JP2001302744A - Active energy ray-curable composition - Google Patents

Abstract

(57) [Summary] An active energy ray-curable composition capable of obtaining a cured product having small volume shrinkage upon curing and excellent in mechanical properties such as tensile strength, tensile elongation and impact resistance. object. Kind Code: A1 Two radically polymerizable (meth) acryloyloxy groups, at least one amide group, and at least two urethane groups in a molecule obtained by reacting specific components (a1) to (a4). Urethane (meta)
Acrylate compound (A) 15 to 75 parts by mass, selected from vinyl ethers, mono (meth) acrylates, mono (meth) acrylamides or di (meth) acrylate compounds having a B-type viscosity of 200 mPa · s or less at 25 ° C. of 200 mPa · s or less. 10 to 70 parts by weight of at least one kind (b1), 5 to 60 parts by weight of at least one kind (b2) selected from compounds having a (meth) acryloyl group having a specific structure, and 100 parts by weight in total thereof. ,
An active energy ray-curable composition comprising 0.05 to 10 parts by mass of a photopolymerization initiator (C).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable composition which imparts unprecedented excellent mechanical properties such as tensile strength and tensile elongation to a film cured by irradiation with active energy rays. TECHNICAL FIELD The present invention relates to a curable composition having excellent transparency for forming a film having an excellent protective function on various substrates, or for producing a molded article having excellent mechanical strength by a cast polymerization method.

[0002]

2. Description of the Related Art A radical polymerization type active energy ray-curable composition is rapidly cured by irradiation with active energy rays and gives a film having excellent scratch resistance, chemical resistance and the like. It's being used. In addition, by using it for casting polymerization, a molded article having excellent mechanical strength and physical properties can be obtained in a short molding time. Radical polymerization type active energy ray-curable compositions used for coating agents, photoresists, lens materials, dental materials, etc. include, as main components, unsaturated polyesters, epoxy (meth) acrylates, urethane (meth) acrylates, (Meth) acrylic acid ester monomers and the like have been conventionally used, and in recent years, Japanese Patent Application Laid-Open No.
JP-A-2-28261, JP-A-3-104626
In Japanese Patent Application Laid-Open Publication No. H10-207, it can be used for an optical three-dimensional printing method.

[0003] Urethane (meth) acrylate, which is widely used for radical polymerization type active energy ray-curable compositions, is used in various applications in order to impart excellent tensile strength, tensile elongation, and flexibility to cured films. However, since the tensile strength and the tensile elongation are opposite to each other, it is difficult to satisfy both at the same time, and attempts to improve the physical properties of these coating films have been made for a long time. Conventionally, to improve the toughness of the cured film, a flexible (meth) acrylate compound obtained by converting (meth) acrylated alkyl polyol-modified urethane acrylate or polyfunctional polyol with ethylene oxide or propylene oxide added to give a flexible cured product is mainly used. Has been used for However, in these methods, the tensile elongation tends to decrease in a composition that increases the tensile strength of the cured product, and conversely, if the tensile elongation is to be improved, the strength is reduced and it is difficult to achieve both performance and performance. . As a method for improving this, for example, JP-A-54-127994 discloses that a urethane (meth) acrylate having an amide group and a urethane group in a plurality of molecules gives a film having excellent film strength. ing.

[0004] However, although the above-mentioned improved urethane (meth) acrylate has excellent tensile strength and tensile elongation due to having an amide group in the molecule, the introduction of a large number of amide groups increases the urethane (meth) acrylate. In addition to the viscosity, the composition has a bad influence on coatability, and also has a problem that the stability of the compound is deteriorated so that the compound cannot be produced. In this case, it can be used by diluting with an organic solvent or the like to reduce the viscosity, but depending on the substrate to be coated, not only the solvent may not be used together, but also in view of global environmental protection in recent years. Casting polymerization processes that cannot meet the objectives of reducing organic solvent emissions and require solventless compositions,
It was a curable composition that could not be used for the 2P method, stereolithography, and the like.

[0005]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a low-viscosity liquid which is solvent-free, has excellent handleability, can be cured in a short photocuring time, and has a volume shrinkage when cured by light. Obtain protective coatings, molded products, three-dimensional molded products, and other cured products that are compatible with various substrates that are small, have excellent dimensional accuracy, and are also excellent in mechanical properties such as transparency, tensile strength, tensile elongation, etc. It is to provide an active energy ray-curable composition which can be used.

[0006]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, a urethane (meth) acrylate compound having a specific chemical structure is extremely effective in achieving the above-mentioned object. And this urethane (meta)
More specific low viscosity monofunctionality to the acrylate compound,
Alternatively, when a bifunctional radical polymerizable compound and a photopolymerization initiator are added, a liquid active energy ray-curable composition having a low viscosity and excellent handleability is obtained, and the curable composition is irradiated with an active energy ray. Then it cures in a short time, the volume shrinkage during curing is small, tensile strength, tensile elongation,
It has been found that a coating film or a molded product having excellent mechanical properties such as impact resistance can be obtained.

That is, the present invention relates to a component (A): two radically polymerizable (meth) acryloyloxy groups and at least one amide in a molecule obtained by reacting the following components (a1) to (a4): (A1) an amide having at least one amide group and at least two NCO-reactive hydroxy groups in a molecule thereof, in an amount of 15 to 75 parts by mass of a urethane (meth) acrylate compound having at least two urethane groups; Hydroxy compound (a2) at least one diol selected from polyether diol, polyester diol and polycarbonate diol (a3) organic diisocyanate compound or triisocyanate compound (a4) one (meth) acrylate group in the molecule, and Having one NCO-reactive hydroxy group (meth) Hydroxy group-containing alkyl esters of acrylic acid, (b1) component: the B-type viscosity at 25 ° C. 200 mPa
10 to 70 parts by mass of at least one compound selected from vinyl ethers, mono (meth) acrylates, mono (meth) acrylamides and di (meth) acrylates, which are not more than s; Component (b2): (I) and / or (II)
5 to 60 parts by mass of at least one selected from compounds having a (meth) acryloyl group represented by the formula

Embedded image (Where R ¹ is hydrogen or a methyl group, and R ² is carbon 3
R ₃ is a branched, cyclic, or linear hydrocarbon group having 2 to 15 carbon atoms, or a hydrocarbon group having an aromatic ring, and an ester structure is included in the structure. May be. n and m may be the same or different, and represent an integer of 1 to 5. )

Embedded image (Where R ¹ is hydrogen or a methyl group, and R ⁴ is C 2
R ⁵ is a branched, cyclic, straight-chain hydrocarbon group or a hydrocarbon group having an aromatic ring having 2 to 20 carbon atoms, and R ⁵ is an ester structure in the structure. May be included. P is an integer of 1 to 7 and p in the molecule is
, Q represents an integer of 2 to 6, and r represents an integer of 0 to 3. Component (C): Component (A), (b1) and (b2)
The active energy ray-curable composition comprises 0.05 to 10 parts by mass of a photopolymerization initiator based on 100 parts by mass of the total amount of the components.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, each component of the present invention will be described in detail. In the present invention, “(meth) acrylic acid” means “acrylic acid and / or methacrylic acid”
"(Meth) acrylate" means "acrylate and / or methacrylate", and "(meth) acryloyloxy group" means "acryloyloxy group and / or methacryloyloxy group", respectively.

The urethane (meth) acrylate compound (A) constituting the present invention comprises two radically polymerizable (meth) acryloyloxy groups, at least one amide group, and at least two urethane groups in a molecule. A coating or molded article having unprecedented bending strength and tensile strength, and excellent tensile elongation by curing an active energy ray-curable composition containing the compound by irradiation with active energy rays. Can be obtained.

The urethane (meth) acrylate compound (A) comprises (a1) an amide hydroxy compound having at least one amide group and at least two NCO-reactive hydroxy groups in a molecule, (a2) a polyester polyol, and At least one alkyl polyol selected from polyether polyols, (a3) an organic diisocyanate compound, or a triisocyanate compound;
And (a4) can be synthesized by an addition reaction of a hydroxy group-containing alkyl ester of (meth) acrylic acid having one (meth) acrylate group and one NCO-reactive hydroxy group in the molecule. As a specific synthesis method, for example, 0.9 mol equivalent of the total hydroxyl group-containing equivalent of (a1) and (a2) is charged into a synthesis kettle, and isocyanate 2.a.
By dropping 0 molar equivalents, a precursor isocyanate-terminated polyurethane is obtained. Further, 1.1 to 1.3 molar equivalents of the component (a4) are added dropwise thereto, and the mixture is heated and added to obtain a urethane (meth) acrylate compound as the component (A). Here, the molar equivalent refers to the number obtained by multiplying the number of moles of the compound used by the number of functional groups.

The amide hydroxy compound having at least one amide group and at least two NCO-reactive hydroxy groups in the molecule as the component (a1) is a cured product of the urethane (meth) acrylate compound as the component (A). While maintaining the tensile elongation of, to improve the strength, that is, has the effect of improving the toughness, cyclic hydroxycarboxylic acid ester and ammonia, or a compound containing one primary or secondary amino nitrogen Is the reaction product of

Specific examples of the cyclic hydroxycarboxylic acid ester include, for example, γ-butyrolactone, γ-valerolactone, δ-valerolactone, ε-caprolactone, and these may be used alone or in combination of two or more. Can be used in combination, and among the above, γ-butyrolactone and γ-valerolactone are particularly preferred.

Specific examples of the compound containing one primary or secondary amino nitrogen include, for example, ethanolamine, diethanolamine, N-methylethanolamine, N-ethylethanolamine, N-phenylethanolamine, -Amino-1-butanol, 2-amino-2-ethyl-1,3-propanediol, 6-amino-1-hexanol, 1,4-diaminobutane, 1,2
-Diaminocyclohexane, 1,10-diaminodecane and the like. These can be used alone or in combination of two or more. Among them, ethanolamine, diethanolamine, and N-methylethanolamine are particularly preferable.

The reaction of the cyclic hydroxycarboxylic acid ester with the compound containing one primary or secondary amino nitrogen is carried out by mixing equimolar amounts of both and heating at about 200 ° C. for at least 24 hours. The most preferred (a1) compound is N-methyl-N- (2-hydroxyethyl) -3
-Hydroxypropylamide.

At least one diol selected from the group consisting of polyether diol, polyester diol and polycarbonate diol as component (a2) is
(A) has the effect of improving the flexibility and tensile elongation of the cured product of the urethane (meth) acrylate compound as the component,
Various are commercially available.

Specific examples thereof include, for example, polyethylene glycol (n = 6 to 20), polypropylene glycol (n = 6 to 20), polybutylene glycol (n = 6 to 20), and 1-methylbutylene glycol (n
= 6 to 20), polycaprolactone diol, caprolactone addition of alkylene (C2-10) diol (n =
2-10) diol, polycarbonate diol (C4
-C6 aliphatic skeleton), polyester diol derived from phthalic acid and alkylene diol, polyester diol derived from maleic acid and alkylene diol, polyester diol derived from fumaric acid and alkylene diol, and the like. Molecular weight 30
About 0 to 2000 are preferable, and one kind can be used alone or two or more kinds can be used in combination. Among the above, polybutylene glycol (n = 6 to 20), polycaprolactone diol, alkylene (C2 -10)
Caprolactone-added (n = 2 to 10) diols of diols are particularly preferred.

Specific examples of the organic diisocyanate compound as the component (a3) include, for example, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, bis (4-isocyanatophenyl) methane, bis (3-chloro-4) -Isocyanatophenyl) methane,
2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, tris (4-isocyanatophenyl) methane, 1,2-xylylene diisocyanate,
1,4-xylylene diisocyanate, 1,2-hydrogenated xylylene diisocyanate, 1,4-hydrogenated xylylene diisocyanate, tetramethyl xylylene diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, and one of these One or a combination of two or more thereof can be used. Among them, isophorone diisocyanate, bis (4-isocyanatocyclohexyl) methane, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,
1,2-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,2-hydrogenated xylylene diisocyanate, and 1,4-hydrogenated xylylene diisocyanate are preferred, and isophorone diisocyanate is further preferred from the viewpoint of weatherability of the cured product. Particularly preferred are those having an aliphatic or alicyclic skeleton such as bis (4-isocyanatocyclohexyl) methane, 1,2-hydrogenated xylylene diisocyanate, and 1,4-hydrogenated xylylene diisocyanate.

The hydroxy group-containing alkyl ester of (meth) acrylic acid having one (meth) acrylate group and one NCO-reactive hydroxy group in the molecule, which is the component (a4), is used for preparing the polyurethane precursor. It has an effect of imparting radical reactivity by being added to the terminal, and specific examples thereof include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate , 6-hydroxyhexyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate,
Examples include adducts of 2-hydroxyethyl (meth) acrylate and caprolactone, and adducts of 4-hydroxybutyl (meth) acrylate and caprolactone. These can be used alone or in combination of two or more. , Among the above, 2-hydroxyethyl (meth)
Acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate are particularly preferred.

In the present invention, the use ratio of (a1) to (a4) constituting the urethane (meth) acrylate compound (A) is [(a3)] / [(a1) + in molar equivalent.
(A2)] / [(a4)] = 2.0 / 0.8 to 1.2 /
0.8 to 1.2, and (a1) / (a2) = 0.2 to
1.0 / 1.0 to 0.2. In order to improve the tensile strength and tensile elongation of the cured film, it is preferable that the amount of the component (a1) is large. However, if the amount is too large, the viscosity becomes too high during the production of the urethane (meth) acrylate compound (A), causing gelation. There is a tendency. The preferred (a1) / (a2) ratio is (a
1) / (a2) = 0.3 to 0.8 / 0.9 to 0.4.

In the case of the organic diisocyanate compound (a3), the term "molar equivalent" as used herein means a value obtained by multiplying the number of NCO groups (2) in the molecule by the number of moles used, and one or more amide groups in the molecule. And an amidohydroxy compound having at least two NCO-reactive hydroxy groups (a
In the case of 1), and at least one kind of alkyl polyol (a2) selected from polyester polyol and polyether polyol, it refers to the number obtained by multiplying the number of hydroxyl groups (2) in the molecule by the number of moles used. In the case of a hydroxy group-containing alkyl ester (a4) of (meth) acrylic acid having one (meth) acrylate group and one NCO-reactive hydroxy group in the molecule, it indicates the number of moles used.

The compounding ratio of the component (A) is preferably in the range of 15 to 75 parts by mass, more preferably 20 to 100 parts by mass of the total amount of the component (A) and the components (b1) and (b2). It is in the range of 70 parts by mass. (A) Component is 1
When the amount is less than 5 parts by mass, not only the mechanical strength of the cured film or the molded product is insufficient, but also the volume shrinkage rate accompanying polymerization increases. When the component (A) exceeds 75 parts by mass,
The liquid viscosity of the curable composition increases, so that the coatability deteriorates, and it becomes difficult to obtain a precise molded product.

At least one selected from vinyl ethers, mono (meth) acrylates, mono (meth) acrylamides and di (meth) acrylates compounds having a B-type viscosity at 25 ° C. of 200 mPa · s or less constitutes the present invention. One type (b1) uses a highly viscous urethane (meth) acrylate of the component (A) for the purpose of reducing the viscosity of the entire curable composition while suppressing the deterioration of its physical properties.

Specific examples of the component (b1) include, for example,
Styrene, α-methylstyrene, α-chlorostyrene,
Aromatic vinyl monomers such as vinyltoluene and divinylbenzene; vinyl acetate, vinyl butyrate, N-vinylformamide, N-vinylacetamide, N-vinyl-2-
Vinyl ester monomers such as pyrrolidone, N-vinylcaprolactam and divinyl adipate; vinyl ethers such as ethyl vinyl ether and phenyl vinyl ether; allyl compounds such as diallyl phthalate, trimethylolpropane diallyl ether and allyl glycidyl ether; acrylamide; -Dimethylacrylamide, N, N-dimethylmethacrylamide, N-methylolacrylamide, N-methoxymethylacrylamide, N-butoxymethylacrylamide, Nt-
Acrylamides such as butylacrylamide, acryloylmorpholine, and methylenebisacrylamide; (meth) acrylic acid, methyl (meth) acrylate, (meth)
Ethyl acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (meth) acrylic acid 2-ethylhexyl, lauryl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, morpholyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, (meth) acrylic acid 2 -Hydroxypropyl, 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, benzyl (meth) acrylate, (meth) acrylic acid Cyclohexyl, phenoxyethyl (meth) acrylate, ( Data) acrylate tricyclodecane, (meth) acrylic acid dicyclopentenyl (meth)
Mono (meth) acrylates such as allyl acrylate, 2-ethoxyethyl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, ethylene glycol di (meth) acrylate, di (meth) acrylic acid Diethylene glycol, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate (n = 5 to 14), propylene glycol di (meth) acrylate, di (meth) acrylate ) Dipropylene glycol acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate (n = 5 to 14), di (meth) acrylic acid 1 , 3-butylene glycol, (Meth) acrylic acid 1,4-butanediol, di (meth) acrylate and polybutylene glycol (n = 3 to 16), di (meth) polyacrylic acid (1-
Methylbutylene glycol) (n = 5 to 20), 1,6-hexanediol di (meth) acrylate, di (meth) acrylate
1,9-nonanediol acrylate, neopentyl glycol di (meth) acrylate, neopentyl glycol hydroxypivalate di (meth) acrylate,
And di (meth) acrylate of dicyclopentanediol.

Among the above-mentioned components (b1), particularly preferred are, for example, acryloyl morpholine, methacryloyl morpholine, tetrahydrofurfuryl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylate Mono- (meth) acrylates having a ring structure in the molecule, such as trimethylcyclohexyl acrylate, phenoxyethyl (meth) acrylate, tricyclodecane (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N Mono (meth) acrylamides such as dimethylacrylamide,
Triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, di (meth) acrylate
Examples thereof include tripropylene glycol acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, and neopentyl glycol di (meth) acrylate. These can be used alone or in combination of two or more.

Further, as a component for improving the tensile strength and the tensile elongation of the cured product film or molded product of the active energy ray-curable composition of the present invention, two to four (meth) acryloyl groups are included in the molecule. Having di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate
At least one compound (b2) selected from acrylates
It is particularly preferable to use the component in combination with the component (b1) described above. The component (b2) is particularly preferably at least one selected from the following formulas (I) and (II).

[0026]

Embedded image (Where R ¹ is hydrogen or a methyl group, and R ² is carbon 3
R ₃ is a branched, cyclic, or linear hydrocarbon group having 2 to 15 carbon atoms, or a hydrocarbon group having an aromatic ring, and an ester structure is included in the structure. N and m may be the same or different, and each represents an integer of 1 to 5. )

[0027]

Embedded image (Where R ¹ is hydrogen or a methyl group, and R ⁴ is C 2
R ⁵ is a branched, cyclic, straight-chain hydrocarbon group or a hydrocarbon group having an aromatic ring having 2 to 20 carbon atoms, and R ⁵ is an ester structure in the structure. May be included. P is an integer of 1 to 7 and p in the molecule is
, Q represents an integer of 2 to 6, and r represents an integer of 0 to 3. )

As a specific example of the component (b2) represented by the general formula (I) or (II), in the general formula (I), for example, a dialcohol 1 having an aliphatic, alicyclic or aromatic skeleton 2 to 10 moles of γ-butyrolactone or ε
A compound obtained by methacrylate or diacrylate at the end of a dialcohol to which caprolactone has been added. Among them, di (meth) of an ε-caprolactone adduct of neopentyl glycol hydroxypivalate (n + m = 2 to 5) is preferable. Acrylic acid esters,
Di (meth) acrylic acid ester of γ-butyrolactone adduct of neopentyl glycol hydroxypivalate (n + m = 2 to 5) and di (meth) acrylic acid ester of caprolactone adduct of neopentyl glycol (n + m = 2 to 5) Di (meth) acrylic acid ester of caprolactone adduct of butylene glycol (n + m = 2 to 5), di (meth) acrylic acid ester of caprolactone adduct of cyclohexanedimethanol (n + m = 2 to 5), dicyclopentanediol Di (meth) acrylate of caprolactone adduct (n + m = 2 to 5) of
Bisphenol A caprolactone adduct (n + m = 2
To 5), and a di (meth) acrylate of a caprolactone adduct of bisphenol F (n + m = 2 to 5).

Further, specific examples of the general formula (II) include, for example, poly (p =) having an aliphatic, alicyclic or aromatic skeleton.
2-6) Compounds in which 2 to 15 moles of ethylene oxide or propylene oxide are added to 1 mole of alcohol and methacrylate or diacrylate is added to a polyalcohol terminal, and among them, bisphenol A ethylene oxide adduct ( p =
1-7) di (meth) acrylate, bisphenol A propylene oxide adduct (p = 1-7) di (meth) acrylate, bisphenol F ethylene oxide adduct (p = 1-7) Di (meth) acrylates such as di (meth) acrylates of (meth) acrylic acid esters and bisphenol F propylene oxide adducts (p = 1 to 7), and trimethylolpropane ethylene oxide adducts (p = 1 to 5) Tri (meth) acrylate of trimethylolpropane propylene oxide adduct (p = 1-5)
Acrylate, tri (meth) acrylate of glycerin ethylene oxide adduct (p = 1 to 5), tetra (meth) acrylate of ditrimethylolpropane ethylene oxide adduct (p = 1 to 5), pentaerythritol Tri (meth) acrylate of ethylene oxide adduct (p = 1 to 5), pentaerythritol ethylene oxide adduct (p = 1
To 15) tetra (meth) acrylate and pentaerythritol propylene oxide adduct (p = 1 to
5) Tri (meth) acrylate and pentaerythritol propylene oxide adduct (p = 1 to 15)
Penta (meth) acrylate of dipentaerythritol ethylene oxide adduct (p = 1 to 5) and hexa (meth) acrylate of dipentaerythritol ethylene oxide adduct (p = 1 to 15) ) Acrylates and poly (meth) acrylates such as N, N ', N "-tris ((meth) acryloxypoly (p = 1-4) (ethoxy) ethyl) isocyanurate.

Among the above, R ₃ in the general formula (I) is a compound represented by the following general formula (III) and R ₃ in the general formula (II) is 2,2′-bisphenylpropane, propane,
And a compound which is tetramethylmethane is particularly preferred because it imparts sufficient tensile elongation to a cured film or molded article cured by irradiation with active energy rays.

[0031]

Embedded image

The most preferred specific example of the component (b2) is, for example, di (meth) of a caprolactone adduct of neopentyl glycol hydroxypivalate (n + m = 2 to 5).
Γ-butyrolactone adduct of acrylic acid ester and neopentyl glycol hydroxypivalate (n + m = 2
5) di (meth) acrylic acid ester, bisphenol A ethylene oxide adduct (p = 1 to 7) di (meth) acrylic acid ester, bisphenol A propylene oxide adduct (p = 1 to 7) di ( (Meth) acrylic acid ester, tri (meth) acrylic acid ester of trimethylolpropane ethylene oxide adduct (p = 1 to 5), tri (meth) acrylic acid of trimethylolpropane propylene oxide adduct (p = 1 to 5) Ester, pentaerythritol ethylene oxide adduct (p = 1-5) tri (meth) acrylate, pentaerythritol ethylene oxide adduct (p = 1)
To 15) tetra (meth) acrylate and pentaerythritol propylene oxide adduct (p = 1 to
5) Tri (meth) acrylate and pentaerythritol propylene oxide adduct (p = 1 to 15)
At least one selected from tetra (meth) acrylic acid esters. These may be used alone or in combination with two or more.
More than one species can be used in combination.

With respect to 15 to 75 parts by mass of the component (A),
The component (b1) is 10 to 70 parts by mass, and the component (b2) is 5 to 70 parts by mass.
It is preferably 60 parts by mass, more preferably (b)
1) The component is 20 to 60 parts by mass, and the component (b2) is 10 to 5 parts by mass.
The range is 0 parts by mass. When the amount of the component (b1) exceeds 70 parts by mass, the mechanical strength of the cured film or molded article decreases, and when the amount is less than 10 parts by mass, the viscosity of the composition increases and the coating workability decreases. When the amount of the component (b2) exceeds 60 parts by mass, the elasticity of the cured film or molded product is lowered, or sufficient tensile strength cannot be obtained. Elongation decreases.

Specific examples of the photopolymerization initiator (C) constituting the present invention include, for example, benzophenone, 4,4-bis (diethylamino) benzophenone, 2,4,6-trimethylbenzophenone, methylorthobenzoylbenzoate, 4-phenylbenzophenone, t-butylanthraquinone, 2-ethylanthraquinone, 2,4-
Thioxanthones such as diethylthioxanthone, isopropylthioxanthone and 2,4-dichlorothioxanthone; diethoxyacetophenone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one, 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl)
Acetophenones such as butanone; benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-
Acylphosphine oxides such as dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, methylbenzoylformate, and 1,7-bisacridinyl Heptane, 9-phenylacridine and the like can be mentioned.

When a compound having a cationically polymerizable group such as an epoxy group together with a radically polymerizable group is used as the radically polymerizable compound, a cationic photopolymerization initiator is used in combination with the above-mentioned radical photopolymerization initiator. The kind of the cationic photopolymerization initiator in that case is not particularly limited, and a conventionally known one can be used.

These photopolymerization initiators can be used alone or in combination of two or more, and preferably 0 to 100 parts by mass of the composition comprising the components (A) and (B) of the present invention. 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass. When the addition amount of the photopolymerization initiator is less than 0.05 parts by mass, the photocurability is extremely reduced and is not substantially suitable for industrial production. On the other hand, when the amount exceeds 10 parts by mass, an odor may remain in the cured film when the irradiation light amount is small, which is not preferable.

Further, the photocurable composition of the present invention may contain, if necessary, ethanolamine, diethanolamine,
Known photosensitizers such as triethanolamine, N-methyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, amyl 4-dimethylaminobenzoate and 4-dimethylaminoacetophenone may also be added. it can.

The photocurable composition of the present invention further comprises a releasing agent, a lubricant, a plasticizer, an antioxidant, an antistatic agent, a light stabilizer, an ultraviolet absorber, a flame retardant, a flame retardant auxiliary, and a polymer. Known additives such as an inhibitor, a filler, and a silane coupling agent can be appropriately used depending on the application.

The viscosity of the active energy ray-curable composition of the present invention can be adjusted according to the use and the mode of use. Generally, the viscosity is measured at room temperature (25 ° C.) when measured using a rotary B-type viscometer. ), The viscosity is 10 to 100000 m
It is about Pa · s that handleability, coatability, moldability,
It is preferable from the viewpoint of three-dimensional molding property, etc.
More preferably, it is about mPa · s. The viscosity of the curable composition can be adjusted by adjusting the types of the components (A), (b1), and (b2) and the mixing ratio thereof.

The active energy ray-curable composition of the present invention is rapidly cured when cured with light such as ultraviolet light, and is also excellent in transparency and mechanical properties such as tensile strength and tensile elongation. Therefore, it is possible to form beautiful coatings having a protective function on various substrates such as plastics, films, papers, and metals, and optical lenses and lenses formed by a casting method or casting. It can be used for production of various molded articles such as sheets and light condensing sheets, and for coating. It can also be used for optical three-dimensional modeling.

As a method for applying the active energy ray-curable composition of the present invention to an object to be coated, known methods such as a bar coater method, an applicator method, a curtain flow coater method and a roll coater method can be applied. .

As the active energy ray for curing, an electron beam, ultraviolet ray, visible light ray, or the like can be used. From the viewpoint of apparatus cost and productivity, it is preferable to use ultraviolet ray. Ultra-high-pressure mercury lamps, high-pressure mercury lamps, medium-pressure mercury lamps, low-pressure mercury lamps, metal halide lamps, Ar lasers, He-Cd lasers, solid-state lasers, xenon lamps, high-frequency induction mercury lamps, and sunlight are suitable. The atmosphere at the time of curing may be any of air, nitrogen, or an inert gas such as argon, or a sealed space between a film or glass and a metal mold.

[0043]

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited by the following examples.

<< Synthesis Example 1 >> [Urethane acrylate (U
A1: Production of A Component)] (1) In a 5 liter three-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser, 1112 g (10 molar equivalents) of isophorone diisocyanate and 0 parts of dibutyltin dilaurate were placed. After charging 0.5 g, the mixture was heated in a water bath so that the internal temperature became 70 ° C. (2) N-methyl-N- (2-hydroxyethyl) -3
A solution obtained by uniformly mixing and dissolving 175 g (2.4 mol equivalent) of hydroxypropylamide and 1102 g (2.6 mol equivalent) of polybutylene glycol (n = 12; average molecular weight: 850) is placed in a dropping funnel with a side tube. The liquid in the dropping funnel was added dropwise at a constant rate for 4 hours while maintaining the temperature in the flask at 65 to 75 ° C. while stirring the contents in the flask of (1) above, and the solution was kept at the same temperature for 2 hours. The reaction was carried out with stirring. (3) Then, after lowering the temperature of the contents of the flask to 60 ° C., 633 g (5.5 molar equivalents) of 2-hydroxyethyl acrylate and 1.5 g of hydroquinone monomethyl ether charged in another dropping funnel are uniformly mixed and dissolved. The solution was dropped at a constant speed for 2 hours while maintaining the temperature inside the flask at 55 to 65 ° C., and then the temperature of the contents of the flask was reduced to 75 ° C.
The reaction was maintained for 4 hours at -85 ° C to produce urethane acrylate (UA1). After confirming that the end point of the reaction was less than 1% by measuring the residual isocyanate equivalent, acryloylmorpholine (component b1) 1008
g ((A) / (b1) = 75/25 mass ratio) was dropped and diluted. (4) The resulting reaction product was a colorless, transparent, viscous liquid at room temperature (25 ° C.) of about 15,000 mPa · s.

<< Synthesis Example 2 >> [Urethane acrylate (U
A2: Production of A Component)] (1) In a three-necked flask having an internal volume of 5 liters equipped with a stirrer, a temperature controller, a thermometer, and a condenser, 1,260 g (10 molar equivalents) of bis (4-isocyanatocyclohexyl) methane is placed. ) And 0.5 g of dibutyltin dilaurate were charged and heated in a water bath so that the internal temperature became 70 ° C. (2) N-methyl-N- (2-hydroxyethyl) -3
A liquid obtained by uniformly mixing and dissolving 250 g (3.4 molar equivalents) of hydroxypropylamide and 660 g (1.6 molar equivalents) of polybutylene glycol (n = 12; average molecular weight: 850) is placed in a dropping funnel with a side tube. The liquid in the dropping funnel was added dropwise at a constant rate for 4 hours while maintaining the temperature in the flask at 65 to 75 ° C. while stirring the contents in the flask of (1) above, and the solution was kept at the same temperature for 2 hours. The reaction was carried out with stirring. (3) Then, after lowering the temperature of the contents of the flask to 60 ° C., 633 g (5.5 molar equivalents) of 2-hydroxyethyl acrylate and 1.5 g of hydroquinone monomethyl ether charged in another dropping funnel are uniformly mixed and dissolved. The solution was dropped at a constant speed for 2 hours while maintaining the temperature inside the flask at 55 to 65 ° C., and then the temperature of the contents of the flask was reduced to 75 ° C.
The reaction was maintained for 4 hours at -85 ° C to produce urethane acrylate (UA2). After confirming that the end point of the reaction is less than 1% by measuring the residual isocyanate equivalent, 934 g of acryloylmorpholine (b1 component)
((A) / (b1) = 75/25 mass ratio) was dropped and diluted. (4) The resulting reaction product was a colorless, transparent, viscous liquid at room temperature (25 ° C.) of about 25,000 mPa · s.

<< Synthesis Example 3 >> [Urethane acrylate (U
A3: Production of B Component)] (1) 1354 g (12 molar equivalents) of isophorone diisocyanate and 0 parts of dibutyltin dilaurate were placed in a three-neck flask having a 5 liter internal volume equipped with a stirrer, a temperature controller, a thermometer, and a condenser. After charging 0.5 g, the mixture was heated in a water bath so that the internal temperature became 70 ° C. (2) 1665 g of 2-hydroxyethyl acrylate
(12.8 molar equivalents) and 1.5 g of hydroquinone monomethyl ether were uniformly mixed and dissolved in a dropping funnel with a side tube, and the liquid in the dropping funnel was added to the contents in the flask of (1) above. While maintaining the temperature inside the flask at 65 to 75 ° C., the mixture was added dropwise at a constant speed for 6 hours, and the mixture was stirred and reacted at the same temperature for 4 hours to produce urethane acrylate (UA3). The end point of the reaction was confirmed to be less than 1% by measuring the residual isocyanate equivalent, and then acryloylmorpholine (b1 component) 1
007 g ((A) / (b1) = 75/25 mass ratio) was dropped and diluted. The resulting reaction product was a colorless and transparent viscous liquid at room temperature (25 ° C.) of about 25,000 mPa · s.

<< Synthesis Example 4 >> [Urethane acrylate (U
A4: Production of Component B) (1) 867 g (7.8 molar equivalents) of isophorone diisocyanate and dibutyltin were placed in a 5-liter three-necked flask equipped with a stirrer, a temperature controller, a thermometer, and a condenser. 0.5 g of dilaurate was charged and heated in a water bath so that the internal temperature became 70 ° C. (2) 1651 g (3.9 molar equivalents) of polybutylene glycol (n = 12; average molecular weight: 850) was charged into a dropping funnel with a side tube, and the liquid in the dropping funnel was added to the flask in (1) above. While stirring the contents, the mixture was added dropwise at a constant rate for 4 hours while maintaining the temperature inside the flask at 65 to 75 ° C, and the mixture was stirred at the same temperature for 2 hours to react. (3) Then, after lowering the temperature of the contents of the flask to 60 ° C., 494 g (4.2 molar equivalents) of 2-hydroxyethyl acrylate and 1.5 g of hydroquinone monomethyl ether charged in another dropping funnel are uniformly mixed and dissolved. The solution was dropped at a constant speed for 2 hours while maintaining the temperature inside the flask at 55 to 65 ° C., and then the temperature of the contents of the flask was reduced to 75 ° C.
The reaction was maintained for 4 hours at -85 ° C to produce urethane acrylate (UA1). After confirming that the end point of the reaction was less than 1% by measuring the residual isocyanate equivalent, acryloylmorpholine (b1 component) 1004
g ((B) / (b1) = 75/25 mass ratio) was dropped and diluted. (4) The resulting reaction product was a colorless and transparent viscous liquid of about 10,000 mPa · s at room temperature (25 ° C.).

<< Synthesis Example 5 >> [Urethane acrylate (U
A5: Production of B Component)] (1) 1535 g (2 molar equivalents) of isophorone diisocyanate and dibutyltin dilaurate 0 were placed in a three-neck flask having a capacity of 5 liters equipped with a stirrer, a temperature controller, a thermometer and a condenser. After charging 0.5 g, the mixture was heated in a water bath so that the internal temperature became 70 ° C. (2) N-methyl-N '-(2-hydroxyethyl)-
602 g (0.4 molar equivalents) of 3-hydroxypropylamide was charged into a dropping funnel with a side tube, and the liquid in the dropping funnel was stirred while stirring the contents in the flask of (1) above, and the temperature inside the flask was lowered. While maintaining the temperature at 65 to 75 ° C., the mixture was added dropwise at a constant rate for 4 hours, and the mixture was stirred and reacted at the same temperature for 2 hours. (3) Then, after lowering the temperature of the contents of the flask to 60 ° C., 874 g (2.2 molar equivalents) of 2-hydroxyethyl acrylate and 1.5 g of hydroquinone monomethyl ether charged in another dropping funnel are uniformly mixed and dissolved. The solution was dropped at a constant speed for 2 hours while maintaining the temperature inside the flask at 55 to 65 ° C., and then the temperature of the contents of the flask was reduced to 75 ° C.
The reaction was maintained for 4 hours at -85 ° C to produce urethane acrylate (UA1). After confirming that the end point of the reaction was less than 1% by measuring the residual isocyanate equivalent, acryloylmorpholine (b1 component) 1004
g ((B) / (b1) = 75/25 mass ratio) was dropped and diluted. (4) The resulting reaction product was a colorless and transparent viscous liquid of about 30,000 mPa · s at room temperature (25 ° C.).

<< Example 1 >> [Preparation of active energy ray-curable composition] A 5-liter three-necked flask equipped with a stirrer, a cooling tube and a dropping funnel with a side tube was obtained in Synthesis Example 1. 2400 g of a reaction product containing urethane acrylate (UA1) and acryloyl morpholine (product name: ACMO; manufactured by Kojin Co., Ltd .: component b1), 600 g of acryloyl morpholine,
N, N-dimethylacrylamide (product name: DMAA;
200 g of Kojin Co., Ltd .: b1 component) and a diacrylate of a caprolactone adduct of neopentyl glycol hydroxypivalate (n + m = 2) (product name:
Kayarad HX220; manufactured by Nippon Kayaku Co., Ltd .: b2 component)
800 g was charged and the atmosphere was replaced by degassing under reduced pressure. Then, 1-hydroxycyclohexyl phenyl ketone (product name: Irgacure 184; Ciba Geigy Co., Ltd .: C component; photoradical polymerization initiator) 12
0 g was added and mixed and stirred at a temperature of 25 ° C. until completely dissolved (mixing and stirring time: about 1 hour), and an active energy ray-curable composition as a colorless transparent viscous liquid (viscosity at room temperature: about 980 mPa · s) ) Got. The results of the viscosity measurement are described in Table 1. The UA1 shown in the synthesis example contains 25% by weight of acryloylmorpholine (ACMO).
, The parts by mass of ACMO are described in the column of the component (B). The produced active energy ray-curable composition was 980 mPa · s at 25 ° C. The evaluation criterion for the viscosity is preferably 2000 mPa · s or less from the viewpoint of workability in film-like coating and molding.

[Production and Evaluation of Cured Film Film] The active energy ray-curable composition prepared in the above Example 1 was coated on a glass substrate using an applicator so as to have a thickness of about 200 μm. It was cured by irradiating it with ultraviolet rays of about 1000 mJ / cm 2 using a high-pressure mercury lamp. After curing, the glass plate was cut off from the glass plate with a cutter knife to conduct a coating film tensile strength test.

(Measurement of Mechanical Strength) JIS K 7113
The tensile properties (tensile strength, tensile elongation and tensile modulus) were measured according to Table 1. The results are as shown in Table 1 below. In addition, from the viewpoint of the mechanical strength of the coating, the tensile strength is 40 Mpa or more, the tensile elongation is 10% or more, and the tensile modulus is 1200 MPa or more.

[Production of Photocured Molded Article by Molding Method] The active energy ray-curable composition prepared in Example 1 above was placed in a transparent silicon mold having a mold cavity in the form of a dumbbell specimen in accordance with JIS 7113. After injecting, a 30 W ultraviolet lamp was used to irradiate the entire surface of the silicon mold with ultraviolet rays for 15 minutes to cure the active energy ray-curable composition to produce a light-cured dumbbell test piece-shaped molded product. A molded product (dumbbell-shaped test piece) having excellent properties was obtained. (1) The volume shrinkage of the manufactured molded article was measured by measuring the specific gravity (d1) of the active energy ray-curable composition used for molding before curing and the obtained molded article (dumbbell-shaped test piece). The specific gravity (d2) was measured, and the volumetric shrinkage (%) was determined by the following equation (1). The result was as shown in Table 1 below.

[0053]

(Equation 1) The volume shrinkage is 8% to achieve the dimensional accuracy of the molded product.
Less than good.

(2) Measurement of Heat Deformation Temperature The heat distortion temperature of the flat specimen obtained above was measured according to JIS K7.
It was as shown in Table 1 below when measured by Method A (load: 18.5 kg / mm ² ) in accordance with 207. In addition, from the point of time-lapse dimensions and shape stability of the molded product, 70 ° C.
The above is regarded as good.

(3) Measurement of Mechanical Strength The tensile properties (tensile strength, tensile elongation and tensile modulus) of the material were measured in accordance with JIS K 7113. The results are shown in Table 1 below. In addition, from the viewpoint of the mechanical strength of the molded product, the tensile strength is preferably 40 Mpa or more, the tensile elongation is 10% or more, and the tensile modulus is 1200 MPa or more.

Example 2 The urethane acrylate (UA2) obtained in Synthesis Example 2 was used as the urethane acrylate (Component A), and the urethane acrylate (UA3) obtained in Synthesis Example 3 was used as one type of the component (B). An active energy ray-curable composition was prepared in the same manner as in Example 1 except that the composition was used, and a cured film film and a molding method were produced. The results are shown in Table 1.

<< Examples 3 to 6, Comparative Examples 1 to 6 >> The active energy ray-curable compositions shown in Table 1 were prepared in the same manner as in Example 1, and a cured film film was produced and produced by a molding method. And evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0058]

[Table 1]

The abbreviations of the compound names in the table are as follows. UA1: urethane acrylate obtained in Synthesis Example 1 (however, the parts by mass in the table are ACMO of a diluting monomer (25%)
Not included. The total mass parts of ACMO are described in the column of ACMO. ) UA2: Urethane acrylate obtained in Synthesis Example 2 (however, the mass parts in the table are ACMO (25
%). The total mass parts of ACMO are described in the column of ACMO. ) ACMO: acryloylmorpholine (product name: ACMO; manufactured by Kojin Co.); B-type viscosity at 25 ° C. is 12 mPa · s DMAA: N, N-dimethylacrylamide (product name:
DMAA; manufactured by Kojin Co.);
5 mPa · s TCMMA: trimethylcyclohexyl methacrylate (manufactured by Mitsubishi Rayon Co., Ltd.), B-type viscosity at 25 ° C. is 25 mPa · s HPCDA: diacrylate of caprolactone addition of neopentyl glycol hydroxypivalate (n + m = 2) (product name: (Kayarad HX-220; manufactured by Nippon Kayaku Co., Ltd.) BAPPP: Bisphenol A ethylene oxide 10
Diacrylate of molar adduct (Product name: A-BPE-1)
0; manufactured by Shin-Nakamura Chemical Co.) TMPEOA: triacrylate of trimethylolpropane ethylene oxide 3 mol adduct (product name: NK ester A-TMPT-3EO; manufactured by Shin-Nakamura Chemical Co.) UA3: urethane obtained in Synthesis Example 3 Acrylate (However, the parts by mass in the table are ACMO of the diluent monomer (25%)
Not included. The total mass parts of ACMO are described in the column of ACMO. UA4: urethane acrylate obtained in Synthesis Example 4 (however, mass parts in the table are ACMO of a diluting monomer (for 25%)
Not included. The total mass parts of ACMO are described in the column of ACMO. UA5: urethane acrylate obtained in Synthesis Example 5 (provided that mass parts in the table are ACMO of a diluting monomer (for 25%)
Not included. The total mass parts of ACMO are described in the column of ACMO. EPA1: Bisphenol A type epoxy resin (Product name:
(Epicoat 828; manufactured by Yuka Shell Co., Ltd.) Epoxy acrylate obtained by adding 2.1 mol of acrylic acid to 1 mol

[0060]

As described above, the active energy ray-curable composition of the present invention has low viscosity and low shrinkage, and can be cured in a short time, so that it can be used as a coating material for various substrates. Ideal for casting polymerization, potting, optical stereolithography, etc. The cured product has tensile strength,
Since it has excellent mechanical strength such as tensile elongation, it can respond to various required performances.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Koji Hayama 4-160 Sunadabashi, Higashi-ku, Nagoya-shi, Aichi F-term in the Mitsubishi Rayon Co., Ltd. Product Development Laboratory 4J011 AA03 AA05 AC04 BA03 CA08 QA03 QA06 QA07 QA08 QA09 QA13 QA20 QA34 QA37 QA38 QA39 QA46 QB12 QB15 QB23 QC10 SA05 SA06 SA22 SA24 SA25 SA34 SA54 SA61 SA63 SA64 SA78 SA84 UA01 UA02 UA03 VA01 WA02 WA07 4J027 AB03 AB10 AB18 AB28 AC02 AC03 AC04 AG03 AG04 AG06 AG03 AG04 AG06 AG03 AG04 AG06 BA04 BA05 BA07 BA08 BA09 BA10 BA11 BA12 BA13 BA14 BA15 BA17 BA19 BA20 BA21 BA22 CB10 CC04 CC05 CC06 CD01 CD04 CD08 4J038 CC001 CC002 CE051 CE052 CF001 CF002 CG141 CG142 CG171 CG172 CH051 CH052 CH071 CH072 CH141 CH142 CH202 CH162 CH201 CH201 CH202 JA33 JA60 KA04 NA01 NA11 NA27 PA17 PB08 PC02 PC08 PC10

Claims (1)

[Claims] 1. Component (A): two radically polymerizable (meth) acryloyloxy groups and at least one amide group in a molecule obtained by reacting the following components (a1) to (a4), and at least one 15 to 75 parts by mass of a urethane (meth) acrylate compound having two urethane groups, (a1) an amide hydroxy compound having at least one amide group and at least two NCO-reactive hydroxy groups in the molecule (a2 ) At least one diol selected from polyether diols, polyester diols and polycarbonate diols (a3) organic diisocyanate compound or triisocyanate compound (a4) one (meth) acrylate group and one NCO Hydroxy of (meth) acrylic acid having reactive hydroxy group Group-containing alkyl ester, (b1) component: B type viscosity at 25 ° C. is 200mPa
10 to 70 parts by mass of at least one compound selected from vinyl ethers, mono (meth) acrylates, mono (meth) acrylamides and di (meth) acrylates, which are not more than s; Component (b2): (I) and / or (II)
5 to 60 parts by mass of at least one selected from compounds having a (meth) acryloyl group represented by the formula: (Where R ¹ is hydrogen or a methyl group, and R ² is carbon 3
R ₃ is a branched, cyclic, or linear hydrocarbon group having 2 to 15 carbon atoms, or a hydrocarbon group having an aromatic ring, and an ester structure is included in the structure. May be. n and m may be the same or different, and represent an integer of 1 to 5. ) (Where R ¹ is hydrogen or a methyl group, and R ⁴ is C 2
R ⁵ is a branched, cyclic, straight-chain hydrocarbon group or a hydrocarbon group having an aromatic ring having 2 to 20 carbon atoms, and R ⁵ is an ester structure in the structure. May be included. P is an integer of 1 to 7 and p in the molecule is
, Q represents an integer of 2 to 6, and r represents an integer of 0 to 3. Component (C): Component (A), (b1) and (b2)
An active energy ray-curable composition, comprising a photopolymerization initiator in an amount of 0.05 to 10 parts by mass based on 100 parts by mass of the total amount of the components.