JP6777414B2 - Active energy ray curable resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition. More specifically, the present invention relates to an active energy ray-curable resin composition that provides a cured product having a high shielding property against visible light (hereinafter, simply referred to as light).

Conventionally, a pigment such as titanium oxide has been added to the resin composition as a means for making the cured product of the resin composition opaque.

However, white pigments such as titanium oxide are generally expensive, and since the resin composition containing the pigment is a non-uniform system before curing, there is a problem that the pigment particles settle over time. .. Further, titanium oxide is not preferable because the resin tends to deteriorate when it acts as a photocatalyst.

Japanese Unexamined Patent Publication No. 2014-133864

An object of the present invention is to provide an active energy ray-curable resin composition having a high light-shielding property after curing, while being a uniform liquid resin composition having excellent storage stability before curing.

The present inventors have arrived at the present invention as a result of studies for achieving the above object.
That is, the present invention is an active energy ray-curable resin composition containing a radically polymerizable monomer component (A), a non-radical polymerizable component (B), and a radical type photopolymerization initiator (C). There,
The radically polymerizable monomer component (A) comprises at least one monomer (a) having a (meth) acryloyl group.
The non-radical polymerizable component (B) comprises at least one non-radical polymerizable compound (b) selected from the group consisting of polybutadiene (b1), polyether compound (b2) and polyester (b3).
The radically polymerizable monomer component (A) and the non-radical polymerizable component (B) satisfy the following condition (i) or condition (ii).
A total light transmittance of Ri der 90%
An active energy ray in which the ratio [(A): (B)] of the total weight of the radically polymerizable monomer component (A) to the total weight of the non-radical polymerizable component (B) is 45:55 to 90:10. Curable resin composition: A cured product of the active energy ray-curable resin composition.
(I) Satisfy all of the following relational expressions (1) to (4).
(Ii) Both the following relational expressions (1) and (5) are satisfied.
Relational expression (1): Mn _B ≤ 95.0 x ΔHLB ₁ + 2200
Relational expression (2): Mn _B ≧ -70.0 × ΔHLB ₁ +600
Relational expression (3): Mn _B ≧ -14800 × ΔHLB ₂ +17000
Relational expression (4): Mn _B ≧ −52.3 × ΔHLB ₂ +500
Relational expression (5): Mn _B ≧ −350 × ΔHLB ₁ +3800
[In the relational expressions (1) to (5), Mn _B represents the chemical formula amount or the number average molecular weight of the non-radical polymerizable component (B), and the non-radical polymerizable component (B) has two or more non-radical polymerizable components (B). When it is composed of the radically polymerizable compound (b), it is a value obtained by weighting and averaging the number average molecular weight of the non-radical polymerizable compound (b) based on its molar ratio.
In the relational expressions (1), (2) and (5), ΔHLB ₁ is the HLB value (HLB _A ) of the polymer obtained by polymerizing the monomer component ( _A ) and the non-radical polymerizable component (B). ) Represents the absolute value of the difference from the HLB value (HLB _B ), and when the non-radical polymerizable component (B) is composed of two or more non-radical polymerizable compounds (b), HLB _B is non-radical polymerizable. It is a value obtained by weighting and averaging the HLB value of the compound (b) based on its weight ratio.
In the relational expressions (3) and (4), ΔHLB ₂ has the monomer component (A) of one kind of monomer (a) and the non-radical polymerizable component (B) of one kind. When composed of the non-radical polymerizable compound (b), it is the absolute value of the difference between the HLB value of the homopolymer obtained by polymerizing the monomer (a) and the HLB value of the non-radical polymerizable compound (b). , The monomer component (A) is composed of two or more kinds of monomers (a) and / or the non-radical polymerizable component (B) is made of two or more kinds of non-radical polymerizable compound (b). If, using the monomer (a) the homopolymerized HLB value of the polymer obtained when the a (HLB _a), HLB value of each non-radical polymerizable compound (b) and (HLB _b), HLB is the minimum value among the absolute value of the difference between HLB _a and HLB _b obtained by calculation for all the combinations of _a and HLB _b. ]

Since the active energy ray-curable resin composition of the present invention does not contain pigment particles or the like, it is a uniform liquid resin composition having excellent storage stability before curing, but exhibits light shielding properties after curing.

The active energy ray-curable resin composition of the present invention contains a radically polymerizable monomer component (A), a non-radical polymerizable component (B), and a radical-type photopolymerization initiator (C).
Here, the radically polymerizable monomer component (A) is composed of at least one monomer (a) having a (meth) acryloyl group.
Further, the non-radical polymerizable component (B) is composed of at least one non-radical polymerizable compound (b) selected from the group consisting of polybutadiene (b1), polyether (b2) and polyester (b3).

The radically polymerizable monomer component (A) and the non-radical polymerizable component (B) contained in the active energy ray-curable resin composition of the present invention may satisfy the following condition (i) or condition (ii). is necessary.
(I) Satisfy all of the following relational expressions (1) to (4).
(Ii) Both the following relational expressions (1) and (5) are satisfied.
Relational expression (1): Mn _B ≤ 95.0 x ΔHLB ₁ + 2200
Relational expression (2): Mn _B ≧ -70.0 × ΔHLB ₁ +600
Relational expression (3): Mn _B ≧ -14800 × ΔHLB ₂ +17000
Relational expression (4): Mn _B ≧ −52.3 × ΔHLB ₂ +500
Relational expression (5): Mn _B ≧ −350 × ΔHLB ₁ +3800

These relational expressions (1) to (5) are relational expressions about the HLB (Hydrophile-Lipophile Balance) value and the molecular weight of the radically polymerizable monomer component (A) and the non-radical polymerizable component (B).
In the relational expressions (1) to (5), Mn _B represents the chemical formula amount or the number average molecular weight of the non-radical polymerizable component (B), and the non-radical polymerizable component (B) contains two or more non-radical components. When composed of the polymerizable compound (b), it is a value obtained by weight-averaging the number average molecular weight of the non-radical polymerizable compound (b) based on its molar ratio.
In the general formulas (1) to (5), the number average molecular weight of the non-radical polymerizable component (B) represented by Mn _B is 200 to 10,000 from the viewpoint of light shielding property and compatibility after curing. It is preferable, and 500 to 2,500 is more preferable.

In the relational expressions (1), (2) and (5), ΔHLB ₁ is the HLB value (HLB _A ) of the polymer obtained by polymerizing the monomer component ( _A ) and the non-radical polymerizable component (B). ) Represents the absolute value of the difference from the HLB value (HLB _B ), and when the non-radical polymerizable component (B) is composed of two or more non-radical polymerizable compounds (b), HLB _B is non-radical polymerizable. It is a value obtained by weighting and averaging the HLB value of the compound (b) based on its weight ratio.
When the monomer component (A) is composed of one kind of monomer (a), HLB _A is the HLB value of the copolymer of the monomer (a), and the monomer component (A) is HLB _A when composed of two or more kinds of monomers (a) is the HLB value of the copolymer of the monomer (a). As the HLB value of the copolymer of the monomer (a), the HLB value of the homopolymer of the monomer (a) is weighted and averaged based on the weight ratio of each monomer (a). ΔHLB ₁ is preferably 1.0 or more from the viewpoint of light shielding property after curing.

In the relational expressions (3) and (4), ΔHLB ₂ has the monomer component (A) of one kind of monomer (a) and the non-radical polymerizable component (B) of one kind. When composed of the non-radical polymerizable compound (b), it is the absolute value of the difference between the HLB value of the homopolymer obtained by polymerizing the monomer (a) and the HLB value of the non-radical polymerizable compound (b). , The monomer component (A) is composed of two or more kinds of monomers (a) and / or the non-radical polymerizable component (B) is made of two or more kinds of non-radical polymerizable compound (b). If, using the monomer (a) the homopolymerized HLB value of the polymer obtained when the a (HLB _a), HLB value of each non-radical polymerizable compound (b) and (HLB _b), HLB is the minimum value among the absolute value of the difference between HLB _a and HLB _b obtained by calculation for all the combinations of _a and HLB _b. ΔHLB ₂ is preferably 1.0 or more from the viewpoint of light shielding property after photocuring.

When the active energy ray-curable resin composition satisfies the condition (i) or the condition (ii), the micro-order phase separation structure required for the development of light shielding property is contained in the cured resin (also referred to as a cured product). It is possible to obtain a cured product having a high haze value (preferably 90% or more) measured by the method described in JIS-K7136.
In a normal two-component mixed system, the larger the polarity difference (difference in HLB value) of the two components and / or the larger the molecular weight of each component, the easier it is for the two components to be phase-separated. If (1) is not satisfied, the molecular weight of the non-radical polymerizable component (B) is too large, resulting in insufficient phase separation. Further, when the relational expression (3) or the relational expression (4) is not satisfied, a dispersant (also a compatibilizer) between the polymer of the radically polymerizable monomer component (A) and the non-radical polymerizable component (B). It represents here and here, which contains a component that functions as (referred to as), and prevents the phase separation required for light shielding from occurring.
The active energy ray-curable resin composition of the present invention is usually a uniform solution, but when a cured product is prepared by irradiation with active energy rays, the monomer (A) is polymerized and the active energy ray-curable resin composition. A component containing an increased molecular weight of a component contained in the resin composition and having a different refractive index contained in the active energy ray-curable resin composition [a polymer of a radically polymerizable monomer component (A) and a non-radical polymerizable component ( B)] phase separation progresses, and as a result of light being scattered at the interface between the two separated phases, high light shielding properties are exhibited.

Here, the HLB value is a measure showing the balance between inorganic / organic, and the higher the HLB value, the higher the inorganic property. As the HLB value in the present invention, a value calculated by the following formula by the Oda method is used.
HLB ≒ 10 x Inorganic / Organic (Reference: "Introduction to Surfactants" 2007, published by Sanyo Chemical Industries, Ltd. P212)
Further, examples of the active energy ray include ultraviolet rays (wavelength 14 to 400 nm), visible light (wavelength 400 to 800 nm), electron beams and the like.

The radically polymerizable monomer component (A) of the first essential component in the present invention comprises at least one monomer (a) having a (meth) acryloyl group.
As long as the monomer (a) has a (meth) acryloyl group in the molecule, the number of the acryloyl group is not particularly limited.
In this application, the notation "(meth) acryloyl group" means an acryloyl group and a methacryloyl group.

Examples of the monomer (a) include a monomer (a1) having one (meth) acryloyl group and a monomer (a2) having two or more (meth) acryloyl groups.

Preferred monomers (a1) having one (meth) acryloyl group are ethyl (meth) acrylate, isobutyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isostearyl (meth). Acrylate, Isobornyl (meth) acrylate, Phenoxyethyl (meth) acrylate, (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) Acrylamide, N, N'-dimethyl (meth) acrylamide, N, N'-diethyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-hydroxypropyl (meth) acrylamide, N-hydroxybutyl (meth) acrylamide And acryloyl morpholine and the like.

Preferred monomers (a2) having two or more (meth) acryloyl groups are 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, 1,10-decanediol diacrylate, and dimethylol. -Tricyclodecanedi (meth) acrylate, polybutadiene diacrylate and the like can be mentioned.

Pentaerythritol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate and the like are preferable as the monomer (a3) having three (meth) acryloyl groups.

Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and dipenta are preferable as the monomer (a4) having four or more (meth) acryloyl groups. Hexaacrylate, which is an adduct of 12 mol of ε-caprolactone of erythritol, and the like can be mentioned.

Further, as the monomer (a2) having two or more (meth) acryloyl groups, urethane (meth) acrylate oligomer (a21) can also be preferably used.

As the urethane (meth) acrylate oligomer (a21) in the present invention, a known method (Japanese Patent Laid-Open No. 2016-20489) includes a polyhydric alcohol (α), a polyisocyanate (β), and a (meth) acrylate (γ) having a hydroxyl group. A reaction product obtained by reacting with the method described in Japanese Patent Publication or the like can be used.

The polyhydric alcohol (α) includes an aliphatic polyhydric alcohol (α1) having 2 to 20 carbon atoms, an alicyclic polyhydric alcohol (α2) having 6 to 20 carbon atoms, and an aromatic aliphatic polyhydric alcohol having 8 to 16 carbon atoms. Examples thereof include valent alcohols (α3), aromatic polyhydric alcohols (α4) having 6 to 15 carbon atoms, and alcohols in which alkylene oxides having 2 to 8 carbon atoms are added in a block shape and / or randomly.

As the aliphatic polyhydric alcohol (α1) having 2 to 20 carbon atoms, the chain aliphatic dihydric alcohol having 2 to 12 carbon atoms [ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4- Linear alcohols such as butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol and 1,10-dodecanediol; 1,2-, 1,3- or 2,3-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 2,2-diethyl-1,3-propanediol, 2-methyl-1 , 5-Pentanediol and branched alcohols such as 3-methyl-1,5-Pentanediol];
4-8-valent alcohols with 5 to 20 carbon atoms [fatty polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.);
Sugars (sucrose, glucose, mannose, fructose, methyl glucoside and its derivatives)]; and the like.

Examples of the alicyclic polyhydric alcohol (α2) having 6 to 20 carbon atoms include an alicyclic dihydric alcohol having 6 to 20 carbon atoms [1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,3-. Cyclopentanediol, 1,4-cycloheptanediol, 1,4-bis (hydroxymethyl) cyclohexane and 2,2-bis (4-hydroxycyclohexyl) propane, etc.];
Trihydric alcohol with 3 to 20 carbon atoms [1,3,5-cyclohexanetriol, etc.];
And so on.

Examples of the aromatic aliphatic polyhydric alcohol (α3) having 8 to 16 carbon atoms include dimethylolphenol and the like.

Examples of the aromatic polyhydric alcohol (α4) having 6 to 15 carbon atoms include catechol, resorcinol, hydroquinone, dihydroxynaphthalene, bisphenol A, bisphenol F and bisphenol S.

Examples of the alkylene oxide having 2 to 8 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 2,3- or 1,3-butylene oxide, tetrahydrofuran, 3-methyltetrahydrofuran and styrene. Examples include oxide.
As the polyol (α), one of these may be used alone, or two or more thereof may be used in combination.
Further, an aliphatic polyhydric alcohol having 2 to 12 carbon atoms (α1), an alicyclic polyhydric alcohol having 6 to 20 carbon atoms (α2), an aromatic aliphatic polyhydric alcohol having 7 to 16 carbon atoms (α3) or carbon. The number of moles of the alkylene oxide having 2 to 8 carbon atoms added to 1 mol of the aromatic polyhydric alcohol (α4) of the number 6 to 15 is preferably 1 to 400 mol from the viewpoint of compatibility.

Examples of the polyisocyanate (β) include an aliphatic polyisocyanate having 4 to 20 carbon atoms (β1), an alicyclic polyisocyanate having 6 to 17 carbon atoms (β2), and an aromatic aliphatic polyisocyanate having 10 to 17 carbon atoms (β3). ), Aromatic polyisocyanate (β4) having 8 to 22 carbon atoms, and the like.
Examples of the aliphatic polyisocyanate (β1) having 4 to 20 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and lysine diisocyanate.
Examples of the alicyclic polyisocyanate (β2) having 6 to 17 carbon atoms include isophorone diisocyanate, 4,4-dicyclohexylmethane diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, and bis (2-isocyanatoethyl) -4-cyclohexene-. 1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate and the like can be mentioned.
Examples of the aromatic aliphatic polyisocyanate (β3) having 10 to 17 carbon atoms include m- or p-xylylene diisocyanate, α, α, α', α'-tetramethylxylylene diisocyanate and the like.
As the aromatic polyisocyanate (β4) having 8 to 22 carbon atoms, 1,3- or 1,4-phenylenediocyanate, 2,4- or 2,6-tolylene diisocyanate, 4,4'-or 2,4 '-Diphenylmethane diisocyanate), 1,5-naphthalenediisocyanate and 4,4', 4''-triphenylmethane triisocyanate and the like.
As the polyisocyanate (β), one of these may be used alone, or two or more thereof may be used in combination.

Examples of the (meth) acrylate (γ) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and two. Mono (meth) acrylates of valent alcohols (ethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, polyethylene glycol, etc.) and trivalent alcohols (trimethylol ethane) , Trimethylol propane, glycerin, etc.) mono (meth) acrylate or di (meth) acrylate and the like.
As the (meth) acrylate (γ) having a hydroxyl group, one of them may be used alone or two or more thereof may be used in combination.

The number average molecular weight of the urethane (meth) acrylate oligomer (a21) is preferably 500 to 10,000, more preferably 500 to 5,000, from the viewpoint of compatibility. The number average molecular weight of the urethane (meth) acrylate oligomer (a21) can be measured by GPC (gel permeation chromatography) under the following conditions.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together"
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polyethylene glycol

The non-radical polymerizable component (B) of the second essential component in the present invention needs to have no radically polymerizable group such as a (meth) acryloyl group.
When a compound having a (meth) acryloyl group is used, a polymerization reaction with the monomer (A) occurs during irradiation with active energy rays, and the radically polymerizable monomer component (A) and the non-radical polymerizable component (B) are separated. Since they coexist in the same molecule, it is not possible to form the micro-order phase-separated structure required for the development of light shielding properties.

The non-radical polymerizable component (B) in the present invention is at least one non-radical polymerizable compound selected from the group consisting of polybutadiene (b1), polyether (b2) and polyester (b3).
Of these, polybutadiene (b1) is preferable from the viewpoint of water resistance of the cured product of the active energy ray-curable resin composition, and polyether (b2) is preferable from the viewpoint of compatibility.

The polybutadiene (b1) in the present invention includes a polymer obtained by adding 1,3-butadiene and / or 1,4-addition (hereinafter, simply referred to as polybutadiene) and a modified product thereof (polybutadiene). Examples thereof include compounds in which maleic acid and the like are added, compounds in which a hydroxyl group is introduced at the terminal, and compounds in which hydrogen is added to a double bond in these compounds).
The polymer of 1,3-butadiene may be a mixture of trans-1,4-polybutadiene and cis-1,4-polybutadiene, and the ratio thereof is not particularly limited.

As a compound in which a hydroxyl group is introduced at the end of the molecule, it can be obtained as G-1000 [manufactured by Nippon Soda Co., Ltd.] or the like.

For Mn _B of polybutadiene (b1), the value of the number average molecular weight measured by GPC (gel permeation chromatography) under the following conditions is used.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together"
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polyethylene glycol

The number average molecular weight of the polybutadiene (b1) is preferably 1,000 to 10,000, more preferably 1,500 to 3,000, from the viewpoint of light shielding and compatibility after curing.
The HLB value of polybutadiene (b1) is preferably 0 to 2, more preferably 0 to 1, from the viewpoint of light shielding and compatibility after curing.

As the polybutadiene (b1), one of them may be used alone, or two or more of them may be used in combination.
Among these, polybutadiene is mentioned as a preferable polybutadiene (b1).

Examples of the polyether (b2) in the present invention include a compound in which water or a compound having active hydrogen having 1 to 20 carbon atoms is added with an alkylene oxide having 2 to 8 carbon atoms in a block shape and / or in a random shape. Be done.

Examples of the compound having active hydrogen having 1 to 20 carbon atoms include a chain aliphatic alcohol having 1 to 20 carbon atoms, an alicyclic alcohol having 6 to 20 carbon atoms, an aromatic aliphatic alcohol having 8 to 16 carbon atoms, and a carbon number of carbon atoms. Examples thereof include 6 to 15 aromatic alcohols.

Examples of the chain fatty alcohol having 1 to 20 carbon atoms include chain aliphatic monohydric alcohols having 1 to 12 carbon atoms [methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol, 1-hexanol, 1 -Heptanol, 1-octanol, 1-nonanol, 1-decanol];
Chain aliphatic dihydric alcohol having 2 to 12 carbon atoms [ethylene glycol, 1,2- or 1,3-propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, dodecanediol, tetradecanediol, neopentyl glycol and 2,2-diethyl-1,3-propanediol, etc.];
Chain aliphatic 4- to 8-valent alcohols having 5 to 20 carbon atoms [pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.];
Sugars [sucrose, glucose, mannose, fructose, methyl glucoside and derivatives thereof]; and the like can be mentioned.

Examples of the alicyclic alcohol having 6 to 20 carbon atoms include hydroxycyclohexane, 1,3-cyclopentanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cycloheptanediol, and 2,2. -Bis (4-hydroxycyclohexyl) propane, 1,3,5-cyclohexanetriol and the like can be mentioned.

Examples of the aromatic aliphatic alcohol having 8 to 16 carbon atoms include benzyl alcohol and dimethylolphenol.

Examples of aromatic alcohols having 6 to 15 carbon atoms include phenol, catechol, resorcinol, hydroquinone, dihydroxynaphthalene, bisphenol A, bisphenol F and bisphenol S.

The polyether (b2) in the present invention may have one or more ether groups, and the polyether (b2) includes 2-ethylhexyl glycidyl ether [trade name "Denacol EX-121", Nagasekemutex. Made by Co., Ltd.] and the like can also be used.
Examples of other commercially available polyethers include neopentyl glycol diglycidyl ether [trade name "Denacol EX-211", manufactured by Nagase Chemmutex Co., Ltd.] and the like.

Examples of the alkylene oxide having 2 to 8 carbon atoms include ethylene oxide, 1,2- or 1,3-propylene oxide, 1,2-, 1,3-, 1,4- or 2,3-butylene oxide, styrene oxide and the like. Examples thereof include epichlorohydrin (epicchlorohydrin, etc.).
The number of moles of alkylene oxide having 2 to 8 carbon atoms added to 1 mol of water or an active hydrogen-containing compound having 1 to 20 carbon atoms is preferably 1 to 400 mol, more preferably 1 mol, from the viewpoint of compatibility. It is 2 to 30 mol.

Further, as the polyether (b2), a derivative of the polyether (glycidyl etherified product or the like) can also be preferably used.
Examples of the derivatives of the polyether include polyoxyethylene glycol diglycidyl ether and polyoxypropylene glycol diglycidyl ether.

The Mn _B of the polyether (b2) is preferably 200 to 100,000, more preferably 500 to 2,500, from the viewpoint of light shielding and compatibility after curing.
For Mn _B of polyether (b2), when the chemical formula amount of the theoretical chemical formula obtained by calculation from the ratio of the raw materials used in the synthesis is 1,000 or less, the value of the chemical formula amount of the theoretical chemical formula is used. When the chemical formula of the chemical formula exceeds 1000, the value of the number average molecular weight measured by the same method as Mn _{B of} polybutadiene (b1) is used.

The HLB value of the polyether (b2) is preferably 3 to 25, more preferably 4 to 20, from the viewpoint of light shielding and compatibility after curing.

As the polyether (b2), one of them may be used alone, or two or more of them may be used in combination.
Among these, preferred polyethers (b2) are dipropylene glycol, polyoxyethylene glycol (HLB _B : 20 to 25, Mn _B : 150 to 1,000), and polyoxypropylene glycol (HLB _B : 4 to 16). , Mn _B : 200 to 5,000), polyoxyethylene polyoxypropylene glycol (HLB _B : 4 to 25, Mn _B : 200 to 5,000), tetramethylene glycol (HLB _B : 9 to 12, Mn _B : 200-1,000), polyoxyethylene glycol diglycidyl ether (HLB _B : 11-17, Mn _B : 200-1,000) and polyoxypropylene glycol diglycidyl ether (HLB _B : 4-6, Mn _B : 200 to 5,000).

Examples of the polyester (b3) in the present invention include a polycondensate of a polyhydric alcohol and a polyvalent carboxylic acid having 2 to 20 carbon atoms.

As the polyhydric alcohol, the polyhydric alcohol (α) exemplified in the description of the urethane (meth) acrylate oligomer can be used.
As the polyhydric alcohol, one of them may be used alone, or two or more thereof may be used in combination.
As a polyvalent carboxylic acid having 2 to 20 carbon atoms,
Aliphatic polyvalent carboxylic acids [oxalic acid, malonic acid, dipropyl malonic acid, succinic acid, 2,2-dimethylsuccinic acid, glutaric acid, 2-methylglutaric acid, 2,2-dimethylglutaric acid, 2,4- Didimethylglutaric acid, 3-methylglutaric acid, 3,3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, 3-methyladipic acid, pimelic acid, 2,2,6,6-tetramethyl Pimeric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, pentadecanedioic acid, tetradecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecandioic acid, eicosandioic acid and 1,4-cyclohexanedicarboxylic acid, etc. ];
Alicyclic polyvalent carboxylic acid [cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl-4,4'-dicarboxylic acid and gypsum acid];
Aromatic polyvalent carboxylic acids [terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 4,4-stilbendicarboxylic acid, naphthalenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, diphenoxyetanedicarboxylic acid, diphenyletherdicarboxylic acid Acids and diphenylsulfonedicarboxylic acids, etc.] and the like.
As the polyvalent carboxylic acid having 2 to 20 carbon atoms, one type may be used alone or two or more types may be used in combination.

Further, as the polyester (b3), a polyester derivative (a compound obtained by reacting a terminal hydroxyl group or a carboxy group with an alcohol having 1 to 20 carbon atoms) can also be preferably used.

The number average molecular weight of the polyester (b3) is preferably 500 to 10,000, more preferably 1,000 to 3,000, from the viewpoint of light shielding and compatibility after curing. For Mn _B of polyester (b3), when the chemical formula of the theoretical chemical formula that can be estimated from the ratio of the raw materials used in the synthesis is 1,000 or less, the value of the chemical formula of the theoretical chemical formula is used and the chemical formula of the theoretical chemical formula is used. When is more than 1000, the value of the number average molecular weight measured by the same method as Mn _{B of} polybutadiene (b1) is used.

The HLB value of the polyester (b3) is preferably 3 to 25, more preferably 4 to 20, from the viewpoint of light shielding and compatibility after curing.

As the polyester (b3), one of them may be used alone, or two or more of them may be used in combination.
Among these, preferable polyester (b3) includes a polycondensate of 3-methyl-1,5-pentanediol and adipic acid (HLB value: 4 to 20, Mn _B : 300 to 6,000). ..

The radical photopolymerization initiator (C) as the third essential component in the present invention includes benzoin compounds [compounds having 14 to 18 carbon atoms, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether and benzoin isobutyl ether. ];
Alkylphenone compounds with 8 to 18 carbon atoms [acetophenone, 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl Propane-1-one, diethoxyacetophenone, 1-hydroxycyclohexylphenylketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, etc.];
Anthraquinone compounds having 14 to 19 carbon atoms [2-ethylanthraquinone, 2-t-butyl anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone, etc.];
Thioxanthone compounds having 13 to 17 carbon atoms [2,4-diethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, etc.];
Ketal compounds having 16 to 17 carbon atoms [acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.];
Benzophenone compounds having 13 to 21 carbon atoms [benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 4,4'-bismethylaminobenzophenone, etc.];
Phosphine oxides with 22-28 carbon atoms [1,3,5-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis- (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc.];
Oxime ester compounds with 20 to 30 carbon atoms [1,2-octanedione-1- (4- [phenylthio) -2- (O-benzoyloxime)] and ethanone-1- (9-ethyl-6- (2-) Methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime));
And so on.
As the radical type photopolymerization initiator (C), one of them may be used alone, or two or more thereof may be used in combination.

The active energy ray-curable resin composition of the present invention has a total light transmittance of 90% or more. The method for increasing the total light transmittance to 90% or more is not particularly limited, but this includes the monomer (a) having a (meth) acryloyl group contained in the radically polymerizable monomer component (A) and the non-radical. By adjusting the HLB value and molecular weight of the non-radical polymerizable compound (b) contained in the polymerizable component (B) to a range satisfying at least one of the following (iii ) to (v), the total light beam A method of increasing the transmittance to 90% or more is preferable.
(Iii) The number average molecular weight of all the monomers (a) contained in the active energy ray-curable resin composition is less than 1000.
(Iv) The number average molecular weight of all the non-radical polymerizable compounds (b) contained in the active energy ray-curable resin composition is less than 1000.
(V) The active energy ray-curable resin composition contains a monomer (a) having a number average molecular weight of 1000 or more and a non-radical polymerizable compound (b) having a number average molecular weight of 1000 or more, and further numbers. The monomer (a) having an average molecular weight of 1000 or more and the non-radical polymerizable compound (b) having a number average molecular weight of 1000 or more satisfy the relational expression (6).
Relational expression 6:
x × Mn _a1 + y × Mn _b1 ≦ −103 × ΔHLB ₃ +1240 (6)

In the relational expression (6), x has a number average molecular weight of 1000 or more with respect to the total weight of the radically polymerizable monomer component (A) and the non-radical polymerizable component (B) in the active energy ray-curable resin composition. Represents the weight ratio of a certain monomer (a).
y is a non-radical polymerizable compound having a number average molecular weight of 1000 or more with respect to the total weight of the radically polymerizable monomer component (A) and the non-radical polymerizable component (B) in the active energy ray-curable resin composition. b) represents the weight ratio.
Mn _a1 represents the number average molecular weight of the monomer (a) having a number average molecular weight of 1000 or more, and the active energy ray-curable resin composition comprises a monomer (a) having a number average molecular weight of 1000 or more. When two or more kinds are contained, it is a value obtained by weight-averaging the number average molecular weight of the monomer (a) having a number average molecular weight of 1000 or more based on the molar ratio.
Mn _b1 represents the number average molecular weight of the non-radical polymerizable compound (b) having a number average molecular weight of 1000 or more, and the active energy ray-curable resin composition is a non-radical polymerizable compound having a number average molecular weight of 1000 or more. When two or more kinds of (b) are contained, the number average molecular weight of the non-radical polymerizable compound (b) having a number average molecular weight of 1000 or more is a weighted average value based on the molar ratio.
ΔHLB ₃ is the HLB value (HLB _a1 ) of the monomer (a) having a number average molecular weight of 1000 or more and the HLB value (HLB _b1 ) of the non-radical polymerizable compound (b) having a number average molecular weight of 1000 or more. Represents the absolute value of the difference between the HLB value and.
When the active energy ray-curable resin composition contains two or more types of monomers (a) having a number average molecular weight of 1000 or more, HLB _a1 is a monomer (a) having a number average molecular weight of 1000 or more. ) Is weighted and averaged based on its weight ratio.
When the active energy ray-curable resin composition contains two or more non-radical polymerizable compounds (b) having a number average molecular weight of 1000 or more, HLB _b1 is non-radical polymerization having a number average molecular weight of 1000 or more. A weighted average of the HLB values of the sex compound (b) based on its weight ratio is used.

The number average molecular weight of the monomer (a) having a number average molecular weight of 1000 or more and the non-radical polymerizable compound (b) having a number average molecular weight of 1000 or more is the same as that of Mn _{B of} polybutadiene (b1). The number average molecular weight measured by the above method is used.

Preferred combinations of the radically polymerizable monomer component (A) and the non-radical polymerizable component (B) used in the present invention include the following.
Monomer (a) having an HLB _A of 3.5 to 10 [dimethylol-tricyclodecanedimethacrylate (HLB _A : 3.88), 1,10-decanediol diacrylate (HLB _A : 3.88), 1,9-Nonandiol diacrylate (HLB _A : 4.13), dimethylol-tricyclodecanedimethacrylate (HLB _A : 4.13), phenoxyethyl acrylate (HLB _A : 4.41), dipentaerythritol hexa (HLB _A : 4.41) Meta) acrylate (HLB _A : 7.54), dipentaerythritol penta (meth) acrylate (HLB _A : 9.35) and mixtures thereof, etc.] and polybutadiene [HLB _B : 0 to 1, Mn _B : 1,000. ~ 3,000];
Monomer (a) with HLB _A of 3 to 20 [isobornyl acrylate (HLB _A : 3.10), dimethylol-tricyclodecane methacrylate (HLB _A : 3.88), 1,10-decanediol Diacrylate (HLB _A : 3.88), 1,9-nonanediol diacrylate (HLB _A : 4.13), Dimethylol-tricyclodecanedimethacrylate (HLB _A : 4.13), Phenoxyethyl acrylate (HLB _A) : 4.41), Dipentaerythritol hexa (meth) acrylate (HLB _A : 7.54), Dipentaerythritol penta (meth) acrylate (HLB _A : 9.35), Acryloylmorpholine (HLB _A : 15.9) And mixtures thereof, etc.] and polyoxypropylene glycol [HLB _B : 4 to 16, Mn _B : 200 to 5,000];
Monomer (a) with HLB _A of 3 to 20 [isobornyl acrylate (HLB _A : 3.10), dimethylol-tricyclodecane methacrylate (HLB _A : 3.88), 1,10-decanediol Diacrylate (HLB _A : 3.88), 1,9-nonanediol diacrylate (HLB _A : 4.13), Dimethylol-tricyclodecanedimethacrylate (HLB _A : 4.13), Phenoxyethyl acrylate (HLB _A) : 4.41), Dipentaerythritol hexa (meth) acrylate (HLB _A : 7.54), Dipentaerythritol penta (meth) acrylate (HLB _A : 9.35), Acryloylmorpholin (HLB _A : 15.9) And mixtures of these, etc.] and polyoxyethylene polyoxypropylene glycol [HLB _B : 4 to 25, Mn _B : 200 to 5,000];
Monomer (a) with HLB _A of 3 to 20 [isobornyl acrylate (HLB _A : 3.10), dimethylol-tricyclodecane methacrylate (HLB _A : 3.88), 1,10-decanediol Diacrylate (HLB _A : 3.88), 1,9-nonanediol diacrylate (HLB _A : 4.13), Dimethylol-tricyclodecanedimethacrylate (HLB _A : 4.13), Phenoxyethyl acrylate (HLB _A) : 4.41), Dipentaerythritol hexa (meth) acrylate (HLB _A : 7.54), Dipentaerythritol penta (meth) acrylate (HLB _A : 9.35), Acryloylmorpholin (HLB _A : 15.9) And a mixture of these, etc.] and polyoxyethylene glycol diglycidyl ether [HLB _B : 11-17, Mn _B : 200-1,000];
Monomer (a) with HLB _A of 3 to 20 [isobornyl acrylate (HLB _A : 3.10), dimethylol-tricyclodecane methacrylate (HLB _A : 3.88), 1,10-decanediol Diacrylate (HLB _A : 3.88), 1,9-nonanediol diacrylate (HLB _A : 4.13), Dimethylol-tricyclodecanedimethacrylate (HLB _A : 4.13), Phenoxyethyl acrylate (HLB _A) : 4.41), Dipentaerythritol hexa (meth) acrylate (HLB _A : 7.54), Dipentaerythritol penta (meth) acrylate (HLB _A : 9.35), Acryloylmorpholin (HLB _A : 15.9) And a mixture of these, etc.] and polyoxypropylene glycol diglycidyl ether [HLB _B : 4 to 6, Mn _B : 200 to 5,000];
Monomer (a) with HLB _A of 3 to 20 [isobornyl acrylate (HLB _A : 3.10), dimethylol-tricyclodecane methacrylate (HLB _A : 3.88), 1,10-decanediol Diacrylate (HLB _A : 3.88), 1,9-nonanediol diacrylate (HLB _A : 4.13), Dimethylol-tricyclodecanedimethacrylate (HLB _A : 4.13), Phenoxyethyl acrylate (HLB _A) : 4.41), Dipentaerythritol hexa (meth) acrylate (HLB _A : 7.54), Dipentaerythritol penta (meth) acrylate (HLB _A : 9.35), Acryloylmorpholine (HLB _A : 15.9) And a mixture thereof, etc.] and a polycondensate of 3-methyl-1,5-pentanediol and adipic acid [HLB _B : 4 to 9, Mn _B : 500 to 3,000].

The weight ratio [(A): (B)] of the radically polymerizable monomer component (A) to the non-radical polymerizable component (B) is 45: 55 to 90:10 from the viewpoint of promoting phase separation during curing. It is preferably 50:50 to 85:15.

The active energy ray-curable resin composition of the present invention contains a radically polymerizable monomer component (A), a non-radical polymerizable component (B), and a radical type photopolymerization initiator (C). Further, a polymerization inhibitor, a surfactant, an antioxidant, a chain transfer agent and the like may be contained.

The active energy ray-curable resin composition of the present invention usually contains 20 to 20 to a radically polymerizable monomer component (A), a non-radical polymerizable component (B), and a radical type photopolymerization initiator (C). It can be obtained by uniform mixing in a temperature range of 80 ° C. by using a known mechanical mixing method (for example, a method using a mechanical stirrer or a magnetic stirrer).

The active energy ray-curable resin composition of the present invention can obtain a cured product by irradiating it with active energy rays.
As the active energy ray, it is preferable to use a light beam having a wavelength of 250 nm to 830 nm.
When the resin composition of the present invention is cured by active energy rays, various active energy ray irradiation devices [for example, an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.] can be used. Examples of the lamp used include a high-pressure mercury lamp and a metal halide lamp. The irradiation amount of the active energy ray (mJ / cm ² ) is preferably 10 to 10,000, more preferably 100 to 5,000, from the viewpoint of curability of the composition and flexibility of the cured product.

Since the cured product of the active energy ray-curable resin composition of the present invention has high light shielding properties, it can be preferably used as an opaque resin such as a reflective material for LEDs.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates a weight% and a part indicates a weight part.
The GPC in the examples was measured under the following conditions.
Equipment: "Waters Alliance 2695" [manufactured by Waters]
Column: "Guardcolum SuperH-L" (1), "TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (all manufactured by Tosoh Corporation) connected together"
Sample solution: 0.25 wt% tetrahydrofuran solution Solution injection volume: 10 μl
Flow rate: 0.6 ml / min Measurement temperature: 40 ° C
Detector: Refractive index detector Reference substance: Standard polyethylene glycol

Production Example 1 [Synthesis of ethylenically unsaturated monomer (A-11) having a urethane group]
Polypropylene glycol [trade name "PPG-400", manufactured by Sanyo Chemical Industries, Ltd., number average molecular weight = 400] 400 parts, dicyclohexylmethane-4,4'-diisocyanate 524 parts and urethanization catalyst [bismastri (2) -Ethylhexanoate) (2-ethylhexanoic acid 50 wt% solution) The same shall apply hereinafter. ] 0.5 part is charged and reacted at 80 ° C. for 4 hours, then 232 parts of 2-hydroxyethyl acrylate is added and reacted at 80 ° C. for 8 hours to form an ethylenically unsaturated monomer having a urethane group (A-11). ) Was obtained. The number average molecular weight of the obtained ethylenically unsaturated monomer (A-11) having a urethane group was 1,156.

Production Example 2 [Synthesis of ethylenically unsaturated monomer (A-12) having a urethane group]
Polytetramethylene glycol [trade name "PTMG-1000", manufactured by Sanyo Kasei Kogyo Co., Ltd., number average molecular weight: 1000] 1000 parts, dicyclohexylmethane-4,4'-diisocyanate 524 parts and urethanization catalyst 0. 5 parts were charged and reacted at 80 ° C. for 4 hours, then 232 parts of 2-hydroxyethyl acrylate was added and reacted at 80 ° C. for 8 hours to obtain an ethylenically unsaturated monomer (A-12) having a urethane group. It was. The number average molecular weight of the obtained ethylenically unsaturated monomer (A-12) having a urethane group was 1,756.

Production Example 3 [Synthesis of ethylenically unsaturated monomer (A-13) having a urethane group]
A caprolactone adduct of 2-hydroxyethyl acrylate [trade name "Placel FA4DT", manufactured by Daicel Chemical Industry Co., Ltd., number average molecular weight: 572] 1144 parts, isophorone diisocyanate 222 parts and urethanization catalyst 0.5 parts are placed in a reaction vessel. The mixture was charged and reacted at 80 ° C. for 8 hours to obtain an ethylenically unsaturated monomer (A-13) having a urethane group. The number average molecular weight of the obtained ethylenically unsaturated monomer (A-13) having a urethane group was 1,366.

Production Example 4 [Production of Pigment Dispersion Liquid (D-1)]
50 parts of titanium oxide [trade name: "Typake CR-60", manufactured by Ishihara Sangyo Co., Ltd.] as a pigment, 2.5 parts of an acidic dispersant [trade name: "BYK-111", manufactured by Big Chemie Co., Ltd.] as a pigment dispersant. , Isobornyl acrylate [trade name "light acrylate IBXA", manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups = 1] After mixing 47.5 parts, bead mill "Dynomill Multilab" [Symmal Enterprises (Symmal Enterprises) Co., Ltd.] was pulverized using zirconia beads having a particle size of 1 mm to obtain a pigment dispersion liquid (D-1).

Examples 1-20 and Comparative Examples 1-14
The resin compositions of Examples and Comparative Examples were obtained by uniformly mixing with the compounding compositions (parts by weight) shown in Tables 1 to 3.

The contents indicated by the symbols in Tables 1 to 3 are as follows.
(A-1): Acryloyl morpholine [trade name "ACMO", manufactured by KJ Chemicals Co., Ltd., number of functional groups = 1]
(A-2): Isobornyl acrylate [trade name "light acrylate IBXA", manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 1]
(A-3): Phenoxyethyl acrylate "trade name" light acrylate PO-A ", manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 1]
(A-4): Dimethylol-tricyclodecanediacrylate [trade name "light acrylate DCP-A", manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 2]
(A-5): Dimethylol-tricyclodecanedimethacrylate [trade name "light ester DCP-M", manufactured by Kyoeisha Chemical Co., Ltd., number of functional groups = 2]
(A-6): 1,9-nonanediol diacrylate [trade name "A-NOD-N", manufactured by Shin Nakamura Chemical Industry Co., Ltd., number of functional groups = 2]
(A-7): 1,10-decanediol diacrylate [trade name "A-DOD-N", manufactured by Shin Nakamura Chemical Industry Co., Ltd., number of functional groups = 2]
(A-8): "Neomer DA-600" (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate: manufactured by Sanyo Chemical Industries, Ltd., average number of functional groups = 5.4)
(A-9): Polybutadiene diacrylate [trade name "BAC-45", manufactured by Osaka Organic Chemical Industry Co., Ltd., number of functional groups = 2]
(A-10): Hexaacrylate with 12 mol of ε-caprolactone of dipentaerythritol [trade name "KAYARAD DPCA-120", manufactured by Nippon Kayaku Chemical Co., Ltd., number of functional groups = 6]

(B-1): Dipropylene glycol [manufactured by Nacalai Tesque, Inc., Mn _B = 134]
(B-2): 2-Ethylhexyl glycidyl ether [trade name "Denacol EX-121", manufactured by Nagase Kemutex Co., Ltd., Mn _B = 186]
(B-3): Polyoxypropylene glycol [trade name "Sannicks PP-200", manufactured by Sanyo Chemical Industries, Ltd., Mn _B = 200]
(B-4): Neopentyl glycol diglycidyl ether [trade name "Denacol EX-211", manufactured by Nagase Kemutex Co., Ltd., Mn _B = 216]
(B-5): Diethylene glycol diglycidyl ether [trade name "Denacol EX-851", manufactured by Nagase Chemmutex Co., Ltd., Mn _B = 218]
(B-6): Polyoxypropylene glycol diglycidyl ether [trade name "Glycyre PP-300P", manufactured by Sanyo Chemical Industries, Ltd., Mn _B = 513]
(B-7): Polyoxyethylene glycol diglycidyl ether [trade name "Denacol EX-832", manufactured by Nagase ChemteX Corporation, Mn _B = 527]
(B-8): Polyoxypropylene glycol diglycidyl ether [ Mn _B = 769 ]
(B-9): Polyoxypropylene glycol [trade name "Sannicks PP-1000", manufactured by Sanyo Chemical Industries, Ltd., Mn _B = 1000]
(B-10): Poly (3-methyl-1,5-pentanediol adipate) [Product name "Kuraray polyol P-1010", manufactured by Kuraray Co., Ltd., Mn _B = 1000]
(B-11): Polyoxyethylene polyoxypropylene glycol [trade name "Nieuport PE-71", manufactured by Sanyo Chemical Industries, Ltd., Mn _B = 2271]
(B-12): Polybutadiene [trade name "RICON130", manufactured by CRAY VALLEY, Mn _B = 2500]

(C-1): 1,3,5-trimethylbenzoyldiphenylphosphine oxide [trade name "IRGACURE TPO", manufactured by BASF Limited]
(C-2): 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one [trade name "IRGACURE 907", manufactured by BASF Limited]

Regarding the molecular weight of the monomer (a), (A-1) to (A-8) use the chemical formulas, and (A-9) to (A-13) are the number average molecular weights obtained by the above-mentioned GPC measurement. Was used.
Regarding Mn _B of the non-radical polymerizable compound (b), (B-1) to (B-10) used chemical formulas, and (B-11) to (B-12) were obtained by the above-mentioned GPC measurement. The number average molecular weight was used.

The total light transmittance and storage stability of the active energy ray-curable resin composition and the haze of the cured product of the active energy ray-curable resin composition were evaluated by the following methods. The results are shown in Tables 1-3.

<Haze>
(1) Preparation of test piece A resin composition was applied to a surface-treated 100 μm-thick polyethylene terephthalate (PET) film [Cosmoshine A4300 manufactured by Toyo Boseki Co., Ltd.] using a bar coater so as to have a thickness of 500 μm. After coating, the film was irradiated with ultraviolet rays at 1000 mJ / cm ² by an ultraviolet irradiation device [model number "VPS / I600", manufactured by Fusion UV Systems Co., Ltd.] to obtain a test piece of a PET film coated with a photocurable product. The haze was measured with the obtained test piece still attached with the PET film.

(2) Measurement of haze Using the test piece obtained in (1), in accordance with JIS-K7136, using a total light transmittance measuring device [trade name "haze-garddual" manufactured by BYK gardener Co., Ltd.] , Haze (unit:%) was measured.
The larger the haze value, the higher the light shielding property, and it can be generally said that it is opaque when the haze value exceeds 90%.

<Total light transmittance>
A quartz cell (thickness: 10 mm, depth: 50 mm, manufactured by BYK gardener Co., Ltd.) filled with each active energy ray-curable resin composition is used as a sample, and is based on JIS-K7136, and is a total light transmittance measuring device. The total light transmittance (unit:%) was measured using [trade name "haze-garddual", manufactured by BYK gardener Co., Ltd.].

<Storage stability>
50 g of each active energy ray-curable resin composition was placed in a glass bottle with a lid and stored at 25 ° C. for 1 month. The state after storage after 1 month was visually observed and evaluated based on the following criteria.
Judgment was made according to the following criteria.
◯: The resin composition remains uniform.
X: Phase separation or sedimentation occurs in the resin composition, and the resin composition is non-uniform.

From the results in Tables 1 to 3, it can be seen that the composition of the present invention is excellent in storage stability before curing and excellent in light shielding property after curing as compared with the comparative one.
On the other hand, Comparative Examples 1 to 4 and Comparative Examples 6 to 10 which do not satisfy the relational expression (5) and do not satisfy any of the relational expressions (2) to (4) are the curing of the active energy ray-curable resin composition. The haze value of the object is low.
Further, in Comparative Example 5 which does not satisfy the relational expression (1), the haze value of the cured product of the active energy ray-curable resin composition is also low.
Further, Comparative Examples 11 to 13 in which the total light transmittance of the active energy ray-curable resin composition is less than 90% have low storage stability.
In addition, Comparative Example 14 containing titanium oxide also has poor storage stability.

Since the active energy ray-curable resin composition of the present invention has high light shielding properties after curing, it can be suitably used as an opaque resin.
Further, since it is a uniform liquid resin composition having excellent storage stability before curing, it is suitable as a photosensitive resin composition for applications such as a reflective material for LEDs, which requires stable physical properties during production.

Claims (5)

An active energy ray-curable resin composition containing a radically polymerizable monomer component (A), a non-radical polymerizable component (B), and a radical-type photopolymerization initiator (C).
The radically polymerizable monomer component (A) comprises at least one monomer (a) having a (meth) acryloyl group.
The non-radical polymerizable component (B) comprises at least one non-radical polymerizable compound (b) selected from the group consisting of polybutadiene (b1), polyether (b2) and polyester (b3).
The radically polymerizable monomer component (A) and the non-radical polymerizable component (B) satisfy the following condition (i) or condition (ii).
A total light transmittance of Ri der 90%
The active energy ray in which the ratio [(A): (B)] of the total weight of the radically polymerizable monomer component (A) to the total weight of the non-radical polymerizable component (B) is 45:55 to 90:10. Curable resin composition.
(I) Satisfy all of the following relational expressions (1) to (4).
(Ii) Both the following relational expressions (1) and (5) are satisfied.
Relational expression (1): Mn _B ≤ 95.0 x ΔHLB ₁ + 2200
Relational expression (2): Mn _B ≧ -70.0 × ΔHLB ₁ +600
Relational expression (3): Mn _B ≧ -14800 × ΔHLB ₂ +17000
Relational expression (4): Mn _B ≧ −52.3 × ΔHLB ₂ +500
Relational expression (5): Mn _B ≧ −350 × ΔHLB ₁ +3800
[In the relational expressions (1) to (5), Mn _B represents the chemical formula amount or the number average molecular weight of the non-radical polymerizable component (B), and the non-radical polymerizable component (B) has two or more non-radical polymerizable components (B). When it is composed of the radically polymerizable compound (b), it is a value obtained by weighting and averaging the number average molecular weight of the non-radical polymerizable compound (b) based on its molar ratio.
In the relational expressions (1), (2) and (5), ΔHLB ₁ is the HLB value (HLB _A ) of the polymer obtained by polymerizing the monomer component ( _A ) and the non-radical polymerizable component (HLB _A ). HLB _B represents the absolute value of the difference from the HLB value (HLB _B ) of _B ), and when the non-radical polymerizable component (B) is composed of two or more non-radical polymerizable compounds (b), HLB _B is non-radical polymerization. It is a value obtained by weighting and averaging the HLB value of the sex compound (b) based on its weight ratio.
In the relational expressions (3) and (4), ΔHLB ₂ has the monomer component (A) of one kind of monomer (a) and the non-radical polymerizable component (B) of one kind. When composed of the non-radical polymerizable compound (b), it is the absolute value of the difference between the HLB value of the homopolymer obtained by polymerizing the monomer (a) and the HLB value of the non-radical polymerizable compound (b). , The monomer component (A) is composed of two or more kinds of monomers (a) and / or the non-radical polymerizable component (B) is made of two or more kinds of non-radical polymerizable compound (b) If, using the monomer (a) the homopolymerized HLB value of the polymer obtained when the a (HLB _a), HLB value of each non-radical polymerizable compound (b) and (HLB _b), HLB is the minimum value among the absolute value of the difference between HLB _a and HLB _b obtained by calculation for all the combinations of _a and HLB _b. ] The active energy ray-curable resin composition according to claim 1 , wherein ΔHLB ₁ is 1.0 or more. The active energy ray-curable resin composition according to claim 2 , wherein ΔHLB ₂ is 1.0 or more. The active energy ray-curable resin composition according to any one of claims 1 to 3 , wherein the haze of the cured product of the active energy ray-curable resin composition is 90% or more. A cured product of the active energy ray-curable resin composition according to any one of claims 1 to 4 .