• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    For example, it can be used suitably as various additives, such as an anti-blocking agent of a food packaging material, and provides the (meth) acrylic crosslinked fine particle excellent in heat resistance, and its manufacturing method. A monomer composition containing a (meth) acrylic monomer such as methyl methacrylate is subjected to suspension polymerization using an organic peroxide (polymerization initiator) such as lauroyl peroxide, and then the resulting polymer is in a range of 80 to 95 ° C. In, 1.5 hours or more. As a result, the amount of the (meth) acrylic monomer remaining is 2000 ppm or less, and at the same time, the thermal decomposition start temperature is 260 ° C. or more, and more preferably (meth) having a crosslinked structure having an average particle diameter in the range of 0.1 to 500 μm. It is possible to obtain acrylic crosslinked fine particles.
    公开号:KR20030027850A
    申请号:KR1020020059077
    申请日:2002-09-28
    公开日:2003-04-07
    发明作者:오오이시히데끼；시미즈수지；이노우에마사후미；야마모토야스히로
    申请人:니폰 쇼쿠바이 컴파니 리미티드；
    IPC主号:
    专利说明:

    (Meth) acrylic crosslinked fine particles and its manufacturing method {(METH) ACRYLIC CROSSLINKED FINE PARTICLES AND METHOD OF MANUFACTURING THE SAME}
    [1] TECHNICAL FIELD This invention relates to the (meth) acrylic crosslinked fine particle which can be suitably used as various additives, such as an antiblocking agent of a food packaging material, and its manufacturing method, for example.
    [2] Conventionally, the (meth) acrylic-type polymer which has a crosslinked structure formed by superposing | polymerizing the monomer composition containing a (meth) acrylic-type monomer is known. In particular, (meth) acrylic crosslinked fine particles having an average particle diameter of about 0.1 to 500 µm include, for example, antiblocking agents for resin films, toner additives for electrostatic charge development, powder coatings and water dispersions. It is expected to be applied in applications such as body paints, cosmetic plate additives, artificial marble additives, cosmetic fillers, chromatography column fillers, light diffusing agents and abrasives. And, as described in Japanese Patent Application Laid-Open No. 05-127049 (published May 28, 1993) and Japanese Patent Application Laid-Open No. 06-73106 (published March 15, 1994), the method for producing the fine particles includes the monomer The method of obtaining (meth) acrylic crosslinked fine particles is known by suspension-polymerizing a composition using 2,2'- azobisisobutyronitrile (AIBN).
    [3] However, the (meth) acrylic crosslinked fine particles produced by the above-mentioned conventional method contains decomposition products of AIBN as impurities. The decomposition products are toxic, and therefore, the crosslinked fine particles can be suitably used as various additives such as antiblocking agents for films other than foods, but they cannot be used as antiblocking agents for food packaging materials. For example, Japanese Patent Application Laid-Open No. 01-43504 (published February 15, 1989) discloses suspension polymerization of a monomer composition using an organic peroxide, but a method of reducing the remaining monomers by aging. Since the (meth) acrylic crosslinked microparticles | fine-particles manufactured by the said method are large, the quantity of the (meth) acrylic-type monomer remaining in the said microparticles | fine-particles is large, and heat resistance is bad. Therefore, the said microparticles | fine-particles also cannot be used as an antiblocking agent of a food packaging material. In addition, the film for food packaging materials, as well as the film in other applications, may require transparency, and the fine particles as the antiblocking agent accordingly require physical properties that do not affect the transparency of the film even if added. . In particular, when the (meth) acrylic crosslinked fine particles are used in a film resin for a purpose different from an antiblocking agent, since the thermoplastic resin is usually used as a film resin, the film resin is thermally melted and processed into a film. . Therefore, the (meth) acrylic crosslinked fine particles are dried at a high temperature in a processing step for a film or the like as a film resin.
    [4] In the polymerization step of the production step of obtaining the (meth) acrylic crosslinked fine particles, when an aromatic organic peroxide (specifically, benzoyl peroxide) is used, the (meth) acrylic crosslinked fine particles obtained are easily discolored by heat. It also proved in this review that it affects the transparency of the film. Therefore, it is desired that the microparticles are suppressed in yellowing when dried at high temperature, particularly at high temperature.
    [5] That is, in the above conventional manufacturing method, the obtained (meth) acrylic crosslinked fine particles contained decomposition products of AIBN as impurities, and thus could not be used as an antiblocking agent for food packaging materials. In addition, even if the (meth) acrylic crosslinked fine particles obtained by using a polymerization initiator other than AIBN contain many unreacted (meth) acrylic monomers, or because they are weak to heat resistance, particularly yellowing at high temperatures, the polymers It has a problem that it is impossible to use suitably with various additives, such as an anti blocking agent of a packaging material. Therefore, in the prior art, there is no document that specifically discloses the object of the present invention, and there is no document presenting the solution.
    [6] Moreover, in the said prior art, it was impossible to obtain the (meth) acrylic crosslinked fine particle which can achieve the objective of this invention.
    [7] An object of the present invention is to provide (meth) acrylic crosslinked fine particles excellent in heat resistance and can be suitably used as various resin additives or coating agents, such as antiblocking agents for food packaging materials, for example. Furthermore, it is an index when manufacturing the said (meth) acrylic crosslinked microparticles | fine-particles in providing the suitable physical property which should be achieved.
    [8] In order to achieve the above object, the (meth) acrylic crosslinked fine particles of the present invention have a (meth) acrylic crosslinked polymer having a mean particle size of 0.1 to 500 µm obtained by polymerizing a monomodal composition containing a (meth) acrylic monomer. It is microparticles | fine-particles, does not contain the decomposition product derived from azoisobutyronitrile, and the quantity of the (meth) acrylic-type monomer which remain | survives in the said (meth) acrylic crosslinked microparticles is 2000 ppm or less, and at the same time, the thermal decomposition of the said (meth) acrylic crosslinked microparticles | fine-particles The starting temperature is 260 ° C or higher, and furthermore, the Hunter whiteness after heating the (meth) acrylic crosslinked fine particles at 260 ° C for 30 minutes is characterized by being 85% or higher. The (meth) acrylic crosslinked fine particles may include at least one selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds, and azo ester compounds. It is preferable to polymerize the monomer composition containing a (meth) acrylic monomer using a kind of polymerization initiator.
    [9] According to the above structure, the amount of the (meth) acrylic monomer remaining in the fine particles is 2000 ppm or less, and at the same time, the thermal decomposition start temperature is 260 ° C or higher, and the hunter of the (meth) acrylic crosslinked fine particles after heating at 260 ° C for 30 minutes. Whiteness is more than 85%. Specifically, the (meth) acrylic crosslinked fine particles have less amount of unreacted (meth) acrylic monomers than before, and at the same time, have heat resistance and heat discoloration resistance. For this reason, for example, it is possible to provide (meth) acrylic crosslinked fine particles which can be suitably used as an antiblocking agent for food packaging materials such as food packaging films. In addition, since AIBN is not used as a polymerization initiator, there are no AIBN decomposition products remaining in the fine particles. In the present invention, the heat resistance yellowing resistance of the (meth) acrylic crosslinked fine particles is based on the Hunter whiteness represented by the (meth) acrylic crosslinked fine particles after the heating test at 260 ° C.
    [10] Moreover, in order to achieve the said objective, the manufacturing method of the (meth) acrylic-type crosslinked fine particle of this invention is a monomer composition containing a (meth) acrylic-type monomer, The organic peroxide, an azo-type acyclic azine compound, an azo-type cyclic arm After the polymerization was carried out using at least one polymerization initiator selected from the group consisting of a gin compound, an azo amide compound, an azo alkyl compound and an azo ester compound, the obtained polymer was polymerized at a temperature within a range of 80 to 95 ° C. It is characterized by aging more than time.
    [11] According to the above constitution, the amount of (meth) acrylic monomers remaining in the fine particles, containing no impurities such as decomposition products of toxic AIBN, is 2000 ppm or less, and the thermal decomposition initiation temperature is 260 ° C or higher and 260 ° C. The (meth) acrylic crosslinked fine particles having a Hunter whiteness of 85% or more after heating for 30 minutes at, i.e., the amount of unreacted (meth) acrylic based monomers are smaller than before, and at the same time, the (meth) acrylic crosslinked particles having heat resistance, It is possible to manufacture simply.
    [12] Other objects, features, and excellent points of the present invention will be fully understood by the description below.
    [13] EMBODIMENT OF THE INVENTION One Embodiment of this invention is demonstrated as follows.
    [14] The (meth) acrylic crosslinked fine particles in the present invention are selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds and azo ester compounds. It is a (meth) acrylic crosslinked fine particle which has a crosslinked structure formed by superposing | polymerizing the monomer composition containing a (meth) acrylic-type monomer using at least 1 type of polymerization initiator, and has an average particle diameter in the range of 0.1-500 micrometers, There is no decomposition product derived from butyronitrile, and the amount of (meth) acrylic monomer remaining in the fine particles is 2000 ppm or less, and at the same time, the thermal decomposition start temperature is 260 ° C or higher, and further, the above-mentioned (meta) after heating at 260 ° C for 30 minutes. ) Hunter whiteness of acrylic crosslinked fine particles is more than 85%. In addition, in this invention, although there is a provision called "(meth) acrylic-type monomer remaining in the said microparticles | fine-particles", "in the said microparticles | fine-particles" means that it is contained in the said microparticles, and a (meth) acrylic-monomer etc. It also includes the case where it exists in the surface of the said microparticles | fine-particles.
    [15] Moreover, in this invention, the manufacturing method of a (meth) acrylic-type crosslinked microparticles | fine-particles is after polymerizing the monomer composition containing a (meth) acrylic-type monomer using the said polymerization initiator, and the obtained polymer inside the range which is 80-95 degreeC. It is a method of aging at temperature for 1.5 hours or more. In the present invention, "monomer composition containing a (meth) acrylic monomer" refers to a monomer composition containing a (meth) acrylic monomer as a main component (50 wt% or more, 99.5% or less).
    [16] The monomer composition contains at least a crosslinking monomer which copolymerizes the (meth) acrylic monomer with the (meth) acrylic monomer to cause a crosslinked structure (molecular crosslinking structure) to the (meth) acrylic crosslinked fine particles.
    [17] Specific examples of the (meth) acrylic monomers include acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, n-octyl acrylate, dodecyl acrylate, Acrylic acid type, such as stearyl acrylate, 2-ethylhexyl acrylate, and tetrahydrofurfuryl acrylate; Methacrylic acid, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-octyl methacrylate, methacrylic acidity Methacrylic acid, such as a decyl, a stearyl metal methacrylate, 2-ethylhexyl methacrylate, and tetrahydrofurfuryl methacrylate; is mentioned. One type of these (meth) acrylic monomers may be used, or may use two or more types together. Among the (meth) acrylic monomers of the above examples, methyl methacrylate is more preferable. Therefore, it is especially preferable that the monomer composition contains methyl methacrylate as a main component (50 wt% or more, 99.5% or less).
    [18] Said crosslinkable monomer may be a monomer having several polymerizable double bonds in a molecule. Specific examples of the crosslinkable monomer include trimethacrylate propane, aryl methacrylate, ethylene dimethacrylate, diethylene glycol dimethacrylate, deethylene glycol dimethacrylate, and dimethacryl. Acid decaethylene glycol, dimethacrylate pentadecethylene ethylene glycol, dimethacrylate pentaconta hexethylene glycol, dimethacrylic acid 1,3-butylene, trimethacrylate trimetholpropane, tetramethacrylate pentaery (Meth) acrylic acid-based crosslinking monomers such as stall and diethylene glycol phthalate diethylene glycol; Aromatic divinyl compounds such as divinylbenzene and divinyl naphthalene; Derivatives of these aromatic divinyl compounds; N, N-divinyl aniline, divinyl ether, divinyl sulfide, divinyl sulfonic acid, polybutadiene, polyisoprene; Etc. can be mentioned. These crosslinkable monomers may use only one type, or may use two or more types together. Among the crosslinkable monomers in the above-mentioned examples, the (meth) acrylic crosslinked fine particles have a (meth) acrylic acid system in order to retain weather resistance and heat resistance, which are physical properties derived from a (metal) acrylic monomer, and particularly the heat yellowing resistance of the present invention. More preferred are monomers.
    [19] In addition, the monomer composition may contain monomers other than a (meth) acrylic monomer and a crosslinkable monomer, ie, a monomer copolymerizable with a (meth) acrylic monomer, as needed. Specific examples of the monomers include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-methokistylene, pt-butylstyrene, p-phenylstyrene, and o Styrenes such as -chloro styrene, m-chloro styrene and p-chloro styrene; Ethylene, propylene, butylene, vinyl chloride, vinyl acetate, acrylonitrile, acrylamide, methacrylamide, N-vinyl-2-pyrrolidone; Although these etc. are mentioned, it is not specifically limited. You may use two or more types of these monomers as needed. The monomers other than the said (meth) acrylic monomer and a crosslinkable monomer are obtained in order that the obtained (meth) acrylic crosslinked fine particles may retain the weather resistance and heat resistance which are the physical properties derived from a (meth) acrylic monomer, and especially the heat yellowing resistance which focuses on this invention. The monomer composition is 100% by weight, preferably 0 to 20% by weight, more preferably 0 to 10% by weight, still more preferably 0 to 5% by weight.
    [20] The content of the (meth) acrylic monomer in the monomer composition is preferably 50 to 99.5% by weight, more preferably 60 to 95% by weight of the monomer composition. Therefore, the content of the crosslinkable monomer in the monomer composition is preferably 0.5% by weight to 50% by weight, more preferably 5% by weight to 40% by weight of the monomer composition. In addition, the solubility parameter value (SP value) of the monomer composition is preferably 9.0 (dl / cm 3) 1/2 or less.
    [21] When polymerizing a monomer composition, it is preferable to use water as a solvent. That is, in the manufacturing method which concerns on this invention, it is preferable to suspend-polymerize a monomer composition.
    [22] A well-known method can be employ | adopted for the density | concentration (content rate) of a monomer composition in a suspension, and the preparation method of a suspension.
    [23] In the suspension polymerization of the polymerization initiator monomer composition, at least one member selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds and azo ester compounds Polymerization initiator is used.
    [24] Specific examples of the organic peroxide include o-chlorobenzoyl peroxide, o-methoxyoxybenzoyl peroxide, lauroyl peroxide, octanoyl peroxide, methyl ethyl ketopaoxide, diisopropylpaoxydicarbonate, xmenhydropaoxide and cyclohexa. Nonpaoxide, t-butyl hydropaoxide, diisopropyl benzene hydropaoxide, etc. are mentioned.
    [25] These organic peroxides may be used independently and may use two or more types together. That is, among the organic peroxides, organic peroxides (organic peroxides having an acyclic aliphatic alkyl structure) having no aliphatic alkyl structure and not having a benzene ring structure are preferable. In the organic peroxide having a benzene ring structure, the decomposition products of the peroxide may adversely affect the heat yellowing resistance of the (meth) acrylic crosslinked fine particles. In particular, the decomposition products of benzoyl peroxide affect the thermal yellowing resistance of the crosslinked fine particles. Therefore, in the present invention, when benzoyl peroxide is used in combination with the specific polymerization initiators listed above, the amount of benzoyl peroxide is preferably set to 0 to 10% by weight of the amount of the polymerization initiator used. More preferably, it is 0-5 weight%, More preferably, it is 0-1 weight%. Most preferably, it is not used.
    [26] Specifically as an azo acyclic amide compound, For example, 2,2'- azobis (2-methyl-N-phenyl propionamide) dihydrochloride, 2,2'- azobis [N- (4- Chlorophenyl) -2-methylpropionamizine] dihydrochloride, 2,2'-azobis [N- (4-hydroxyphenyl) -2-methylpropionamizine] dihydrochloride, 2,2'-azo Bis [2-methyl-N- (phenylmethyl) propionamide] dihydrochloride, 2,2'-azobis [2-methyl-N- (2-propenyl) propionamide] dihydrochloride, 2, 2'-azobis (2-methylpropionamide) dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamide] dihydrochloride, etc. are mentioned. . Specific examples of the azo cyclic amide compound include 2,2'-azobis [2- (5-methyl-2-imidasolin-2-yl) propane] dihydrochloride, 2,2'- Azobis [2- (2-imidasolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3- Diazepin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2 '-Azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2'-azobis {2- [1- ( 2-hydroxyethyl) -2-imidazolin-2-yl] propane} dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], etc. are mentioned. have. Specific examples of the azo amide compound include 2,2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}. , 2'-azobis {2-methyl-N- [1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl ) Propionamide], 2,2'- azobis (2-methylpropionamide) dihydrate, etc. are mentioned. As an azo alkyl compound, 2,2'- azobis (2,4,4-trimethyl pentane), 2,2'- azobis (2-methyl propane) etc. are mentioned specifically ,. Specific examples of the azo ester compound include dimethyl-2,2'-azobis (2-methylpropionate) and the like. These azo polymerization initiators may be used independently or may use two or more types together. Therefore, azo-nitrile compounds, such as 2,2'- azobisisobutyronitrile (AIBN), are not contained in the category of the polymerization initiator (azo-type polymerization initiator) in this invention.
    [27] As for the usage-amount of the polymerization initiator with respect to a monomer composition, as for the quantity of the monomer composition used 100 weight%, it is more preferable to exist in the range of 0.01-20 weight%, and it is especially preferable to exist in the range of 0.1-10 weight%. . When the usage-amount of a polymerization initiator is less than 0.01 weight%, long time may be required until superposition | polymerization is complete. On the other hand, when the usage-amount of a polymerization initiator exceeds 20 weight%, the polymerization degree of a (meth) acrylic crosslinked fine particle may fall. In addition, the addition method of a polymerization initiator is not specifically limited, A well-known method can be used.
    [28] Moreover, in the manufacturing method which concerns on this invention, in order to stabilize the suspension (reaction liquid), it is preferable to add a dispersion stabilizer to the said suspension as needed. Specific examples of the dispersion stabilizer include water-soluble polymers such as polyvinyl alcohol, gelatin, tragacanth, starch, methyl cellulose, carboxymethyl cellulose, hydroxyethyl cellulose, sodium polyacrylate, and sodium polymethacrylate; Anionic surfactants; Cationic surfactants; Cationic surfactants; Nonionic surfactants; Alginate, zein, casein, barium sulfate, calcium sulfate, barium carbonate, magnesium carbonate, calcium phosphate, tolk, clay, diatomaceous earth, bentite, titanium hydroxide, thorium hydroxide, etc. are mentioned. Specific examples of the anionic surfactants include alkali metal salts of fatty acid oils such as sodium oleate and castor oil caryl; Alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate; Alkylbenzene sulfonates, such as sodium dodecyl benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfonate, dialkyl sulfo carboxylate, alkyl ester ester salt, naphthalene sulfonic acid-formaldehyde condensate, polyoxyethylene alkyl phenyl ether sulfate Ester salts and polyoxyethylene alkyl sulfate ester salts; Etc. can be mentioned. Specific examples of the cationic surfactant include alkylamine salts such as laurylamine acetate and stearylamine acetate; Quaternary ammonium salts such as lauryltrimethylammonium chloride; Etc. can be mentioned. As said amphoteric surfactant, lauryl dimethylamine oxide etc. are mentioned specifically ,. As said nonionic surfactant, specifically, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxy sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin Fatty acid ester, an oxyethylene oxypropylene block copolymer, etc. are mentioned. It is also possible to use powders of various metal oxides as dispersion stabilizers. These dispersion stabilizers may be used independently as needed, and may use two or more types together.
    [29] As for the usage-amount of the dispersion stabilizer with respect to a monomer composition, it is more preferable to exist in the range of 0.01-29 weight%, and it is especially preferable to exist in the range which is 0.1-10 weight%. By setting the amount of the dispersion stabilizer to be within the above range, the particle diameter of the (meth) acrylic crosslinked fine particles obtained is within a predetermined size, for example, within a range of 0.1 to 500 µm, more preferably 0.5 to 100 µm. More preferably, it is possible to carry out in the range of 0.5-30 micrometers. In addition, a well-known method can be used for the addition method of a dispersion stabilizer.
    [30] In addition, in the present invention, the production method, in order to suppress the formation of fine particles to obtain particles with a substantially uniform particle size (narrow particle size distribution), more specifically, particles having an average particle diameter in the range of 0.1 to 500 µm. In order to obtain, the suspension is substantially insoluble in water (1012 h㎩, solubility of 1% by weight or less under the condition of 25 ± 5 ° C), and at the same time, poorly soluble in the monomer composition (solubility of 50% by weight or less under the same condition). It is preferable to add a compound (henceforth a compound (a)).
    [31] The compound (a) is preferably a compound having at least one functional group or structural unit selected from the group consisting of -SH group, -COOH group, -NO 2 group, -OH group, and -SS-bond. Specific examples of the compound having an —SH group include thiocresol, thiophenol, methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, 2-ethylhexyl thioglycolic acid, dithiohydrokinone, and xylenedithiol. Mercaptonaphthalene, and the like. As a compound which has a -COOH group, a cinnamic acid, a benzoic acid, a chlorobenzoic acid, a phthalic acid, an isophthalic acid etc. are mentioned specifically ,. Specific examples of the compound having a —NO 2 group include nitrobenzene, nitrotoluene, nitronaphthalene, nitroaniline, and the like. Specific examples of the compound having an —OH group include, for example, aminocresol, naphthol, aminonaphthol, m-cresol, oxycanthracene, dioxyanthracene, oxycyanchinone, deoxyanthracinone, oxanthrone, and 3-oxy-. 9-anthrone, oxynaphthynone, 1, 5- dioxy naphthalene, 1, 8- dioxy naphthalene, 2, 6- dioxy naphthalene, 3, 5- dimethyl phenol, etc. are mentioned. Specific examples of the compound having a -SS- bond include diaryl disulfide, dithiodipropionate dioctyl ester and the like. Specific examples of the compound having a plurality of structural units include salicylic acid, thiosalicylic acid, dithiosalicylic acid, nitrobenzoic acid, 3,4-dinitrobenzoic acid, nitrophenol, and the like. These compounds (a) may be used independently as needed, and may use two or more types together.
    [32] The amount of the compound (a) added to the monomer composition is more preferably in the range of 0.0001 to 20% by weight, still more preferably in the range of 0.001 to 10% by weight, and in the range of 0.01 to 5% by weight. Particularly preferred. When the addition amount of the compound (a) is less than 0.0001% by weight, it may be difficult to suppress the production of fine particles. On the other hand, when the addition amount of a compound (a) exceeds 20 weight%, the polymerization degree of a (meth) acrylic crosslinked fine particle may fall. In addition, the addition method of a compound (a) is not specifically limited.
    [33] A (meth) acrylic crosslinked fine particle can be obtained by adding a monomer composition and a polymerization initiator to water, preparing a suspension by adding a dispersion stabilizer and / or a compound (a) as needed, and then carrying out suspension polymerization. The (meth) acrylic crosslinked fine particles have a crosslinked structure. The order and timing of adding the monomer composition, polymerization initiator, dispersion stabilizer, and compound (a) to water are not particularly limited. The polymerization temperature of suspension polymerization is suitably in the range of 10 to 90 ° C, and most preferably in the range of 30 to 80 ° C. In addition, it is more preferable to perform suspension polymerization in the atmosphere of inert gas, such as nitrogen gas. As a stirring method in suspension polymerization, in order to prevent the (meth) acrylic crosslinked microparticles obtained from enlarging or agglomerating particle | grains, the method of using the apparatus which can stir more powerfully, for example, It is preferable to use a so-called high speed stirrer and a homo mixer such as a line mixer. Since the particle size can be controlled by the suspension polymerization, it is possible to obtain (meth) acrylic crosslinked particles having an even particle diameter (narrow particle size distribution). In addition, the suspension is within the range that does not interfere with the polymerization, and at the same time, corresponding to the use of the (meth) acrylic crosslinked fine particles, colorants such as pigments and dyes, plasticizers, polymerization stabilizers, fluorescent whitening agents, Various additives, such as a component, a ultraviolet absorber, an antistatic agent, and a flame retardant, may be added and mixed. Specific examples of the pigments include inorganic pigments such as lead white, briquette, sulfur lead, carbon black, ultramarine blue, zinc oxide, cobalt oxide, titanium dioxide, iron oxide, silica, sulfur titanium, and titanium black; Organic pigments such as isoindrinone, kinacridone, dioxane violet, putarosyanine blue, perinone pigment, perylene pigment, insoluble azo pigment, soluble azo pigment, and dyed lake. Specific examples of the dyes include nitroso dyes, nitro dyes, azo dyes, stilbenazo dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrizin dyes, chinoline dyes, methine dyes, and poly Methine dye, thiazole dye, indamine dye, indophenol dye, azine dye, oxazine dye, thiazine dye, sulfide dye and the like. In addition, when the said additive is a powder form, a granule form, etc., for example, surface treatment may be given for the purpose of the improvement of dispersibility.
    [34] After the monomer composition is polymerized and the polymerization rate is confirmed to be 85% or more, the (meth) acrylic crosslinked fine particles having a crosslinked structure can be obtained in the present invention by heating the mixture as it is and stirring the mixture. It is preferable that the said polymerization rate is 85% or more in order to efficiently reduce the (meth) acrylic-type monomer component which remain | survives in the aging of the superposition | polymerization performed after this. The said polymerization rate is obtained by calculating solid content by sampling the polymerization liquid which superposed | polymerized the monomer component. Hereinafter, suspension polymerization as a preferred embodiment of the present invention will be taken as an example, and more specifically, a method for calculating the polymerization rate will be defined.
    [35] The polymerization rate here is calculated as follows. 2 g of the suspension is sampled, its weight is measured, and the weight of the monomer composition at the time of making the sampled suspension is calculated from the ratio produced. While cooling the sampled suspension, 1 ml of polymerization inhibitor solution (acetone solution adjusted to 2000 ppm hydrokinone) was added, placed in an aluminum cup with a measuring unit, dried at 110 ° C. for 30 minutes, and then left in an aluminum cup. The weight of the remaining solid is measured. From these results, the polymerization rate is calculated as the ratio of the weight of the remaining solid to the weight of the monomer composition produced. As said polymerization inhibitor, a metokinone (brand name, SEIKO CORPORATION) etc. are mentioned, for example. The above aging is carried out for the purpose of further reducing the amount of unreacted (meth) acrylic monomers contained in the (meth) acrylic crosslinked fine particles and further improving heat resistance. As a aging method, the suspension containing the (meth) acrylic crosslinked microparticles | fine-particles (polymer) obtained by the superposition | polymerization process of this invention is in the range of 80-95 degreeC, More preferably, it is in the range of 85-95 degreeC. A method of stirring (aging) for 1.5 hours or more is suitable. Moreover, it is more preferable to carry out aging of a polymer in atmosphere of inert gas, such as nitrogen gas. When the said aging process uses the specific polymerization initiator employ | adopted by this invention, in order to reduce the (meth) acrylic-type monomer component which remain | survives in the (meth) acrylic crosslinked fine particle obtained, it becomes a preferable embodiment. In the above aging step, the suspension containing the (meth) acrylic crosslinked fine particles (polymer) obtained by suspension polymerization is more preferably aged.
    [36] Since the polymerization proceeds further by aging, when the amount of the (meth) acrylic monomer remaining in the (meth) acrylic crosslinked fine particles is 2000 ppm or less (that is, the (meth) acrylic monomer is composed of methyl methacrylate, 2000 ppm or less), More preferably, it is 1800 ppm or less, More preferably, it is 1500 ppm or less. In addition, preferably, the amount of the crosslinkable monomer remaining in the fine particles can be 50 ppm or less. In addition, since heat resistance can be imparted, it is possible to set the thermal decomposition start temperature to 260 ° C or higher. That is, the crosslinkable monomer which has several polymerizable double bonds in the molecule | numerator used in the monomer composition for obtaining the (meth) acrylic-type crosslinked particle of this invention although it is the (meth) acrylic-type monomer measured on the basis of the said residual monomer is Not applicable The crosslinkable monomer has high polymerizability, and the remaining amount can be sufficiently evaluated by the remaining amount of the (meth) acrylic monomer in the (meth) acrylic crosslinked fine particles as an index indicating the degree of ripening performed in the (meth) acrylic crosslinked fine particles. . In the present invention, the remaining amount of the crosslinkable monomer is defined as a more preferable embodiment. That is, when the (meth) acrylic crosslinked fine particles of the present invention use a monomer other than the (meth) acrylic monomer or the crosslinkable monomer, in which the (meth) acrylic monomer and the crosslinkable monomer can be copolymerized, the other monomers remain. Amount shall be included in the quantity of a (meth) acrylic-type monomer. In addition, the (meth) acrylic crosslinked fine particles obtained through the aging composition in this way are excellent in water resistance and oil resistance.
    [37] According to the production method of the present invention, the average particle diameter of the (meth) acrylic crosslinked fine particles is in the range of 0.1 to 500 µm, more preferably in the range of 0.5 to 100 µm, and more preferably 0.5 to 30 µm. The particle size distribution can be narrowed at the same time. In addition, when using (meth) acrylic crosslinked fine particles as an antiblocking agent (to be described later), the average particle size is preferably in the range of 0.1 to 30 µm, more preferably in the range of 0.3 to 25 µm, It is more preferable to exist in the range of 0.5-20 micrometers.
    [38] The amount of the (meth) acrylic monomer remaining in the fine particles is a value measured based on the method prescribed by the Food and Drug Administration (FDA). The above-mentioned thermal decomposition start temperature is a temperature at which the weight of the sample begins to decrease due to thermal decomposition in differential thermal gravimetric analysis (TG-DTA) in air under predetermined conditions. An average particle diameter is the value measured using the coalta counter.
    [39] As a method of extracting the (meth) acrylic crosslinked fine particles from the suspension, a method of filtration and a method of using a separator such as a centrifugal separator are simple, but are not particularly limited. The (meth) acrylic crosslinked fine particles after extraction from the suspension may be washed and dried as necessary, but the drying temperature and the drying method are not particularly limited.
    [40] The water content after drying of the (meth) acrylic crosslinked fine particles of the present invention is 10% or less, preferably 7% or less, more preferably 5% or less, even more preferably 3% or less. The moisture content after drying of this (meth) acrylic crosslinked fine particle is measured by weight reduction before and after drying of the (meth) acrylic crosslinked fine particle.
    [41] By the method described above, the amount of (meth) acrylic monomers remaining in the fine particles is 2000 ppm or less without containing impurities such as decomposition products of toxic 2,2'-azobisisobutyronitrile (AIBN), At the same time, the pyrolysis initiation temperature is 260 ° C or higher, and furthermore, (meth) acrylic crosslinked fine particles having a hunter whiteness of 85% or more after heating at 260 ° C for 30 minutes, that is, unreacted. The amount of the (meth) acrylic monomer is less than that of the prior art, and at the same time, the (meth) acrylic crosslinked fine particles having heat resistance and heat discoloration resistance can be easily produced.
    [42] In the present invention, the (meth) acrylic crosslinked fine particles are (meth) acrylic crosslinked fine particles having a mean particle size in the range of 0.1 to 500 µm obtained by polymerizing a monomer composition containing a (meth) acrylic monomer, and azoisobuty The amount of (meth) acrylic monomers remaining in the (meth) acrylic crosslinked fine particles not included in the decomposition product derived from ronitrile was 2000 ppm or less, and the thermal decomposition initiation temperature of the (meth) acrylic crosslinked fine particles was 260 ° C or higher. Furthermore, the Hunter whiteness of the (meth) acrylic crosslinked fine particles after heating the (meth) acrylic crosslinked fine particles at 260 ° C for 30 minutes is 85% or more. That is, the amount of the (meth) acrylic crosslinked fine particles is less than that of the conventional unreacted (meth) acrylic monomer, and at the same time, it has heat resistance that can withstand the processing temperature of the packaging material. Furthermore, the (meth) acrylic crosslinked fine particles of the present invention also have good heat discoloration resistance. Specifically, the above-mentioned heat discoloration resistance is discolored to the (meth) acrylic crosslinked fine particles even when dried at a high processing temperature when processing the resin composition containing the (meth) acrylic crosslinked fine particles of the present invention as a packaging material. This is a difficult property to occur. These physical properties are obtained by polymerizing the (meth) acrylic crosslinked fine particles of the present invention using a specific polymerization initiator without using AIBN, and bringing them together by sufficiently performing aging after polymerization. For this reason, the (meth) acrylic crosslinked fine particles are, for example, food packaging materials such as food packaging films produced from polyolefins such as polyethylene and polypropylene, or thermoplastic resins such as polyethylene terephthalate (PET): polyester. Or as an antiblocking agent of pharmaceutical packaging materials, such as a pharmaceutical packaging film, it can use especially suitably. Of course, the (meth) acrylic crosslinked fine particles of the present invention can also be used as an antiblocking agent for packaging materials such as general packaging films. When using as an anti blocking agent, the compounding quantity of the (meth) acrylic crosslinked fine particles is preferably in the range of 0.001 to 5% by weight, more preferably in the range of 0.005 to 3% by weight with respect to the thermoplastic resin. Although within the range of 2 weight% is more preferable, it is not specifically limited. Usually, it is difficult to mix such a small amount in the manufacturing process, so that the anti-blocking agent master batch is prepared, and the thermoplastic resin composition for film, in which the thermoplastic resin and the predetermined amount are blended, is melted to form a film.
    [43] That is, when the aromatic benzoyl peroxide is used in the organic peroxide as the polymerization initiator, the (meth) acrylic crosslinked fine particles having no problem in the amount of (meth) acrylic monomers remaining in the fine particles, the thermal decomposition initiation temperature, etc. due to the extension of the aging time. Is obtained. However, in the case of producing a film using (meth) acrylic crosslinked fine particles obtained by polymerization using benzoyl peroxide as an antiblocking agent, the fine particles are dried by heat at the processing temperature in this film production to cause discoloration and transparency. Situations that are impossible to use with this required film may occur. Moreover, also in the film which colored anything or has a design other than a transparency film, the discoloration of a film becomes a problem because the said (meth) acrylic crosslinked fine particle mix | blended with an antiblocking agent discolors.
    [44] Therefore, the (meth) acrylic crosslinked fine particles obtained by polymerizing with benzoyl peroxide tend to become particles which do not satisfy the Hunter whiteness with the heat dissipation resistance properties defined in the present invention, and do not agree with the object of the present invention. There is also. Moreover, when using benzoyl peroxide which is an organic peroxide and superposition | polymerization initiator other than this, the conditions, such as the upper limit of benzoyl peroxide which can be used together, are needed. Moreover, when benzoyl peroxide is used together, the decomposition product of a little benzoyl peroxide is contained in the said (meth) acrylic crosslinked microparticles | fine-particles, and an influence on heat-heat discoloration resistance arises. Therefore, the form which does not use benzoyl peroxide is the most preferable in this invention. In addition, about the heat-resistant yellowing of the (meth) acrylic crosslinked microparticles | fine-particles, the color change of the said (meth) acrylic crosslinked microparticles | fine-particles after drying a (meth) acrylic crosslinked fine particle in air | atmosphere at 260 degreeC for 30 minutes by measuring Hunter whiteness with a color difference meter. Determine. This hunter whiteness puts 8 g of dry powder ((meth) acrylic crosslinked fine particles) in a 7 cm x 10 cm uncolored transparent polyethylene bag (thickness 0.02 mm), and makes it almost the thickness of the said dry powder, and is standard. It is measured with the color difference meter which zero-calibrated on the white board.
    [45] In contrast, when lauroyl peroxide as an aliphatic organic peroxide, which is a preferred embodiment of the present invention, is used, the inclusion of the decomposition product derived from AIBN in the above-mentioned (meth) acrylic crosslinked fine particles, and the problem in the benzoyl peroxide. It is possible to eliminate phosphorus heat discoloration (yellowing). That is, the (meth) acrylic crosslinked fine particles of the present invention have a Hunter whiteness of 85% or more, preferably 88% or more, and almost no yellowing.
    [46] Therefore, the (meth) acrylic crosslinked fine particles of the present invention do not contain AIBN decomposition products, and have little effect on the transparency of the film even when used as an antiblocking agent for film, or as an additive or light diffusing agent for resin. It hardly yellows under the influence of processing temperature even if used.
    [47] That is, the (meth) acrylic crosslinked fine particles of the present invention can be particularly preferably used as an antiblocking agent in a film, for example. Specifically, the film is a thermoplastic resin film such as polyethylene, polypropylene, polyvinyl chloride or polyester. The thermoplastic resin film is a thermoplastic resin composition containing the (meth) acrylic crosslinked fine particles of the present invention as an antiblocking agent (antiblocking agent (ABA) masterbatch) for film, and the antiblocking agent (ABA) described above. A thermoplastic resin composition for film containing a masterbatch and the thermoplastic resin composition can be produced by hot melt molding. At this time, the master batch and the thermoplastic resin composition are blended so that the amount of the (meth) acrylic crosslinked fine particles to be blended is a predetermined amount. The hot melt molding is, for example, extrusion molding.
    [48] Moreover, when the said thermoplastic resin is a polypropylene resin etc. which require an extending process in polyolefin resin, what is necessary is just to perform a well-known extending process. Further, in the extrusion molding, the hot melt while controlling the thickness of the thermoplastic resin composition for film by cota or doctor blade so that the film thickness is 5 to 500 m, more preferably the film thickness is 10 to 300 m. It is good to mold. The said antiblocking agent (ABA) masterbatch mix | blends 1-50 weight part of said (meth) acrylic crosslinked fine particles with respect to 100 weight part of thermoplastic resins. In addition, this antiblocking agent (ABA) master batch has a thermoplastic resin composition for film 100 parts by weight, the content of the (meth) acrylic crosslinked fine particles is 0.001 to 5 parts by weight, preferably 0.005 to 3 parts by weight, more preferably Preferably it is mix | blended with the thermoplastic resin composition for films so that it may be 0.01-2 weight part. In the following, the case of adapting to the polyolefin resin is specifically shown. For example, a stretched polyolefin resin film stretches the film composition which mix | blended the polyolefin resin composition containing the said (meth) acrylic crosslinked microparticles as an antiblocking agent with an antiblocking agent (ABA) masterbatch, and a polyolefin resin. It is possible to obtain by doing.
    [49] More specifically, the (meth) acrylic crosslinked fine particles of the present invention can be suitably used as an antiblocking agent in an antiblocking agent masterbatch used in an oriented polyolefin resin film produced by stretching at least in the uniaxial direction. . The said antiblocking agent masterbatch is mix | blended 1-50 weight part of said (meth) acrylic crosslinked fine particles with respect to 100 weight part of polyolefin resin compositions. The antiblocking agent masterbatch has a content of the (meth) acrylic crosslinked fine particles of the present invention in the film composition when the total weight of the film composition is 100 parts by weight in the stretched polyolefin resin film. It is mix | blended with a film composition so that it may be less than 1 weight part. By stretching the film composition at least in the uniaxial direction, it is possible to produce a stretched polyolefin resin film excellent in transparency.
    [50] As said polyolefin resin composition, homopolymers or copolymers, such as propylene, ethylene, butene-1, hexene-1, 4-methylpentene-1, or a mixture of these polymers are mentioned, for example, It is preferable among these, One is a polypropylene resin. The polypropylene resin includes a polypropylene homopolymer, a copolymer of propylene with another α-olefin, such as propylene-ethylene copolymer, propylene-ethylene block copolymer, propylene-butene-1 copolymer, and propylene- Butene-1 block copolymers, and mixtures thereof.
    [51] In addition, polyolefin-based polymer additives such as polyethylene, polybutene, styrene-based resin, ethylene-propylene rubber, and ethylene-propylene-diene copolymer may be added to the polyolefin resin composition as necessary.
    [52] Particularly preferred as the polypropylene resin is a crystalline propylene homopolymer or a crystalline propylene air containing 2 wt% or less of ethylene, butene-1, hexene-1,4-methylpentene-1 as the polyolefin polymer additive. It is polypropylene resin containing coalescence.
    [53] In addition, since the heat discoloration characteristic at the high temperature dried at the time of the above processing can be important properties even in light scattering agent use, the (meth) acrylic crosslinked fine particles of the present invention can be suitably used as a light scattering agent. Do.
    [54] In the present invention, the (meth) acrylic crosslinked fine particles include, for example, lubricants such as a film made of polyethylene terephthalate and a magnetic tape; Fillers in cosmetics; Toner, makeup plate, or additives of artificial marble; Powder coating, water dispersion coating; Column fillers for chromatography; It can also be used suitably as various additives, such as these, or as a space of a liquid crystal display panel, a carrier of an immunodiagnostic agent, etc.
    [55] (Example)
    [56] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. In addition, "part" described in this Example represents a "weight part."
    [57] Example 1
    [58] Polyoxyethylene alkylsulfurammonium as a dispersion stabilizer in a flask equipped with a reflux condenser, a thermometer, a nitrogen gas introduction pipe, a TK homogenizer (agitator, etc.); 0.5 parts of hytenol N-08) is dissolved in 600 parts of deionized water to form an aqueous solution. On the other hand, a monomer composition comprising 75 parts of methyl methacrylate as a (meth) acrylic monomer and 25 parts of trimethacrylate trimethacrylate as a crosslinking monomer, 1.0 part of lauroyl peroxide as a polymerization initiator (organic peroxide), and The mixture which mixed 1 part of 3, 4- dinitro benzoic acid of compound (a) was prepared. And after adding the said mixture to the aqueous solution in a flask, the content was stirred vigorously at rotation speed 4000rpm for 5 minutes, and the uniform suspension was obtained.
    [59] Subsequently, the suspension was heated to 75 ° C. while nitrogen gas was put into the flask, and suspension polymerization was carried out with stirring at the same temperature for 1 hour. At this time, when the polymerization rate was confirmed, it was 89%. Thereafter, the suspension was heated to 90 ° C, and the polymer was aged while stirring at the same temperature for 4 hours. After completion of aging, the suspension was cooled, filtered and dried to obtain (meth) acrylic crosslinked fine particles in the present invention.
    [60] The amount of methyl methacrylate remaining in the obtained (meth) acrylic crosslinked fine particles was 750 ppm. Moreover, the thermal decomposition start temperature of the (meth) acrylic crosslinked fine particle was 270 degreeC, and the average particle diameter was 9.6 micrometers. In addition, the residual amount of the crosslinkable monomer was 50 ppm or less. In addition, the moisture content of the said (meth) acrylic-type crosslinked fine particle was 2%.
    [61] In addition, 15 parts by weight of the (meth) acrylic crosslinked fine particles and 85 parts by weight of polyethylene resin (MFR 2.0 g / 10 min, density 0.91 g / cm 3) are mixed and melt-extruded using a machine that pushes out the mixture. To masterbatch. In order to dilute 1 part by weight of the masterbatch, 7.5 parts by weight of the polyethylene resin was further mixed, and an analytical film having a thickness of 500 μm was prepared using an extruder at 240 ° C. The analytical film was immersed in a solvent (methanol: water = 95: 5) in an amount of 10 ml per 1 in 2 (2.54 2 cm 2) of the analytical film for 30 minutes at 150 degrees Fahrenheit and 10 days at 104 degrees Fahrenheit for the dissolution test. Was performed.
    [62] The solvent (eluate) was quantified by methyl chromate monomer and AIBN decomposition product by gas chromatography. As a result, the elution amount of the methyl methacrylate monomer was 100 ppb, and the AIBN decomposition product was not detected at the detection limit of 50 ppb. In the analytical film, the amount of the elution to the solvent was a very good level.
    [63] Moreover, when the said (meth) acrylic-type crosslinked fine particle heated at 260 degreeC for 30 minutes, the Hunter whiteness was 90.5%.
    [64] Example 2
    [65] Polyoxyethylene alkylsulfurammonium as a dispersion stabilizer in a flask equipped with a reflux condenser, a thermometer, a nitrogen gas introduction pipe, a TK homogenizer (agitator, etc.); Hytenol N-08) is dissolved in 600 parts of deionized water to form an aqueous solution. On the other hand, a monomer composition comprising 176 parts of methyl methacrylate as a (meth) acrylic monomer and 44 parts of diethylene methacrylate as a crosslinking monomer, 2.2 parts of lauroyl peroxide as a polymerization initiator (organic peroxide), and a compound ( The mixture which mixed 2.2 parts of thiosalicylic acid as a) was prepared. And after adding the said mixture to the aqueous solution in a flask, the content was stirred vigorously at rotation speed 4000rpm for 5 minutes, and the uniform suspension was obtained.
    [66] Subsequently, the suspension was heated to 75 ° C. while blowing nitrogen gas into the flask, and suspension polymerization was carried out with stirring at the same temperature for 1 hour. At this time, when the polymerization rate was confirmed, it was 91%. Thereafter, the suspension was heated to 90 ° C, and the polymer was aged while stirring at the same temperature for 4 hours. After completion of aging, the suspension was cooled, filtered and dried to obtain (meth) acrylic crosslinked fine particles in the present invention.
    [67] The amount of methyl methacrylate remaining in the obtained (meth) acrylic crosslinked fine particles was 860 ppm. Moreover, the thermal decomposition start temperature of the (meth) acrylic crosslinked fine particle was 268 degreeC, and the average particle diameter was 10.5 micrometer. In addition, the residual amount of the crosslinkable monomer was 50 ppm or less. The moisture content of the (meth) acrylic crosslinked fine particles was 2.2%.
    [68] Further, the (meth) acrylic crosslinked fine particles obtained in the present Example were subjected to the dissolution test after obtaining a film in the same manner as in Example 1. As a result, the elution amount of methyl methacrylate was 150 ppb, and the AIBN decomposition product was not detected for the detection limit of 50 ppb. In the analytical film, the amount of the eluate to the solvent was very low and a good level.
    [69] In addition, when the said (meth) acrylic-type crosslinked fine particle heated at 260 degreeC for 30 minutes, Hunter whiteness was 89%.
    [70] Example 3
    [71] In Example 1, instead of 1.0 part of lauroyl peroxide, 1.0 part of dimethyl 2,2-azobis (2-methylpropionate) was used, and suspension polymerization was similarly performed. At this time, when the polymerization rate was confirmed, it was 88%. Thereafter, the suspension was heated to 90 ° C, and the polymer was aged while stirring at the same temperature for 6 hours. After completion of aging, the suspension was cooled, filtered and dried to obtain (meth) acrylic crosslinked fine particles in the present invention.
    [72] The amount of methyl methacrylate remaining in the obtained (meth) acrylic crosslinked fine particles was 1100 ppm. Moreover, the thermal decomposition start temperature of the (meth) acrylic crosslinked fine particle was 260 degreeC, and the average particle diameter was 9.9 micrometers. In addition, the residual amount of the crosslinkable monomer was 50 ppm or less. The moisture content of the (meth) acrylic crosslinked fine particles was 2.5%.
    [73] Further, the (meth) acrylic crosslinked fine particles obtained in the present Example were subjected to the dissolution test after obtaining a film in the same manner as in Example 1. As a result, the elution amount of methyl methacrylate was 180 ppb, and the AIBN decomposition product was not detected for the detection limit of 50 ppb. In the analytical film, the amount of the solvent eluted was very low.
    [74] Moreover, when the said (meth) acrylic-type crosslinked fine particle heated at 260 degreeC for 30 minutes, Hunter whiteness was 87%.
    [75] Comparative Example 1
    [76] Polyoxyethylene alkylsulfurammonium as a dispersion stabilizer in a flask equipped with a reflux condenser, a thermometer, a nitrogen gas introduction pipe, a TK homogenizer (agitator, etc.); 0.5 parts of hytenol N-08) is dissolved in 600 parts of deionized water to form an aqueous solution. On the other hand, a monomer composition comprising 75 parts of methyl methacrylate as a (meth) acrylic monomer and 25 parts of trimethacrylate trimethacrylate as a crosslinking monomer, 1.5 parts of benzoyl peroxide as a polymerization initiator (organic peroxide), and a compound (a The mixture which mixed 1 part of 3, 4- dinitro benzoic acid as) was prepared. And after adding the said mixture to the aqueous solution in a flask, the content was stirred vigorously at rotation speed 4000rpm for 5 minutes, and the uniform suspension was obtained.
    [77] Subsequently, the suspension was heated to 75 ° C. while nitrogen gas was put into the flask, and suspension polymerization was carried out with stirring at the same temperature for 1 hour. At this time, when the polymerization rate was confirmed, it was 88%. Thereafter, the suspension was heated to 90 ° C, and the polymer was aged while stirring at the same temperature for 4 hours. After completion of aging, the suspension was cooled, filtered and dried to obtain (meth) acrylic crosslinked fine particles in the present invention.
    [78] The amount of methyl methacrylate remaining in the obtained (meth) acrylic crosslinked fine particles was 950 ppm. Moreover, the thermal decomposition start temperature of the (meth) acrylic crosslinked fine particle was 270 degreeC, and the average particle diameter was 9.8 micrometers.
    [79] In addition, the (meth) acrylic crosslinked fine particles obtained in the present comparative example were subjected to the dissolution test in the same manner as in Example 1 after obtaining a film. As a result, the elution amount of methyl methacrylate was 100 ppb, and the AIBN decomposition product was not detected for the detection limit of 50 ppb. In the analytical film, the amount of the elution to the solvent was a very good level.
    [80] Moreover, when the said (meth) acrylic crosslinked fine particle heated at 260 degreeC for 30 minutes, Hunter whiteness was 82.5%.
    [81] Comparative Example 2
    [82] In Comparative Example 1, (meth) acrylic crosslinked fine particles were obtained by polymerization under the same conditions using 1.0 parts of AIBN instead of benzoyl peroxide as the polymerization initiator. Moreover, it was 92% when the polymerization rate was confirmed.
    [83] The amount of methacrylic acid remaining in the obtained meta) acrylic crosslinked fine particles was 1100 ppm. Moreover, the thermal decomposition start temperature of the (meth) acrylic crosslinked fine particle was 272 degreeC, and the average particle diameter was 10.4 micrometers.
    [84] In addition, the (meth) acrylic crosslinked fine particles obtained in the present comparative example were subjected to the dissolution test in the same manner as in Example 1 after obtaining a film. As a result, the elution amount of methyl methacrylate was 100 ppb, but the elution amount of the AIBN decomposition product was 150 ppb. Therefore, the (meth) acrylic crosslinked fine particles of the present comparative example may be considered to be unsuitable as food packaging materials because AIBN decomposition products are eluted.
    [85] Comparative Example 3
    [86] After obtaining a uniform suspension under the same conditions as in the example, the suspension was heated to 75 ° C while nitrogen gas was put into the flask, and the suspension was polymerized while stirring at the same temperature for 1 hour. The polymerization rate at that time was 91%. Then, the (meth) acrylic-type crosslinked fine particle was obtained, without passing through aging conditions, stirring at 75 degreeC for 4 hours.
    [87] The amount of methyl methacrylate remaining in the (meth) acrylic crosslinked fine particles obtained without undergoing aging was 6000 ppm and the crosslinking monomer was 250 ppm. Moreover, the thermal decomposition start temperature of the (meth) acrylic crosslinked fine particle was 260 degreeC, and the average particle diameter was 9.7 micrometers.
    [88] In addition, the (meth) acrylic crosslinked fine particles obtained in this comparative example were subjected to the eluting test after obtaining a film in the same manner as in Example 1. As a result, the elution amount of methyl methacrylate was 700 ppb, and the AIBN decomposition product was not detected with respect to the detection limit of 50 ppb. As a large amount of eluate is used for food packaging materials, it can be determined that it is unsuitable. In addition, when the (meth) acrylic crosslinked fine particles obtained in this comparative example were heated at 260 ° C for 30 minutes, the Hunter Whiteness was 87%.
    [89] Specific embodiments or examples described in the detailed description of the present invention are for clarity only, and are not to be construed as limited to such specific embodiments only. In the claims, it is possible to carry out various modifications.
    [90] The (meth) acrylic crosslinked fine particles of the present invention are (meth) acrylic crosslinked fine particles having a mean particle size in the range of 0.1 to 500 µm obtained by polymerizing a single-component composition containing a (meth) acrylic monomer, and azoisobutyronitrile The amount of (meth) acrylic monomers remaining in the (meth) acrylic crosslinked fine particles not included in the decomposed product derived therefrom is 2000 ppm or less, and the thermal decomposition initiation temperature of the (meth) acrylic crosslinked fine particles is 260 ° C or higher. Further, Hunter whiteness after heating the (meth) acrylic crosslinked fine particles at 260 ° C for 30 minutes is characterized by being 85% or more. The (meth) acrylic crosslinked fine particles may include at least one selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds, and azo ester compounds. It is preferable to polymerize the monomer composition containing a (meth) acrylic monomer using a kind of polymerization initiator.
    [91] According to the above structure, the amount of the (meth) acrylic monomer remaining in the fine particles is 2000 ppm or less, and at the same time, the thermal decomposition start temperature is 260 ° C or higher, and the hunter of the (meth) acrylic crosslinked fine particles after heating at 260 ° C for 30 minutes. Whiteness is more than 85%. Specifically, the (meth) acrylic crosslinked fine particles have less amount of unreacted (meth) acrylic monomers than before, and at the same time, have heat resistance and heat discoloration resistance. For this reason, for example, it is possible to provide (meth) acrylic crosslinked fine particles which can be suitably used as an antiblocking agent for food packaging materials such as food packaging films. In addition, since AIBN is not used as a polymerization initiator, there are no AIBN decomposition products remaining in the fine particles. In the present invention, the heat resistance yellowing resistance of the (meth) acrylic crosslinked fine particles is based on the Hunter whiteness represented by the (meth) acrylic crosslinked fine particles after the heating test at 260 ° C.
    [92] Moreover, in order to achieve the said objective, the manufacturing method of the (meth) acrylic-type crosslinked fine particle of this invention is a monomer composition containing a (meth) acrylic-type monomer, The organic peroxide, an azo-type acyclic azine compound, an azo-type cyclic arm After the polymerization was carried out using at least one polymerization initiator selected from the group consisting of a gin compound, an azo amide compound, an azo alkyl compound and an azo ester compound, the obtained polymer was polymerized at a temperature within a range of 80 to 95 ° C. It is characterized by aging more than time.
    [93] According to the above constitution, the amount of (meth) acrylic monomers remaining in the fine particles, containing no impurities such as decomposition products of toxic AIBN, is 2000 ppm or less, and the thermal decomposition initiation temperature is 260 ° C or higher and 260 ° C. The (meth) acrylic crosslinked fine particles having a Hunter whiteness of 85% or more after heating for 30 minutes at, that is, the amount of unreacted (meth) acrylic based monomers are smaller than before, and at the same time, the (meth) acrylic crosslinked fine particles having heat resistance, It is possible to manufacture simply.
    权利要求:
    Claims (15)
    [1" claim-type="Currently amended] In the (meth) acrylic crosslinked fine particles having an average particle diameter obtained by polymerizing a monomer composition containing a (meth) acrylic monomer, in a range of 0.1 to 500 µm,
    It does not include decomposition products derived from azoisobutyronitrile,
    The amount of (meth) acrylic monomers remaining in the (meth) acrylic crosslinked fine particles is 2000 ppm or less, and at the same time, the thermal decomposition initiation temperature of the (meth) acrylic crosslinked fine particles is 260 ° C or higher, and further, the (meth) acrylic crosslinked fine particles (Meth) acrylic crosslinked fine particles having a crosslinked structure, characterized in that the Hunter whiteness after heating at 260 ° C. for 30 minutes is 85% or more.
    [2" claim-type="Currently amended] The method according to claim 1, wherein at least one polymerization initiator selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds and azo ester compounds is used. And (meth) acrylic crosslinked particles obtained by polymerizing a monomer composition containing a (meth) acrylic monomer.
    [3" claim-type="Currently amended] The (meth) acrylic crosslinked fine particle according to claim 2, wherein the content of the (meth) acrylic monomer in the monomer composition is 50 to 99.5% by weight of the monomer composition.
    [4" claim-type="Currently amended] In the (meth) acrylic crosslinked fine particles having an average particle diameter obtained by polymerizing a monomer composition containing a (meth) acrylic monomer, in a range of 0.1 to 500 µm,
    It does not include decomposition products derived from azoisobutyronitrile,
    The amount of (meth) acrylic monomers remaining in the (meth) acrylic crosslinked fine particles is 2000 ppm or less, and at the same time, the thermal decomposition initiation temperature of the (meth) acrylic crosslinked fine particles is 260 ° C or more, and further, the (meth) acrylic crosslinked fine particles The method of using (meth) acrylic crosslinked fine particles having a crosslinked structure as an antiblocking agent for a film, characterized in that the Hunter whiteness after heating for 30 minutes at 260 ° C is 85% or more.
    [5" claim-type="Currently amended] The method of claim 4, wherein the (meth) acrylic crosslinked fine particles are selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds and azo ester compounds. (Meth) acrylic crosslinked fine particles having a crosslinked structure characterized in that the (meth) acrylic crosslinked fine particles obtained by polymerizing a monomer composition containing a (meth) acrylic monomer using at least one kind of polymerization initiator. How to use as anti blocking agent.
    [6" claim-type="Currently amended] The (meth) acrylic crosslinked resin having a crosslinked structure according to claim 4, wherein 1 to 50 parts by weight of the (meth) acrylic crosslinked fine particles are blended with respect to 100 parts by weight of the thermoplastic resin composition and used as an antiblocking agent for a film. A method of using fine particles as an antiblocking agent for a film.
    [7" claim-type="Currently amended] 7. The film according to claim 6, wherein the film is formed by heat-molding a thermoplastic resin composition in which the antiblocking agent for film is used as a masterbatch and further comprising a thermoplastic resin composition so as to have a thickness of 5 to 500 mu m. A method of using a (meth) acrylic crosslinked fine particle having a crosslinked structure to be used as an antiblocking agent for a film.
    [8" claim-type="Currently amended] In the (meth) acrylic crosslinked fine particles having an average particle diameter obtained by polymerizing a monomer composition containing a (meth) acrylic based monomer in the range of 0.1 to 500 µm, the (meth) acrylic based monomer remaining in the (meth) acrylic crosslinked fine particles. The amount is 2000 ppm or less, and at the same time, the thermal decomposition initiation temperature of the (meth) acrylic crosslinked fine particles is 260 ° C or more, and furthermore, the Hunter whiteness after heating the (meth) acrylic crosslinked fine particles at 260 ° C for 30 minutes is 85% or more ( In the manufacturing method of a meta) acrylic crosslinked fine particle,
    Polymerizing with at least one polymerization initiator selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds and azo ester compounds, A method for producing a (meth) acrylic crosslinked particulate, wherein the obtained polymer is aged at a temperature within the range of 80 to 95 ° C for 1.5 hours or more.
    [9" claim-type="Currently amended] The method for producing a (meth) acrylic crosslinked fine particle according to claim 8, wherein the aging is performed after confirming the polymerization rate after the polymerization.
    [10" claim-type="Currently amended] The method according to claim 8, wherein the polymerization initiator is an organic peroxide having a non-cyclic aliphatic alkyl structure.
    [11" claim-type="Currently amended] The method for producing a (meth) acrylic crosslinked particulate according to claim 10, wherein the polymerization initiator is lauroyl peroxide.
    [12" claim-type="Currently amended] The compound according to claim 8, wherein at least one compound having at least one functional group or structural unit selected from the group consisting of -SH group, -COOH group, -NO 2 group, -OH group, and -SS-bond is added A method for producing a (meth) acrylic crosslinked particulate, comprising polymerizing a monomer composition containing a (meth) acrylic monomer.
    [13" claim-type="Currently amended] The thiogresol, thiophenol, methyl thioglycolate, ethyl thioglycolate, butyl thioglycolate, 2-ethylhexyl, dithiohydrokinone, xylenedithiol, 2-mercaptonaphthalene, and cinnamic acid , Benzoic acid, chlorobenzoic acid, phthalic acid, isophthalic acid, nitrobenzene, nitrotoluene, nitronaphthalene, nitroaniline, aminocresol, naphthol, aminonaphthol, m-cresol, oxanthracene, deoxyanthracene, oxanthraquinone, Deoxyanthraquinone, oxanthrone, 3-oxy-9-anthrone, oxynaftkinone, 1,5-dioxynaphthalene, 1,8-dioxynaphthalene, 2,6-dioxynaphthalene, 3,5- Add at least one compound selected from dimethylphenol, diaryldisulfide, dithiodipropionate dioctyl ester, salicylic acid, thiosalicylic acid, dithiosalicylic acid, nitrobenzoic acid, 3,4-dinitrobenzoic acid, and nitrophenol (Meta) ah (Meth) acrylic crosslinked fine particles of a method comprising a step of polymerizing a monomer composition comprising a monomer rilgye.
    [14" claim-type="Currently amended] In the film composition containing a thermoplastic resin composition and (meth) acrylic crosslinked fine particles,
    The film composition is made by blending 1 to 50 parts by weight of (meth) acrylic crosslinked fine particles with respect to 100 parts by weight of the thermoplastic resin composition,
    The (meth) acrylic crosslinked fine particles are at least one member selected from the group consisting of organic peroxides, azo acyclic amide compounds, azo cyclic amide compounds, azo amide compounds, azo alkyl compounds and azo ester compounds. In the (meth) acrylic crosslinked fine particles having a crosslinked structure obtained by polymerizing a monomer composition containing a (meth) acrylic monomer using a polymerization initiator,
    The average particle diameter is in the range of 0.1 to 500 mu m,
    The amount of the (meth) acrylic monomer remaining in the fine particles is 2000 ppm or less, and at the same time, the thermal decomposition initiation temperature is 260 ° C or more, and furthermore, the film composition has a Hunter whiteness of 85% or more after heating at 260 ° C for 30 minutes. .
    [15" claim-type="Currently amended] The film composition according to claim 14, wherein the thermoplastic resin composition is a polyolefin resin composition.
    类似技术:
    公开号 | 公开日 | 专利标题
    TW460488B|2001-10-21|Core-shell impact modifier composition and process for preparing the same
    US7067188B1|2006-06-27|Polymeric articles having a textured surface and frosted appearance
    CA2129481C|1998-08-18|Method of manufacturing monodisperse poly| acrylate particles
    US6180694B1|2001-01-30|Process for warp-free pigmenting of polyolefins
    US5756573A|1998-05-26|Seed polymerized latex polymer having a gradient polymeric morphology and process for preparing the same
    CN1764691B|2013-03-06|Polymer encapsulation of high aspect ratio materials and methods of making same
    ES2644515T3|2017-11-29|acrylic blends
    US4221862A|1980-09-09|Method of producing finely divided polymer particles
    EP2810965B1|2018-10-03|Asa-based graft copolymer composition
    JP3740201B2|2006-02-01|Dispersants for dyes and / or pigments in standard plastics and copolymer mixtures containing them
    CN104829777A|2015-08-12|Preparation method of micron-sized highly-crosslinked polymethyl methacrylate | microspheres
    EP2727961B1|2016-08-24|Acrylic thermoplastic resin composition and molded article thereof
    TWI519582B|2016-02-01|Resin particle and use thereof
    Bivigou-Koumba et al.2010|Thermoresponsive amphiphilic symmetrical triblock copolymers with a hydrophilic middle block made of poly |: synthesis, self-organization, and hydrogel formation
    EP1238026B1|2004-06-23|Pigment concentrates and methods for production thereof
    JP2790595B2|1998-08-27|Resin particles, production method and use thereof
    JPH0693056A|1994-04-05|Modifier for making thermoplastic resin impact-resistant and thermoplastic molding material containing same
    KR100225268B1|1999-10-15|Core/shell impact modifiers and process for preparing the same
    EP0009179A2|1980-04-02|Process for preparing readily dispersible titanium dioxide pigments
    Fonseca et al.2010|Miniemulsion vs. conventional emulsion polymerization for pressure-sensitive adhesives production
    EP1045004B1|2005-04-13|Processing aid for vinyl chloride resin and vinyl chloride resin composition containing the same
    EP1710284A1|2006-10-11|Aqueous polymer dispersions
    EP0245647B2|1996-09-25|Polymethacrylate moulding masses showing a higher heat resistance and higher heat stability
    Panayiotou et al.2007|Synthesis and characterisation of thermo-responsive poly | microgels
    EP2910397B1|2020-04-01|Methacrylic resin-containing cover for vehicle members
    同族专利:
    公开号 | 公开日
    EP1300428A3|2003-07-30|
    EP1300428A2|2003-04-09|
    KR100587766B1|2006-06-09|
    CN1408739A|2003-04-09|
    EP1300428B8|2009-08-05|
    EP1300428B1|2009-01-14|
    CN100451041C|2009-01-14|
    DE60230845D1|2009-03-05|
    US20030064237A1|2003-04-03|
    TWI254719B|2006-05-11|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2001-09-28|Priority to JPJP-P-2001-00304272
    2001-09-28|Priority to JP2001304272
    2002-09-28|Application filed by 니폰 쇼쿠바이 컴파니 리미티드
    2003-04-07|Publication of KR20030027850A
    2006-06-09|Application granted
    2006-06-09|Publication of KR100587766B1
    优先权:
    申请号 | 申请日 | 专利标题
    JPJP-P-2001-00304272|2001-09-28|
    JP2001304272|2001-09-28|
    [返回顶部]