such as divinyl benzene and dicyclopentadiene; Epoxidized compounds of ring-opening polymers of 4-vinylcyclohexene-1-oxide using peracid; Epoxy resins containing heterocyclic rings such as triglycidyl isocyanurate; Phenol aralkyl type epoxy resin. In addition, chain extended compounds may also be used. The chain extended compound is obtained by combining two or more of the epoxy resin molecules with a chain extender such as a polybasic acid, a polyphenol compound, a polyfunctional amino compound, and a polythiol. One or more of these species may be used.
[56] Additionally, the alcoholic hydroxyl group of the epoxyacrylate is partially reacted with a compound such as a polyisocyanate compound, a polyvinyl ether and a dibasic anhydride of a tetrabasic acid, or a carboxyl group and a polyfunctional epoxy compound and a polyfunctional oxazoline compound Higher molecular weight epoxyacrylates prepared by reacting a compound such as (the carboxyl group described above is produced by the partial addition reaction of an alcoholic hydroxyl group of an acid anhydride with an epoxy acrylate) can also be used.
[57] When the above-mentioned epoxy acrylate is prepared by the addition reaction of an epoxy resin and an unsaturated monobasic acid by ring opening, for reaction conditions such as reaction temperature and reaction time, well-known reaction conditions can be adopted. In other words, the production method of the epoxy acrylate is not particularly limited.
[58] As the aforementioned unsaturated polyesters, polymers containing both ester linkages and unsaturated double bonds can be obtained by condensation of unsaturated dicarboxylic acids and polyhydric alcohols. The aforementioned unsaturated polyesters are polymers having unsaturated bonds obtained by polycondensation of an acid component mainly containing an unsaturated polybasic acid and a polyhydric alcohol component mainly comprising a polyhydric alcohol and / or an epoxy compound.
[59] The aforementioned acid components may further comprise saturated polybasic acids such as aliphatic saturated polybasic acids and aromatic saturated polybasic acids, or monobasic acids such as acrylic acid, methacrylic acid, cinnamic acid and their carboxyl groups. Unsaturated monobasic acids (unsaturated monocarboxylic acids) and saturated monobasic acids (saturated monocarboxylic acids) such as derivatives of acids may be further included. The polyhydric alcohol components described above may further comprise monohydric alcohols such as hydroxydicyclopentadiene, benzyl alcohol and allyl alcohol, as desired. Monobasic acids and monohydric alcohols are not particularly limited. In addition, (meth) acrylate modified unsaturated polyesters obtained by ring-opening addition of glycidyl (meth) acrylate and terminal carboxyl groups of unsaturated polyesters can also be used.
[60] As the above-mentioned unsaturated polybasic acid to be used as the acid component, any compound containing both at least one double bond and two or more substituents polymerizable with the vinyl monomer in the same molecule can be used. The aforementioned substituents are substituents (e.g., carboxyl groups) capable of forming ester linkages by reaction with functional groups (i.e., hydroxyl and / or epoxy groups) of the polyhydric alcohol and / or epoxy compound used as the polyhydric alcohol component. The unsaturated polybasic acid used as the acid component is not particularly limited.
[61] Suitable for use as the aforementioned unsaturated polybasic acids include, for example, α, β-unsaturated polybasic acids such as maleic acid, fumaric acid, aconic acid and itaconic acid; β, γ-unsaturated polybasic acids such as dihydromuconic acid. In addition, derivatives of unsaturated polybasic acids can be used in place of unsaturated polybasic acids. Such derivatives suitably include, for example, anhydrides, halides and alkylesters of the unsaturated polybasic acids described above. These unsaturated polybasic acids and derivatives may be used alone or in combination of two or more species.
[62] If necessary, suitable for use as the saturated polybasic acid described above to be used as the acid component are, for example, aliphatic saturated polybasic acids such as malonic acid, succinic acid, methylsuccinic acid, 2,2-dimethylsuccinic acid, 2,3- Dimethyl succinic acid, hexyl succinic acid, glutaric acid, 2-methyl glutaric acid, 3-methyl glutaric acid, 2,2-dimethyl glutaric acid, 3,3-dimethyl glutaric acid, 3,3-diethyl glutaric acid Acids, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid; Aromatic saturated polybasic acids such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid; And cycloaliphatic saturated polybasic acids such as 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, 1,2-hexahydrophthalic acid, 1, 1-cyclobutane dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, and trans-1,4-cyclohexane dicarboxylic acid. In addition, derivatives of saturated polybasic acids may also be used in place of saturated polybasic acids. Such derivatives suitably include, for example, anhydrides, halides and alkylesters of the saturated polybasic acids described above. These saturated polybasic acids and derivatives may be used alone or in combination of two or more species.
[63] Suitable for use as the aforementioned polyhydric alcohols used as polyhydric alcohol components are ethylene glycol, diethylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,3 -Butanediol, 2,3-butanediol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2-ethyl-1 , 4-butanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,4-cyclohexanediol, 1,4-dimethylol cyclohexane, 2,2-diethyl-1,3-propanediol, 3-methyl-1,4-pentanediol, 2,2-diethyl-1,3-butanediol, 4,5-nonanediol, triethylene glycol, glycerin , Trimethylol propane, pentaerythritol, dipentaerythritol, hydrogenated bisphenol A, alkylene oxide adducts of hydrogenated bisphenol A, and alkylene oxide adducts of bisphenol A. These may be used alone or in combination of two or more species.
[64] Epoxy compounds used as the above-mentioned polyhydric alcohol component are suitably ethylene oxide, propylene oxide, butylene oxide, styrene oxide, glycidyl acrylate, glycidyl methacrylate, and diglycidyl of bisphenol A. Ethers are included. These may be used alone or in combination of two or more species.
[65] When the polyhydric alcohol and the epoxy compound are used in combination as the aforementioned polyhydric alcohol component, the ratio between them may be selected according to the kind of the polyhydric alcohol and the epoxy compound, and is not particularly limited. In addition, the ratio of the aforementioned monohydric alcohols to the polyalcohol component is preferably less than 50 mass%.
[66] When the aforementioned unsaturated polyesters are prepared by condensation polymerization of an acid component and a polyhydric alcohol component, well-known reaction conditions can be adopted for reaction conditions such as reaction temperature and reaction time. In other words, the method for producing an unsaturated polyester is not particularly limited.
[67] As the above-mentioned phenol resin, for example, phenol novolak, cresol novolak; Cocondensates of formaldehyde and phenolic compounds such as phenol, o-cresol, m-cresol and naphthol; Phenolic compounds such as o-cresol, m-cresol and naphthol, and copolycondensates of aromatic aldehydes containing phenolic hydroxyl groups; Polyphenols obtained by the addition reaction of phenol compounds and diolefin compounds such as divinyl benzene and dicyclopentadiene; Copolycondensates of xylylene glycol and phenolic compounds such as phenol, o-cresol, m-cresol and naphthol; Phenolbiphenyl aralkyl, phenoldiphenyl ether aralkyl, naphtholbiphenyl aralkyl, and naphtholdiphenyl ether aralkyl. These may be used alone or in combination of two or more species.
[68] As the above-mentioned epoxy resin, any hydroxyl group containing epoxy resin used for forming the above-mentioned epoxy acrylate can be used. As the epoxy resin, for example, a chain extended epoxy resin can be suitably used. The chain extended epoxy resins include epoxy resins having two or more functional groups, such as bisphenol type epoxy resins, phenol novolac epoxy resins and cresol novolac epoxy resins, as chain extenders such as polybasic acids, polyphenol compounds, polyfunctionals. Obtained by reaction with an amino compound, and a polyfunctional thiol compound. One or more of these species may be used.
[69] As the above-mentioned phenoxy resin, a polymer having both a phenoxy structure represented by the following formula (4) and at least two alcoholic hydroxyl groups in a molecule may be used:
[70]
[71] (In formula, R <^10> , R <^11> , R <^12> and R <^13> represent a hydrogen atom, a halogen, or a C1-C5 alkyl group each independently. The polymer can be obtained by reacting bisphenol A or tetrabromobisphenol A with a bisphenol A epoxy resin or tetrabromobisphenol A epoxy resin.
[72] The above-described hydroxyl group-containing polymer is not particularly limited as long as the polymer contains two or more hydroxyl groups formed by the polymerization of the monomer component. The method of incorporating a hydroxyl group is not particularly limited, and suitably, for example, (1) a method of copolymerizing a monomer containing a hydroxyl group, (2) a monomer containing a carboxyl group is copolymerized, and then glycy (3) copolymerizing the monomer containing a glycidyl group, and then adding the compound containing a carboxyl group, and adding the compound containing a carboxyl group to the said carboxyl group by addition-reacting the compound which has a dill group To produce a hydroxyl group, and (4) a method in which each of them uses a polymerization initiator or a chain transfer agent containing a hydroxyl group. These methods may be used alone or in combination of two or more methods. The aforementioned monomer component is not particularly limited and may be (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2 -Hydroxypropyl (meth) acrylate, (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, diethylene glycol mono (meth) acrylate, propylene glycol mono (Meth) acrylate, and glycidyl (meth) acrylate; Styrenes such as styrene, p-methyl styrene, p-hydroxy styrene, and α-methyl styrene; Vinyl ester monomers such as vinyl acetate, vinyl propionate, and vinyl butyrate; N-vinyl compounds such as N-vinyl pyrrolidone, N-vinyl formamide, N-vinyl acetamide, and N-vinyl caprolactam; Vinyl ethers such as methylvinyl ether, ethylvinyl ether, butylvinyl ether, and hydroxybutylvinyl ether; Maleic acid, fumaric acid, itaconic acid, citraconic acid and esters thereof.
[73] The reaction molar ratio between the compound having at least two functional groups and the compound having both a (meth) acryloyl group and a vinyl ether group may be selected according to the application and the desired physical properties of the compound having a (meth) acryloyl group. For example, the amount of the compound having both a (meth) acryloyl group and a vinyl ether group is preferably 0.02 to 50 moles, more preferably 0.04 to 10 moles, and even more preferably 1 mole of the functional groups in the compound having two or more functional groups. Preferably it is 0.1-2 mol.
[74] As the reaction method in the above-mentioned production method, the addition method when reacting a compound having two or more functional groups and a compound having both a (meth) acryloyl group and a vinyl ether group includes (1) simultaneously supplying these compounds to the initial stage of the reaction. Or (2) adding one or both of them to the reaction system continuously or intermittently. In addition, the reaction described above is preferably carried out in the presence of a catalyst. Catalysts usable in the present invention are suitably acids. Suitable for use as the acid are aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butanoic acid, trichloroacetic acid, dichloroacetic acid, pyruvic acid, and glycolic acid; Aliphatic polycarboxylic acids such as oxalic acid, maleic acid, oxalacetic acid, malonic acid, fumaric acid, tartaric acid, and citric acid; Aromatic carboxylic acids such as benzoic acid and terephthalic acid; Aromatic sulfonic acids and salts thereof such as benzenesulfonic acid, p-toluenesulfonic acid, pyridinium p-toluenesulfonate, and quinolinium p-toluenesulfonate; Sulphates such as sodium sulphate, potassium sulphate, magnesium sulphate, calcium sulphate, nickel sulphate, copper sulphate and zirconium sulphate; Hydrogensulfates such as sodium hydrogensulfate and potassium hydrogensulfate; Inorganic acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, phosphoric acid and polyphosphoric acid; Heteropoly acids such as phosphomolylic acid, phosphotungstomolybic acid and silicotungstomolybic acid; Acid zeolites; And acidic ion exchange resins, wherein the main structure is a phenolic resin or a styrene resin, and has any form of gel type, porous type and macroporous type, and at least one ion exchange group selected from the group consisting of sulfone groups and alkylsulfon groups Having). These may be used alone or in combination of two or more species. Among them, oxalic acid, maleic acid, potassium hydrogensulfate and hydrochloric acid are preferable. Other acid catalysts, in addition to acting as catalysts for addition reactions, sometimes act as cationic polymerization initiators for vinyl ethers, and therefore, a tight control of the temperature is required. However, hydrochloric acid does not act as a cationic polymerization initiator, but selectively affects the addition reaction, so that tolerance for temperature control is large; As a result, it is very advantageous in manufacture.
[75] The amount of the catalyst described above can be appropriately adjusted according to the chemical species, combinations, and the like of the compound having two or more functional groups and the compound having both (meth) acryloyl and vinyl ether groups to be used in the reaction. However, from the viewpoint of yield, stability of the catalyst, productivity and cost efficiency, the amount is preferably 0.0005 to 1 part by mass, relative to 100 parts by mass of the compound having both a (meth) acryloyl group and a vinyl ether group, for example. More preferably, it is 0.001-0.5 mass part. When halogen acid is used as the catalyst, the catalyst is neutralized with alkali, such as sodium hydroxide, or by adding an epoxy group-containing compound such as glycidyl (meth) acrylate, and an epoxy resin and allowing the catalyst to be added to the epoxy group, after the reaction It is preferable to deactivate the catalyst.
[76] In addition, in the manufacturing method of this invention, the compound which has both a (meth) acryloyl group and a vinyl ether group, and the compound which has a (meth) acryloyl group which is a product are both polymeric compounds. Thus, the reaction is preferably carried out in the presence of a polymerization inhibitor which can inhibit the polymerization and improve the yield.
[77] The aforementioned polymerization inhibitors suitably include: quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; Alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert- Butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; Amine based polymerization inhibitors such as alkylated diphenylamines, N, N'-diphenyl-p-phenylenediamines, and phenothiazines; N-oxyl such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; And copper dithiocarbamate-based polymerization inhibitors such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These may be used alone or in combination of two or more species. Of these, quinone-based polymerization inhibitors and N-oxyl polymerization inhibitors are preferred, and hydroquinone, methoxyhydroquinone, benzoquinone, p-tert-butylcatechol, phenothiazine, and 4-hydroxy-2,2,6, 6-tetramethylpiperidine-N-oxyl is suitably used.
[78] The addition amount of the above-described polymerization inhibitor can be appropriately adjusted according to the chemical species of the compound having two or more functional groups and the compound having both the (meth) acryloyl group and the vinyl ether group. However, from the viewpoint of polymerization inhibition effect, yield, productivity and cost efficiency, the amount is preferably 0.001 to 5 parts by mass, more preferably 0.005 to 1 mass, based on 100 parts by mass of (meth) acrylate, for example. Part, particularly preferably 0.01 to 0.1 parts by mass.
[79] In the production method of the present invention, the solvent need not be used in particular, but one or two or more species of organic solvents may be used. Organic solvents suitably include: aromatic hydrocarbons such as benzene, toluene, and xylene; Aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and heptane; Ethers such as diethyl ether, and diisopropyl ether; Ketones such as acetone and methylethyl ketone; Polar solvents such as dimethyl formamide and dimethyl sulfoxide; Halogenated hydrocarbons such as chloroform, methylene chloride, dichloroethane, and chlorobenzene; Ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate , Diethylene glycol monopropyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monophenyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-meth Methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 2-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acete , 3-ethyl-3-methoxybutyl acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, 4-propoxybutyl acetate, 2-methoxypentyl acetate, 3-methoxypentyl acetate, 4- Methoxypentyl acetate, 2-methyl-3-methoxypentyl acetate, 3-methyl-3-methoxypentyl acetate, 3-methyl-4-methoxypentyl acetate, 4-methyl-4-methoxypentyl acetate, ( Di) methyl glutarate, (di) methyl succinate, (di) methyl adipate; Acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, cyclohexanone, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl -3-methoxy propionate, ethyl-3-methoxy propionate, ethyl-3-ethoxy propionate, ethyl-3-propoxy propionate, propyl-3-methoxy propionate, iso Propyl-3-methoxy propionate, methyl lactate, ethyl lactate, propyl lactate, isopropyl lactate, butyl lactate, amyl lactate, ethyl ethoxyacetate, ethyl oxyacetate, methyl acetate, ethyl acetate, Propyl acetate, isopropyl acetate, butyl acetate, isoamyl acetate, methyl carbonate, ethyl carbonate, propyl carbonate, Methyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, benzyl methyl ether, benzyl ethyl ether, dihexyl ether, benzyl acetate, ethyl benzoate, diethyl Oxalate, diethyl maleate, γ-butyrolactone.
[80] The amount of the organic solvent described above may be appropriately adjusted according to the chemical species, combinations, etc. of the compound having two or more functional groups and the compound having both (meth) acryloyl and vinyl ether groups. However, in view of yield, productivity and cost efficiency, the amount is preferably 0 to 200 parts by mass, more preferably 0 to 100 parts by mass, particularly preferably 0 to 100 parts by mass of the total mass of these compounds. It is-70 mass parts.
[81] As reaction conditions in the manufacturing method of this invention, reaction temperature is preferably -40-150 degreeC from a viewpoint of a yield, productivity, and cost efficiency, for example. The reaction temperature is more preferably -30 to 100 ° C, particularly preferably -20 to 70 ° C. The reaction time may be appropriately adjusted to complete the above-mentioned reaction according to the compound, the combination, the amount of use, etc. of the compound having two or more functional groups to be used, the compound having both (meth) acryloyl group and vinyl ether group, catalyst and solvent. The reaction pressure may be appropriately adjusted according to the chemical species and reaction temperature of the compound having two or more functional groups and the compound having both (meth) acryloyl and vinyl ether groups, and, if the reaction system can be maintained in the liquid state, the normal pressure (atmospheric pressure) ), Decompression and pressurization.
[82] The present invention also relates to the addition of a functional group of the compound (A) having two or more functional groups and a vinyl ether group of the compound (B) having both a (meth) acryloyl group and a vinyl ether group (the functional group of the compound (A) Is selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group) relates to a compound having a (meth) acryloyl group obtained.
[83] According to the invention, compounds (A) having two or more functional groups selected from the group consisting of hydroxyl groups, carboxyl groups and thiol groups and compounds (B) having both (meth) acryloyl groups and vinyl ether groups are each alone or two The above species may be used in combination. When any one or both of these compounds are used in two or more species, the compound having a (meth) acryloyl group to be prepared becomes two or more species. The compounds of the present invention may also be in the form of low molecular weight compounds or oligomers or polymers.
[84] The above compound (A) having two or more functional groups selected from the group consisting of hydroxyl groups, carboxyl groups and thiol groups preferably comprises epoxy acrylates, unsaturated polyesters, phenol resins, epoxy resins, phenoxy resins and hydroxyl groups It is selected from the group consisting of polymers. As such compounds, the compounds mentioned above are suitable.
[85] As a manufacturing method of the compound which has a (meth) acryloyl group of this invention, the manufacturing method mentioned above is applied suitably. Therefore, it is a preferred embodiment of the present invention to produce a compound having a (meth) acryloyl group of the present invention by such a production method. Specifically, the following preparation method is preferable: A manufacturing method comprising reacting a compound having two or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group with a (meth) acrylate represented by the formula (3).
[86] The present invention also provides a compound having a (meth) acryloyl group having at least two (meth) acryloyl group-containing groups in one molecule, wherein the (meth) acryloyl group-containing group is represented by the following formula (1) and / Or a group represented by the following formula (2):
[87]
[88] (Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic moiety, R ³ represents a hydrogen atom or an organic moiety, and X represents an oxygen or sulfur atom),
[89]
[90] (Wherein, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic moiety, and R ⁶ represents a hydrogen atom or an organic moiety).
[91] In the compound having a (meth) acryloyl group of the present invention, the number of functional groups represented by the formula (1) and / or the formula (2) in one molecule of the compound having a (meth) acryloyl group is, in particular, if it is two or more, It is not limited. However, when the number of (meth) acryloyl groups in one molecule of the compound is greater than 2, a curable material having more excellent curability and higher Tg can be obtained. The compounds of the present invention may also be in the form of low molecular weight compounds or oligomers or polymers.
[92] In addition, the molecular structure connected with the groups represented by the formula (1) and / or 2 may be appropriately selected according to the use of the compound, etc., is not particularly limited. Suitable structures are those comprising the structure of an epoxy acrylate, unsaturated polyester, phenolic resin, epoxy resin, phenoxy resin or hydroxyl group containing polymer.
[93] As a manufacturing method of the compound which has a (meth) acryloyl group of this invention, the manufacturing method mentioned above is applied suitably, for example. It is a preferred embodiment of the present invention to prepare a compound having a (meth) acryloyl group by the above production method. Specifically, the method preferably includes reacting a compound containing a hydroxyl group with a (meth) acrylate represented by the formula (3).
[94] The compound which has a (meth) acryloyl group of this invention is a compound which has both (meth) acryloyl group and a vinyl ether group the compound (A) which has two or more functional groups selected from the group which consists of a hydroxyl group, a carboxyl group, and a thiol group. Obtainable by reacting with (B). The compound thus obtained essentially includes a (meth) acryloyl group, and may further include a carboxyl group in combination with the (meth) acryloyl group. By including a carboxyl group, the compound exhibits sufficient photocurability and alkali developability for precision pattern formation, and excellent photo flatness when used as a photoresist material.
[95] Methods for obtaining the above-mentioned compounds having both a (meth) acryloyl group and a carboxyl group suitably include: (1) at least one chemical group of a functional group selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group The ratio of the compound (A) having a species to the compound (B) having both a (meth) acryloyl group and a vinyl ether group is set, and these are reacted in such a manner as to leave a hydroxyl group and a thiol group, and then (meth) acrylic When a compound having a royl group is obtained as described above, an acid anhydride is added by ring opening to the remaining hydroxyl group and thiol group to entrain the carboxyl group, and (2) Compound (A) and Compound A room involving setting the ratio of (B) and reacting them in such a way that a carboxyl group is left when a compound having a (meth) acryloyl group is obtained. method; However, it is obvious that the present invention is not meant to be limited to these methods.
[96] In the above-mentioned compound having both a (meth) acryloyl group and a carboxyl group, the concentration of the carboxyl group is preferably 20 to 200 mg KOH / g, more preferably 30 to 150 mg KOH / g as the acid value. If the acid value is less than 20 mg KOH / g, the removal of the uncured portion of the alkaline developer after exposure is hardly made quickly, and it may be difficult for the precision pattern to be formed with good reproducibility and accuracy. If the acid value is more than 200 mg KOH / g, the photocured portion is also susceptible to corrosion during alkali development, and precise patterns may be difficult to form with good reproducibility and accuracy.
[97] Acid anhydrides used for incorporation of the carboxyl group into the compound by ring opening addition to the hydroxyl and thiol groups contained in the aforementioned compounds having a (meth) acryloyl group suitably include: phthalic anhydride, Succinic anhydride, octenylsuccinic anhydride, pentadodecenyl succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 3,6-endmethylene tetrahydrophthalic anhydride, methylene methylene tetrahydro Compounds obtained by reacting phthalic anhydride, tetrabromophthalic anhydride, dibasic anhydride, such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10oxide, with itaconic anhydride or maleic anhydride; Trimellitic anhydride; Aliphatic or aromatic tetrabasic dianhydrides such as biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, diphenyl ether tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclopentane tetracarboxylic acid Dianhydride, pyromellitic dianhydride and benzophenone tetracarboxylic dianhydride. These may be used alone or in combination of two or more species.
[98] The compound which has the (meth) acryloyl group of this invention is highly polymerizable, and is highly crosslinkable. In addition, since the compound can block or reduce the polar groups in the compound, a reduction in permittivity and viscosity is possible. Such compounds having a (meth) acryloyl group can be used alone or as a composition containing a crosslinking agent, an additive, a reinforcing agent and the like. Such compounds and compositions containing such compounds can be cured by heat or light and can form cured materials with high glass transition temperatures (Tg) and excellent physical properties such as heat resistance, so that they can be used in housing, construction and building, electrical It can be suitably applied to various applications such as matrix for composite materials, casting materials, inks, coatings, paints, adhesives, printing plates, and various resist materials related to electronic components in the fields of electronics, information and transportation.
[99] In addition, the production method of the present invention can easily and easily prepare the above-mentioned compound having a (meth) acryloyl group under mild conditions.
[100] As the above-mentioned crosslinking agent, a reactive diluent or the like is suitable. Reactive diluents include radically polymerizable monomers, which include: aromatic vinylic monomers such as styrene, α-methylstyrene, α-chlorostyrene, vinyltoluene, divinylbenzene, diallylphthalate, and di Allylbenzenephosphonate; Vinyl ester monomers such as vinyl acetate and vinyl adipate; (Meth) acrylic monomers such as alkyl (meth) acrylates having 1 to 18 carbon atoms, alcohol ethylene oxide derivatives (meth) acrylates having 1 to 8 carbon atoms, and (alkyl) phenol ethylene oxide derivatives (meth) acryl having 1 to 18 carbon atoms Rate, diol di (meth) acrylate having 2 to 9 carbon atoms, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenol A ethylene oxide derivative di (meth) acrylate, and glycerin ethylene oxide Derivative tri (meth) acrylates; Vinyl (thio) ether compounds containing radically polymerizable double bonds such as 2- (vinyloxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxy) ethyl (meth) acrylate, 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate and 2- (isopropenoxyethoxyethoxyethoxy) ethyl (meth) acrylate; And triallyl cyanurate. These may be used alone or in combination of two or more species depending on the application.
[101] Additionally, the aforementioned (meth) acrylic monomers include: methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, β-hydroxyethyl (meth) acrylate , (2-oxo-1,3-dioxolan-4-yl) methyl (meth) acrylate, (di) ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di ( Tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and tris (hydroxyethyl) isocyanurate Meth) acrylate.
[102] As the above-mentioned additives and reinforcing agents, suitably, release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, thickeners, thermal (or photo) polymerization initiators, polymerization inhibitors, diluent solvents, photosensitizers, colorants, antifoaming agents, coupling agents, Leveling agents, surfactants, wetting agents, dispersion stabilizers, thixotropic agents, inorganic fillers such as talc, clays, and barium sulphate; Conductivity donors, drying inhibitors, penetrants, pH adjusters, metal sequestrants, antibacterial and antifungal agents, and other well known additives. Additionally, depending on the purpose of the application, the following compounds may be added in a range without reducing the above-mentioned characteristics: epoxy resins, unsaturated polyesters, urethane (meth) acrylates, polyester (meth) acrylics Acrylates, epoxy acrylates, oxazoline compounds, oxetane compounds, or epoxy curing agents such as dicyandiamide or imidazole compounds. In addition, various reinforcing fibers can be used as the support fibers to yield a fiber reinforced composite material.
[103] When the composition containing the compound having a (meth) acryloyl group of the present invention is cured by heat or light, a heat or photopolymerization initiator is used.
[104] As the above-mentioned thermal polymerization initiator, well-known compounds including the following may be used: organic peroxides such as methylethylketone peroxide, benzoyl peroxide, dicumyl peroxide, t-butyl hydroperoxide, cumene hydroperox Seeds, t-butylperoxyoctoate, t-butylperoxybenzoate, and lauroyl peroxide; And azo compounds such as azobisisobutyronitrile. In addition, curing accelerators can be mixed and used during thermal polymerization. Curing accelerators suitably include cobalt naphthenate, cobalt octylate, and tertiary amines and the like. The usage-amount of a thermal polymerization initiator becomes like this. Preferably it is 0.05-5 mass parts with respect to 100 mass parts of compositions mentioned above.
[105] As the above-mentioned photopolymerization initiators, well-known compounds including the following may be used: benzoin and alkyl ethers thereof such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin Isobutyl ether; Acetophenones such as acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldioxy-1-methylethyl) acetophenone, 2-methyl -1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone , 1-hydroxycyclohexylphenyl ketone, and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone oligomer; Anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone; Thioxanthones such as 2,4-dimethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chlorothioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxycytoxanthone, and 2- (3-dimethylamino-2-hydroxy) -3,4-dimethyl- 9H-Tioxanthone-9-one mesochloride; Ketals such as acetophenone dimethylketal and benzyl dimethylketal; Benzophenones such as benzophenone, 4- (1-t-butyldioxy-1-methylethyl) benzophenone, 3,3 ', 4,4'-tetrakis (t-butyldioxycarbonyl) benzophenone, Methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, 3,3 ', 4,4'-tetra (t-butylperoxylcarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethaneammonium bromide, and (4-benzoylbenzyl) Trimethylammonium chloride; Acylphosphine oxide and xanthone. The photopolymerization initiator is used as one species or as a mixture of two or more species, and the amount of the polymerization initiator is preferably 0.1 to 25 parts by mass based on 100 parts by mass of the above-mentioned composition.
[106] When the composition containing the compound having a (meth) acryloyl group of the present invention is applied to a substrate and obtained by light irradiation, for example, to obtain a cured film, the organic solvent is in view of applicability, printability, workability, and the like. In the composition. These may be used alone, or two or more of them may be used in combination.
[107] The amount of the solvent described above may be suitably used such that the viscosity is optimal during the application operation, and is preferably 1000 parts by mass or less, more preferably 500 parts by mass or less with respect to 100 parts by mass of the composition.
[108] When a composition containing a compound having a (meth) acryloyl group of the present invention is used for photolithography, if the composition contains a compound having a (meth) acryloyl group without allowing carboxyl groups to be introduced thereto, The composition is applied to a substrate and exposed to obtain a cured film, and then the unexposed portions can be solvent developed using a halogen-based solvent such as trichloroethylene or the aforementioned solvents.
[109] Additionally, when the composition contains a compound having a (meth) acryloyl group in which a carboxyl group is introduced therein, alkali development can be carried out because the unexposed portion is dissolved in the alkaline solution.
[110] Developers used in the above-mentioned alkali development suitably include: metal alkaline solutions such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate, sodium silicate, calcium hydroxide and the like; Aqueous ammonium solution; And aqueous solutions of water-soluble amines such as monomethyl amine, dimethyl amine, trimethyl amine, monoethyl amine, diethyl amine, triethyl amine, monopropyl amine, dimethylpropyl amine, monoethanol amine, diethanol amine, triethanol amine, ethylenediamine , Diethylene triamine, dimethylaminoethyl methacrylate, and polyethylene imine. Among these, one species or a mixture of two or more species may be used. In particular, the dilute alkaline aqueous solution of 1.5 mass% or less is used suitably.
[111] The composition containing the compound which has the (meth) acryloyl group of this invention is suitable to set it as (1) photocurable composition or (2) aqueous photocurable composition. The photocurable composition of (1) contains a compound having a (meth) acryloyl group of the present invention and a photopolymerization initiator, wherein, in the photocurable composition, the above can be used for the photopolymerization initiator. The usage-amount of a photoinitiator is 0.1 mass% or more with respect to 100 mass% of photocurable compositions, Preferably it is 25 mass% or less. If the amount is less than 0.1% by mass, it may fail to generate curing upon exposure. When exceeding 25% by mass, after exposure, the film coating property, abrasion resistance and chemical resistance of the cured film may be embrittled. More preferably, they are 0.5 mass% or more and 15 mass% or less.
[112] In addition, the photocurable composition of the above-mentioned (1) may be formulated with a radically polymerizable compound capable of participating in a photopolymerization reaction.
[113] The radically polymerizable compound described above includes, in addition to the radically polymerizable monomer described above, radically polymerizable oligomers in which unsaturated polyesters, urethane acrylates, epoxy acrylates, polyester acrylates and the like can be used. These radically polymerizable compounds may be used alone or as a mixture of two or more species, and depending on the application and the required physical properties, based on 100 parts by mass of the compound having a (meth) acryloyl group, preferably 5 to 500 parts by mass Mixed in amount.
[114] The addition of a thermosetting component such as an oxazoline compound, an oxetane compound or an epoxy resin or a curing agent such as a dicyandiamide or an imidazole compound to the photocurable composition of the above-mentioned (1), due to post curing of the film after image formation, The heat resistance, solvent resistance and water resistance of the obtained cured film can be improved. In particular, when a composition containing a compound having a (meth) acryloyl group having a carboxyl group introduced thereto is used, the carboxyl group in the hydrophilic group is reacted with the above-mentioned thermosetting component in the post-curing step, which is more effective. In this case, it is preferable to use an oxazoline compound because no hydroxyl group is generated. The above-mentioned thermosetting component is preferably formulated in an amount of 5 to 500 parts by mass with respect to 100 parts by mass of the compound having a (meth) acryloyl group. The curing agent described above is preferably formulated in an amount of 0.05 to 100 parts by mass with respect to 100 parts by mass of the above-mentioned thermosetting component, preferably in an amount of 1 to 20 parts by mass and 100 parts by mass of a compound having a (meth) acryloyl group. do.
[115] With the use of the photocurable composition of the above-mentioned (1), a dried dry film (protective film may be attached) for use by applying the composition directly to a substrate in a liquid phase and also to a film such as polyethylene terephthalate. ) Is included. In this case, the dry film may be laminated on the substrate, and the film may be peeled off before or after exposure.
[116] In addition, imaging methods by direct scanning (CTP, computer to plate), which are laser-exposed to the film using digitized data without using the film for pattern formation during exposure, as used in printing plate manufacturing. ) May be adopted. Thus, the above-mentioned photocurable composition of (1) is preferably used as the photocurable resin composition for image formation, and such a photocurable resin composition for image formation is also one of the preferred embodiments of the present invention.
[117] The above-mentioned photocurable resin composition for image forming may include solder resist for etching printed circuit board, etching resist, electroless plating resist, insulating layer of printed circuit board by buildup method, black matrix for liquid crystal display, color filter, photo spacer ( photo spacers), and various applications such as printing plate manufacturing.
[118] Preferred photocurable compositions prepared by adding inorganic powder to the photocurable composition of (1), and inorganic powders suitably include: glass fritters such as lead borosilicate glass, zinc Borosilicate glass, or bismuth borosilicate glass (these are PbO-SiO ₂ based, PbO-B ₂ O ₃ -SiO ₂ based, ZnO-SiO ₂ based, ZnO-B ₂ O ₃ -SiO ₂ based, BiO-SiO ₂ based , BiO-B ₂ O ₃ -SiO ₂ system); Oxides such as cobalt oxide, iron oxide, chromium oxide, nickel oxide, copper oxide, manganese oxide, neodymium oxide, vanadium oxide, cerium oxide, Tipaque yellow, cadmium oxide, alumina, silica, magnesia, spinel, and Na Oxides such as, K, Mg, Ca, Ba, Ti, Zr, Al; And fluorescent powders such as ZnO: Zn, Zn ₃ (PO ₄ ) ₂ : Mn, Y ₂ SiO ₅ : Ce, CaWO ₄ : Pb, BaMgAl ₁₄ O ₂₃ : Eu, ZnS: (Ag, Cd), Y ₂ O ₃ : Eu, Y ₂ SiO ₅ : Eu, Y ₃ Al ₅ O ₁₂ : Eu, YBO ₃ : Eu, (Y, Gd) BO ₃ : Eu, GdBO ₃ : Eu, ScBO ₃ : Eu, LuBO ₃ : Eu, Zn ₂ SiO ₄ : Mn, BaAl ₁₂ O ₁₉ : Mn, SrAl ₁₃ O ₁₉ : Mn, CaAl ₁₂ O ₁₉ : Mn, YBO ₃ : Tb, BaMgAl ₁₄ O ₂₃ : Mn, LuBO ₃ : Tb, GdBO ₃ : Tb, ScBO ₃ : Tb, Sr ₆ Si ₃ O ₃ Cl ₄ : Eu, ZnS: (Cu, Al), ZnS: Ag, Y ₂ O ₂ S: Eu, ZnS: Zn, (Y, Cd) BO ₃ : Eu, BaMgAl ₁₂ 0 ₂₃ : Eu, etc. These may be used alone or in combination of two or more thereof. In addition, when the inorganic powder-containing photocurable composition of the present invention is used for conductive pattern formation or the like, the addition of conductive particles such as iron, nickel, copper, aluminum, silver, and gold may achieve the object. .
[119] The usage-amount of the above-mentioned inorganic powder is 30 mass% or more with respect to 100 mass% of photocurable compositions containing an inorganic powder, Preferably it is 95 mass% or less. If the amount is less than 30% by mass, embrittlement problems such as film coatability, printability, and shrinkage after firing may occur. If the amount exceeds 95% by mass, there may be a possibility that the photocurability is reduced.
[120] Usage of the photocurable composition containing the above-described inorganic powders preferably includes, for example: (1) applying the composition to the entire surface or partial surface of the substrate or forming a pattern using imaging or the like, Or a method involving forming a shaped shape, followed by curing by irradiating light such as ultraviolet light, and (2) obtaining a cured pattern or shape by photolithography and then firing. By curing and firing the photocurable composition containing the inorganic powder, in addition to the inorganic powders being fused and alloyed with each other, the organic components in the cured material including the compound having a (meth) acryloyl group are decomposed and volatilized. Thus, moldings such as strong films, and patterns are constructed from inorganic components such as inorganic powders and the like.
[121] The photocurable composition and the inorganic powder-containing photocurable composition described above are partition walls, electrodes, resistors, fluorescent materials, color filters, and blacks of plasma display panels (PDPs), such as by imaging or photolithography. It is suitably applicable to manufacture of a matrix, an LCD, an organic EL element, a printed circuit board, a multilayer printed circuit board, a multichip module, an electrode pattern constituting an LSI, and the like, and a conductive pattern to a ceramic board.
[122] In the aqueous photocurable composition of the above (2), the content ratio (weight ratio) of the compound having a (meth) acryloyl group to water (compound / water having a (meth) acryloyl group) is preferably 1/99 or more, Preferably it is 99/1 or less. When the content of the compound having a (meth) acryloyl group is less than 1, the curing power of the aqueous photocurable composition and the physical properties of the curing material cannot be properly obtained. If the content exceeds 99, the viscosity increases, and thus workability may decrease. The ratio is more preferably 5/95 or more and 90/10 or less.
[123] The above-mentioned aqueous photocurable composition preferably contains a photoinitiator. Among the initiators, acetophenone, benzophenone, or acylphosphine oxide is preferred. In particular, water-soluble photo radical polymerization initiators are preferable.
[124] In the above-mentioned aqueous photocurable composition, the amount of the photopolymerization initiator used is preferably 0.1% by mass or more, preferably 20% by mass or less with respect to 100% by mass of the compound having a (meth) acryloyl group. If the amount is less than 0.1 mass%, sufficient curability cannot be obtained. If the amount exceeds 20% by mass, it may be disadvantageous in terms of cost efficiency. The amount is more preferably 0.5% by mass or more and 15% by mass or less.
[125] The above-mentioned aqueous composition preferably further contains a colorant. Colorants suitably include dyes and pigments, which may be used alone or in combination of two or more species. In addition, dyes and pigments may be used in combination.
[126] The aforementioned dyes suitably include the following: Direct dyes such as C.I. Direct Black 17, 19, 32, 51, 62, 71, 108, 146, 154; C.I.Direct Blue 6, 22, 25, 71, 86, 90, 106, 199; C.I.Direct Red 1, 4, 17, 28, 83; C.I.Direct Yellow 12, 24, 26, 44, 86, 98, 100, 142; C.I. Direct Orange 34, 39, 44, 46, 60; C.I. Direct Violet 47, 48; C. I. Direct Brown 109; C.I. Direct Green 59; Acid dyes such as C.I. Acid Black 2, 7, 24, 24, 26, 31, 52, 63, 112, 118; C.I. Acid Blue 9, 22, 40, 59, 93, 102, 104, 113, 117, 120, 167, 229, 234, 254; C.I.AcidRed 1, 6, 8, 32, 37, 51, 52, 80, 85, 87, 92, 94, 115, 180, 256, 317, 315; C.I.Acid Yellow 11, 17, 23, 25, 29, 42, 49, 61, 71; C. I. Acid Orange 7, 19; C.I. Acid Violet 49; Reactive dyes such as CIReactive Yellow 2, 3, 13, 15, 17, 18, 23, 24, 37, 42, 57, 58, 64, 75, 76, 77, 79, 81, 84, 85, 87, 88 , 91, 92, 93, 95, 102, 111, 115, 116, 130, 131, 132, 133, 135, 136, 137, 139, 140, 142, 143, 144, 145, 146, 147, 148, 151 , 162, 163; CIReactive Orange 5, 7, 11, 12, 13, 15, 16, 35, 45, 46, 56, 62, 70, 72, 74, 82, 84, 87, 91, 92, 93, 95, 97, 99 ; CIReactive Red 3, 13, 16, 21, 22, 23, 24, 29, 31, 33, 35, 45, 49, 55, 63, 85, 106, 109, 111, 112, 113, 114, 118, 126 , 128, 130, 131, 141, 151, 170, 171, 174, 176, 177, 183, 184, 186, 187, 188, 190, 193, 194, 195, 196, 200, 201, 202, 204, 206 , 218, 221; C.I.Reactive Violet 1, 4, 5, 6, 22, 24, 33, 36, 38; CIReactive Blue 2, 3, 5, 8, 10, 13, 14, 15, 18, 19, 21, 25, 27, 28, 38, 39, 40, 41, 49, 52, 63, 71, 72, 74 , 75, 77, 78, 79, 89, 100, 101, 104, 105, 119, 122, 147, 158, 160, 162, 166, 169, 170, 171, 172, 173, 174, 176, 179, 184 , 190, 191, 194, 195, 198, 204, 211, 216, 217; C.I. Reactive Green 5, 8, 12, 15, 19, 23; C.I.Reactive Brown 2, 7, 8, 9, 11, 16, 17, 18, 21, 24, 26, 31, 32, 33; C.I.Reactive Black 1, 5, 8, 13, 14, 23, 31, 34, 39; Other dyes, including C.I. Basic Black 2; C.I. Basic Blue 1, 3, 5, 7, 9, 24, 25, 26, 28, 29; C.I.Basic Red 1, 2, 9, 12, 13, 14, 37; C.I. Basic Violet 7, 14, 27; C. I. Food Black 1, 2; And fat soluble dyes such as C.I. Solvent Black 6, C.I. Solvent Black 18, 24, 28, 29, 33, 36, 37, 38, 51; C.I. Solvent Yellow 1, 49, 62, 74, 79, 82, 83, 89, 90, 120, 121, 151, 153, 154; C.I. Solvent Red 25, 31, 86, 92, 97, 118, 132, 160, 186, 187, 219; C.I. Solvent Blue 33, 38, 42, 45, 53, 65, 67, 70, 104, 114, 115, 135.
[127] The aforementioned pigments suitably include the following: uncoloured pigments such as carbon black, titanium oxide and calcium carbonate, and rapeseed organic pigments. Organic pigments suitably include: insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, and pyrazolone red; Soluble azo pigments such as Lithol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B; Derivatives from bat dyes such as Alizarin, Indanthrone, and Thioindigo Maroon; Phthalocyanine-based organic pigments such as phthalocyanine blue and phthalocyanine green; Quinacridone-based organic pigments such as quinacridone red and quinacridone magenta; Perylene-based organic pigments such as perylene red and perylene scarlet; Isoindolinone-based organic pigments such as isoindolinone yellow and isoindolinone orange; Pyrantrone-based organic pigments such as pyrantrone red and pyrantrone orange; Thioindigo-based organic pigments; Condensed azo organic pigments; Benzimidazolone organic pigments; Quinophthalone-based organic pigments such as quinophthalone yellow; Isoindolinone-based organic pigments such as isoindolinone yellow; And other pigments including Flavantron yellow, Acylamide yellow, Nickel azo yellow, Copper azo methine yellow, Perinone orange, Antron orange, Dianthraquinonyl red, Dioxazine violet and the like.
[128] In particular, carbon blacks used as black inks include: No. commercially available from Mitsubishi Chemical. 2300, No. 900, MCF88, No. 33, No. 40, no. 45, No. 52, MA7, MA8, MA100, No. Raven 5750, Raven 5250, Raven 5000, Raven 3500, Raven 1255, Raven 700, Regal 400R, Regal 330R, Regal 660R, Mogul L, Monarch 700, Monarch 800, Monarch 880 available from 2200B, Colombia Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S150, Color Black S160, available from Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, and Degussa Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special Black 4.
[129] In the above-mentioned aqueous photocurable composition, the amount of the colorant used is preferably 0.5 mass% or more and 30 mass% or less with respect to 100 mass% of the aqueous photocurable composition. If the amount is less than 0.5 mass%, sufficient coloring effect cannot be obtained. If the amount exceeds 30% by mass, it may be disadvantageous in cost efficiency. The amount is more preferably 1% by mass or more and 25% by mass or less.
[130] The aforementioned aqueous photocurable compositions may contain additional additives such as: dispersion stabilizers, antifoams, mold release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, fillers, thickeners, heat (or light) for pigments and the like. ) Polymerization initiators, photosensitizers, colorants, coupling agents, leveling agents, surfactants, wetting agents, thixotropic agents, inorganic fillers such as talc, clays, and barium sulphate; Conductive donors, drying inhibitors, penetrants, pH adjusters, metal sequestrants, antibacterial and antifungal agents, and other well known additives. The aforementioned aqueous photocurable compositions are suitably used in a wide variety of fields such as various paints, adhesives, resists, printing inks and the like. Usage of the aqueous photocurable composition suitably includes: methods of using brushes, bar coaters, spray coaters, spinners, roll coaters, and the like. In addition, the curing method suitably includes a thermal curing method and a method by activated energy rays. Among these, the hardening method by irradiating an activated energy ray is more preferable.
[131] The aforementioned activated energy rays may be energy rays capable of reacting a compound having a (meth) acryloyl group contained in the aqueous photocurable composition to cure the material, and preferably include ultraviolet rays and electron beams. Among these, ultraviolet rays are suitable when used in fields such as paint.
[132] As the equipment for irradiating ultraviolet rays, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a fluorescent chemical lamp, and a fluorescent blue lamp may be used.
[133] The compound which has the (meth) acryloyl group of this invention which is said structure is highly polymerizable, and is applicable suitably for various uses. In addition, the compound is highly crosslinkable and has a high glass transition temperature (Tg), thereby forming a curable material having excellent physical properties such as heat resistance. In addition, the compounds can have low dielectric constant and viscosity, and these properties can be appropriately set according to various applications. In addition, the method for producing a compound of the present invention comprising the steps described above can easily and easily prepare a compound having such a (meth) acryloyl group under mild conditions. In addition, the photocurable composition and the aqueous photocurable composition of the present invention contain a compound having such a (meth) acryloyl group, and thus are useful compositions that are suitably applicable to various applications.
[134] Best Mode for Carrying Out the Invention
[135] The present invention will be discussed in more detail below using examples, but the invention is not meant to be limited to these examples. Also, unless stated otherwise, "parts" refers to "parts by weight".
[136] Example 1
[137] 114.2 g (hydroxyl group = 1 mol) of bisphenol A, 0.017 g (0.1 mmol) of p-toluenesulfonic acid, and 300 g of 2-butanone as solvent, equipped with a stirrer, thermometer, condenser and nitrogen inlet tube Put into a 1 L flask. The material was stirred and then cooled to 10 ° C. in an ice bath. Thereafter, 186.2 g (1 mol) of 2- (vinyloxyethoxy) ethyl acrylate (hereinafter referred to as "VEEA") was added dropwise to the resulting solution over 1 hour, and the temperature was returned to room temperature. The mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and then the product was reprecipitated with n-hexane, filtered and dried.
[138] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. 9 shows a ¹ H-NMR diagram of the reaction product, and FIG. 1 shows an IR spectrum of the product.
[139] Example 2
[140] 183.5 g of bisphenol A epoxy resin (YD-127, manufactured by Tohto Kasei Co., Ltd.), and 0.734 g of triethylbenzyl ammonium chloride were added to a 1 L flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube. Put in. Thereafter, 72 g of acrylic acid was added dropwise over 2 hours while the mixture was allowed to react at 115 ° C. over 5 hours. 0.729 g of hydrochloric acid and 445.5 g of 2-butanone as a solvent were added and stirred to 255.5 g of epoxy acrylate (hydroxyl group = 1 mol), and then the mixture was cooled to 10 ° C in an ice bath. Thereafter, 186.2 g (1 mol) of VEEA was added dropwise to the resulting solution over 1 hour, the temperature was returned to room temperature, and the mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and then the product was reprecipitated with n-hexane, filtered and dried.
[141] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. 10 shows a ¹ H-NMR diagram of the reaction product, and FIG. 2 shows an IR spectrum of the product.
[142] Example 3
[143] 90 g (0.9 mol) of methyl methacrylate, 13 g (0.1 mol) of 2-hydroxyethylmethacrylate, and 240 g of 2-butanone are equipped with a stirrer, thermometer, condenser and nitrogen inlet tube Into a 0.5 L flask. After sufficiently replacing the air with nitrogen, the temperature was raised to 70 ° C. Thereafter, 1.03 g of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 2-butanone was introduced into the reaction mixture over 1 hour, and then at 70 ° C over 5 hours. Polymerized. To 103 g of the methacrylate polymer thus obtained, 0.073 g of hydrochloric acid was added, and the material was cooled to 10 ° C in an ice bath. Thereafter, 20.02 g (0.1 mol) of 2- (vinyloxyethoxy) ethyl methacrylate (hereinafter referred to as "VEEM") was added dropwise to the resulting solution over 1 hour, and the temperature was returned to room temperature, The mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and the reaction product was reprecipitated with n-hexane, filtered and dried.
[144] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. FIG. 11 shows a ¹ H-NMR diagram of the reaction product, and FIG. 3 shows an IR spectrum of the product.
[145] Example 4
[146] 53.9 g (0.55 mol) maleic anhydride, 66.7 g (0.45 mol) phthalic anhydride, 18.6 g (0.30 mol) ethylene glycol and 57.1 g (0.75 mol) propylene glycol were introduced with a stirrer, thermometer, condenser and nitrogen The tube was placed in a 0.5 L flask equipped with a tube. After the air had been sufficiently replaced with nitrogen, condensation was carried out at 210 ° C. over 6 hours to yield an unsaturated polyester having an acid value of 30. After adding 0.078 g of hydrochloric acid and 120 g of 2-butanone to 100 g of the above obtained unsaturated polyester, the mixture was cooled to 10 ° C in an ice bath. Thereafter, 19.9 g of VEEA was added dropwise to the resulting solution over 1 hour, the temperature was returned to room temperature, and the mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and the reaction product was reprecipitated with n-hexane, filtered and dried.
[147] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. 12 shows a ¹ H-NMR diagram of the reaction product, and FIG. 4 shows an IR spectrum of the product.
[148] Example 5
[149] 256.9 g of bisphenol A epoxy resin (YD-127, manufactured by Tohto Kasei Co., Ltd.), 177.3 g of bisphenol A and 0.217 g of triethylbenzyl ammonium chloride, equipped with a stirrer, thermometer, condenser and nitrogen inlet tube Into a 1 L flask, and reacted at 120 ° C. over 5 hours. 1.134 g of hydrochloric acid and 310.2 g of 2-butanone as a solvent were added to 434.2 g of the phenoxy resin obtained above, and after stirring, the mixture was cooled to 10 ° C in an ice bath. Thereafter, 289.6 g of VEEA was added dropwise to the resulting solution over 1 hour, the temperature was returned to room temperature, and the mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and the reaction product was reprecipitated with n-hexane, filtered and dried.
[150] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. FIG. 13 shows a ¹ H-NMR diagram of the reaction product, and FIG. 5 shows an IR spectrum of the product.
[151] Example 6
[152] 90 g (0.9 mol) of methyl methacrylate, 8.6 g (0.1 mol) of methacrylic acid, and 230 g of 2-butanone were placed in a 0.5 L flask equipped with a stirrer, thermometer, condenser and nitrogen inlet tube. . After sufficiently replacing the air with nitrogen, the temperature was raised to 70 ° C. 0.986 g of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 2-butanone was introduced into the reaction mixture over 1 hour, followed by polymerization at 70 DEG C over 5 hours. . 0.0017 g hydrochloric acid was added to 98.6 g of the obtained methacrylate polymer and the material was cooled to 10 ° C. in an ice bath. Thereafter, 20.02 g (0.1 mol) of VEEM was added dropwise to the resulting solution over 1 hour, the temperature was returned to room temperature, and the mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and the reaction product was reprecipitated with n-hexane, filtered and dried.
[153] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. FIG. 14 shows a ¹ H-NMR diagram of the reaction product, and FIG. 6 shows an IR spectrum of the product.
[154] Example 7
[155] 116.1 g of fumaric acid, 0.0344 g of p-toluenesulfonic acid and 488.5 g of 2-butanone were placed in a 1 L flask equipped with a stirrer, thermometer, condenser and nitrogen introduction tube, and then cooled to 10 ° C in an ice bath. Thereafter, 372.4 g (2 mol) of VEEA were added dropwise to the resulting solution over 1 hour, the temperature was returned to room temperature, and the mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and the reaction product was reprecipitated with n-hexane, filtered and dried.
[156] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. FIG. 15 shows a ¹ H-NMR diagram of the reaction product and FIG. 7 shows an IR spectrum of the product.
[157] Example 8
[158] 194 g (1 mol) of tetraethylene glycol and 1.46 g of hydrochloric acid were placed in a 1 L flask equipped with a stirrer, thermometer, condenser and nitrogen introduction tube, and then cooled to 10 ° C in an ice bath. Thereafter, 372.4 g (2 mol) of VEEA were added dropwise to the resulting solution over 1 hour, the temperature was returned to room temperature, and the mixture was allowed to react for an additional 2 hours. The reaction solution was neutralized with 1 mol / L sodium hydroxide solution, filtered and the reaction product was reprecipitated with n-hexane, filtered and dried.
[159] The material thus obtained was confirmed using ¹ H-NMR and IR. As a result, it was confirmed that the above-mentioned substance of the reaction product is a novel compound having acryloyl group according to the present invention. FIG. 16 shows a ¹ H-NMR diagram of the reaction product and FIG. 8 shows an IR spectrum of the product.
[160] Example 9
[161] Two parts of benzoyl peroxide was added to 100 parts by weight of the compound of Example 2 dissolved in 100 parts by weight of acetone, and the resulting solution was coated on a glass plate, after which the solution was removed and cured at 90 ° C. over 2 hours. . The glass transition temperature of the cured material was measured using a differential scanning calorimeter (DSC) at a rate of temperature rise of 10 ° C./min and found to be 90 ° C.
[162] Comparative Example 1
[163] The bisphenol A epoxy resin used as a raw material in Example 2 was a liquid at room temperature, and its glass transition temperature was clearly lower than the glass transition temperature of the cured material obtained in Example 2.
[164] Example 10
[165] The glass transition temperature of the cured material obtained by curing the compound of Example 5 using a method similar to that of Example 9 was measured at 110 ° C.
[166] Comparative Example 2
[167] The glass transition temperature of the phenoxy resin itself synthesized in Example 5 was measured at 80 ° C.
[168] Example 11
[169] 134 g (hydroxyl group = 3 mol) trimethylolpropane and 600 g (3 mol) VEEM are placed in a 1 L flask equipped with a stirrer, thermometer, condenser and nitrogen introduction tube, and the solution is stirred to 60 ° C. By heating, a homogeneous mixed solution was prepared. Thereafter, the resulting solution was cooled to 25 ° C, and a solution prepared by diluting 0.104 g of hydrochloric acid (35% aqueous solution, 0.01 mol as an HCl component) with 10 g of bis (2-methoxyethyl) ether was added to the above solution. It dripped slowly, paying attention to heat generation. When the exotherm subsided, the solution was heated to 60 ° C. and allowed to react for 4 hours. The reaction product (1) thus obtained was analyzed using an IR spectrometer; It was found that the peak wave near 3500 cm ⁻¹ due to the hydroxyl group was almost gone.
[170] Example 12
[171] 263 g (hydroxyl group = about 3.5 mol) of fully dehydrated polyglycerin (trade name: Polyglycerin # 750, product of Sakamoto Yakuhin Kogyo Co., Ltd.) and 700 g (3.5 mol) of VEEM were added to a stirrer, thermometer. Into a 1 L flask equipped with a condenser and a nitrogen inlet tube, and the solution was stirred. At 25 ° C., a solution prepared by diluting 1.1 g of hydrochloric acid (35% aqueous solution, 0.011 mol as an HCl component) with 10 g of bis (2-methoxyethyl) ether was slowly added dropwise to the solution, paying attention to exotherm. . When the exotherm subsided, the solution was heated to 60 ° C. and allowed to react for 4 hours. The reaction product (2) thus obtained was analyzed using an IR spectrometer; It was found that the peak wave near 3500 cm ⁻¹ due to the hydroxyl group was almost gone.
[172] Example 13
[173] 50 g (0.5 mol) of methyl methacrylate, 65.1 g (0.5 mol) of 2-hydroxyethyl methacrylate, and 173.5 g of bis (2-methoxyethyl) ether were mixed with a stirrer, thermometer, condenser and nitrogen The flask was placed in a 0.5 L flask equipped with an introduction tube. After the air was sufficiently replaced with nitrogen, the temperature was raised to 70 ° C. Thereafter, 0.61 g of n-dodecyl mercaptan was charged to the solution, and 0.58 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to bis (2-methoxyethyl) ether. The solution prepared by dissolving in was charged into the resultant system over 1 hour, and polymerization was carried out at 70 ° C over 5 hours. To 289 g of a mixed solution of bis (2-methoxyethyl) ether and methacryl polymer obtained thereby, 0.17 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl and 50 g (as an inhibitor) 0.25 mol) of VEEM was added and stirred. At 25 ° C., a solution prepared by diluting 0.078 g of hydrochloric acid (35% aqueous solution, 7.5 × 10 ⁻⁴ mol as an HCl component) with 10 g of bis (2-methoxyethyl) ether was added to the system. Slowly dropping. When the exotherm subsided, the solution was heated to 60 ° C. and allowed to react for 6 hours. The curable resin solution thus obtained was analyzed using an IR spectrometer; It was confirmed that the intensity of the peak wave near 3500 cm ⁻¹ due to the hydroxyl group was reduced.
[174] 339 g of a mixed solution of bis (2-methoxyethyl) ether and the polymer thus obtained, 38 g (0.25 mol) of tetrahydrophthalic anhydride and 1.51 g of tetraphenylphosphonium bromide were mixed, followed by acid anhydride to a hydroxyl group. The addition reaction was carried out at 100 ° C. over 4 hours under a mixed gas atmosphere. The acid value of curable resin solution (3) thus obtained was measured at 37 mg KOH / g.
[175] Example 14
[176] 60 g (0.6 mol) of methyl methacrylate, 28.8 g (0.4 mol) of methacrylic acid, and 134.1 g of bis (2-methoxyethyl) ether, equipped with a stirrer, thermometer, condenser and nitrogen inlet tube Into a 0.5 L flask. After sufficiently replacing the air with nitrogen, the temperature was raised to 70 ° C. Thereafter, 0.61 g of n-dodecyl mercaptan was charged to the solution, and 0.45 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to bis (2-methoxyethyl) ether. The solution prepared by dissolving was charged in the resultant system over 1 hour, and superposition | polymerization was performed at 70 degreeC over 5 hours. To 224 g of a mixed solution of bis (2-methoxyethyl) ether and methacryl polymer thus obtained, 0.13 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl and 40 g (as an inhibitor) 0.2 mol) of VEEM was added and stirred. At 25 ° C., a solution prepared by diluting 0.063 g of hydrochloric acid (35% aqueous solution, 6 × 10 ⁻⁴ mol as an HCl component) with 10 g of bis (2-methoxyethyl) ether was added to the system, paying attention to heat generation. Slowly dropping. When the exotherm had subsided, the solution was heated to 60 ° C. and allowed to react for 3 hours. The acid value of the curable resin solution (4) thus obtained was measured at 43 mg KOH / g.
[177] Examples 15-18
[178] On the basis of the composition (parts by weight) as shown in Table 1, a photocurable resin composition was prepared using the respective reaction products and the curable resin solutions obtained in Examples 11 to 14, and thermally decomposable, solvent developable and alkali. The developability was evaluated by the following method. The results are shown in Table 2.
[179] Comparative Examples 3 and 4
[180] 60 g (0.6 mol) of methyl methacrylate, 28.8 g (0.4 mol) of methacrylic acid, and 134.1 g of bis (2-methoxyethyl) ether, equipped with a stirrer, thermometer, condenser and nitrogen inlet tube Into a 0.5 L flask. After sufficiently replacing the air with nitrogen, the temperature was raised to 70 ° C. Thereafter, 0.61 g of n-dodecyl mercaptan was charged to the solution, and then 0.45 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to bis (2-methoxyethyl) ether. The solution prepared by dissolving in was charged into the resultant system over 1 hour, and polymerization was carried out at 70 ° C. over 5 hours. To 224 g of a mixed solution of bis (2-methoxyethyl) ether and methacryl polymer thus obtained, 0.13 g of 4-hydroxy-2,2,6,6-tetramethylpiperidinoxyl as an inhibitor, and esterification 1.01 g of tetraphenylphosphonium bromide and 28.4 g (0.2 mol) of glycidyl methacrylate as catalyst were added and stirred. The solution was then allowed to react at 110 ° C. for 4 hours. The acid value of the curable resin solution (5) thus obtained was measured at 45 mg KOH / g.
[181] The curable resin solution (5) thus obtained was prepared on the basis of the composition (parts by weight) as shown in Table 1 to prepare a photocurable resin composition, and evaluated by the following method for thermal decomposability, solvent developability and alkali developability. It was. The results are shown in Table 2.
[182]
[183] In Table 1, "TMPTMA" refers to trimethylolpropane trimethacrylate, and "PMMA" means polymethyl methacrylate (number average molecular weight = 35,000, weight average molecular weight = 50,000).
[184]
[185] Assessment Methods
[186] [Thermal decomposition]
[187] 5 parts of Irgacure 907 (product of Ciba Specialty Chemicals Co., Ltd.) were added to 100 parts of solvent-free components in each of the above photocurable compositions, and the resulting material was applied to the glass plate with a thickness of 20 to 30 μm, It was dried at 80 ° C. for 1 hour in a hot air circulation drying oven. The plate was covered with a transparent film and irradiated with a light amount of 2000 mJ / cm 2 using a 250 W ultrahigh pressure mercury lamp to yield a cured coating. The thermal degradability of the cured coatings was tested by TGA (thermal gravity analysis, product of Mac Science Corp., TG-DTA 2000). The coating was heated at 25 ° C. to 500 ° C. under an air atmosphere at a rate of temperature rise of 20 ° C./min to determine the temperature at which the weight loss rate was 98%.
[188] [Solvent developability]
[189] Each photocurable composition was applied to a copper plate with a thickness of 20 to 30 μm and then dried at 80 ° C. for 1 hour in a hot air circulation drying oven to obtain a coating. Thereafter, development was carried out at 30 ° C. for 60 seconds using propylene glycol monomethyl ether acetate. Thereafter, the remaining coating was visually evaluated.
[190] O: The coating was fully developed.
[191] (Triangle | delta): A little adhesive substance remains.
[192] X: A large amount of adhesive remains.
[193] [Alkali developability]
[194] Each photocurable composition was applied to a copper plate with a thickness of 20 to 30 μm, and then dried in a hot air circulation drying oven at 80 ° C. for 1 hour to obtain a coating. The development was then carried out at 30 ° C. for 60 seconds using a 1% Na ₂ CO ₃ aqueous solution. Thereafter, the remaining coating was visually evaluated.
[195] O: The coating was fully developed.
[196] (Triangle | delta): A little adhesive substance remains.
[197] X: A large amount of adhesive remains.
[198] Examples 19 to 24
[199] The composition formulated according to the formulation composition (mass parts) of Table 3 was kneaded with a ceramic triple roll to obtain a photocurable paste composition. The composition was applied to a copper plate with a thickness of 20 to 30 μm, and then dried in a hot air circulation drying oven at 80 ° C. for 1 hour to obtain a coating. The coating thus obtained was coated with a pattern film and irradiated with a light amount of 2000 mJ / cm 2 using a 250W ultrahigh pressure mercury lamp. Thereafter, each coating was developed at 30 ° C. for 60 seconds using a developer as shown in Table 3, and then calcined at a firing temperature (600 to 800 ° C.) for 10 minutes as shown in Table 3. The line pattern thus obtained was visually evaluated.
[200] O: The contrast between the exposed portion and the non-exposed portion was clearly distinguished, and no dashed line or disconnection was present.
[201] (Triangle | delta): The etching of an exposed part is insufficient.
[202] X: Etching is impossible or the whole is melted.
[203] The results are summarized in Table 3.
[204]
[205] In Table 3, "glass frit" is ZnO / PbO / B ₂ O ₃ / SiO ₂ -based glass frit, and "Irgacure 907" is Ciba Specialty Chemicals Co., Ltd. It is a photoinitiator which is a product of. Additionally, in the "developer" section, "1" refers to developer 1 which is propylene glycol monomethyl ether acetate, and "2" means developer 2 which is a 1% Na ₂ CO ₃ aqueous solution.
[206] Example 25
[207] A reactor equipped with a stirrer, a condenser, a nitrogen inlet tube and a thermometer was charged with 438 parts of cresol novolak type epoxy resin "EOCN-104S" (product of Nippon Kayaku Co., Ltd., epoxy equivalent 219), 144 parts of acrylic acid, 313 parts of Charged with propylene glycol monomethyl ether acetate, 2.9 parts of triphenylphosphine as esterification catalyst, and 0.5 parts of methylhydroquinone as polymerization inhibitor, the reaction was carried out at 110 ° C. for 10 hours. The acid value of the reaction product was assured to 5 mg KOH / g. Thereafter, 60 parts of propylene glycol monomethyl ether acetate, 112 parts of VEEA, 0.2 parts of hydrochloric acid as addition reaction catalyst, and 0.6 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N as polymerization inhibitors -Oxyl was added above and the reaction was carried out at 40 ° C. for 1 hour. Thereafter, 0.3 parts of glycidyl methacrylate was added thereto, and the deactivation treatment of hydrochloric acid was carried out at 40 ° C. for 1 hour, so that the mixture containing 65% of the resin and propylene glycol monomethyl ether acetate of the present invention [ Curable resin solution (6)].
[208] Example 26
[209] To 500 parts of the curable resin solution (6) obtained in Example 25, 41 parts of propylene glycol monomethyl ether acetate and 76 parts of tetrahydrophthalic anhydride were added, and the reaction was carried out at 100 ° C. for 5 hours to give an acid value of 77 mg KOH. A mixture [curable resin solution (7)) containing 65% of the present invention and propylene glycol monomethyl ether acetate, which is / g, is obtained.
[210] Example 27
[211] The same reactor as in Example 25 was conducted with 438 parts of cresol novolac type epoxy resin "EOCN-104S", 83 parts of p-hydroxyphenyl-2-ethanol, 101 parts of acrylic acid, 335 parts of propylene glycol monomethyl ether acetate, esterification Charged with 3.1 parts of triphenylphosphine as catalyst and 0.7 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl as polymerization inhibitor, the reaction was carried out at 110 ° C. for 12 hours. . The acid value of the reaction product was assured to 6 mg KOH / g. Thereafter, 60 parts of propylene glycol monomethyl ether acetate, 112 parts of VEEA, and 0.2 parts of hydrochloric acid as an addition reaction catalyst were added, and the reaction was carried out at 40 ° C. for 1 hour. Thereafter, 0.3 parts of glycidyl methacrylate was added thereto, and deactivation of hydrochloric acid was performed at 40 ° C. for 1 hour. Subsequently, 93 parts of propylene glycol monomethyl ether acetate were added thereto, and the reaction was carried out at 100 ° C. for 5 hours to give 65% of the resin and propylene glycol monomethyl ether acetate of the present invention having an acid value of 77 mg KOH / g. A mixture containing [curable resin solution (8)] was obtained.
[212] Example 28
[213] The same reactor as in Example 25 was carried out with 400 parts of cresol novolac type epoxy resin "SUMI-EPOXY ESCN195XHH", 144 parts of acrylic acid, 293 parts of propylene glycol monomethyl ether acetate, 0.5 parts of chromium bromide hexahydrate as esterification catalyst, and Charged with 0.7 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl as polymerization inhibitor, the reaction was carried out at 100 ° C. for 9 hours. The acid value of the reaction product was assured to 4 mg KOH / g. Thereafter, 60 parts of propylene glycol monomethyl ether acetate, 112 parts of VEEA, and 0.2 parts of hydrochloric acid as an addition reaction catalyst were added and the reaction was carried out at 40 ° C. for 1 hour. Thereafter, 0.3 parts of glycidyl methacrylate was added thereto, and deactivation of hydrochloric acid was performed at 40 ° C. for 1 hour. Then 111 parts of propylene glycol monomethyl ether acetate, 206 parts of tetrahydrophthalic anhydride, and 1 part of triphenylphosphine as esterification catalyst were added above and the reaction was carried out at 100 ° C. for 5 hours. Thereafter, 23 parts of propylene glycol monomethyl ether acetate and 42 parts of bisphenol A type epoxy resin "EPO TOHTO YD-127" (product of Tohto Kasei Co., Ltd., epoxy equivalent 184) were added to the resulting solution, and the reaction was carried out. Was carried out at 110 ° C. for 5 hours to extend the chain so that the mixture contained 65% of the resin and propylene glycol monomethyl ether acetate having an acid value of 74 mg KOH / g [curable resin solution (9)] Obtained.
[214] Examples 29-34
[215] Photocurable compositions were prepared using the respective curable resin solutions obtained in Examples 25 to 28 according to the formulation compositions of Table 4, and evaluated in the following manner. The results are shown in Table 5.
[216] Comparative Examples 5 and 6
[217] The same reactor as in Example 25 was made with 438 parts of cresol novolac type epoxy resin "EOCN-104S", 144 parts of acrylic acid, 313 parts of propylene glycol monomethyl ether acetate, 2.9 parts of triphenylphosphine as esterification catalyst, and polymerization inhibitor Charged with 0.5 parts of 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl as and the reaction was carried out at 110 ° C. for 10 hours. The acid value of the reaction product was assured to 5 mg KOH / g. Thereafter, 73 parts of propylene glycol monomethyl ether acetate and 136 parts of tetrahydrophthalic anhydride were added thereto, and the reaction was carried out at 100 ° C. for 5 hours to give an acid value of 78 mg KOH / g, 65% of resin and propylene A mixture [curable resin solution 10] containing glycol monomethyl ether acetate was obtained.
[218] According to the formulation composition of Table 4, the photocurable composition was prepared using the obtained curable resin solution 10, and evaluated by the following method. The results are shown in Table 5.
[219]
[220] Next, description in Table 4 is demonstrated. Each numerical value in Table 4 is a unit of mass part. "Irgacure 907" is a phosphorescent polymerization initiator product of Ciba Specialty Chemicals Co., Ltd., "YDPN-638P" is a phenol novolac type epoxy product of Tohto Kasei Co., Ltd., and "Floren AC300" is KYOEISYA CHEMICAL Co. Antifoaming agent.
[221] [Phenomena-1]
[222] Each photocurable composition was applied at a thickness of 20-30 μm to a degreased and washed copper coated laminate plate having a thickness of 1.6 mm and dried at 80 ° C. for a specific time in a hot air circulation drying oven to obtain a film. Each was then developed using propylene glycol monomethyl ether acetate at 30 ° C. for 90 seconds under a pressure of 2.06 × 10 ⁻¹ MPa and visually evaluated for the remaining resin.
[223] O: The film was completely developed.
[224] : Some deposits remain.
[225] X: A large amount of deposit remains.
[226] [Phenomena-2]
[227] Each photocurable composition was applied at a thickness of 20-30 μm to a degreased and washed copper coated laminate plate having a thickness of 1.6 mm and dried at 80 ° C. for a specific time in a hot air circulation drying oven to obtain a film. Each was then developed at 30 ° C. for 90 seconds using a 1% Na ₂ CO ₃ aqueous solution under a pressure of 2.06 × 10 ⁻¹ MPa and visually evaluated for the remaining resin.
[228] O: The film was completely developed.
[229] : Some deposits remain.
[230] X: A large amount of deposit remains.
[231] [Exposure Sensitivity]
[232] Each photocurable composition was applied at a thickness of 20-30 μm to a 1.6 mm thick degreased and washed copper coated laminate plate and dried at 80 ° C. for 30 minutes in a hot air circulation drying oven to form a film. Thereafter, a stopper 21 step tablet was adhered to the film and irradiated with a light amount of 500 mJ / cm 2 using a 1 kW ultra-high pressure mercury lamp. The film was developed under the same conditions as in the evaluation of the developability, and the number of steps of the remaining step tablet was confirmed.
[233] [Solder heat resistance]
[234] The dry film was formed as in the exposure sensitivity evaluation. Thereafter, the solder mask pattern film was brought into close contact with the film, and was irradiated with a light amount of 500 mJ / cm 2 using a 1 kW ultrahigh pressure mercury lamp. The film was developed under the same conditions as in the evaluation of developability, and after dissolving and removing the non-exposed portions, the film was further heated at 150 ° C. for 30 minutes to obtain a cured film. Thereafter, the obtained film was immersed in a solder bath at 260 ° C. for 20 seconds according to the JIS D-0202 test method, and then the film state after immersion was evaluated.
[235] O: No abnormal part was observed in the appearance of the film.
[236] X: Swelling, melting or peeling was observed in the appearance of the film.
[237] [Electroless Gold Plating Resistance]
[238] A cured film was obtained as in the case of solder heat resistance evaluation. Thereafter, gold plating was carried out at a current density of 1 A / dm ² for 15 minutes using "AUTRONEX CI" (a gold plating solution commercially available from Sel-Rex Corp., USA), and then peeled off to the film using an adhesive tape. The test was applied to assess the peel state visually.
[239] O: No peeling occurred at all.
[240] (Triangle | delta): Peeling a little generate | occur | produces.
[241] X: 20% or more of the total area was peeled off.
[242] [PCT resistance]
[243] A cured film was obtained as in the case of solder heat resistance evaluation. The film was then placed at 121 ° C. at atmospheric pressure of 2.03 × 10 ² kPa under saturated steam pressure for 168 hours, and then the appearance of the film was visually evaluated.
[244] O: No abnormal part was observed in the appearance of the film.
[245] X: Swelling, melting or peeling was observed in the appearance of the film.
[246]
[247] Examples 35-44
[248] A four neck flask equipped with a stirring device, a thermometer, a purification column and a nitrogen introduction tube was charged with 200 parts of succinic anhydride, 600 parts of polyethylene glycol # 600, and 0.8 parts of triethyl benzyl ammonium chloride. The mixture was gradually heated to 100 ° C. under a nitrogen stream, and then allowed to react at this temperature for 5 hours to obtain a carboxyl group-containing mixture (1).
[249] Each raw material was charged to a four neck flask equipped with a stirring device, a thermometer, a purification column and a gas introduction tube in the formulation as shown in Tables 6 and 7. The resulting material was heated to a temperature as shown in Tables 6 and 7 under air flow. Thereafter, 0.01 part of hydrochloric acid diluted to 1% with bis (2-methoxyethyl) ether was slowly added dropwise to 100 parts of the raw material, and the resulting material was added and reacted at each temperature for 5 hours. Reduction of the amount of hydroxyl groups and carboxyl groups was confirmed using IR spectra and acid values, respectively. As a result, compounds (11) to (20) having a (meth) acryloyl group were obtained.
[250]
[251]
[252] Examples 45-54
[253] Compounds (11) to (20) obtained above having a (meth) acryloyl group, demineralized water, a colorant and a photopolymerization initiator are mixed in a formulation as shown in Tables 8 and 9, and are sufficiently mixed using a stirrer to form an aqueous solution. A photocurable composition was obtained. 25 g of the composition was placed in a 50 ml glass container and allowed to stand to observe the dissolution stability of the colorant.
[254] O: Separation did not occur at all within 30 minutes of calm.
[255] X: Separation occurs within 30 minutes.
[256] Thereafter, the composition was applied to one copy paper using a No. 18 bar coater, and then cured with a UV irradiation equipment (250 W ultra-high pressure mercury lamp) at a power of 1 J / cm 2. The copy paper on which the composition was applied was immersed in water at 25 ° C. for 1 minute and then visually evaluated for the degree of fading.
[257] O: No color change.
[258] (Triangle | delta): Some fading arises.
[259] X: Almost no color remains.
[260] These evaluations are compared with that of polyethylene glycol diacrylate as shown in the comparative examples. These results are summarized in Tables 8 and 9.
[261]
[262]
[263] Comparative Examples 7-12
[264] Each raw material was mixed in the formulation as shown in Table 10 and the reaction products were evaluated as in Examples 45-54. These results are summarized in Table 10.
[265]
[266] The contents of Tables 6-10 will be discussed below.
[267] Units of numerical values in the tables above are parts by mass unless otherwise indicated. VEEA: 2- (vinyloxyethoxy) ethyl acrylate; VEEM: 2- (vinyloxyethoxy) ethyl methacrylate; TEG: tetraethylene glycol; Polyglycerine; Polyglycerin # 750 (trade name, product of Sakamoto Yakuhin Kogyo Co., Ltd.); TMP-30EO: trimethylolpropane having 30 oxyethylene groups; Irgacure 2959: 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, water soluble photopolymerization initiator (trade name, product of Ciba Specialty Chemicals) ; Benzofurfurin 4B: red direct dye, also called Direct Red 2; Direct Fast Brown BX: Brown Direct Dye; Direct Fast Red 3B; Red direct dyes; Monomer (1): diacrylate of polyethylene glycol (PEG) having a number average molecular weight of 400; Monomer (2): Diacrylate of PEG with a number average molecular weight of 1000.
[268] The present invention provides a compound having a (meth) acryloyl group suitably used in various applications, a method for simply preparing the compound under mild conditions, and useful photocurable compositions and aqueous photocurable compositions containing the compound. .

权利要求:
Claims (7)
[1" claim-type="Currently amended] A method for producing a compound having a (meth) acryloyl group, comprising: reacting a compound having both a (meth) acryloyl group and a vinyl ether group with a compound having two or more functional groups capable of addition reaction with the vinyl ether group. .
[2" claim-type="Currently amended] As a compound having a (meth) acryloyl group, a functional group of the compound (A) having two or more functional groups (the functional group of the compound (A) is selected from the group consisting of a hydroxyl group, a carboxyl group and a thiol group), and a (meth) acryl The compound obtained by addition reaction of the vinyl ether group of compound (B) which has both a loyl group and a vinyl ether group.
[3" claim-type="Currently amended] The compound according to claim 2, wherein the compound (A) is selected from the group consisting of an epoxy acrylate, an unsaturated polyester, a phenol resin, an epoxy resin, a phenoxy resin and a hydroxyl group-containing polymer.
[4" claim-type="Currently amended] As a compound having a (meth) acryloyl group, two or more (meth) acryloyl group-containing groups are present in one molecule, and the (meth) acryloyl group-containing group is represented by the following Formula 1 and / or the following Formula 2 Compounds characterized in that:
[Formula 1]
(Wherein R ¹ represents a hydrogen atom or a methyl group, R ² represents an organic moiety, R ³ represents a hydrogen atom or an organic moiety, and X represents an oxygen or sulfur atom),
[Formula 2]
(Wherein, R ⁴ represents a hydrogen atom or a methyl group, R ⁵ represents an organic moiety, and R ⁶ represents a hydrogen atom or an organic moiety).
[5" claim-type="Currently amended] A photocurable composition containing both a compound having a (meth) acryloyl group according to any one of claims 2 to 4 and a photopolymerization initiator as a photocurable composition.
[6" claim-type="Currently amended] The photocurable composition according to claim 5, further comprising an inorganic powder.
[7" claim-type="Currently amended] An aqueous photocurable composition containing the compound and water which have a (meth) acryloyl group in any one of Claims 2-4, and water.

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KR100653144B1|2006-12-01|

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引用文献:

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公开号 | 申请日 | 公开日 | 申请人 | 专利标题

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法律状态:
2001-11-01|Priority to JP2001336860

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2001-11-01|Priority to JPJP-P-2001-00336860

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2002-10-31|Application filed by 가부시키가이샤 닛폰 쇼쿠바이

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2003-05-16|Publication of KR20030038394A

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2006-12-01|Application granted

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2006-12-01|Publication of KR100653144B1

优先权:

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申请号 | 申请日 | 专利标题

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JP2001336860|2001-11-01|

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JPJP-P-2001-00336860|2001-11-01|