JPH0686578B2 - Coating composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to a coating composition, particularly a coating capable of forming a cured coating which is flexible and tough and has good adhesion within a short curing time. Composition.

In this specification, "coating" is used in the broadest sense and means that a coating film is provided on a substrate so as to cover at least a part thereof.

[Prior Art] Conventionally, various coating compositions for coating a substrate have been known, but it is possible to always form a coating having sufficient flexibility, toughness and adhesion in a wide temperature range. There are few such coating compositions.

This will be explained by taking an optical fiber used for optical transmission as an example. The glass fiber, which is the main body of the transmission body, is brittle, is easily scratched, and lacks flexibility, so that it is easily broken even by a slight external force. Therefore, a resin coating is provided on the outer circumference of the optical transmission fiber made of glass to protect it. Conventionally, epoxy resins, urethane resins, etc. have been used as such coating resin materials, but these have sufficient flexibility and toughness in the normal operating temperature range of optical fibers, −40 to 80 ° C. And the workability is poor because it takes a relatively long time to cure. Therefore, there is a demand for the appearance of a resin material capable of providing a coating excellent in flexibility and toughness with a relatively short curing time,
Actually, some suggestions have been made. For example, JP-A-57-
92553 proposes the use of a diacrylate of a polyether polyol having a molecular weight of 2000 or more, and JP-A-58-223638 discloses a polymerizable oligomer having an amide urethane structure and a polyalkylene polyether structure.
It has been proposed to use a composition containing a polymerizable monomer giving a low glass transition point polymer and a polymerizable monomer capable of forming a strong hydrogen bond as essential components.

[Problems to be Solved by the Invention] The inventors of the present invention have long been engaged in various studies to provide a coating composition excellent in flexibility, toughness and adhesion. In particular, in the case of a coating composition for an optical fiber, as is clear from the above description, a coating which always exhibits good flexibility and toughness in a normal operating temperature range of −40 to 80 ° C. is short-cured. It must be a resin material that can be formed in time.

[Means for Solving the Problems] As a result of research, the present inventors have found that the use of a polymerizable compound having an acylurethane structure meets the above purpose, and complete the present invention based on this finding. Came to.

A polymerizable compound having an acylurethane structure has not been produced so far, and therefore, it may be said what properties such a polymerizable compound has, and also what a polymer of such a polymerizable compound has. It was not known to have such characteristics.

According to the research conducted by the present inventors, a polymerizable compound having an acyl urethane structure has an extremely high vinyl bond existing therein, and it is easy and efficient to irradiate a high energy ray or a radical polymerization catalyst. The fact that they were well polymerized and cured became clear. Further, it has been clarified that the polymer obtained by such polymerization and curing has high flexibility, high toughness, and good adhesion. Such characteristics of the polymerizable compound having an acyl urethane structure and the polymer thereof indicate that they are suitable as the main component of the coating composition.

The gist of the present invention lies in a coating composition containing a polymerizable compound having an acyl urethane structure as an essential component.

Since the above-mentioned polymerizable compound having an acylurethane structure has an extremely high polymerization activity, the polymerization reaction is promptly promoted by the irradiation of high energy rays and the addition of a catalyst to cure. Further, the coating film obtained by curing has excellent flexibility, toughness and adhesion.

[Operation] As described above, the coating composition of the present invention is characterized in that it contains a polymerizable compound having an acyl urethane structure as an essential component. A typical example of the acyl urethane structure is represented by the following formula. Can be shown: [In the formula, R represents hydrogen or lower alkyl. ].

Specific examples of the acyl urethane structure include an acryloyl urethane structure, a methacryloyl urethane structure, and an ethacryloyl urethane structure.

To produce a polymerizable compound having the above-mentioned acyl urethane structure (A), a compound having a specific hydroxyl group and a formula: [In the formula, R has the same meaning as described above. ] It suffices to react an acyl isocyanate represented by
This reaction is carried out in the presence or absence of an inert solvent by -40 to 10
It proceeds easily at 0 ° C., preferably under ice cooling or at room temperature (0 to 30 ° C.). If necessary, an appropriate polymerization inhibitor may be present in order to prevent the progress of side reactions relating to the vinyl bond.

The compound having a hydroxyl group has at least one hydroxyl group and is selected from: Polyether polyols such as polyalkylene glycols (eg polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyhexamethylene glycol). ) Or alkylene oxides (eg ethylene oxide, propylene oxide,
Tetrahydrofuran is used as a polyol (for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, trimethylolpropane, 1,3-butanediol, 1,4-butanediol, 1,5-hexanediol, 1,2,6 -Hexanetriol, pentaerythritol, sorbitol, sorbitan, sucrose) and other polyether polyols obtained; polyester polyols such as polybasic acids (eg phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tetrachlorophthale) Acid, tetrabromophthalic acid, hexahydrophthalic acid, hymic acid, het acid,
Succinic acid, maleic acid, fumaric acid, adipic acid, sebacic acid, dodecenylsuccinic acid, trimellitic acid, pyromellitic acid) or their anhydrides and polyhydric alcohols (for example ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerol, Trimethylolpropane, 1,3-butadiol, 1,4
-Butanediol, 1,6-hexanediol, neopentyl glycol, 1,2,6-hexanetriol, pentaerythritol, sorbitol, bisphenol A), a polyester polyol obtained by a condensation reaction with the polyhydric alcohol, and an epoxy compound (For example, cardura E, n-butyl glycidyl ether, allyl glycidyl ether) and the above-mentioned polybasic acid, a polyester polyol, a polyester polyol obtained by the above-mentioned epoxy compound and the above-mentioned polybasic acid, a higher fatty acid (for example, Soybean oil, linseed oil, safflower oil, coconut oil, dehydrated castor oil, tung oil, rosin) and an alkyd polyol obtained by reacting the polybasic acid with the polyhydric alcohol, ε-caprolactam and the polyhydric alcohol. Ring-opening polymerization Polymerizable polyester polyols and the like obtained by the following: Acrylic polyols, for example, ethylenically unsaturated monomers having a hydroxyl group (eg 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-
Hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxybutyl acrylate, 2-hydroxybutyl methacrylate) is an essential monomer, and if necessary, other monomers (for example, methyl acrylate, methyl methacrylate, ethyl acrylate,
Ethyl methacrylate, n-butyl acrylate, n-
Butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate,
Ethylhexyl methacrylate, styrene, α-methylstyrene, vinyltoluene, t-butylstyrene, ethylene, propylene, vinyl acetate, vinyl propionate,
Acrylopolyol obtained by polymerization reaction with acrylonitrile, methacrylonitrile, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, etc .; Polyurethane polyols, such as isocyanate compounds (eg ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, 1 -Methyl-2,4-diisocyanate cyclohexane, 1-methyl-2,6-diisocyanate cyclohexane, ω, ω'-diisocyanate diethylbenzene, ω, ω'-diisocyanate dimethylaminotoluene, ω, ω'-diisocyanate dimethylxylene, ω, ω'-diisocyanate diethyl xylene, lysine diisocyanate, 4,4'-methylenebis (cyclohexyl Isocyanate), 4,4'-ethylenebis (cyclohexyl isocyanate), omega,
ω'-diisocyanate-1,3-dimethylbenzene,
ω, ω′-diisocyanate-1,4-dimethylbenzene, isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,5-
Naphthylene diisocyanate, 4,4'-methylenebis (phenylisocyanate), triphenylmethane triisocyanate) or multimers thereof and an excess amount of low molecular weight polyols (eg ethylene glycol, propylene glycol, 1,3-butyl glycol). ,
Neopentyl glycol, 2,2,4-trimethyl-1,3-pentanediol, hexamethylene glycol, cyclohexanedimethanol, trimethylolpropane, hexanetriol, glycerin, sorbitol, sorbitan, sucrose, pentaerythritol, etc.) Polyurethane polyol obtained by the reaction, polyether polyol, polyester polyol as described above, polyester polyol, a polymerizable polyester polyol and acrylic polyol of a relatively low molecular weight of the polyol compound and an isocyanate compound such as monoisocyanate, diisocyanate, triisocyanate Polyurethane polyol and the like obtained by addition reaction; Epoxy compounds such as bisphenol A type epoxy resin, bisphenol F type epoxy resin Resins, polycarboxylic acid type epoxy resins, epoxidized resins of aliphatic unsaturated compounds, etc .; Polybutadienes, such as hydrogenated or non-added 1,4-polybutadiene diols having terminal hydroxyl groups; Amino resins, such as melamine , Guanamine, urea, etc. are polymerized with addition reaction products of formaldehyde and modified with alcohols such as methanol, butanol, isobutanol, and have a high degree of methylolation and a low degree of alkoxyetherification, especially 2 per triazine nucleus.
Butylated melamine resin having at least one methylol group; Star polymer, such as a star polymer having active hydrogen at the end obtained by cationic polymerization of pentol and ethylene oxide; Phenol resin, such as novolak obtained by reaction of phenol and formaldehyde -Type or resol-type phenol resin or rosin-modified phenol resin, alkylphenol resin, butylated or allyl etherified resole resin, etc .; xylene resin; vinyl compounds such as polyvinyl alcohol, polyvinyl acetal; cellulose compounds such as cellulose and nitrocellulose. Etc .; oligosaccharides such as maltose, amylose and other oligosaccharides and their derivatives.

The inert solvent is not particularly limited as long as it does not adversely affect the reaction, and various ones can be used, for example, aliphatic hydrocarbons such as pentane, hexane and heptane, aromatic hydrocarbons such as benzene, toluene and xylene. Hydrocarbons, cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane and decalin, hydrocarbon solvents such as petroleum ether and petroleum benzine, carbon tetrachloride, chloroform, 1,2
-Halogenated hydrocarbon solvents such as dichloroethane, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran,
It may be appropriately selected from ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone and isophorone, esters such as ethyl acetate and butyl acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide and the like. These may be used alone or as a mixture.

In order to collect the above-mentioned polymerizable compound having an acyl urethane structure from the reaction mixture, a conventional separation means such as a solvent extraction method or a distillation method may be adopted.

In addition, a polymerization inhibitor may be present in order to avoid unnecessary polymerization of the vinyl bond of the acylisocyanate (I) during the above reaction and separation operation. Specific examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, 2,6-di-t-butyl-4-methylphenol, 4
-T-butylcatechol, bisdihydroxybenzylbenzene, 2,2'-methylenebis (6-t-butyl-3-
Methylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol), p-nitrosophenol, diisopropylxanthogen sulfide, N-nitrosophenylhydroxylamine ammonium salt, 1,
1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl, 2,6-di-t-butyl-α-
(3,5-di-t-butyl-4'-oxo-2,5-cyclohexagen-1-ylidene) -p-trioxy, 2,2,6,
6-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, p, p'-ditolyl trisulfide, p, p'-ditolyl tetrasulfide, dibenzinyl tetrasulfide, tetraethyl thiuramdyl sulfide, etc. .

As a result of the above reaction, the active hydrogen atom of the active hydrogen-containing compound is added to the isocyanate group of the acyl isocyanate (I), and the polymerizable compound having the acyl urethane structure (A) is produced. The reaction proceeds extremely smoothly in a short time, and the polymerizable compound can be obtained in good yield and purity.

The coating composition of the present invention contains a polymerizable compound having an acylurethane structure as an essential component in an amount of at least 0.5% by weight based on the weight of the composition.

As other components, if necessary, a polymerizable monomer as a crosslinking agent or a diluent, a polymerization initiator as a curing accelerator, and the like may be blended. The polymerizable monomer used here is not particularly limited as long as at least one polymerizable double bond is present, and specific examples thereof include acrylic acid esters (eg, methyl acrylate, ethyl acrylate, acrylic acid). Butyl, dodecyl acrylate, acrylic acid 2-
Ethylhexyl, ethyldiethylene glycol acrylate), methacrylic acid ester (eg methyl methacrylate, ethyl methacrylate, butyl methacrylate, dodecyl methacrylate, 2-ethylhexyl methacrylate, ethyldiethylene glycol methacrylate), allyl ester, crotonic acid ester, maleic acid ester, Vinylpyrrolidone, diacetone acrylamide, isobutoxymethyl acrylamide, acrylamide, N,
Examples include N-dimethylacrylamide, acrylic acid, itaconic acid, and dimethylaminoethyl acrylate. Further, as the polymerization initiator, benzoyl peroxide, t-
Butyl peroxybenzoate, acetophenone, benzophenone and the like may be used. Usual amounts are 50% by weight or less of the composition for the polymerizable monomer and 10% by weight or less of the composition for the polymerization initiator.

In addition to the above, a modifying resin and various additives may be blended as other optional components. As the modifying resin, epoxy resin, polyamide, polyurethane, polyether,
Polyamideimide, silicone resin, phenol resin, etc. can be mentioned. Other various additives include cobalt naphthenate, zinc naphthenate, curing accelerators such as dimethylaniline, organic silicon compounds, and surfactants.

The coating composition of the present invention is cured by irradiation with various types of high energy rays. High-energy rays include ultraviolet rays, electron rays, X-rays, and radiation (eg, alpha rays, beta rays, gamma rays, hard x-rays) and the like, and any of them may be used, but the use of ultraviolet rays is common.

Incidentally, in order to coat the glass fiber with the coating composition of the present invention, a conventional method such as a die ironing method, a spray method, or a fluidized dipping method may be adopted.
Also, German Patent 2,459,320 and Japanese Patent Publication 53-139545.
It may be performed by the method disclosed in the specification or the like. When the glass fiber is coated by these methods and cured by ultraviolet irradiation, the drawing speed of the glass fiber is 3
It may be ~ 5 m / sec or more. In addition, one layer of coating is sufficient for coating on the glass fiber, but a two-layer coating may be applied. The performance of the obtained optical fiber is very excellent and has a practical value.

Originally, a resin that is polymerized and cured by irradiation with a high-energy ray can be cured in seconds, so that productivity can be increased. In addition, since electric energy can be used for curing and there is almost no evaporation of the solvent, low pollution can be achieved. Further, since high temperature is not required for curing, the object to be coated is not thermally deformed and the curing device can be downsized, so that space can be saved.
Furthermore, since the wavelength of the energy rays is short, the image reproducibility is good. Since the coating composition of the present invention also has such advantages, in addition to the use as the above-mentioned coating agent for optical fiber, an ultraviolet curable coating material, an electron beam curing coating material, a photoresist, an electron beam resist, an x-ray resist, It has a wide range of uses as a plate-making material in the paint, printing industry, electronic industry and the like.

A resin composition that is cured by high energy rays generally has a basic composition such as a photocrosslinkable (or non-crosslinkable) polymer or oligomer, a photopolymerizable monomer or a low molecular weight oligomer, a photopolymerization initiator (or a sensitizer) and a thermal polymerization. It contains an inhibitor (or a stabilizer) and, if necessary, an additive such as a sensitization aid and a colorant.

As the polymer or oligomer of (1), unsaturated polyester resin, urethane acrylate resin, epoxy acrylate resin, polyester acrylate resin, spirane acrylate resin, polyether acrylate resin and the like are well known. Examples of the photopolymerizable monomer or low molecular weight oligomer of the above include, in addition to the low molecular weight oligomers of the above polymers, styrene, vinyltoluene, divinylbenzene, vinyl acetate, acrylonitrile, methacrylonitrile, acrylic acid ester (for example, methyl acrylate, acrylic acid). Ethyl, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate,
Ethylene glycol diacrylate, trimethylolpropane triacrylate), methacrylic acid esters (eg methyl methacrylate, ethyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate) , Diethyl itaconate, dibutyl itaconate, diethyl fumarate, diethyl maleate and the like are known. Known sensitizers include benzoin, benzoin methyl ether, benzoin propyl ether, benzoin butyl ether, benzophenone, diacetyl, benzyl, dibutyl sulfide and dibenzyl sulfide. Examples of known thermal polymerization inhibitors include hydroquinone, t-butylhydroquinone, p-methoxyphenol, catechol and benzoquinone.

The polymerizable compound having an acyl urethane structure of the present invention may be used as all or a part of the above-mentioned components and / or components, particularly as a whole or a part of the components.

The photocurable resin composition as described above is used as a plate material or a cured printing ink for letterpress, planographic printing, intaglio and screen printing plates in the printing industry, as a paint, packaging material or adhesive in the color materials industry, and in the electronic industry. Is a shadow mask, printed wiring, resist for electronic parts such as IC, LSI, dry film or encapsulant, in metal surface treatment industry, ceramics industry, glass industry, precision machinery industry, building materials industry, automobile industry or shipbuilding industry. It can be used as a photoresist for plates and parts, as a surface-treating agent in the textile industry, and as an oxygen immobilizing agent and a cavity filling agent in the biomedical industry.

[Examples] The present invention will be described in more detail below with reference to Reference Examples and Examples.

Reference Example 1 (Synthesis of methacryloyl isocyanate) To a suspension of 17.9 g of methacrylamide and 0.18 g of hydroquinone in 100 ml of chloroform, a solution of 20 ml of oxalyl chloride in 15 ml of chloroform was added dropwise under nitrogen cooling at 0 ° C. After the dropping, the temperature was returned to room temperature and the mixture was stirred for about 100 minutes. Hydroquinone (0.18 g) was added, and the mixture was heated and stirred at 60 ° C. for 4 hours. After cooling, the reaction solution was concentrated under reduced pressure, and the concentrate was distilled under reduced pressure to obtain methacryloyl isocyanate as a colorless liquid boiling at 52 to 53 ° C / 39 mmHg.

Reference Example 2 (Synthesis of Acryloyl Isocyanate) To a solution of 95.25 g of oxalyl chloride in 150 ml of 1,2-dichloroethane, a solution of 200 ml of 1,2-dichloroethane in an amount of 35.5 g of acrylamide and 0.54 g of hydroquinone at -30 to 0 ° C for about 30 minutes. It was dripped at. After the dropping, the mixture was heated under reflux for about 1 hour, allowed to cool, and then distilled under reduced pressure to obtain 44.7 g of β-clopropionyl isocyanate as a colorless liquid having a boiling point of 74 to 75 ° C./25 mmHg.

20 g of Molecular Sieve 4A was added to a solution of 13.35 g of β-chloropropionyl isocyanate in 20 ml of toluene, and the mixture was heated under reflux for 13.5 hours in a nitrogen stream. After cooling down,
The molecular sieve was filtered off, and the filtrate was distilled under reduced pressure to obtain acryloyl isocyanate. Boiling point 82-83 ℃.

Reference Example 3 To a reaction vessel equipped with a stirrer, a thermometer, and a reflux condenser, 165 g of xylene was added, and 50 parts of styrene and 125 parts of methyl methacrylate were added while heating the temperature to carry out nitrogen gas purging.
A mixture of 150 parts of hydroxyethyl acrylate, 150 parts of ethylhexyl acrylate, 25 parts of methyl acrylate, 25 parts of lauryl mercaptan and 10 parts of Kayaester O was added dropwise over 3 hours to give a molecular weight of 5500 and a hydrogen group value of 14
Acrylic oligomer (1) of 4 was produced.

After the temperature of the reaction vessel was lowered to 30 ° C., the methacryloyl isocyanate 28.5 obtained in Reference Example 1 was substituted so that 2/10 of all the hydroxyl groups of the acrylic oligomer (1) were replaced.
Parts and 1.0 part of hydroquinone were added dropwise over 30 minutes. After the dropwise addition, when the reaction of methacryloyl isocyanate with a hydroxyl group was checked by infrared absorption spectroscopy, the disappearance of the peak at 2250 cm ¹ due to the -NCO group, -NH
The appearance of the peak at 3300 cm ¹ due to the group and the appearance of the peak at 1760 cm ¹ shifted from the usual carbonyl group due to the acylcarbonyl group were confirmed. Furthermore, by nuclear magnetic resonance spectroscopy (NMR method), the appearance of a signal due to the proton of the -NH group and the chemical shift of the signal due to the vinyl proton to a high magnetic field of about 0.3 ppm were confirmed. All of these results show that the -OH group is replaced by the acyl urethane group of formula (A).

The reaction mixture thus obtained was distilled under reduced pressure to remove volatile matter to obtain a reactive acrylic oligomer (2) having a nonvolatile content of 98%, a molecular weight of 5900 and a viscosity of 200 poise.

Reference Example 4 In the same manner as in Reference Example 3, while maintaining a mixture of 200 parts of polytetramethylene glycol having a molecular weight of 200 and 0.4 part of hydroquinone at 30 ° C., methacryloyl isocyanate so that all the hydroxyl groups of the polytetramethylene glycol are replaced. 22.2 parts was added dropwise over 30 minutes. After completion of the dropping, the disappearance of the absorption peak of the -NCO group and the appearance of the absorption peak due to the -NH group were detected by the infrared absorption spectrum method, and the appearance of the signal due to the -NH group and the high magnetic field of the vinyl proton were detected by the NMR method. Was confirmed to obtain a reactive polyether acrylate oligomer (1) having a molecular weight of 2,200.

Reference Example 5 Silicone oil having a primary alcoholic hydroxyl group at both ends of dimethylsiloxane in the same reaction vessel as in Reference Example 3 (trade name "X-22-160AS"; manufactured by Shin-Etsu Chemical Co., Ltd.);
200 parts of an average molecular weight of 1000 and a hydroxyl value of 112) were added, and 39 parts of acryloyl isocyanate was added dropwise over 30 minutes so that all the hydroxyl groups of the silicone oil were replaced while maintaining the temperature at 30 ° C. After completion of the dropping, the disappearance of the -NCO group and the appearance of the -NH group were confirmed by infrared absorption spectroscopy and NMR to obtain a reactive silicon acrylate oligomer having a molecular weight of 1200.

Reference Example 6 Using the same apparatus as in Reference Example 3, 37 parts of maleic anhydride, 101 parts of sebacic acid, and a long-chain aliphatic dibasic acid having 20 carbon atoms (trade name "SB-20"; manufactured by Okamura Oil Co., Ltd.) ) 170 parts and 93 parts of ethylene glycol were charged and reacted at 180 to 200 ° C. until the acid value became 10, and then cooled to room temperature to obtain a polyester oligomer having a molecular weight of 2000 and a hydroxyl value of 52.

After adding 0.8 parts of hydroquinone, 18 parts of the acryloyl isocyanate obtained in Reference Example 2 was replaced with 30 parts of the polyester oligomer so that 5/10 of all the hydroxyl groups were replaced.
The solution was added dropwise over 30 minutes while maintaining the temperature at 0 ° C. After completion of the dropping, disappearance of the absorption peak of -NCO group and appearance of absorption peak of -NH group were confirmed by infrared absorption spectroscopy to obtain a reactive polyester acrylate oligomer having a molecular weight of 2100.

Reference Example 7 In the same manner as in Reference Example 4, while maintaining a mixture of 300 parts of polyethylene glycol having a molecular weight of 300 and 0.4 part of hydroquinone at 30 ° C., 220 parts of methacryloyl isocyanate were mixed so that all hydroxyl groups of polyethylene glycol were replaced.
It dripped over 0 minutes. After completion of the dropping, the mixture was confirmed by infrared absorption spectroscopy and NMR to obtain a reactive polyether oligomer (2) having a molecular weight of 520.

Reference Example 8 Using the same device as in Reference Example 3, bisphenol A type epoxy resin (Toto Kasei Co., Ltd. "YD-011"; epoxy equivalent
450-500; 2 hydroxyl groups / molecule; molecular weight 90-1000) 41.7
And 12.5 parts of xylene were charged, the internal temperature was heated to 150 ° C., and xylene was refluxed for about 2 hours to dissolve the epoxy resin. 29.2 parts of propylene glycol monomethyl ether acetate was added, the internal temperature was lowered to room temperature while diluting, and then 4.6 parts of methacryloyl isocyanate was added dropwise over 20 minutes. After confirming the disappearance of the —NCO group, the reaction was terminated to obtain a reactive epoxy acrylate oligomer having a molecular weight of 2300.

Reference Example 9 200 parts of polyethylene glycol having a molecular weight of 200, 0.1 part of dibutyltin dilaurate and 0.2 part of hydroquinone were placed in a reaction vessel similar to that of Reference Example 3, and 112 parts of hexamethylene diisocyanate was added for 2 hours while keeping the temperature at 50 to 60 ° C. Is added dropwise, and the mixture is stirred for an additional 1 hour to give a molecular weight of 950
Of polyurethane resin was obtained.

In order to replace 9/10 of all hydroxyl groups of the polyurethane resin, 67 parts of methacryloyl isocyanate was added dropwise over 30 minutes to obtain a reactive polyurethane acrylate oligomer having a molecular weight of 1200.

Reference Example 10 Using the same device as in Reference Example 3, butyl acetate 342
Parts, 1028 parts of polytetramethylene glycol having a molecular weight of 2000 and 222 parts of isophorone diisocyanate were added and sufficiently stirred, then 1.25 parts of dibutyltin dilaurate was added, and the temperature was gradually raised to 80 ° C. and maintained for 1 hour. Next, 1.4 parts of hydroquinone was added, 116 parts of 2-hydroxyethyl acrylate was added dropwise over 30 minutes, and the mixture was kept at 80 ° C. for 3 hours. Infrared absorption spectrum method attributed to -NCO group 2
The completion of the reaction was confirmed by confirming the disappearance of the peak at 250 cm ¹ . After completion of the reaction, the solvent was removed by heating under reduced pressure to obtain a reactive polyether oligomer (3).

Example 1 To 100 parts of the reactive polyether acrylate oligomer (1) obtained in Reference Example 4 was added 1.5 parts of benzoyl methyl ether, and the mixture was sufficiently stirred to obtain a UV-curable optical fiber coating composition. This composition was coated on a clean glass plate with a doctor blade so as to have a dry film thickness of 200 μ, left at room temperature for 2 hours, and then treated with ultraviolet rays under the conditions described below to obtain a cured film. This coating was transparent and good without tack. Next, when the cured coating was peeled off from the glass plate and a tensile test was performed,
The initial Young's modulus was 0.22 kg / mm ² , and the elongation rate was 54%.

Ultraviolet treatment conditions The high-voltage mercury lamp HI-20N (80W / cm reflector, using a concentrator) used by Nippon Batteries Co., Ltd. is placed with the lamp length direction at right angles to the conveyor traveling direction, and the height is 80 mm from the conveyor surface. Speed
5m / min.

Tensileon Tensile Test Conditions Tensilon Tensile Tester (TOYO Baldwin HI-
100 type) with a film length of 50 mm and a width of 10 mm for a sample with a pulling speed of 50 mm / min.

Example 2 By mixing 20 parts of the reactive polyether acrylate oligomer (1) obtained in Reference Example 4, 80 parts of the reactive polyether oligomer (3) obtained in Reference Example 10 with 1.5 parts of benzoyl methyl ether. A coating composition for an optical fiber was obtained.

Using this composition, a cured film was obtained in the same manner as in Example 1 and subjected to a tensile test. At 20 ° C., the initial Young's modulus was 0.40 kg / mm ² , the elongation rate was 63%, and the breaking strength was 0.25 kg / mm. ² , 60
Initial Young's modulus 0.37kg / mm ² , elongation 55%, breaking strength at ℃
It was 0.20 kg / mm ² .

Comparative Example 1 A coating composition for an optical fiber was obtained from 100 parts of the reactive polyether oligomer (3) obtained in Reference Example 10 and 1.5 parts of benzoyl methyl ether.

Using this composition, a cured film was obtained in the same manner as in Example 1 and subjected to a tensile test. At 20 ° C., the initial Young's modulus was 0.61 kg / mm ² , the elongation rate was 45%, and the breaking strength was 0.19 kg / mm. ² , 60
Initial Young's modulus 0.58kg / mm ² , elongation 35%, breaking strength at ℃
It was 0.16 kg / mm ² .

Example 3 100 parts of the reactive silicon acrylate oligomer obtained in Reference Example 5 was mixed with 3 parts of diacetophenone to obtain a coating composition for an optical fiber.

Coating testSpin glass fiber from the base material mainly composed of quartz glass so that the diameter becomes 100μ, and immediately after spinning, apply the above composition by ironing through a die so that the film thickness becomes 100μ, and then perform UV treatment. Thus, a primary coated glass fiber was obtained. The coating film of the obtained coated fiber had sufficient strength without cracking or peeling even when the fiber was bent.

Example 4 The reactive polyester acrylate oligomer obtained in Reference Example 6 was roll-coated on 200 μ art paper so that the coating thickness was 2 μ. After setting for 10 minutes, electronic energy 30
Irradiation with electron beam of 0keV under electron current of 30mA, dose 3Mrad
By giving, a cured film having no surface tackiness was obtained.
The hardness of the coating film was H when measured with a pencil hardness, and the adhesion of the coating film was good even when the tape was peeled off by the cross cut method.

Example 5 100 parts of the reactive epoxy acrylate oligomer solution obtained in Reference Example 8 was used as a radical curing catalyst in 5 parts of Kayamec A (manufactured by Kayaku Nouri Co., Ltd .; 55% by weight solution of methyl ethyl ketone peroxide in dimethyl phthalate) and 6% naphthene. 2.5 parts of cobalt acid salt was blended to obtain a curable composition.

This composition was applied to a 200 mm × 25 mm tin plate so as to have a thickness of 100 μm. After setting for 20 minutes, similar tin plates were overlapped, pressed with a force of 5 kg / cm ² , and baked at 100 ° C. for 30 minutes to bond the tin plates. When the T peel test of this tin plate was carried out, the peel strength was 5kg / 25mm
Met.

Example 6 500 parts of polyvinyl alcohol having a degree of saponification of 80.7 mol% and an average degree of polymerization of 500 in a kneader and 325 parts of polyvinyl alcohol having a degree of saponification of 87.7 mol% and an average degree of polymerization of 500 and deionized water.
680 parts were added and dissolved at a temperature of 90 ° C. for 30 minutes. After the dissolution was completed, the temperature inside the tank was lowered to 60 ° C and a mixed solution of 1.2 parts of hydroquinone and 1673 parts of 2-hydroxyethyl methacrylate was added.
It dripped over 30 minutes. After the dropping, a solution prepared by dissolving 50 parts of benzoyl methyl ether in 215 parts of dimethyl sulfoxide was added and mixed at 60 ° C. for 15 minutes to obtain a resin composition. To 135 parts of this resin composition, 15 parts of the polyether oligomer (2) obtained in Reference Example 7 was added and further mixed with a kneader.
After the completion of mixing, defoaming was performed under reduced pressure to obtain a photocurable resin composition.

This composition was kept warm at 60 ° C., a liquid prepared from polyvinyl alcohol and a red iron oxide pigment was applied onto a tin plate and extruded through a slit on a support obtained, and a hard vinyl sheet was placed on it and pressed. It was pressed with a machine at a pressure of 20 kg / cm ² for 5 minutes and further dried at 60 ° C. to obtain a photopolymer plate. A negative was brought into close contact with this plate, exposed with a mercury lamp for 3 minutes, and then developed by spraying tap water to obtain an uneven plate. The image reproducibility of the obtained plate was good, and it had a good shoulder angle and a chevron shape in cross section.

Example 7 100 parts of the acrylic oligomer (2) obtained in Reference Example 3 and 1.2 parts of an acrylic leveling agent were placed in a stainless beaker, thoroughly stirred with a disperser, defoamed and desolvated to obtain an X-ray curing composition. Got

This composition is made of polymethylmethacrylate and has a thickness of 5 m.
A plastic plate of m was coated with a doctor blade so that the cured film thickness was 200μ. A cured film was obtained by irradiating X-rays with a dose of 1.2 million roents under an acceleration voltage of 50 kV and a current of 40 mA using tungsten as the anticathode. The coating was transparent and had a pencil hardness of 2H.

Example 8 100 parts of the reactive polyurethane acrylate oligomer obtained in Reference Example 9 was mixed with 2 parts of benzoyl methyl ether to obtain a leather coating composition.

This composition was coated on cowhide to a film thickness of 10μ,
The leather was coated by irradiating it with ultraviolet rays. The resulting coating film had sufficient flexibility.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kei Aoki 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Co., Ltd. (72) Inventor Ryuzo Mizuguchi 19-17 Ikedanaka-cho, Neyagawa-shi, Osaka Japan Paint Within the corporation

Claims (2)

[Claims] (1) Polyether polyol, polyester polyol, acrylic polyol, polyurethane polyol, epoxy compound, polybutadiene, amino resin, star polymer, phenol resin, xylene resin,
At least one or more of the hydroxyl groups of the compound having a hydroxyl group selected from the group consisting of vinyl compounds, cellulosics, oligosaccharides and mixtures thereof has the formula: [In the formula, R represents hydrogen or lower alkyl. ] At least 0.5% by weight as an essential component of a polymerizable compound substituted with an acyl urethane group represented by, and (2) a polymerizable monomer having at least one polymerizable double bond in the molecule, Alternatively, a coating composition containing either one or both of a polymerization initiator. 2. The coating composition according to claim 1, which is used for coating glass fibers.