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    • 专利摘要:
    Gel-forming condensation products of aldehydes or ketones can be used in cyanoacrylates with polyols to obtain stericly stable adhesion, coating and sealing materials. It is stable on storage and is particularly suitable for bonding porous substrates such as paper or wood. It is particularly easy to handle when produced in the form of a rub stick.
    公开号:KR20010107993A
    申请号:KR1020017006731
    申请日:1999-11-30
    公开日:2001-12-07
    发明作者:클라인요한；보이어베른트；클라우크볼프강；마이어볼프강
    申请人:한스 크리스토프 빌크, 미하엘 베르크만；헨켈 코만디트게젤샤프트 아우프 악티엔；
    IPC主号:
    专利说明:

    SUBSTANCE FOR BONDING, COATING AND SEALING, CONSISTING OF CYANOACRYLATES AND ALDEHYDE OR KETONE CONDENSATION PRODUCTS} consisting of cyanoacrylate and aldehyde or ketone condensation products
    [1] The present invention relates to the bonding, coating and sealing compositions of a mixture of A) cyanoacrylate and B) condensation products of aldehydes and ketones.
    [2] Such cyanoacrylate adhesives are known. DE 43 17 886, for example, describes cyanoacrylate adhesives containing 1 to 40% by weight of fatty derivatives in the form of certain aliphatic alcohols or certain aliphatic carboxylic acid esters in order to reduce adhesion to the skin. 10 to 100,000 ppm of anionic polymerization promoter is added to the mixture. Particular mention is made of hydroxyl-containing compounds, including, for example, ethers of sorbitol and polyalkylene oxides, and formaldehyde and acetaldehyde condensation products. Specifically mention is made of polyoxyethylene sorbitan esters and polyoxyethylene / sorbitol addition products. To make the cyanoacrylate (low viscosity liquid) more viscous or thixotropic, thickeners such as polymethyl methacrylate, acrylate rubber, cellulose derivatives or silicates are dissolved or dispersed. According to an embodiment, the thickener is added in an amount of 0 to 10% by weight. A disadvantage of the composition is that even at high concentrations of the thickener, the cyanoacrylate pressure sensitive adhesive is a liquid and therefore cannot be used as a sealing compound or is for example unsuitable for bonding porous substrates and very generally difficult to apply.
    [3] Against the background of the prior art, the problem addressed by the present invention is that the characteristics of the outstanding performance for bonding, coating and sealing, and above all, improved handling behavior that is at least convenient for handling, even without adequate stability when stored at room temperature. It is provided to a noacrylate composition. In addition, the production is simple.
    [4] The solution provided by the present invention is defined in the claims and is directed to the use of gel formers based on condensation products of polyols with aldehydes and ketones on cyanoacrylates to produce a stericly stable composition at essentially 20 ° C. have.
    [5] The steric stability is that when the cylindrical composition is stored vertically in an open tube of 1.5 cm in diameter and 5 cm in length at 20 ° C., the composition does not change shape due to the influence of its own weight only for a period of 10 days at 20 ° C. ; This means that at least the stick protrudes out of the tube to less than 10 mm, preferably less than 0.1 mm. On the other hand, however, the steric stability is also just so great that the composition is rubbed onto the paper by applying light external pressure in the same way as commercially available adhesive sticks.
    [6] Suitable gel formers are certain condensation products of aldehydes or ketones with polyols
    [7] Compounds comprising at least one acetal or ketal group are used as gel formers. The compounds can be obtained by condensation reactions and are also aldehydes, for example with an acid as catalyst (OH: = C = O) in a ratio of 1: 0.5 to 1: 0.01, preferably 1: 0.5 to 1: 0.1. Or by partial or complete dehydration of ketones and polyols. Acetals and ketals according to the invention may also be acetals or ketals which are prepared by the reaction of derivatives of aldehydes or ketones with polyols, for example by reaction of isocyanate dichlorides with hydrogen chloride volatilized. Suitable compounds have a melting point of at least 50 ° C, more particularly at least 100 ° C, preferably at least 150 ° C. Mixtures of acetals and ketals may also be used.
    [8] Suitable polyols include one or more 1,2-diol, 1,3-diol or 1,4-diol groups. Other functional groups may also be present, such as ether, acid, ester, amide, cyano, hemiacetal and halide groups. Examples of such polyols are ethane-1,2-diol, propane-1,3-diol, propane-1,2-diol, butane-2,3-diol, butane-1,4-diol, 2,2-dimethyl Propane-1,3-diol, 2,2-bis- (hydroxymethyl) -propane-1,3-diol, 2- (bromomethyl) -2- (hydroxymethyl) -propane-1,3- Diol, butane-1,3,4-triol, 1-phenylpropane-1,2,3-triol, hexane-1,2-diol, neopentyl glycol, 1,4-bishydroxymethyl cyclohexane, 2-methylpropane-1,3-diol, hexane-1,2,6-triol, 2- (2-hydroxyethoxy) -butane-1,3,4-triol, glycerol, di- and poly Glycerol, diglycerol diacetate, trimethylol propane, di- (trimethylolpropane), trimethylol ethane, pentaerythritol, bicyclo [2.2.1] heptane-2,3,5,6-tetrol, 2,2 , 3,3-tetrahydroxybutanedioic acid, dipentaerythritol, sorbitol, formitol, xylitol, inositol, glutitol, glucose, sucrose, starch, cellulose, ascorbic acid, partial or complete A water-polyvinyl acetate, 9,10-dihydroxy stearic acid methyl ester, diacetyl sorbitol, and methyl glycoside.
    [9] Preferred polyols are sorbitol, xylitol and mannitol, more particularly sorbitol.
    [10] Suitable aldehydes or ketones include one or more substituted or unsubstituted aromatic, heteroaromatic or bicyclic rings. Other functional groups may also be present, such as ether, ester, amide, cyano and halide groups.
    [11] Examples of suitable ketones are cyclopentanone, cyclohexanone, cycloheptanone, 1- (3,3-dimethylcyclohexyl) -ethanone, 1-cyclopropylethanone, 3-methyl-5-propylcyclohex-2 -En-1-one, dicyclopropyl methanone, 4-t.butyl cyclohexanone, dicyclohexyl methanone, 4-methyl cyclohexanone, 1- (1-methylcyclopropyl) -ethanone, (4 -Chlorophenyl) -cyclopropyl methanone, 1- (1H-pyrrole-2-yl) -ethanone, 1- (2,4,6-trimethylphenyl) -ethanone, 1- (2-furanyl)- 2-propanone, 1- (2-naphthalenyl) -ethanone, 1- (2-thienyl) -l-propanone, 1- (4-bromophenyl) -ethanone, 1- (4 -Methoxyphenyl) -ethanone, 1- (naphthalenyl) -ethanone, 1,1-diphenyl-2-propanone, 1,2-diphenyl ethanone, 1,3-diphenyl-2 -Propanone, 1-phenyl-1-butanone, 1-phenyl-1-decanone, 1-phenyl-1-dodecanone, 1-phenyl-1-hexanone, 1-phenyl-1-octanone, 1 -Phenyl-1-pentanone, 1-phenyl-1-penten-3-one, 1-phenyl-1-tetradecanone, 1-phenyl-2-butanone, 1-phenyl-2- Propanone, 1-pyrazinyl ethanone, 2,2,2-trifluoro-1-phenyl ethanone, 1- (2-furanyl) -ethanone, 1- (2-pyridinyl) -ethanone, 1- (2-thienyl) -ethanone, 4-chloro-1- (4-fluorophenyl) -1-butanone, 4-phenyl-2-butanone, 1-phenyl ethanone, bis- (2 -Hydroxyphenyl) -methanone, bis- (4-chlorophenyl) -methanone, cyclopentyl phenyl methanone, cyclopropyl- (4-methoxyphenyl) -methanone, cyclopropyl- (4-methylphenyl)- Methanone, cyclopropyl-2-thienyl methanone, cyclopropyl phenyl methanone, 1,5-diphenyl-1,4-pentadien-3-one, phenyl-2-pyridinyl methanone, 2-bromo -1- (4-nitrophenyl) -ethanone, 2-naphthalenyl phenyl methanone, 3-chloro-1-phenyl-1-propanone, 4- (4-hydroxyphenyl) -2-butanone , 4- (4-methoxyphenyl) -3-buten-2-one, 1- (4-pyridinyl) -ethanone, 1- (4-hydroxyphenyl) -ethanone, 1-phenyl-1- Propanone, 4-phenyl-3-buten-2-one, diphenyl methanone, 1-phenyl-2-butanone, 1-phenyl-2-buten-1-one, S- (4-methylphenyl) -methanone, 2-methyl-1-phenyl-1-propanone, 2-chloro-1-phenyl ethanone, cyclopropyl- (4-fluorophenyl) -methanone, 1- (p-methoxyphenyl) -2-propanone, cyclohexyl phenyl methanone and phenyl- (2-thienyl) -methanone.
    [12] Examples of suitable aldehydes include benzaldehyde, 3-chlorobenzaldehyde, 4-chlorobenzaldehyde, 2,6-dichlorobenzaldehyde, 2,4-dinitrobenzaldehyde, 3,4-dichlorobenzaldehyde, 3-fluorobenzaldehyde, 4-bromobenzaldehyde , 2-methyl tetrahydrobenzaldehyde, tetrahydrobenzaldehyde, 2-methyl-5-isopropylcyclopentene-1-aldehyde, 2,2,4-trimethylcyclohexa-4,6-diene-1-aldehyde, 3 (4 ) -Methyl-1-propylcyclohexene-3-aldehyde, 1,3 (4) -dimethylcyclohexene-3-aldehyde, 2-methyl-1-propylcyclohexene-3-aldehyde, 3-cyclohexene-1- Aldehyde, 2,3,4,5,6-pentafluorobenzaldehyde, 2,4,6-trihydroxybenzaldehyde, 4-tolyl acetaldehyde, 2-methylbenzaldehyde, 4-hydroxybenzaldehyde, 3-methyl benzaldehyde, 2-hydroxy-1-naphthaldehyde, 4-methylbenzaldehyde, 3,5-dimethoxy-4-hydroxyben Aldehyde, cinnamic aldehyde, 3-nitrobenzaldehyde, 2-pentylcinnamaldehyde, 4-diethylaminobenzaldehyde, 4-methoxybenzaldehyde, 2-phenylpropionaldehyde, 2-methoxycinnamaldehyde, 4-methylbenzaldehyde, phenoxyset Aldehyde, methylpyrrole-2-aldehyde, 2,5-dimethoxytetrahydrofuran-3-aldehyde, 2,5-dipropyl-3,4-dihydropyran-2-aldehyde, 2,5-diethyl-3 , 4-dihydropyran-2-aldehyde, 2,5-diisopropyl-3,4-dihydropyran-2-aldehyde, 2,5-dimethyl-3,4-dihydropyran-2-aldehyde, 2 , 5-Dibutyl-3,4-dihydropyran-2-aldehyde, thiophen-3-aldehyde, indole-3-aldehyde, thiophen-3-aldehyde, pyridine-3-aldehyde, pyridine-4-aldehyde And N-methylpyrrole-2-aldehyde.
    [13] Preferred aldehydes are benzaldehyde, 3-chlorobenzaldehyde and 3-fluorobenzaldehyde, more particularly benzaldehyde.
    [14] Examples of acetals and ketals according to the invention are di-0-benzylidene mannitol, di-O- (2-chlorobenzylidene) -mannitol, di-O- (4-nitrobenzylidene) -mannitol, di-O -(3-fluorobenzylidene) -mannitol, 0-benzylidene sorbitol, di-O-benzylidene sorbitol diacetate, di-O- (2-chlorobenzylidene) -sorbitan diacetate, tri-O- ( 4-Chlorobenzylidene) -sorbitol, 0-benzylidene pentitol, 0-benzylidene tartaric acid dimethyl ester, 0-cyclohexylidene glycerol, 0-cyclohexylidene ascorbic acid and 0-benzylidene-9,10- Dihydroxystearic acid methyl ester.
    [15] Preferred acetals and ketals are di-O-benzylidene mannitol, di-O- (3-fluorobenzylidene) -mannitol and di-O-benzylidene sorbitol, more particularly di-O-benzylidene sorbitol.
    [16] The percentage content of aldehyde or ketone condensation products is 0.1 to 10% by weight, preferably 0.4 to 6% by weight, more particularly 1 to 3% by weight, based on the cyanoacrylate composition.
    [17] The cyanoacrylate composition is essentially based on typical cyanoacrylates, ie monoacrylates and / or biscyanoacrylates. Its percentage content is at least 29.5% by weight, preferably at least 50% by weight, based on the entire cyanoacrylate composition.
    [18] Typical monocyanoacrylic acid esters associated with the present invention Is of formula (I)
    [19] [Formula I]
    [20] H 2 C = C (CN) -CO-0-R
    [21] Wherein R is an alkyl, alkenyl, cycloalkyl, aryl, alkoxyalkyl, aralkyl or haloalkyl group, having up to two conjugated CC double bonds, alicyclic 6-rings, and aromatic nucleus benzene Derived from, preferably halogen is Br or Cl, and has 1 to 18, preferably 2, 3 or 4, more particularly methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, pentyl , Hexyl, cyclohexyl, heptyl, 2-ethylhexyl, n-octyl, n-nonyl, oxononyl, n-decyl, d-dodecyl, 2,2,2-trifluoroethyl, hexafluoroisopropyl , Allyl, metallyl, crotyl, propargyl, benzyl, phenyl, cresyl, 2-chloroethyl, 3-chloropropyl, 2-chlorobutyl, tetrahydrofurfuryl, 2-methoxyethyl, butoxyethoxy Ethyl, 3-methoxybutyl and 2-ethoxyethyl groups)
    [22] It is understood that the compound corresponds to. The cyanoacrylates mentioned above are known to adhesive experts (see Ullmann = s Encyclopedia of Industrial Chemistry, Vol. A1, page 240, Verlag Chemie Weinheim (1985), US-PS 3,254, 111). Preferred monomers are allyl, methoxyethyl, ethoxyethyl, methyl, ethyl, propyl, isopropyl or butyl esters of 2-cyanoacrylic acid.
    [23] Biscyanoacrylate Is of formula II:
    [24] [Formula II]
    [25] [H 2 C = C (CN) -CO-0] 2 R 1
    [26] (Wherein R 1 is a branched or unbranched bifunctional alkane group having 2 to 18 carbon atoms, more particularly 6 to 12 carbon atoms, and may also include heteroatoms such as halogen and oxygen, or aliphatic or aromatic rings, , R 1 is preferably a pure hydrocarbon)
    [27] Corresponding compound. It is important that biscyanoacrylates are particularly pure. This requirement is satisfied, for example, by the following production and purification methods: in particular, monocyanoacrylate is transesterified with diols and then the reaction mixture is subjected to fractional crystallization.
    [28] Thus, a suitable method for producing biscyanoacrylate is shown in Formula III:
    [29] [Formula III]
    [30] H 2 C = C (CN) -CO-0-R 2
    [31] Wherein R 2 is a branched or unbranched alkyl group having 1 to 6 carbon atoms
    [32] 2-cyanoacrylic acid or alkyl ester thereof corresponding to Formula IV:
    [33] [Formula IV]
    [34] [HO] 2 R 1
    [35] (Wherein R 2 is a branched or straight-chain bifunctional alkane group having 2 to 18 carbon atoms, which may also include heteroatoms such as halogen and oxygen, or aliphatic or aromatic rings)
    [36] Transesterification with corresponding diols to form biscyanoacrylates corresponding to formula (II), followed by purification of the reaction mixture by fractional crystallization.
    [37] Thus, one starting product is a monofunctional cyanoacrylic acid or alkyl ester thereof corresponding to formula III. The alkyl group should be chosen so that the alcohol formed can be easily removed. Appropriate possibilities are known to the expert in general transesterification reactions. Preferably the alcohol is removed by distillation. Accordingly, R 2 is a branched or unbranched alcohol radical having 1 to 6 carbon atoms, preferably 1 or 2 carbon atoms. Monofunctional cyanoacrylates are stabilized in a common manner.
    [38] Diols (Formula IV) are primary or secondary dihydric alcohols, preferably primary alcohols. The hydroxyl groups are preferably at the alpha / omega position, but can be at any position with each other. Diol has 2 to 18 carbon atoms, preferably 6 to 12 carbon atoms. It may be in a straight chain, branched chain or cyclic arrangement. Aliphatic radicals may also comprise, in addition to hydrogen and carbon atoms, heteroatoms such as chlorine or oxygen atoms, or aromatic groups, preferably in the form of polyethylene or polypropylene glycol units. Specifically hexane diol, octane diol, decane diol and dodecane diol are mentioned as diols.
    [39] Cyanoacrylate is used in excess. Thus, the molar ratio of monofunctional cyanoacrylate to diol is at least 2.0: 1.0, preferably 2.5: 1.0, more preferably 2.2: 1.0.
    [40] The transesterification is catalyzed by strong acids, more particularly sulfonic acids, preferably aromatic sulfonic acids, for example p-toluene sulfonic acid. However, naphthalene sulfonic acid, benzene sulfonic acid and acidic ion exchangers can also be used. The concentration of transesterification catalyst should be 1 to 20% by weight based on monofunctional cyanoacrylate.
    [41] The transesterification reaction is carried out in solution as usual. Suitable solvents are aromatic hydrocarbons and halogenated hydrocarbons. Preferred solvents are toluene and xylene. The concentration of the solution is 10 to 50%, preferably 10 to 20%.
    [42] The monohydric alcohol formed and the water formed are removed in a known manner and are preferably distilled off with the solvent. Conversion of the transesterification reaction is observed, for example, from the NMR spectrum. The reaction takes several hours as usual. When toluene is used as the solvent and p-toluene sulfonic acid is used as the catalyst, the reaction is terminated after 10 to 15 hours in the absence of further separation of the alcohol.
    [43] The operation of the reaction mixture is very important. Acidic ion exchangers are used as catalysts, but they can simply be filtered off. Soluble sulfonic acids such as p-toluene sulfonic acid are used as catalysts, but this is removed by solvent substitution; Toluene is replaced with a mixture of hexane, heptane or decane. Pure biscyanoacrylate is obtained after two fractional crystallizations. According to the NMR spectrum, it is more than 99% pure.
    [44] The biscyanoacrylate obtained is stable when stored with a conventional stabilizer at a usual concentration. That is, its melting point hardly changes even after 6 months storage at 20 ° C.
    [45] However, the biscyanoacrylate obtained polymerizes very quickly in the presence of a base, preferably at substantially the same rate as the corresponding monocyanoacrylate. Trace amounts of water, such as monofunctional cyanoacrylates, are sufficient. Three-dimensional crosslinked polymers with relatively good thermal properties are formed.
    [46] Therefore, in the present invention, this is known cyanoacrylate in an amount of 0.5 to 50% by weight, preferably 1 to 10% by weight, more preferably 2 to 5% by weight, based on the total cyanoacrylate composition. Used for adhesives
    [47] It is known that cyanoacrylates can be used for anionic and radical chain polymerizations to protect the ester composition against both types of polymerization in order to avoid premature solidification of the esters and thus avoid storage obstacles. To prevent anionic polymerization, anionic polymerization inhibitors can be added to the adhesive according to the invention. Any of the above types of anionic polymerization inhibitors used so far in cyanoacrylate adhesives are suitable for this purpose. For example, the anionic polymerization inhibitor may be an acidic gas, a protic acid or anhydride thereof. Preferred anionic polymerization inhibitors for the adhesives according to the invention are sulfur dioxide, preferably from 0.001 to 0.5% by weight, based on the adhesive. Other suitable anionic polymerization inhibitors are dinitrogen monooxide, hydrogen fluoride, hydrochloric acid, sulfuric acid, phosphoric acid, organic sulfonic acids and carboxylic acids and their anhydrides, phosphorus pentoxide and acid chlorides. In a preferred embodiment, the radical chain polymerization inhibitor is also added to the adhesive according to the invention in an amount of 0.01 to 0.05% by weight. The radical chain polymerization inhibitor may be any inhibitor of known radical chain polymerization inhibitors for cyanoacrylate compositions. Phenolic compounds such as hydroquinone, t-butyl catequinone, pyrocatechol and p-methoxyphenol are commonly used. The commercially available ethyl 2-cyanoacrylate preparations mentioned above are already stabilized. If it is necessary to adjust the concentration of stabilizer when such commercial preparations are used, this is not difficult for the expert.
    [48] In another preferred embodiment, the polymer is also added to the cyanoacrylate composition according to the invention, for example to increase the viscosity (thickener), or to vary the adhesion. The polymer can be used in an amount of 1 to 60% by weight, more particularly 10 to 50% by weight, preferably 10 to 30% by weight, based on the entire formulation. Suitable polymers are, among others, vinyl ethers, vinyl esters, esters of acrylic and methacrylic acids having 1 to 22 carbon atoms in the alcohol component, styrene or ethene, styrene copolymers with butadiene and polymers based on terpolymers. Preference is given to vinyl chloride / vinyl acetate copolymers having a vinyl chloride content of 50 to 95% by weight. The polymer may be present in liquid, resin-like or even solid form. It is particularly important that the polymer does not contain impurities from the polymerization process that can inhibit the curing of cyanoacrylate. If the polymer has too high a water content it may have to be dried. The molecular weight (Mw) of the polymer can be distributed over a wide range but must be at least 1500 and up to 1,000,000, otherwise the final viscosity of the adhesive formulation is too high. Mixtures of the aforementioned polymers can also be used. More particularly, the combination of low molecular weight and high molecular weight products has particular advantages with regard to the final viscosity of the adhesive formulation. Examples of suitable polymers based on vinyl acetate include Mowilith types 20, 30 and 60 and Vinnapas types B1.5, B100, B17, B5, B500 / 20VL, B60, UW10, UW1, UW30, UW4 and UW50. Examples of suitable acrylate-based polymers are Acronal 4F and Laromer types 8912, PE55F and PO33F. Examples of suitable methacrylate-based polymers include Elvacite 2042, Neocryl type B 724, B999 731, B 735, B 811, B 813, B 817 and B722, Plexidon MW 134, Plexigum type M 825, M 527, N 742, N 80, P 24, P 28 and PQ 610 are mentioned. An example of a suitable vinyl ether-based polymer is Lutonal A25. Cellulose derivatives and silica gels can also be used for thickening. The addition of polycyanoacrylates is particularly emphasized.
    [49] In addition, the cyanoacrylate composition according to the present invention may contain other adjuvants to obtain certain effects equivalent to the intended application. Such other auxiliaries include, among other things, the polymerization promoters described in DE 43 17 866, ie polyalkylene oxides and their derivatives, in particular esters and ethers. Other polymerization promoters are CROWN ETHERS and its derivatives, silica-crown compounds and cyclosulfur compounds. It is known that the polymerization promoter is added in an amount of 10 to 100,000 ppm, more particularly in an amount of 30 to 10,000 ppm, based on the cyanoacrylate composition. Another promoter is cyclodextrin.
    [50] Fatty derivatives described in DE 197 52 893 and DE 43 17 886 can also be used as plasticizers. These are fatty acid and fatty derivatives, more particularly aliphatic alcohols, aliphatic carboxylic acid esters and carboxylic acid esters of carbocyclic compounds. Additional information can be obtained from the patents cited above. Conventional crosslinking agents can also be used, for example phthalates, citric acid esters, chloroparaffins and trimellitic acid esters.
    [51] It is also possible to add solvents, in particular to increase the solubility of the aldehyde or ketone condensation products or to allow the products to be more easily inserted in solution form. Suitable organic solvents are, for example, alcohols, ethers, ketones and low molecular weight alkyl esters. Particularly suitable organic solvents are isopropanol, methoxypropanol, ethoxypropanol, ethoxyethanol, propoxyethanol, butoxyethanol, methyl ethyl ketone and N-methyl-2-pyrrolidone. However, the content of the solvent in the cyanoacrylate composition should be low in order not to jeopardize steric stability, and preferably less than 20% by weight.
    [52] Other adjuvants are active agents, dyes, pigments, fragrances, preservatives, preservatives and fillers.
    [53] The cyanoacrylate composition according to the invention is produced by essentially dissolving the aldehyde or ketone condensation product with cyanoacrylate and polyol by heating and then solidifying the resulting solution by cooling. Usually, a cyanoacrylate composition stabilized from acrylate and anionic polymerization inhibitor under nitrogen with an inert gas is first prepared and then heated to 50-90 ° C. The necessary ingredients are then dissolved or suspended with thorough stirring until a homogeneous mixture is obtained. The condensation product is then partially added at 80-95 ° C. and dissolved mostly at 90-95 ° C. The mixture is then cooled to preferably about 80 ° C. and poured into the required mold. After about 1 hour, the composition is usually solidified and after 24 hours it is stericly stable enough to be used as an adhesive stick. Despite its steric stability, some pressure may be applied to rub the cyanoacrylate composition onto a substrate, such as paper.
    [54] Because of its steric stability, the cyanoacrylate composition is suitable for converting into a geometric shape, and above all stick. The adhesive stick is preferably produced in the form of a cylinder. Preferably the particular shape is suitable for the intended application. However, any shape is possible, in particular geometric shapes with one or more symmetrical faces or axes, such as spheres, squares, pyramids, cones, cylinders, sticks, tapes, flakes, films and "pillow" shapes. Do. The shape is preferably smaller in two dimensions than in three dimensions. The shape is for example a stick (hot melt stick) or a refill in the form of a wax stick. The basic or geometric element may be angled or specifically triangular, rectangular or hexagonal or circular (eg annular or oval). The diameter may be 2 to 100 mm and the length may be 150 mm or less. Thus, the shapes and amounts of cyanoacrylates according to the invention are very diverse and are determined to be most convenient for the particular application intended.
    [55] Liquid cyanoacrylate compositions with very thixotropic properties can be produced by shearing ready-to-use cyanoacrylate compositions at high rotational speeds. The cyanoacrylate composition according to the invention is suitable for bonding, coating and sealing, and more particularly for bonding porous substrates such as leather, textiles, paper, cardboard, cardboard, wood and skin. Because of its stick form, the cyanoacrylate composition according to the invention can be used particularly advantageously as an adhesive for oral repair, PVC pipes and artificial nails. It is also possible to "stick" the wound, in particular using relatively long chain cyanoacrylates. With primers, for example aliphatic amines, polyolefins can be reliably bound. The primer can also be converted into the form of a stick with the gel former according to the invention. Dyeing and correction sticks may also be produced by adding coating pigments and / or dyes. Since there is no solvent, the stick is particularly environmentally friendly. In a given form, the cyanoacrylate composition according to the invention can also be used as a filling material for filling gaps and holes in various materials. Preferably all of the substrate is coated with an adhesive, for example by rubbing with an adhesive stick. Gap-filled bonding is also possible.
    [56] Although the cyanoacrylate composition is used for sealing, its fast cure rate is worth mentioning.
    [57] Surprisingly, the cyanoacrylate composition according to the invention is extremely stable upon storage. For example, in conventional adhesive stick tubes, they can be stored and handled for several weeks at room temperature without decreasing their adhesion.
    [58] Other advantages of the cyanoacrylate composition according to the present invention include simple application, safe handling (eg not splashing on the eyes or skin), application over a large area, and bonding of vertical substrates.
    [59] The invention is illustrated by the following examples.
    [60] After 6 months at 2-5 ° C., the adhesive stick can still be used. That is, its firmness and adhesiveness were excellent. After 9 months at -18 ° C, the adhesive stick can still be used again. That is, no breakage of the gel structure and polymer formation were observed. After heating to 20 ° C., the cap lid opens easily from the tube. When tested with paper, the settling time and adhesion did not actually change (paper tearing). Stability at -18 ° C for more than 9 months is of primary importance for medical applications.
    [61] 1. Production of Cyanoacrylate Composition
    [62] Stabilized cyanoacrylate was introduced into a three-neck flask under nitrogen and polymethacrylate was added in part with thorough stirring at 50 ° C. After 10 minutes, the solution became clear and homogeneous.
    [63] To form the gel, dibenzylidene sorbitol was added to increase the temperature to 85 ° C. and to avoid lump formation. After 10 minutes, most of the gelling agent was dissolved. After cooling to about 80 ° C., the undissolved particles were removed by filtration. The solution was poured when still hot in a conventional adhesive stick tube. After about 1 hour, it solidified. The next day, the adhesive stick was ready for use and remained stable for several weeks despite repeated opening and closing.
    [64] 2. Test
    [65] a) To test the stability during storage, the cyanoacrylate composition in the adhesive stick tube was tested weekly for adhesion to paper at a relative atmospheric humidity of 23 ° C./50%.
    [66] b) To determine the settling time, the cyanoacrylate composition was applied to one side of an elongated piece of paper 30 cm in length, immediately applied to the second piece of elongated paper and pressed. The elapsed time until the paper was torn when the adhesive bond was released was measured.
    [67] c) In order to measure the tensile shear force of the longitudinal bonds, a) two drops of liquid adhesive were applied to the substrate with an area of 10 x 25 mm, or b) a similar amount was applied to one side by rubbing with an adhesive stick. Immediately, the second substrate was lightly pressed. After 2 days at 23 ° C./50% relative air humidity, tensile shear forces of beech wood and also non-wood samples were tested according to EN 205 (rate 10 mm / min).
    [68] The results are shown as the average of five measurements.
    [69] The base material was previously processed as follows.
    [70] Beech Lumber: Untreated
    [71] PMMA: degreasing
    [72] ABS plastic: degreasing
    [73] PVC: degreasing, and
    [74] -Alu: Grind and degrease by sandblasting.
    [75] 3. Results
    [76] The test results are described in Table 1. This shows that useful adhesion was obtained in all cases, exceeding the adhesion of conventional cyanoacrylate adhesives in the case of beech wood.
    [77] Composition (parts by weight) and Properties of Cyanoacrylate CompositionExample 1Example 2 I. Composition Ethyl cyanoacrylate100100 2.SO 2 ++ 3. Phosphoric Acid, Methanesulfonic Acid++ 4. Polymethacrylate55 5. Dibenzylidene Sorbitol01.8 II. characteristic a) Storage stability-> 10 b) Fixed time (seconds)Do not combine20 c) tensile shear force (MPa) Beech Lumber7.33 TA7.75 -PMMA7.01 MF6.11 MF -ABS plastic8.10 MF6.21 Partial MF - aluminum14.757.08 -PVC14.59 MF4.90 MF
    [78] TA = material is torn
    [79] MF = material failure
    [80] Partial MF = material failure in some test specimens
    权利要求:
    Claims (9)
    [1" claim-type="Currently amended] doing:
    A) at least one cyanoacrylate, and
    B) condensation products of one or more aldehydes or ketones with polyols
    A cyanoacrylate composition for adhering, coating and sealing a mixture of substrates.
    [2" claim-type="Currently amended] The compound according to claim 1, wherein the aldehyde or ketone is of the group
    Benzaldehyde, 3-chlorobenzaldehyde or 3-fluorobenzaldehyde
    At least one of the substances, more particularly benzaldehyde.
    [3" claim-type="Currently amended] The method of claim 1 wherein the polyols are of the following group:
    Sorbitol, xylitol or mannitol
    At least one of the substances, more particularly sorbitol.
    [4" claim-type="Currently amended] The process of claim 1 wherein the condensation product of an aldehyde or ketone with a polyol is of the following group:
    Di-O-benzylidene mannitol, di-O- (3-fluorobenzylidene) -mannitol or di-O-benzylidene sorbitol
    At least one of the substances, more particularly di-O-benzylidene sorbitol.
    [5" claim-type="Currently amended] The composition of claim 1 wherein the composition is based on the entire cyanoacrylate composition:
    A) 99.8 to 29.5 weight percent of one or more cyanoacrylates,
    B) 0.1 to 10% by weight of condensation products of one or more aldehydes or ketones with polyols,
    C) 0.001 to 0.5% by weight stabilizer and
    D) 0 to 60% by weight thickeners, solvents, plasticizers, fillers and other auxiliaries
    Composition having a.
    [6" claim-type="Currently amended] The composition according to claim 1, which is in geometric form, more particularly in stick form.
    [7" claim-type="Currently amended] A method for producing a composition as claimed in claim 1, wherein components A) and B) are first heated to prepare a solution, followed by cooling.
    [8" claim-type="Currently amended] Use of a composition as claimed in any one of claims 1 to 6 for bonding, coating and sealing.
    [9" claim-type="Currently amended] 9. Use according to claim 8 for bonding porous substrates.
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    同族专利:
    公开号 | 公开日
    WO2000032709A1|2000-06-08|
    DE19957677A1|2000-06-08|
    ZA200104538B|2002-09-02|
    NO20012717L|2001-06-01|
    BR9915814A|2001-08-21|
    UA73930C2|2001-10-15|
    TR200101471T2|2001-11-21|
    EP1159362A1|2001-12-05|
    CZ20011972A3|2001-11-14|
    RU2238292C2|2004-10-20|
    SK7432001A3|2002-01-07|
    HU0104526A3|2003-07-28|
    JP2002531629A|2002-09-24|
    NO20012717D0|2001-06-01|
    HU0104526A2|2002-03-28|
    PL348719A1|2002-06-03|
    CN1329648A|2002-01-02|
    ID30447A|2001-12-06|
    CA2353605A1|2000-06-08|
    AU770134B2|2004-02-12|
    AU1778500A|2000-06-19|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    1998-12-02|Priority to DE19855272.6
    1998-12-02|Priority to DE19855272
    1999-11-30|Application filed by 한스 크리스토프 빌크, 미하엘 베르크만, 헨켈 코만디트게젤샤프트 아우프 악티엔
    1999-11-30|Priority to PCT/EP1999/009287
    2001-12-07|Publication of KR20010107993A
    优先权:
    申请号 | 申请日 | 专利标题
    DE19855272.6|1998-12-02|
    DE19855272|1998-12-02|
    PCT/EP1999/009287|WO2000032709A1|1998-12-02|1999-11-30|Substance for bonding, coating and sealing, consisting of cyanoacrylates and aldehyde or ketone condensation products|
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