JPS6351402A - Photo-setting resin composition - Google Patents

Abstract

PURPOSE:To obtain a composition, by dispersing a photopolymerization initiator and internally crosslinked fine resin particles carrying an amine compound in a photo-setting liquid resin and having a high curing rate by irradiation energy as well as excellent storage stability without offensive smell. CONSTITUTION:A photo-setting resin composition obtained by dispersing a photopolymerization initiator, e.g. benzoin, 2-chlorothioxanthone, anthracene, etc., and internally crosslinked fine resin particles, having 0.01-6mu particle diameter and prepared by (co)polymerizing an ethylenically unsaturated monomer, e.g. methyl acrylate, etc., carrying an amine compound, e.g. propylamine, 3-aminopropanol, etc., in a photo-setting liquid resin. The amount of the dispersed above-mentioned fine resin particles is normally preferably 0.1-40pts.wt. based on 100pts.wt. photo-setting liquid resin. EFFECT:Physical properties, e.g. hardness, abrasion resistance, elongation, etc., of cured films are improved. USE:Useful as a coating material for optical fibers, etc.

Description

[Detailed description of the invention]! 1. Resin compositions that harden by irradiation with blood light are used as ultraviolet curing paints, photoresists, and printing plate materials, and more recently, they have been used as primary coatings for optical fibers applied immediately after drawing.
It is attracting attention as an i-material.

Such photocurable resin compositions generally contain a polymer or oligomer into which a radically polymerizable ethylenically unsaturated group has been introduced at the terminal, and a polymerizable ethylenically unsaturated monomer as a crosslinking agent that also serves as a diluent. , further contains a photopolymerization initiator. For example, when used as a coating material for optical fibers, it is desired to shorten the curing time as the drawing speed increases, and for this reason, it has been proposed to add an aliphatic amine compound to the composition. However, such amine compounds are generally volatile, have a strong and unpleasant odor, and have drawbacks such as impairing the storage stability of the composition.

It is also known to add an amine monomer having an ethylenically unsaturated group for the same purpose, but this has disadvantages such as affecting the physical properties of the film after curing, particularly poor water resistance.

Therefore, it is an object of the present invention to provide a photocurable resin composition that does not have the above-mentioned drawbacks, although it contains an amine compound to accelerate the curing rate.

The present invention includes a photopolymerization initiator in a photocurable liquid resin and a particle size of 0. A photocurable resin composition is provided in which internally crosslinked fine resin particles obtained by polymerization or copolymerization of an ethylenically unsaturated monomer supporting an amine compound at O1 to 6μ are dispersed.

In this way, the present invention does not add the amine compound directly to the composition, but adds it to the photocurable resin composition in the form of being supported on fine resin particles. There is no problem of damaging or adversely affecting the physical properties of the cured coating film, and on the contrary, it has the effect of improving the physical properties of the cured coating film.

The amine compound can be supported on fine resin particles by physically adsorbing or absorbing them onto the particles after production.

Another supporting method is to blend an amine compound with a monomer raw material for producing fine resin particles, and incorporate the mixture into the fine resin particles by polymerizing the mixture.

The third method is to use an amine monomer having an ethylenically unsaturated group, and the amine monomer is copolymerized with the monomer constituting the micro resin particles, or polymerized on the surface of the micro resin particles. let

The fine resin particles used in the present invention can be manufactured by a known method for manufacturing fine resin particles, except for supporting an amine compound.

Various methods have been proposed to produce micro resin particles, one of which involves suspension polymerization or emulsion polymerization of an ethylenically unsaturated monomer with a crosslinkable comonomer in an aqueous medium. This method involves creating a dispersion of fine resin particles and removing water by solvent substitution, azeotropy, centrifugation, drying, etc. to obtain fine resin particles.Other methods include using low SP organic solvents such as aliphatic hydrocarbons or esters. The ethylenically unsaturated monomer and the crosslinkable copolymer are copolymerized in a non-aqueous organic solvent that dissolves the polymer but does not dissolve the polymer, such as a high SP organic solvent such as , ketone, or alcohol. This is a method called the NAD method or precipitation method in which the resulting fine resin particle copolymer is dispersed.

The fine resin particles of the present invention may be produced by any of the above methods. The method for producing minute resin particles using a water-soluble resin having an amphoteric group described in JP-A-5A-T29066 by the present inventors may also be used. The particle size needs to be 0.01 to 6 μm from the viewpoint of miscibility, reactivity, and storage stability.

Examples of ethylenically unsaturated monomers include acrylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, isobutyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. or alkyl esters of methacrylic acid or other monomers having ethylenically unsaturated bonds that can be copolymerized with methacrylic acid, such as styrene, α-methylstyrene, vinyltoluene, t-7
``Chylstyrene, ethylene, propylene, vinyl acetate,
Examples include vinyl propionate, acrylonitrile, methacrylonitrile, and dimethylaminoethyl (meth)acrylate. These I! Two or more types of mer may be used.

Crosslinkable comonomers are monomers and/or monomers having two or more radically polymerizable ethylenically unsaturated bonds in the molecule.
Alternatively, it contains two types of ethylenically unsaturated group-containing monomers each carrying groups that can react with each other.

Examples of lff units having two or more radically polymerizable ethylenically unsaturated groups in the molecule include polymerizable unsaturated monocarboxylic acid esters of polyhydric alcohols, polymerizable unsaturated alcohol esters of polybasic acids, and two There are aromatic compounds substituted with the above vinyl groups, examples of which include the following compounds.

Ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol dimethacrylate Acrylate, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, glycerol dimethacrylate , glycerol diacrylate, glycerol allyloxy dimethacrylate, 1.1.1-) lis-hydroxymethylethane diacrylate, 1,1.1-) lis-hydroxymethylethane triacrylate, 1,1.
1-trishydroxymethylethane dimethacrylate,
1.1.1-) Lishydroxymethylethane trimethacrylate, 1.1.1-1-Lishydroxymethylpropane diacrylate, 1,1.1-) Lishydroxymethylpropane triacrylate, 1,1.1-Tris Hydroxymethylpropane dimethacrylate, 1.
1.1-) Lishydroxymethylpropane trimethacrylate, triallyl cyanurate, triallyl isocyanurate, triallyl trimellitate, diallyl terephthalate, diallyl phthalate and divinylbenzene.

In addition, examples of monomers having two types of ethylenically unsaturated groups each carrying mutually reactive groups include epoxy group-containing ethylenically unsaturated monomers such as glycidyl acrylate and glycidyl methacrylate, and acrylic acid and methacrylic acid. Carboxyl group-containing ethylenically unsaturated monomers such as acid and crotonic acid are the most representative, but mutually reactive groups are not limited to these.
For example, a large number of compounds have been proposed, such as amine and carbonyl, epoxide and carboxylic acid anhydride, amine and carboxylic acid chloride, alkyleneimine and carbonyl, organoalkoxysilane and carboxyl, hydroxyl and isocyanate, etc. It broadly encompasses the following.

Micro resin particles produced in an aqueous medium or a non-aqueous organic medium can be isolated by a method such as filtration, spray drying, or freeze drying, and then either left as is or reduced to an appropriate particle size using a mill. It can be used after being pulverized, or a synthesized dispersion can be used by replacing the medium with the solvent.

Generally speaking, it is desirable to control the particle size of the particles obtained by the polymerization method. 0.01~0.6μ
For particles of 0.2 to 2, the emulsion polymerization method and NAD method
The precipitation method is most commonly used for particles with a diameter of 1 to 6 microns, and the suspension polymerization method is most commonly used for particles with a size of 1 to 6 microns. In addition, rheology control is possible by adjusting the particle size distribution by the polymerization process or by mixing the particles after polymerization, if necessary. The glass transition point, solubility parameter, and refractive index of the fine resin particles can be controlled by the constituent components of the particles themselves in relation to the matrix resin. In addition, in the structure, by arranging functional groups or unsaturated groups that can react with each other or with the matrix resin on the surface of the resin particles, interactions between the resin particles and between the resin particles and the matrix resin can be further enhanced.

The first method for supporting microscopic resin with an amine compound that has the function of accelerating the curing rate when using a photopolymerization initiator is to transfer the amine compound to microscopic resin particles that have been synthesized in advance. This is a method of physically absorbing or adsorbing. Supporting by this method can be achieved, for example, by preparing an isolated amine compound as a solution in an organic solvent that dissolves the amine compound but not the minute resin particles, and impregnating the solution into the minute resin particles. It can also be achieved by adding the solution of the amine compound to a dispersion of synthesized resin particles and then isolating the fine resin particles using the method described above.

Amine compounds that can be used for this purpose include aliphatic,
Aromatic and alicyclic monoamines, diamines, polyamines, and piperidine salt conductors, such as propylamine, butylamine, tributylamine, isobutylamine, 1,2-dimethylpropylamine, hexylamine, 2-ethylhexylamine, octylamine. ,
2-Hydroxymethylaminoethanol, 3-aminopropatol, 3-methoxypropylamine, 3-dimethylamitublobanol, 2-aminopropatol.

Butoxypropylamine, caprylylamine, laurylamine, myristyramine, stearylamine, oleylamine, decyloxylpropylamine, lauroxybutylamine, dimethylaminoethylamine, ethylaminoethylamine.

Diethylaminoethylamine, methylaminopropylamine, iminobispropylamine, methylaminobispropylamine, distearylamine.

Dimethyloctylamine, dimethyldecylamine.

dimethyl laurylamine, dimethyl myristylamine,
Examples include dimethylpalmitylamine, dimethylsterylamine, dimethyloctylamine, stearylpropylenediamine, dimethylbenzylamine, N-methylmorpholine, N-ethylmorpholine, piperidine, 3-pipecoline, 3-piperidine methanol, and the like.

The second method is to mix a hairmin compound in a monomer that is a raw material for producing fine resin particles, and polymerize the mixture to incorporate the amine compound into the fine resin particles during synthesis. This method is preferred when the amine compound is soluble in the monomer but difficult to be eluted by the polymerization medium.

In addition, this method uses a surfactant, oligosoap, or polysoap, which has an amine function and a surfactant function, as an emulsifier or a dispersant when synthesizing minute resin particles by emulsion polymerization. It can be imported into.

Examples of the surfactant include quaternary ammonium salts such as stearyltrimethylammonium chloride and laurylpicolinium chloride, alkylamine salts such as laurylamine acetate and hardened beef tallow propylene diamine dioleate, polyoxyethylene alkylamines, and Examples include polyoxyethylene alkylamides.

Oligo soaps include acrylic oligomers, amino acids, and acrylic oligomers polymerized using the general method described in "Introduction to Synthetic Resins for Paints" by Kitaoka, "Introduction to Synthetic Resins for Paints," Kobunshi Kansaikai, pp. 166-170, 186-188, using amine monomer as one of the comonomers. A polyester oligomer obtained by polymerizing a hexamer having a group and a hydroxyl group or an amino group and a carboxyl group as one of the raw materials according to the method described in "Introduction to Synthetic Resins for Paints" by Kitaoka, p. 93-1), Alternatively, epoxy oligomers obtained by modifying epoxy resins with primary or secondary amines can also be used in Fujimoto's "Introduction to New Surfactants" 63-
Commercially available cationic resins such as those described on page 81 are conveniently used.

The third method is to synthesize a monomer or oligomer with an amine function by introducing a polymerizable ethylenically unsaturated group into an amine compound, and copolymerize this with a monomer for synthesizing micro resin particles. This is a method in which an amine compound is supported on resin particles.

Typical examples of polymerizable amine monomers are aminoalkyl acrylates or methacrylates.

Preferably, aminoalkyl groups contain alkyl residues having about 1 to 6 carbon atoms. Examples of these are aminoethyl, aminopropyl and amine hexyl acrylates or methacrylates, N,N-dialkylaminoalkyl acrylates or methacrylates in suitable salts. same(,
Also useful are vinyl- or bicyclic amino compounds, including 5- or 6-membered N-heterocyclic compounds, acrylamide-amino-modified superterminals, and superterminals containing quaternary ammonium groups. In addition, di(lower) alkylamino (lower)
alkanoltanol, dimethylaminoethanol, dimethylaminopropanol, diethylaminoethanol, diethylaminopropanol, N-methyl-N-ethylaminepropanol), di((degree) grade) alkylaminophenol (e.g. O-dimethylaminophenol, m-dimethylaminophenol, p-dimethylaminophenol,
m-diethylaminophenol), lower alkyl-phenylamino (lower) alkanols (e.g. N-methyl-N-phenylaminoethanol, N-methyl-N-
lower alkyl-phenyl (lower) alkylamino (lower) alkanols (e.g. N-methyl-N-hensylaminoethanol, N
-ethyl-N-hensylaminoethanol, N-ethyl-N-phenethylaminopropanol), N-hydroxypyrrolidine, N-hydroxypiperidine, N-hydroxymorpholine, pyrrolidino (lower)alkanol (
(e.g. pyrrolidinoethanol, pyrroliziprobanol), piperidino (lower) alkanols (e.g. piperidinoethanol, piperidinoperopanol), morpholino (lower) alkanols (e.g. morpholinoethanol, morpholinopropanol), di(lower) Reaction products of alkylamino (lower) alkoxy (lower) alkanols (e.g. dimethylaminoethoxyethanol, dimethylaminoethoxypropanol, diethylaminoethoxypropanol), atropine, and vinyl isocyanates such as isocyanate ethyl acrylate and methacryloyl isocyanate, or diisocyanates and hydroxyl groups. It is also possible to use reaction products with (meth)acrylates having .

The polymerizable amine monomer is prepared by a known polymerization method such as solution polymerization method or emulsion polymerization method by adding other polymerizable ethylenically unsaturated monomers that do not have amine functionality as necessary in the presence of pre-synthesized fine resin particles. It can also be supported by polymerizing by polymerizing and forming a polymer film containing these amine-containing polymers on the surface of fine resin particles.

By the above method, not only the amine compound but also other substances such as an initiator and a sensitizer can be supported on the fine resin particles, and such multifunctional fine resin particles may be used.

- H, 1 The photocurable resin composition of the present invention may be the same as known compositions, except that it contains fine resin particles carrying an amine compound. Here, the photocurable resin composition means a photocurable resin composition in a broad sense including an electron beam curable composition.

These generally have the following basic composition: (1) photocrosslinkable (or non-crosslinkable) polymer or oligomer (2) photopolymerizable hexamer or low molecular weight oligomer (3)
Contains a photopolymerization initiator (or sensitizer) (4) thermal polymerization inhibitor (or stabilizer), and optionally contains additives such as a sensitizer and a coloring agent.

Examples of the polymer or oligomer (1) include unsaturated polyester resin, urethane acrylate resin, epoxy acrylate resin, polyester acrylate resin,
Spiran acrylate resin, polyether acrylate resin, etc. are well known.

The photopolymerizable polymer or low molecular weight oligomer in (2) includes the low molecular weight oligomer of the polymer in (1) above, as well as styrene, vinyltoluene, divinylbenzene, vinyl acetate, (meth)acrylonitrile, (meth) Acrylic esters [methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, (meth)
2-ethylhexyl acrylate, glycidyl (meth)acrylate, ethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc.], diethyl itaconate, dibutyl itaconate,
Known examples include diethyl fumarate and diethyl maleate.

Sensitizers for (3) include benzoin ether, benzophenone, acetophenone, and thioxanthone, including benzoin, benzoin methyl ether, benzoin ethyl ether, isoprovirhenzoin ether, isobutylbenzoin ether, and 1-phenyl-1 ，
2-propanedione-2-(0-ethoxycarbonyl)
Oxime, 2I2-dimethoxy-2-phenyl-acetophenone.

Hydroxycyclohexylphenylketone 1 Jetoxyacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, diacetyl, dibutyl disulfide, dibenzyl disulfide 1. Benzophenone, 3.3"-
Dimethyl-4-methoxybenzophenone, methylorthobenzoylbenzonate, benzyl, 2-chlorothioxanthone, isopropylthioxanthone, 2-methylthioxanthone, chlorine-substituted benzophenone, halogen-substituted alkylallyl ketone, anthracene.

α-chloroanthraquinone, hexachlorbutadiene,
Pentachlorbutagel, 1-chlornaphthalene, etc. are known.

(4) Thermal polymerization inhibitors include hydroquinone, t-
Butylhydroquinone, p-methoxyphenol, catechol, benzoquinone, and the like are known.

The amount of the amine-supporting micro resin particles according to the present invention may vary depending on the type of amine compound, the amount supported, the method of supporting, etc., but it can generally be added in the range of 0.1 to 40 parts by weight per 100 parts by weight of the liquid resin. .

The composition may further contain conventional additives such as plasticizers, inorganic particles, thinners, colorants, etc., as required.

By adding the fine resin particles carrying an amine compound according to the present invention, the curing speed by irradiation energy is increased. However, since the amine compound is not liberated, there is no volatilization of the amine, so there are no problems such as odor, and the composition has good storage stability.

Furthermore, physical properties such as hardness, abrasion resistance, and elongation of the cured coating film are improved due to the interaction between the fine resin particles and the matrix resin. In this regard, it is unexpected that the physical properties of the coating film are improved even when compared to the case where fine resin particles not carrying an amine compound are added. This is thought to be because curing by irradiation energy occurs particularly efficiently on the surface of the particles, and as a result of coalescence, a coating film having a non-uniform curing distribution is formed.

Therefore, the photocurable resin composition of the present invention can be used as a UV curable coating, an electron beam curable coating, a photoresist, a printing plate material, etc., and is particularly useful as a material for coating optical fibers.

The present invention will be explained in detail below with reference to Examples. In the example “
"Parts" are based on weight.

Reference Example 1 81 ions 134 parts of bishydroxyethyl taurine, 130 parts of neopentyl glycol were added to a 21 Kolben equipped with a stirrer, a nitrogen inlet pipe, a temperature control device, a content 1J-1, and a decane cooler. 1 part, 236 parts of azelaic acid, 186 parts of phthalic anhydride, and 27 parts of xylene, and the temperature was raised. Water produced by the reaction is azeotroped with xylene and removed. The temperature was raised to 190°C over about 2 hours from the start of refluxing, stirring and dehydration were continued until the acid value equivalent to carboxylic acid reached 145, and then the mixture was cooled to 140°C. Next, while maintaining the temperature at 140°C, 314 parts of Cardura E10j (Persatic acid glycidyl ester manufactured by Shell) was added dropwise over 30 minutes, and then 2
Continue stirring for an hour to complete the reaction. The resulting polyester resin has an acid value of 59 and a hydroxyl value of 90. Mn105
It was 4.

Reference Example 2 Add 400 parts of butyl acetate and 89 parts of dimethylaminoethanol to an IA colchen equipped with a stirrer, nitrogen inlet tube, temperature control device, and cooling tube, maintain the temperature at 70°C, and add 155 parts of isocyanate methyl acrylate while stirring well. 2
The polymerizable amine monomer (A) was obtained by dropping the mixture over a period of time and continuing stirring for another 2 hours to remove the solvent.

Reference Example 3 Using the same apparatus as Reference Example 2, 600 parts of butyl acetate,
Diethylaminobutanol 1) Add 222 parts of isophorone diisocyanate and raise the temperature to 70°C.
After keeping the mixture for 0 minutes, 6 parts of 2-hydroxyethyl acrylate 1) was further added and reacted, and the solvent was removed to obtain a polymerizable amine monomer (B).

Reference Example 4 In a reaction vessel similar to Reference Example 2, 281 parts of deionized water, 30 parts of the oligomer obtained in Reference Example and 3 parts of dimethylethanolamine were charged, and dissolved while stirring while maintaining the temperature at 80°C. A solution prepared by dissolving 1.0 part of azobiscyanovaleric acid in 45 parts of deionized water and 0.9 part of dimethylethanolamine is added to the solution. Then methyl methacrylate 40
parts, n-butyl acrylate 30 parts, styrene 50 parts, 2
- A mixed solution consisting of 5 parts of hydroxyethyl acrylate, 15 parts of dimethylaminopropyl methacrylate, and 60 parts of ethylene glycol dimethacrylate is added dropwise over 60 minutes. After the dropwise addition, 0.5 part of azobiscyanovaleric acid dissolved in 15 parts of deionized water and 0.4 part of dimethylethanolamine was added, and stirring was continued at 80°C for another 2 hours to obtain a solution with a non-volatile content of 40% and a particle size of 0. A .07μ emulsion was obtained. By spray drying this emulsion, fine resin particle powder (A) having an amine compound on the surface was obtained.

Reference Example 5 In a reaction vessel similar to Reference Example 2, 218 parts of deionized water, 1 part of ethylene glycol dimethacrylate, 1.5 parts of methyl methacrylate, 4.5 parts of styrene, 2.0 parts of isobutyl methacrylate, and Reference Example 2 were added. Add 3 parts of the obtained polymerizable amine monomer (A) and raise the temperature to 70°C while stirring.
Increase temperature to ℃. A solution of 0.5 parts of ammonium persulfate dissolved in 10 parts of deionized water was charged and reacted for 10 minutes.
Next, 1 part of ethylene glycol dimethacrylate, 25.5 parts of methyl methacrylate, 35.5 parts of styrene,
18 parts of n-diptylacrylate are added dropwise over a period of 2 hours. After the dropwise addition, a solution of 0.2 parts of ammonium persulfate dissolved in 5 parts of ionized water was added, and the reaction was continued for another 4 hours to obtain an emulsion with a non-volatile content of 32% and 1 particle i'i of 0.35μ. By drying this emulsion, fine resin particles with an amine compound on the surface (
B) was obtained.

Reference Example 6 Into a reaction vessel similar to Reference Example 2, 800 parts of n-octane was placed, and while keeping it at 80°C, 25 parts of ethylene glycol, 10 parts of methyl methacrylate, 10 parts of styrene, and n-octane were added.
5 parts of butyl acrylate, 3 parts of the polymerizable amine monomer (B) obtained in Reference Example 3, and 0.0 parts of azoisobutyronitrile.
Precipitated polymerized particles were obtained by charging 5 parts and maintaining for 6 hours. By washing, separating and drying such particles with n-octane, micro resin particles F powder (C) having an amine compound on the surface are obtained.
I got it. The primary particle size of the resin particles was 1.5 μm according to SEM observation.

Reference Example 7 In a reaction vessel similar to Reference Example 2, 600 parts of deionized water and 10 parts of polyvinyl alcohol (average molecular weight 2000) are placed and kept at 80°C.
0 parts of styrene, 20 parts of n-butyl acrylate, 20 parts of ethylene glycol dimethacrylate, 5 parts of laurylamine and 2 parts of azobisisobutyronitrile was added dropwise over 1 hour, and the mixture was further stirred for 4 hours. When the process was continued, the formation of fine resin particles was observed.

After that, 3 parts of dimethylaminoethyl methacrylate was further added and left for 2 hours to be sufficiently absorbed into the fine resin particles, and then 0.02 part of azobisisobutyronitrile was added.
The reaction was completed over 2 hours.

After the reaction was completed, the fine resin particles were washed with deionized water, separated for one portion, classified, and dried to obtain a fine resin particle powder (D) having an amine compound on the surface with an average particle size of 5.5 μm.

Reference Example 8 An emulsion with a particle size of 0.07 μm was obtained in exactly the same manner as in Reference Example 4 except that dimethylaminopropyl methacrylate was not used, and the emulsion was similarly spray-dried to obtain a fine resin particle powder (E).

Example 1 Polytetramethylene glycol with molecule ff 12000,
Isophorone diisocyanate and Plaxel FA-1
70 parts of polyether urethane acrylate obtained from (Daicel Kagaku Kogyo A, increased production 8 ε-caprolactone modified acrylate), 30 parts of NK ester AMP-60G (Shin Nakamura Chemical!I Kiku, acrylic monomer), obtained from Reference Example 4. A photocurable resin composition was obtained by thoroughly mixing 5 parts of the fine resin particle powder (A) and 2 parts of benzophenone.

The photocurable Tsujiko composition obtained from the Rihoku LK experiment was placed on a quartz glass plate at a temperature of 100%.
Painted so that it becomes μ, made by Nippon Battery, high pressure water TL lamp old -
The U was installed at a height of 39++m from the conveyor surface using a 2ON (80W/(to) type, using a condensing device) lamp.
■The irradiation device is set at a conveyor speed of 20m/min!ii! When I gave it a try, I found that the film had hardened and no signs of sagging due to exposure or touch were observed. Moreover, the odor of the coating film itself was not unpleasant. Further, when a quartz glass plate was coated to a thickness of 100 μm and set for 24 hours, UV irradiation was performed under exactly the same conditions, but no difference was observed in the curing properties.

When Wataru Ai was completed, the cured film was peeled off from the glass plate and tested at 20°C as a tensile test sample. The initial Young's modulus was -0.32 kg/mJ, the elongation rate was 70%, and the result was -40°C.
Then, the initial Young's modulus is −0.35 kg/IIl[+? , the elongation rate was 150%.

Garth fiber - 9-fold glass fiber whose main component is quartz glass with a diameter of 1
By spinning the preform to a thickness of 25μ, coating the composition immediately after spinning to a film thickness of 100μ, and performing ultraviolet treatment, it is possible to obtain a glass fiber primarily coated with a resin containing minute resin particles. did it. The second coated glass fiber had sufficient flexibility even when bent without cracking or peeling.

After storing the resin composition for 10 days at 60°C, a similar curability test was conducted, and it was found to have sufficient curability even at a conveyor speed of 20 m/min.

Comparative Example 1 A photocurable resin composition was obtained in exactly the same manner as in Example 1, except that 1 part of triethylamine was used instead of the fine resin particle powder (A). A hardenability test was also conducted on the curling composition in the same manner as in Example 1, but at a bending speed of 20 m/min.
At the same conveyor speed, the sample was sticky to the touch and was sufficiently cured, with no visible stickiness to the touch at the same conveyor speed. There were differences in gender. In addition, when a tensile test was conducted on the cured coating film, 2
At 0"C, initial Young's modulus = 0.35kg/m1. Elongation rate: 40%; at -40°C, initial Young's modulus is -0.40k.
g/mi, the elongation rate was 70%.

Further, when the resin composition was stored at 60° C. for 10 days and then subjected to a similar curing test, triethylamine was volatilized, and sufficient curing properties were not exhibited at a conveyor speed of 20 m/min.

Comparative Example 2 In place of the fine resin particle powder (A) in Example 1,
Using the fine resin particle powder (E) obtained in Reference Example 8, a photocurable resin composition was obtained in the same manner as in Example 1. However, a cured film without stickiness could only be obtained when the conveyor speed was 10 m/min or less, and it was confirmed that the curing performance was inferior to that of Example 1.

Example 2 A boester urethane acrylate oligomer with molecules ff1l 600 obtained by reacting xylylene diisocyanate and 2-hydroxyethyl acrylate with a polyester oligomer consisting of triethylene glycol and a long-chain aliphatic dibasic acid with a carbon number of 20. -90 parts of vinylpyrrolidone, 10 parts of vinylpyrrolidone, 2 parts of methyl orthobenzoyl benzoate, and the fine resin particle powder obtained in Reference Example 5 (B
) A photocurable resin composition was obtained from 3 parts. When the curability of this composition was examined by the method used in Example 1, it was found that it was cured even at a conhair speed of 25 m/min, and the hardness of the coating film was H.

This composition also had better curability than the system without the addition of micro (side cloth particles), and no decrease in curability was observed after storage.

Example 3 A molecule having hydroxyl groups at both ends of the molecule (polybutadiene resin of i2000 was converted into isocyanate ethyl methacrylate-1
A photocurable resin composition was obtained from 100 parts of polybutadiene urethane acrylate obtained by modification with *, 3 parts of diacetophenone, and 20 parts of the fine resin particle powder (C) obtained in Reference Example 6. The composition passed the finger curing test at a conveyor speed of 19 m/min. The resulting film had an acetone insoluble fraction of 92%, and had better curability than the acetone insoluble fraction of the film under the same conditions, which did not contain fine resin particles, at 45%.

Example 4 Epoxy acrylate with a molecular weight of 2000 obtained by modifying with acrylic acid a lactone-modified epoxy resin obtained from a Bisubi type epoxy resin and a polycaprolactone resin (obtained from 100 parts of degreaser, 30 parts of dimethylacrylamide and Reference Example 7). An electron beam curable composition was obtained from 3 parts of the fine resin particle powder (D).The composition was coated to a thickness of 100 μ, and an electron beam with an electron energy of 250 KeV was applied at a dose of 2 Mrad under an electron current of 30 mA. A cured film was obtained. The hardness of the obtained film was 2H, and the acetone insoluble fraction was 92.
%Met.

Comparative Example 3 An electron beam curable composition was obtained in the same manner as in Example 4 except that the fine resin particles were not used.

A cured film was obtained from this composition in the same manner as in Example 4, but the hardness was 2 H and the acetone insoluble fraction was 70%.

Claims (5)

[Claims] (1) Internally crosslinked microorganisms obtained by polymerization or copolymerization of a photopolymerization initiator and an ethylenically unsaturated monomer having a particle size of 0.01 to 6μ and supporting an amine compound in a photocurable liquid resin. A photocurable resin composition formed by dispersing resin particles. (2) The photocurable resin composition according to item 1, which contains 0.1 to 40 parts by weight of the amine compound-supporting fine resin particles per 100 parts by weight of the photocurable liquid resin. (3) The photocurable resin composition according to item 1 or 2, wherein the amine compound is supported by physical adsorption or absorption onto fine resin particles. (4) The amine compound is blended into a monomer raw material for producing fine resin particles, and the mixture is polymerized to obtain the photocurable property of item 1 or 2 supported on the fine resin particles. Resin composition. (5) Supported by introducing a polymerizable ethylenically unsaturated group into the amine compound and copolymerizing it with a monomer constituting the micro resin particles, or by polymerizing it on the surface of the micro resin particles. The photocurable resin composition according to item 1 or 2.