JPS61185522A - Novel urethane poly(meth)acrylate mixture and photo-setting resin composition containing same - Google Patents

Abstract

PURPOSE:To provide the titled mixture having excellent adhesivity to metal, and consisting of a reaction mixture of a reaction product of a specific polydicyclopentadiene resin with epsilon-caprolactone, an organic polyisocyanate, and a hydroxy ester of (meth)acrylic acid. CONSTITUTION:The objective mixture is composed of a reaction mixture of (A) a compound obtained by reacting (i) a polydicyclopentadiene resin having hydroxyl group in the molecule or a resin having hydroxyl group and obtained by the hydrogenation of the above resin with (ii) epsilon-caprolactone, (B) an organic polyisocyanate and (C) a hydroxyl-containing ester of (meth)acrylic acid.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a novel urethane poly(meth)acrylate mixture and a photocurable resin composition using the same, and in particular, to a novel urethane poly(meth)acrylate mixture and a photocurable resin composition using the same. The present invention relates to a novel photocurable resin composition.

[Conventional technology]

In recent years, prevention of environmental pollution, thicker coating than solvent-based coatings,
Photocurable paints have been attracting attention because of their advantages such as fast curing and good work efficiency. However, since photocurable resin compositions have low adhesion to metal surfaces, they are still not sufficient for practical use as photocurable coatings for various metals.

In order to overcome the drawbacks of the conventional photocurable resin parabolic, JP-A-56-100816 discloses that epoxy acrylate, urethane (meth)acrylate, a monomer having an ethylenically unsaturated group, and phosphoric acid ester A photocurable resin composition comprising a silane compound and a photopolymerization initiator is disclosed.

[Problem that the invention seeks to solve]

However, this photocurable resin composition can only be applied to a limited number of metals, and is not sufficient for a wide range of applications, although there are many types of metals that can make up the base material. [Means for Solving the Problems] In order to solve the drawbacks of conventional photocurable resin compositions, the present inventors have developed a new urethane polyurethane resin composition as a result of intensive research. By discovering and using a (meth)acrylate mixture, we succeeded in providing a photocurable resin composition with good adhesion to metals. That is, the present invention comprises (1) a polydicyclopentadiene resin [I] having a hydroxyl group in its molecule, or a resin [III] having a hydroxyl group which is hydrogenated to the resin, and a compound (2) in which epsilon caprolactone is reacted with an organic polyisocyanate resin; A novel urethane poly(
meth)acrylate mixture.

(2) A polydicyclopentadiene resin [I] having a hydroxyl group in its molecule or a hydrogenated resin having a hydroxyl group [I] A compound plate prepared by reacting I with epsilon caprolactone] and an organic polyisocyanate prisoner ( A urethane poly(meth)acrylate mixture (a) consisting of a reaction mixture of meth)acrylic acid with a hydroxyl group-containing ester [V], a mono- or poly(meth)acrylate or N-vinylpyrrolidone (b), and a radically polymerizable phosphorus-containing mixture This is a photocurable resin composition characterized by containing a compound (c) and a photopolymerization initiator (d).

This novel urethane poly(meth)acrylate mixture (
a) is a compound obtained by reacting polydicyclopentadiene tree MKII or resin [f[] with epsilon caprolactone, which is urethanized with an organic polyisocyanate [separately] and then hydroxyl group-containing ester of (meth)acrylic acid [■ It can be produced by converting it into poly(meth)acrylic ester.

Alternatively, an adduct of organic polyisocyanate [Seki and hydroxyl group-containing ester of (meth)acrylic acid [v] is synthesized, and this adduct having a terminal isocyanate group is reacted with the above compound (1)] to produce urethane. It is also possible to produce poly(meth)acrylates (a).

The polydicyclopentadiene resin [I] having a hydroxyl group in the molecule used in the present invention can be produced by a known method and can be easily obtained from the market. For example, Zeon Corporation, trade name Finton 1700, is obtained from the reaction of dicyclopentadiene and allyl alcohol. Furthermore, a resin obtained by hydrogenating resin [I] (III is a colorless and transparent resin, and is preferable to resin [I] because it not only improves colorability but also has excellent storage stability and weather resistance. The method can be carried out by a generally known method, but in the case of resin [III], it is necessary to hydrogenate only the carbon-carbon double bonds of the resin without reducing the hydroxyl groups of the resin [I]. In this case, hydrogenation conditions must be carefully selected.Therefore, during hydrogenation, platinum.

It is desirable to carry out hydrogenation using a noble metal catalyst such as palladium, and when these catalysts are used, hydrogenation can be carried out under conditions of room temperature to 250°C and normal pressure to 100 kP/crn without reducing the amount of hydroxyl groups. preferable. The degree of hydrogenation is not particularly limited, but hydrogenation of 50% or more, preferably 80% or more of the carbon-carbon double bonds possessed by [N[D] usually results in great effects such as improved coloration as described above. .

Next, in the reaction of the resin [I] or [II] with epsilon caprolactone, a catalytically effective amount of a catalyst is preferably used during the reaction. The amount used is 0.001 to 1.0% by weight based on the weight of epsilon caprolactone, preferably 0.01 to 0.0% by weight.
It is 2% by weight.

Useful catalysts are known, and examples of useful catalysts include organic titanium compounds such as tetraisopropyl titanate and tetrabutyl titanate, tin compounds such as tetraphenyltin, tetraoctyltin, diphenyltin dilaurate, and dilauryltin oxide. Examples include compounds. The reaction between the resin in [I] or (III) and epsilon caprolactone is carried out at a temperature of 50 to 300°C, preferably 110 to 200°C, for a time sufficient to complete the reaction between the charged reactants.Reaction The amount of epsilon caprolactone charged is approximately 1 per OH equivalent of the resin [I] or [II].
~10 moles.

In order to minimize oxidative side reactions, the reaction is preferably carried out under an inert gas atmosphere such as nitrogen. At the end of the reaction, the product consisting of a mixture of the adduct of the resin [I] or [III] and epsilon caprolactone can be used as is.

Further, organic polyisocyanates (examples of bacteria include inphorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane-4,4-diisocyanate, lysine diisocyanate, dimer acid diisocyanate, etc.). Examples of hydroxyl group-containing esters of (meth)acrylic acid [V] include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, and ε-caprolactone-β-hydroxyethyl (meth)acrylate adduct (Daicel Chemical). industrial products, Plaxel FA-1, Plaxel F''M-1, Plaxel FA-2, etc.), pentaerythritol triacrylate, etc. In the above urethanization reaction,
It can be carried out in known procedures and under the reaction conditions in an organic solvent which is inert and also acts as a viscosity-lowering agent. These organic solvents include a number of suitable organic solvents such as ketones such as acetone and methyl ethyl ketone cyclohexanone, esters such as ethyl acetate and butyl acetate, aromatic hydrocarbons such as toluene and xylene, and ethers such as isopropyl ether and ethyl ether. There are solvents available. However, in many cases the nuclear reaction is carried out in a reactive diluent that can be retained in the formulation, used as a formulation of the radiation curable composition, and incorporated into the composition to be cured. It is preferable. Examples of such reactive diluents include:
Vinyl alcohol esters, acrylate esters,
Polyacrylates such as glycol diacrylate, triol and tetraol can be mentioned.

Specifically, they include tetrahydrofurfuryl (meth)acrylate, carpitol acrylate, phenoxyethyl (meth)acrylate, dicyclopentadiene ethoxy (meth)acrylate, 2-ethylhexyl (
meth)acrylate, lauryl(meth)acrylate,
Propylene glycol (meth)acrylate, 1.6-
Hexanethiol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalyl hydroxypiparate di(meth)acrylate, neopentyl glycol di(meth)acrylate, hydroxybivalyl hydroxybiparate-ε- Di(meth)acrylate of caprolactone adduct (Nippon Kayaku ■Shari, trade name, KAYARAD, HX-220゜HX
-620, etc.), )lipropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, N-vinylpyrrolidone, etc.

Moreover, this urethanization reaction temperature is room temperature to 100°C, preferably 50 to 80°C. Then, in the poly(meth)acrylation reaction, (
Hydroxyl group-containing ester of meth)acrylic acid [V]
You can use a little bit in excess. This reaction can be carried out in the presence of a known catalyst such as a tertiary amine, dibutyltin dilaurate, dioctyltin dilaurate, etc., in order to promote the reaction between the incyanate group and the hydroxyl group. In addition, in order to prevent gelation due to radical polymerization during one reaction, 50 to 2000 ppm (based on the compound having a terminal isocyanate group) of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, p-benzoquinone, phenothiazine, etc. is polymerized before the reaction. Preferably, an inhibitor is added.

In producing the reaction mixture of the present invention, 0.6 to 1.0 mol, preferably 1 mol of the organic polyisocyanate is used based on the hydroxyl equivalent of the compound (decoy). The above compound having a terminal isocyanate group [hydroxyl group-containing ester CfI relative to the incyanate group equivalent of the reaction product of bile and organic polyisocyanate] has 1.
0 to 1.5 mol, preferably 1.0 to 1.05 mol is used. In addition, the above-mentioned organic polyisocyanate (IVI) and hydroxyl group-containing ester of (meth)acrylic acid [I
When using the adduct of [I], the amount of the adduct is 0.5 to 1.
0 mol, preferably 1.0 mol is used.

Next, in the photocurable resin composition of the present invention, mono- or poly(meth)acrylate or N-vinylpyrrolidone (b) is used, and specific examples of mono- or poly(meth)acrylate include 2 -Hydroxyethyl (meth)acrylate.

3-hydroxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate.

Carpitol acrylate, phenoxyethyl (meth)
Acrylate, dicyclopentadiene ethoxy (meth)
Mono(meth)acrylates such as acrylates, 1.6-
Hexanethiol di(meth)acrylate, polyethylene glycol di(meth)acrylate, hydroxypivalylhydroxypivalate di(meth)acrylate, hydroxypivalylhydroxypivalate ε-
Di(meth)acrylate of caprolactone adduct (Nippon Kayaku Company Friend, trade name, KAYARAD, HX-22
0, HX-620, etc.), tripropylene glycol di(
Examples include poly(meth)acrylates such as meth)acrylate and trimethylolpropane tri(meth)acrylate. These (meth)acrylates or N-
Vinylpyrrolidone may be used alone or in combination of two or more. The proportion of these (meth)acrylates or N-vinylpyrrolidone (b) used is preferably 50 to 1500 parts by weight per 100 parts by weight of the urethane poly(meth)acrylate (a).
If too little is added, problems will arise in the rheological properties, and if too much is added, the adhesion and rheological properties will be inadequate. Note that component (b) does not need to be newly blended if it already exists in the required amount in component (a) as a reactive diluent for component (a).

The radically polymerizable phosphorus-containing compounds which are component (c) of the present invention include mono(methacryoxyethyl) phosphate, di(methacryoxyethyl) phosphate, and di(acryloxyethyl) phosphate. etc. are mentioned,
These are preferably contained in the composition in an amount of 0.1 to 5% by weight, and if the amount exceeds 5%, photocurability tends to decrease. Photoinitiator (d) used in the present invention
Any known photopolymerization initiator may be used as the initiator, but it is required to have good storage stability after blending. Examples of such photopolymerization initiators include benzoin alkyl ethers such as EVA, hengeine ethyl ether, benzoin isobutyl ether, benzoin isopropyl ether, 2,2-jethoxyacetophenone, 4-phenoxy-2,2-dichloroacetophenone, etc. acetophninone series, 2-hydroxy-2-methylpropiophenone,
Propiophenone series such as 4-improvir-2-hydroxy-2-methylpropiophenone, 4-dodecyl-2-hydroxy-2-methylpropiophenone, benzyl dimethyl ketal, 1-hydroxycyclohexylphenyl ketone and 2-Ethylanthra.

Examples include anthraquinone-based photopolymerization initiators such as quinone and 2-chloroanthraquinone, and thioxanthone-based photopolymerization initiators. These photopolymerization initiators (d) may be used alone or in a mixture of two or more in any proportion.

The amount used is usually o, i to 10% by weight of the resin composition.

〔Example〕

Hereinafter, the present invention will be specifically explained with reference to Examples.

Note that parts in Examples and Production Examples are parts by weight.

A compound obtained by reacting resin [I] or resin [I] I with epsilon caprolactone [Production Example 1] Polydicyclopentadiene resin CD having hydroxyl groups (manufactured by Nippon Zeon Corporation, Quinton 1700)
, hydroxyl equivalent 2 s 8.5) 258.5 parts, ε-caprolactone 228.2 parts, Improvir titanium) 0
．． 24 parts were charged, heated to 150 to 160° C. in nitrogen, and reacted until unreacted ε-caprolactone became 1% by weight or less. The obtained compound (III-1 is
An adduct of 2 moles of ε-caprolactone per hydroxyl equivalent of resin CD, with a hydroxyl value of 115 and a saponification value of 232.4 in liquid form.
The acid value was 4.73.

Production Example 2, in the same reactor as Production Example 1, Finton 1700.25
8.5 parts of ε-caprolactone, 456.5 parts of ε-caprolactone and 0.3 parts of isoprobyl titanate were charged, and the
The mixture was heated to 160° C. and the reaction was carried out in the same manner as in Production Example 1. The obtained compound Cll0-2 is an adduct of 47 ε-caprolactone per hydroxyl equivalent of resin CD, and is in liquid form and has a hydroxyl value of 78.5. Saponification value: 316. The acid value was 2.5.

Preparation Example 3゜Into the same reactor as Preparation Example 1, Finton 1700258
．． 5 parts of e-caprolactone, 684.8 parts of e-caprolactone, and 0.05 part of stannous chloride were charged, and the reaction was carried out in the same manner as in Production Example 1 by heating to 110 to 120°C in nitrogen. The obtained compound [Kawa]-3 is a liquid adduct of 6 moles of ε-caprolactone per hydroxyl equivalent of resin [I], and has a hydroxyl value of 59.4.
．． Saponification value 356.8. The acid value was 3.0.

Production Example 4 100 parts of polydicyclopentadiene resin [I] having a hydroxyl group in the molecule (Nippon Zeon Corporation, Quinton 1700, hydroxyl equivalent: 258.5) was dissolved in 75 parts of xylene, and a palladium concentration of 5 parts was dissolved. Adding 1 part of palladium carbon (manufactured by Nippon Engelhard Co., Ltd., 5% P-C standard product),
The hydrogenation reaction was carried out at a hydrogen pressure of 30 kP/crn and 150°C for about 2 hours, and the solvent was distilled off to obtain the hydrogenated resin [:II]
-4 was obtained. This product has a hydroxyl group equivalent of 290.6
It was 7.

Next, 4,290.7 parts of resin [II], 228.3 parts of ε-caprolactone, and 0.03 parts of stannous chloride were charged into the same reactor as in Production Example 1, and the mixture was heated in nitrogen.

The reaction was carried out in the same manner as in Production Example 1 by heating to 110 to 120°C. The obtained compound [IID-4] is an adduct of 2 moles of ε-caprolactone per hydroxyl equivalent of resin Cm) and has a hydroxyl value of 107. The saponification value was 215 and the acid value was 1.8.

Production Example 5゜Into the same reactor as Production Example 1, 5. 7 parts of the hydrogenated resin obtained in Preparation Example 4, 456.5 parts of ε-caprolactone, and 0.04 parts of stannous chloride were heated to 110 to 120°C in nitrogen. Then, the reaction was carried out in the same manner as in Production Example 1. The obtained compound [IID-5] was an adduct of 4 mol of ε-caprolactone per hydroxyl equivalent of resin [II], and was in a liquid state, with a hydroxyl value of 75.1, The saponification value was 300 and the acid value was 1.5.

Example of urethane poly(meth)acrylate mixture (4) Example 1゜1487.9 parts of the compound obtained in Production Example 1 was placed in a three-part reactor equipped with a stirrer, a temperature controller, a thermometer, and a condenser. , hexamethylene diisocyanate) were charged. The reaction temperature of this mixture was maintained at 75 to 80°C. The reaction was continued until completion as indicated by 6.40% free isocyanate groups. The elapsed time from initial charge of the reactor to completion of the reaction was 8 hours.

Then, while stirring, ε-caprolactone-β-, 241.6 parts of droxyethyl acrylate (Daicel Chemical Industries, Ltd., Plaxel FA-1), 0.45 parts of methylhydroquinone, di-n-butyl dilaurate, IC0
, 18 parts and dicyclobentadiene ethoxy acrylate (Hitachi Chemical, FA-51□2A) as a diluent.
) 560.9 copies.

Hydroxypivalyl hydroxybiparate diacrylate 560.9 parts, ε-caprolactone-hydroxybivalyl hydroxypiparate diacrylate (KAYARAD HX-220, KAYARAD HX-220) 224.4
I prepared a section. The reaction temperature was maintained at 75 to 80°C. The reaction was continued until completion as indicated by less than about 0.3% free isocyanate groups. The obtained reaction product has ε- per hydroxyl equivalent of resin IJI.
Addition of 2 moles of caprolactone to hexamethylene diisocyanate, ε-caprolactone-β-hydroxyethyl acrylate adduct (component a), dicyclopentadiene ethoxy acrylate, hydroxybivalyl hydroxypipalate diacrylate, and ε-cabrolactone A diluted product of hydroxypivalyl hydroxypivalate diacrylate (component b) was obtained.

The obtained product has the following physical properties.

Specific gravity (25℃) 1.1154 Viscosity (25℃) 1866 cps Acid value 1.3
mtpKOH/f refractive index (20°C), 1.49
00 Example 2゜Into the same reactor as Example 1, compound QI obtained in Production Example 2 was added.
D-2714, 8 parts, tolylene diisocyanate and β-
Adduct with hydroxydiethyl acrylate (NCO
300 parts (concentration 14.0%), 0.5 part of methylhydroquinone, and 0.2 part of di-n-butyltin dilaurate were charged. The reaction was carried out in the same manner as in Example 1 while maintaining this mixture at 75 to 80°C. The obtained reaction product is a hydroxyethyl acrylate adduct (component a) of tolylene diisocyanate (TDI) adduct of 4 moles of ε-caprolactone per hydroxyl equivalent of resin [I]. The obtained product has the following physical properties.

Viscosity (60°G) 1572 ps Acid value 1.6 ■KOH/
#Refractive index (20°G) 1.5310 Example 3゜ Compound 010 obtained in Production Example 3 was placed in the same reactor as Example 1.
-3472.3 parts, inphorone diisocyanate) 111
．． I prepared 15 copies. 3.6% under the same conditions as Example 1
The reaction was continued until completion as indicated by free incyanate groups.

Next, 60.9 parts of β-hydroxyethyl acrylate, 0.3 parts of methoquinone, 0.13 parts of di-n-butyltin dilaurate, and 536.9 parts of carpitol acrylate and 536.9 parts of tripropylene glycol diacrylate as diluents. 214.8 parts of N-vinylpyrrolidone,
Dicyclopentadiene ethoxy acrylate 214.8
I prepared a section. This reaction was carried out in the same manner as in Example 1.

The obtained reaction product is a hydroxyethyl acrylate adduct (component a) of carpitol acrylate and tripropylene glycol diacrylate of inphorone diisocyanate addition of an adduct of 6 moles of ε-caprolactone per hydroxyl group equivalent of resin [I]. N-vinylpyrrolidone and dicyclopentadiene ethoxy acrylate (component b)
A dilution of was obtained. The obtained product has the following physical properties.

Specific gravity (25°C) 1.075 Viscosity (25°C) 1000 cps Acid value 3.21 ~ KOH15' refractive index (
20°C) 1.474 Example 4゜Into the same reactor as Example 1, the compound obtained in Production Example 4 [:
III] -4524, 4 parts, an adduct of tolylene diisocyanate and β-hydroxyethyl acrylate (
NC08 degree 14.0%) 300 parts, methylhydroquinone 0.4 part, di-n-butyltin dilaurate 0.1
6 parts, carpitol acrylate 515. as diluent.
2 parts, hydroxybivalyl hydroxypiparate-ε
- Diacrylate of caprolactone adduct (Nippon Kayaku ■
721.4 parts of KAYARAD HX-220) were charged. The reaction was carried out in the same manner as in Example 1 while maintaining this mixture at 75 to 80°C. The obtained reaction product is composed of carpitol acrylate (component a) of hydroxyethyl acrylate adduct (component a) of tolylene diisocyanate addition of 2 moles of ε-caprolactone per half of the amount of hydroxyl groups in resin [II], and carpitol acrylate of ε-caprolactone-hydroxybivari. A diluted product of hydroxypiparate diacrylate (component b) was obtained. The obtained product has the following physical properties.

Specific gravity (25℃) 1.078 Viscosity (
25°C) 615 cps acid value
0.6 1rKjKOH/P refractive index (20°C) 1.4880 Example 5゜Into the same reactor as Example 1, the compound Cl obtained in Production Example 5 was added.
10-5.373.5 parts, an adduct of tolylene diinocyanate and β-hydroxyethyl acrylate (NC
O concentration 14.0%) 150 parts, methylhydroquinone 0.26 part, di-n-butyltin dilaurate 0.1
I prepared a section. The reaction was carried out in the same manner as in Example 1 while maintaining this mixture at 75 to 80°C. The obtained reaction product is tolylene diisocyanate (TDI), an adduct of 4 mol of ε-caprolactone per hydroxyl equivalent of resin [II].
Additional hydroxyethyl acrylate adduct (component a)
It is. The obtained product has the following physical properties.

Viscosity (25°G) 870 ps
Acid value 1.8 ■KO
H/P refractive index (20°G) 1.5120 Application examples 1 to 5° Using the products obtained in Examples 1 to 5, the formulations were prepared as shown in Table 1, and each photocurable resin composition was prepared. was tabulated.

Comparative Application Example 1 Polyethylene glycol (molecules 1400) and tolylene diisocyanate were charged into a reactor at a molar ratio of 2:2.1, and dibutyltin dilaurate 200 was used as a catalyst.
ppm was added, and the mixture was reacted at 60° C. for 4 hours. Then, an excess amount of 2-hydroxyethyl methacrylate was added and the reaction was continued for an additional 2 hours to form a urethane methacrylate. 10 parts of this urethane methacrylate, 30 parts of a reaction product of bisphenol A type epoxy compound (Shell Chemical Co., Ltd., Epicoat 828) and acrylic acid,
+20 parts of 7 methylpropane triacrylate, di(
Resin composition F was prepared by mixing 5 parts of (methacryloxyethyl) phosphate, 1 part of vinyltris(2-methoxyethoxy)silane, and 5 parts of 1-hydroxycyclohexylphenyl ketone. The properties of the resin composition are shown in Table 2.

In Table 2 above, measurement of curability: A, B, C
.

For compositions D, E and F, a high pressure mercury lamp (
Input 80W/cm, lamp output 2KW) was irradiated at a position 8 crn below the light source arranged in parallel (conveyor speed 5
m/min), the irradiation amount until the task disappears on the surface of the film coated with 151Er1 on the aluminum plate (mj 7
cm).

Adhesion: Compositions A, B, C, D, E and F were obtained using a high pressure mercury lamp (input 80W/Crn, output 2KW)
was irradiated at a position of 8 crn under a parallel light source (conveyor speed 5 m/min) to obtain a cured product coated to a thickness of about 15 μm on a zinc plate, chrome plate, aluminum plate, and copper plate. Use this to make straight cuts of 1w width each in the vertical and horizontal directions10
I made 0 digits (denominator number), stuck cellophane tape on it, then peeled off the tape and marked it with the number of digits (numerator number) remaining on the metal plate.

Pencil hardness: The cured product was measured according to JISK5400.

〔Effect of the invention〕

The photocurable resin composition of the present invention provides a cured film with excellent adhesion to metals.

Claims (2)

[Claims] (1) A polydicyclopentadiene resin having a hydroxyl group in the molecule [I] or a resin having a hydroxyl group obtained by hydrogenating the resin [II], a compound obtained by reacting epsilon caprolactone [III], an organic polyisocyanate [IV] and ( Hydroxyl group-containing ester of meth)acrylic acid [V
] A novel urethane poly(meth)acrylate mixture comprising a reaction mixture with. (2) A polydicyclopentadiene resin having a hydroxyl group in the molecule [I] or a hydrogenated resin having a hydroxyl group [II], a compound obtained by reacting epsilon caprolactone [III], and an organic polyisocyanate [IV]
Hydroxyl group-containing ester of (meth)acrylic acid [
urethane poly(meth)acrylate mixture (a) consisting of a reaction mixture with mono- or poly(meth)acrylate or N-vinylpyrrolidone (b), a radically polymerizable phosphorus-containing compound (c), and a photopolymerization initiator ( d) A photocurable resin composition comprising: