JP2024008082A - Urethane (meth)acrylate resin, active energy ray-curable composition, cured product and laminated film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a urethane (meth)acrylate resin capable of forming a cured coating film having high hardness and excellent scratch resistance, flexibility and curl resistance and to provide an active energy ray-curable composition, a cured product and a laminated film containing the same.

SOLUTION: There is provided a urethane (meth)acrylate resin comprising an isocyanate compound (A1) containing no bond derived from an isocyanate group in the molecule, an isocyanate compound (A2) containing a bond derived from an isocyanate group in the molecule and dipentaerythritol (meth)acrylate (B) as essential reaction raw materials, wherein the hydroxyl group value of the dipentaerythritol (meth)acrylate (B) is more than 120 mgKOH/g and 150 mgKOH/g or less.

SELECTED DRAWING: None

COPYRIGHT: (C)2024,JPO&INPIT

Description

The present invention relates to a urethane (meth)acrylate resin that has excellent scratch resistance, flexibility, curl resistance, and impact resistance in a cured coating film, an active energy ray-curable composition containing the same, a cured product, and a laminated film. .

Plastic films manufactured using polyethylene terephthalate resin (PET), acrylic resin, polycarbonate resin, acetylated cellulose resin, etc. are used for industrial purposes such as polarizing plate protection films incorporated inside flat panel displays and touch panel surface protection films. It is widely used in When used alone, these plastic films lack performance, such as the surface being easily damaged, poor workability, and being prone to cracking and cracking. It is used to supplement these performances.

As a coating agent for reinforcing plastic films, for example, a resin composition containing urethane acrylate obtained by reacting dipentaerythritol polyacrylate with a hydroxyl value in the range of 80 to 120 mgKOH/g and hexamethylene diisocyanate is known. (For example, see Patent Document 1.) Although the resin composition has a high surface hardness in the cured product and is excellent in scratch resistance, it tends to curl easily, and the coating film does not have sufficient toughness or flexibility, so it is prone to cracking due to external impact. there were.

Therefore, there has been a need for a material that has excellent scratch resistance and can form a cured coating film that is also excellent in curl resistance, flexibility, and impact resistance.

International Publication No. 2010/146801

The problem to be solved by the present invention is to provide a urethane (meth)acrylate resin that can form a cured coating film with high hardness and excellent scratch resistance, flexibility, and curl resistance, and an active energy ray-curable resin containing the same. The object of the present invention is to provide a composition, a cured product, and a laminated film.

As a result of intensive studies to solve the above problems, the present inventors have discovered a urethane (meth)acrylate containing at least two isocyanate compounds and dipentaerythritol (meth)acrylate having a specific hydroxyl value as essential reaction raw materials. The inventors have discovered that the above problems can be solved by using a resin, and have completed the present invention.

That is, the present invention relates to the following.
[1] An isocyanate compound (A1) that does not contain a bond derived from an isocyanate group in its molecule, an isocyanate compound (A2) that contains a bond derived from an isocyanate group in its molecule, and dipentaerythritol (meth)acrylate (B). A urethane (meth)acrylate resin used as an essential reaction raw material, characterized in that the dipentaerythritol (meth)acrylate (B) has a hydroxyl value in a range of more than 120 mgKOH/g and less than 150 mgKOH/g. (meth)acrylate resin.
[2] The urethane according to [1], wherein the isocyanate compound (A1) has an NCO content of 20 to 55%, and the isocyanate compound (A2) has an NCO content of 10 to 25%. (meth)acrylate resin.
[3] The equivalent ratio of the isocyanate compound (A2) to the isocyanate compound (A1) in the reaction raw material [(A1)/(A2)] is in the range of 70/30 to 95/5 [1] or [2] The urethane (meth)acrylate resin described in ].
[4] The urethane (meth)acrylate resin according to any one of [1] to [3], further comprising a hydroxyl group-containing acrylic ester (C) other than the dipentaerythritol (meth)acrylate (B) as a reaction raw material.
[5] The urethane (meth)acrylate resin according to any one of [1] to [4], wherein the dipentaerythritol (meth)acrylate (B) contains dipentaerythritol hexa(meth)acrylate.
[6] Any one of [1] to [5], wherein the content of the dipentaerythritol hexa(meth)acrylate is in the range of 10 to 50% by mass in the dipentaerythritol (meth)acrylate (B). The urethane (meth)acrylate resin described.
[7] An active energy ray-curable composition containing the urethane (meth)acrylate resin according to any one of [1] to [6] and a photopolymerization initiator.
[8] A cured product of the active energy ray-curable composition according to [7].
[9] A laminated film having a cured coating film made of the cured product according to [8] on one or both sides of a base material.
[10] The laminated film according to [9], wherein the base material has a thickness of 50 to 80 μm, and the cured coating film has a thickness of 5 to 20 μm.

The urethane (meth)acrylate resin of the present invention can form a cured coating film with high hardness and excellent scratch resistance, curl resistance, and flexibility, so it can be suitably used as a protective coating agent for the surfaces of various substrates. Can be done. In addition, the laminated film having the cured coating film has high hardness and excellent scratch resistance and curl resistance, and is also highly flexible and hardly cracks when folded or rolled up.

In the present specification, "(meth)acrylate" is a generic term for methacrylate and acrylate, and "(meth)acryloyl group" similarly refers to a generic term for methacryloyl group and acrylic group.
Further, in this specification, the active energy ray-curable composition is also simply referred to as a composition.
Furthermore, "NCO content" in this specification refers to the amount of isocyanate groups present in the isocyanate compound expressed as a mass fraction.
In the present invention, the isocyanate group may be referred to as "NCO".

[Urethane (meth)acrylate resin]
The urethane (meth)acrylate resin of the present invention comprises an isocyanate compound (A1) that does not contain a bond derived from an isocyanate group in its molecule, an isocyanate compound (A2) that contains a bond derived from an isocyanate group in its molecule, and dipentaerythritol ( meth)acrylate (B) as an essential reaction raw material.

[Isocyanate compound (A1)]
The isocyanate compound (A1) is a compound that does not contain a bond derived from an isocyanate group in its molecule and contains one or more isocyanate groups in one molecule. In the present invention, bonds derived from isocyanate groups include amide bonds (-NHCO-), urethane bonds (-NHCOO-), urea bonds (-NHCONH-), and biuret bonds that are formed by the reaction of isocyanate groups with various nucleophiles. , allophanate bond, isocyanurate bond, uretdione bond, etc.

The NCO content of the isocyanate compound (A1) is preferably in the range of 10 to 70%, more preferably in the range of 15 to 60%, particularly preferably in the range of 20 to 55%. Within these ranges, a urethane (meth)acrylate resin that can form a cured coating film with high hardness and excellent scratch resistance, curl resistance, and flexibility can be obtained.

Examples of the isocyanate compound (A1) include aliphatic isocyanate compounds and isocyanate compounds having an aromatic ring or alicyclic structure in the molecule.

Examples of the aliphatic isocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate. Can be mentioned. These aliphatic isocyanate compounds can be used alone or in combination of two or more.

Examples of the isocyanate compound having an aromatic ring or alicyclic structure in the molecule include alicyclic diisocyanate compounds such as isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane; diphenylmethane diisocyanate, 1,5 - aromatic diisocyanate compounds such as naphthalene diisocyanate;

Examples include polymethylene polyphenyl polyisocyanate having a repeating structure represented by the following structural formula (1). These isocyanate compounds having an aromatic ring or alicyclic structure in the molecule can be used alone or in combination of two or more.

（式中、Ｒ_１はそれぞれ独立に水素原子、炭素原子数１～６の炭化水素基の何れかである。Ｒ_２はそれぞれ独立に炭素原子数１～４のアルキル基、又は構造式（１）で表される構造部位と＊印が付されたメチレン基を介して連結する結合点の何れかである。ｍは０又は１～３の整数であり、ｌは１以上の整数である。）

(In the formula, R ₁ is each independently a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. R ₂ is each independently an alkyl group having 1 to 4 carbon atoms, or the structural formula (1 ) is any bonding point connected via a methylene group marked with *. m is 0 or an integer of 1 to 3, and l is an integer of 1 or more. )

[Isocyanate compound (A2)]
The isocyanate compound (A2) is a compound containing a bond derived from an isocyanate group in the molecule and containing one or more isocyanate groups in one molecule.

The NCO content of the isocyanate compound (A2) is preferably in the range of 10 to 25%, more preferably in the range of 12 to 20%, particularly preferably in the range of 15 to 18%. Within these ranges, a urethane (meth)acrylate resin that can form a cured coating film with high hardness and excellent scratch resistance, curl resistance, and flexibility can be obtained.

As the isocyanate compound (A2), for example, isocyanurate modified products, biuret modified products, allophanate modified products, etc., which are modified products of various isocyanate compounds, can be used.
Various isocyanate compounds include aliphatic diisocyanate compounds such as butane diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, hydrogenated Examples include alicyclic diisocyanate compounds such as diphenylmethane diisocyanate and 1,3-bis(isocyanatomethyl)cyclohexane; and aromatic diisocyanate compounds such as diphenylmethane diisocyanate and 1,5-naphthalene diisocyanate. These isocyanate compounds (A2) can be used alone or in combination of two or more.

Moreover, the isocyanate compound (A2) may be a compound obtained by reacting various isocyanate compounds and polyols. In that case, the method for synthesizing the isocyanate compound (A2) is not particularly limited, and various known methods can be used. For example, polyol (i) and isocyanate compound (ii) are reacted under conditions with an excess of isocyanate groups. One example is how to
Examples of the polyol (i) include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentane glycol, neopentyl glycol, polytetramethylene glycol, and hexane. In addition to triol, trimyrollpropane, ethylene oxide or propylene oxide adducts of bisphenol A, hydrogenated bisphenol A, glycerin, pentaerythritol, etc., condensation products of the above polyols and polybasic acids and polybasic acid anhydrides can be mentioned. . One type or two or more types of these may be used.
Examples of polybasic acids and polybasic acid anhydrides include aromatic polybasic acids such as phthalic acid and phthalic anhydride, and aliphatic polybasic acids such as adipic acid and sebacic acid.
As the isocyanate compound (ii), the compounds listed above as the isocyanate compound (A1) can be used. In addition, one kind or two or more kinds of isocyanate compounds (ii) may be used.

[Equivalent ratio of isocyanate compound (A2) to isocyanate compound (A1)]
The equivalent ratio of the isocyanate compound (A2) to the isocyanate compound (A1) in the reaction raw material [(A1)/(A2)] is preferably in the range of 40/60 to 99/1, preferably 50/50 to 97/1. It is more preferably in the range of 3, and particularly preferably in the range of 70/30 to 95/5. Within these ranges, a urethane (meth)acrylate resin that can form a cured coating film with high hardness and excellent scratch resistance, curl resistance, and flexibility can be obtained.

Note that the "equivalent ratio" in this specification refers to the amount of isocyanate derived from the isocyanate compound (A2) relative to the amount of isocyanate groups derived from the isocyanate compound (A1) used as a raw material for the urethane (meth)acrylate resin of the present invention. It is the ratio of the amount of substance in the group.
To calculate the amount of isocyanate groups derived from the isocyanate compound (A1), multiply the mass of the isocyanate compound (A1) used by its NCO content, and calculate the mass of NCO derived from the isocyanate compound (A1) used. It is obtained by calculating the mass of NCO and dividing it by 42 (molecular weight of NCO). The same applies to the isocyanate compound (A2).
More specifically, for example, when 10 g of isocyanate compound (A1) with an NCO content of 42% is used as a raw material for urethane (meth)acrylate resin, the mass of NCO derived from isocyanate compound (A1) is 4.2 g ( 0.1 mol). Therefore, the amount of the isocyanate group derived from the isocyanate compound (A1) is 0.1 mol.

[Dipentaerythritol (meth)acrylate (B)]
The dipentaerythritol (meth)acrylate (B) is obtained by converting a part of the hydroxyl groups of dipentaerythritol into (meth)acrylate, and has a hydroxyl group that can react with the isocyanate compound (A1) and the isocyanate compound (A2). It may be a single compound or a mixture of a plurality of compounds. That is, in the former case, the dipentaerythritol (meth)acrylate (B) may be dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, or dipentaerythritol tri(meth)acrylate. Erythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate can each be used alone. In the latter case, dipentaerythritol mono(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol penta( It can contain one or more meth)acrylates and be used as a mixture, and can also contain dipentaerythritol hexa(meth)acrylate, if necessary.

The dipentaerythritol (meth)acrylate (B) is a dipentaerythritol (meth)acrylate resin that can form a cured coating film with high hardness and excellent scratch resistance, flexibility, and curl resistance. It is preferable to contain pentaerythritol hexa(meth)acrylate as essential, and in addition to dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol tetra(meth)acrylate, and dipentaerythritol tri (Meth)acrylate may be contained in any ratio.

When the dipentaerythritol (meth)acrylate (B) contains the dipentaerythritol hexa(meth)acrylate, the dipentaerythritol hexa(meth)acrylate in the dipentaerythritol (meth)acrylate (B) The content is preferably in the range of 10 to 50% by mass, since it is possible to obtain a urethane (meth)acrylate resin that can form a cured coating film with excellent scratch resistance, flexibility, curl resistance, and impact resistance. , a range of 15 to 45% by mass is more preferred, and a range of 20 to 40% by mass is particularly preferred.

In the present invention, the content of each component in the dipentaerythritol (meth)acrylate (B) and the ratio of the content of each component are calculated from the area ratio of a liquid chromatography chart measured under the following conditions. is the value.
[Measurement condition]
Equipment: “LCMS-2010EV” manufactured by Shimadzu Corporation
Data processing: “LCMS Solution” manufactured by Shimadzu Corporation
Column: Tosoh Corporation "ODS-100V" (2.0mm ID x 150mm, 3μm) 40°C
Eluent: water/acetonitrile, 0.4 mL/min Detector: PDA, MS
Sample preparation: 1. Dissolve 50mg of material in 10ml of acetonitrile (for LC)
2. Vortex for 30 seconds
3.Stand for 30 minutes
4. Calculation of the area ratio of the measurement sample passed through a 0.2 μm filtration filter: Calculated at a UV wavelength of 210 nm

In addition, the hydroxyl value of the dipentaerythritol (meth)acrylate (B) is a urethane (meth)acrylate resin that can form a cured coating film with excellent scratch resistance, flexibility, curl resistance, and impact resistance. Therefore, it is more than 120 mgKOH/g and less than 150 mgKOH/g, preferably in the range of 122 to 145 mgKOH/g, and more preferably in the range of 122 to 140 mgKOH/g.

In addition, the hydroxyl value of the dipentaerythritol (meth)acrylate (B) is an actual value measured according to JIS K 0070 (1992) neutralization titration method, or each component calculated from the area ratio of a liquid chromatography chart. This is a calculated value calculated from the composition ratio.

Examples of the method for producing the dipentaerythritol (meth)acrylate (B) include a method in which dipentaerythritol and acrylic acid are subjected to an esterification reaction. When produced by this method, a high molecular weight component (b') such as an addition reaction product between dipentaerythritol (meth)acrylate (B) may be produced as a by-product. b') may be purified and removed, or the dipentaerythritol (meth)acrylate (B) crude product containing the high molecular weight component (b') may be used as a raw material for the urethane (meth)acrylate resin. good. At this time, the content of the high molecular weight component (b') in the dipentaerythritol (meth)acrylate (B) crude product is preferably in the range of 1 to 20% by mass.

The urethane (meth)acrylate resin uses the isocyanate compound (A1), the isocyanate compound (A2), and the dipentaerythritol (meth)acrylate (B) as essential reaction raw materials, and further, if necessary, , other hydroxyl group-containing (meth)acrylic esters (C) can also be used.

[Hydroxyl group-containing (meth)acrylic ester (C)]
The hydroxyl group-containing (meth)acrylic acid ester (C) contains one or more hydroxyl groups and (meth)acryloyl groups in one molecule, and has a structure different from the dipentaerythritol (meth)acrylate (B). It is a compound.

Examples of the hydroxyl group-containing (meth)acrylic ester (C) include hydroxy (meth)acrylate compounds.
The hydroxy(meth)acrylate compounds include 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropane di(meth)acrylate, and trimethylolpropane di(meth)acrylate. ) Acrylate, aliphatic (meth)acrylate compounds such as pentaerythritol tri(meth)acrylate; 4-hydroxyphenyl acrylate, β-hydroxyphenethyl acrylate, 4-hydroxyphenethyl acrylate, 1-phenyl-2-hydroxy acrylate Aromatic ring-containing (meth)acrylate compounds such as ethyl, 3-hydroxy-4-acetylphenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate; the above (meth)acrylate compounds, ethylene oxide, propylene oxide, tetrahydrofuran, ethylglycidyl A polyether-modified (meth)acrylate compound obtained by ring-opening polymerization with various cyclic ether compounds such as ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether; Lactone-modified (meth)acrylate compounds obtained by polycondensation with lactone compounds such as caprolactone; ethylene glycol, diethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3 -Methyl-1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, glycerin, glycerin mono(meth)acrylate, trimethylolethane, trimethylolmethane mono(meth)acrylate, Examples include compounds obtained by reacting various polyol compounds such as trimethylolpropane, trimethylolpropane mono(meth)acrylate, pentaerythritol mono(meth)acrylate, and pentaerythritol di(meth)acrylate with (meth)acrylic acid. . These hydroxy (meth)acrylate compounds can be used alone or in combination of two or more. Among these, aliphatic (meth)acrylate compounds or their polyesters are preferred because they can produce urethane (meth)acrylate resins that are highly hard and can form cured coatings with excellent scratch resistance, flexibility, and curl resistance. Ether modified products and lactone modified products are preferred. Furthermore, when these hydroxy(meth)acrylate compounds are used as the hydroxyl group-containing compound (C), the effects of the present invention are sufficiently exhibited. ) The ratio of the dipentaerythritol (meth)acrylate (B) to the total mass of the acrylate compound is preferably 70% by mass or more, more preferably 80% by mass or more.

[Production method of urethane (meth)acrylate resin]
The method for producing the urethane (meth)acrylate resin includes, for example, adding the isocyanate compound (A1) and the isocyanate compound (A2) and the dipentaerythritol (meth)acrylate (B) to the isocyanate (A1) and the isocyanate compound (A2). The molar ratio [(NCO)/(OH)] between the isocyanate group possessed by the isocyanate compound (A2) and the hydroxyl group possessed by the dipentaerythritol (meth)acrylate (B) is 1/1.05 to 1/2. Examples include a method in which the urethanization catalyst is used at a temperature within a range of 20 to 120° C., if necessary, in a proportion within a certain range.

The (meth)acryloyl group equivalent of the urethane (meth)acrylate resin is preferably in the range of 100 to 500 g/eq, since it is possible to form a cured coating film with high hardness, scratch resistance, flexibility, and curl resistance. , a range of 100 to 250 g/eq is more preferable. Note that the (meth)acryloyl group equivalent of the urethane (meth)acrylate resin in the present invention is a value calculated as a theoretical value from the reaction raw materials.

In addition, the weight average molecular weight (Mw) of the urethane (meth)acrylate resin is 1,500 to 100,000 because it can form a cured coating film with high hardness, scratch resistance, flexibility, and curl resistance. The range is preferably from 3,000 to 5,0000, and more preferably from 3,000 to 5,0000.

The weight average molecular weight (Mw) of the urethane (meth)acrylate resin is a value measured by gel permeation chromatography (GPC).

[Active energy ray curable composition]
The active energy ray-curable composition of the present invention contains the urethane (meth)acrylate resin and a photopolymerization initiator.

Examples of the photopolymerization initiator include benzophenone, 3,3'-dimethyl-4-methoxybenzophenone, 4,4'-bisdimethylaminobenzophenone, 4,4'-bisdiethylaminobenzophenone, and 4,4'-dichlorobenzophenone. , Michler's ketone, various benzophenones such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;

Xanthone, thioxanthone such as xanthone, thioxanthone, 2-methylthioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone; various acyloin ethers such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether;

α-diketones such as benzyl and diacetyl; sulfides such as tetramethylthiuram disulfide and p-tolyl disulfide; various benzoic acids such as 4-dimethylaminobenzoic acid and ethyl 4-dimethylaminobenzoate;

3,3'-carbonyl-bis(7-diethylamino)coumarin, 1-hydroxycyclohexylphenylketone, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, 2-hydroxy-2-methyl-1- Phenylpropan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 1-[4-(2-hydroxyethoxy)phenyl]-2- Hydroxy-2-methyl-1-propan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2 -Methylpropan-1-one, 4-benzoyl-4'-methyldimethylsulfide, 2,2'-diethoxyacetophenone, benzyldimethylketal, benzyl-β-methoxyethyl acetal, methyl o-benzoylbenzoate, bis (4-dimethylaminophenyl)ketone, p-dimethylaminoacetophenone, α,α-dichloro-4-phenoxyacetophenone, pentyl-4-dimethylaminobenzoate, 2-(o-chlorophenyl)-4,5-diphenylimidazolyl amount 2,4-bis-trichloromethyl-6-[di-(ethoxycarbonylmethyl)amino]phenyl-S-triazine, 2,4-bis-trichloromethyl-6-(4-ethoxy)phenyl-S-triazine , 2,4-bis-trichloromethyl-6-(3-bromo-4-ethoxy)phenyl-S-triazineanthraquinone, 2-t-butylanthraquinone, 2-amylanthraquinone, β-chloroanthraquinone, and the like. These photopolymerization initiators can be used alone or in combination of two or more.

Furthermore, among the photopolymerization initiators, 1-hydroxycyclohexyl phenyl ketone, which exhibits activity against light in a wider range of wavelengths and can improve the curability of the cured coating film of the active energy ray-curable composition, 2-Hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, thioxanthone and thioxanthone Derivative, 2,2'-dimethoxy-1,2-diphenylethan-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; Alternatively, it is preferable to use a mixed system of two or more types.

Commercially available photopolymerization initiators include, for example, "Omnirad-1173", "Omnirad-184", "Omnirad-127", "Omnirad-2959", "Omnirad-369", "Omnirad-379", " Omnirad-907”, “Omnirad-4265”, “Omnirad-1000”, “Omnirad-651”, “Omnirad-TPO”, “Omnirad-819”, “Omnirad-2022”, “Omnirad-2100”, “Omnirad - 754'', ``Omnirad-784'', ``Omnirad-500'', ``Omnirad-81'' (manufactured by IGM), ``Kayacure-DETX'', ``Kayacure-MBP'', ``Kayacure-DMBI'', ``Kayacure-EPA'', “Kayacure-OA” (manufactured by Nippon Kayaku Co., Ltd.), “Bicure-10”, “Bicure-55” (manufactured by Stouffer Chemical Co., Ltd.), “Trigonal P1” (manufactured by Akzo Co., Ltd.), “Sandray 1000” (manufactured by Sandoz Co., Ltd.) ), "Deep" (manufactured by Upjohn), "Quantacure-PDO", "Quantacure-ITX", "Quantacure-EPD" (manufactured by Ward Blenkinsop), "Runtecure-1104" (manufactured by Runtec) ) etc.

The amount of the photopolymerization initiator added is preferably an amount that can sufficiently exhibit its function as a photopolymerization initiator and does not cause precipitation of crystals or deterioration of the physical properties of the coating film. Specifically, The amount is preferably from 0.05 to 20 parts by weight, more preferably from 0.1 to 10 parts by weight, based on 100 parts by weight of the urethane (meth)acrylate resin.

Moreover, the active energy ray-curable composition can further contain a photosensitizer, since this can improve the curability of the cured coating film of the active energy ray-curable composition.

Examples of the photosensitizer include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, sulfur compounds such as sodium diethyldithiophosphate, and s-benzylisothiuronium-p-toluenesulfonate. Examples include compounds.

In addition to the urethane (meth)acrylate resin, the active energy ray-curable composition of the present invention further contains other photocurable compounds (R), organic solvents, ultraviolet absorbers, antioxidants, and silicone additives. , fluorine-based additives, silane coupling agents, phosphate ester compounds, organic beads, inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, antifogging agents, coloring agents, and the like.

Examples of the other photocurable compounds (R) include various (meth)acrylate monomers, urethane (meth)acrylate resins other than the urethane (meth)acrylate resins, and epoxy (meth)acrylate resins. , dendrimer type (meth)acrylate resin, (meth)acryloyl group-containing acrylic resin, and the like.

The (meth)acrylate monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. ) acrylate, t-butyl (meth)acrylate, glycidyl (meth)acrylate, acryloylmorpholine, N-vinylpyrrolidone, tetrahydrofurfuryl acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isobornyl (meth)acrylate Acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxy Butyl (meth)acrylate, ethyl carbitol (meth)acrylate, phosphoric acid (meth)acrylate, ethylene oxide modified phosphoric acid (meth)acrylate, phenoxy (meth)acrylate, ethylene oxide modified phenoxy (meth)acrylate, propylene oxide modified phenoxy (meth)acrylate, nonylphenol (meth)acrylate, ethylene oxide-modified nonylphenol (meth)acrylate, propylene oxide-modified nonylphenol (meth)acrylate, methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxypropylene glycol (meth)acrylate Acrylate, 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen Phthalate, 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate, dimethylaminoethyl (meth)acrylate, trifluoroethyl (meth)acrylate, tetrafluoropropyl (meth)acrylate , mono(meth)acrylates such as hexafluoropropyl(meth)acrylate, octafluoropropyl(meth)acrylate, octafluoropropyl(meth)acrylate, adamantyl mono(meth)acrylate;

Butanediol di(meth)acrylate, hexanediol di(meth)acrylate, ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate , polypropylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethoxylated neopentyl glycol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, trimethylol Di(meth)acrylates such as propane di(meth)acrylate, pentaerythritol di(meth)acrylate;

Trimethylolpropane tri(meth)acrylate, ethoxylated trimethylolpropane tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, glycerin tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate (meth)acrylate, tri(meth)acrylate such as dipentaerythritol tri(meth)acrylate;

Pentaerythritol Tetra(meth)acrylate, Ditrimethylolpropane Tetra(meth)acrylate, Dipentaerythritol Tetra(meth)acrylate, Dipentaerythritol Penta(meth)acrylate, Ditrimethylolpropane Penta(meth)acrylate, Dipentaerythritol Hexa(meth)acrylate ) acrylate, ditrimethylolpropane hexa(meth)acrylate, and other tetrafunctional or higher functional (meth)acrylates; some or all of the above-mentioned various multifunctional (meth)acrylates have been modified with polyoxyalkylene chains or polyester chains (meth)acrylates; ) acrylate, etc.

Examples of the other urethane (meth)acrylate resins include urethane (meth)acrylate resins using isocyanate compounds other than the isocyanate compound (A1) and isocyanate compound (A2), and dipentaerythritol (meth)acrylate (B). Examples include urethane (meth)acrylate resins using hydroxy (meth)acrylate compounds other than those mentioned above.

Examples of the epoxy (meth)acrylate resin include those obtained by reacting various epoxy resins such as bisphenol-type epoxy resins and novolak-type epoxy resins with (meth)acrylic acid or its derivatives to form (meth)acrylates. .

The dendrimer type (meth)acrylate resin refers to a resin that has a regular multi-branched structure and has a (meth)acryloyl group at the end of each branched chain, and includes dendrimer type, hyperbranched type or It is also called star polymer. Examples of such compounds include, but are not limited to, those represented by the following structural formulas (2-1) to (2-8). Any resin can be used as long as it has a (meth)acryloyl group at the end of each branched chain.

（式中Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素原子数１～４の炭化水素基である。）

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms.)

（式中Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素原子数１～４の炭化水素基である。）

(In the formula, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 4 carbon atoms.)

Examples of such dendrimer-type (meth)acrylate resin include "Viscoat #1000" manufactured by Osaka Organic Chemical Co., Ltd. [weight average molecular weight (Mw) 1,500 to 2,000, average (meth)acryloyl per molecule] Base number 14], “Viscoat 1020” [weight average molecular weight (Mw) 1,000 to 3,000], “SIRIUS501” [weight average molecular weight (Mw) 15,000 to 23,000], “SP-1106” manufactured by MIWON " [Weight average molecular weight (Mw) 1,630, average number of (meth)acryloyl groups per molecule 18], manufactured by SARTOMER "CN2301", "CN2302" [average number of (meth)acryloyl groups per molecule 16], " CN2303” [average number of (meth)acryloyl groups per molecule: 6], “CN2304” [average number of (meth)acryloyl groups per molecule: 18], “Esdrimer HU-22” manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., Shin Nakamura Chemical Co., Ltd. Commercially available products such as "A-HBR-5" manufactured by the company, "New Frontier R-1150" manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and "Hypertech UR-101" manufactured by Nissan Chemical Co., Ltd. may be used.

The weight average molecular weight (Mw) of the dendrimer type (meth)acrylate resin is preferably in the range of 1,000 to 30,000. Further, the average number of (meth)acryloyl groups per molecule is preferably in the range of 5 to 30.

The (meth)acryloyl group-containing acrylic resin is obtained, for example, by polymerizing a (meth)acrylate monomer (α) having a reactive functional group such as a hydroxyl group, a carboxyl group, an isocyanate group, or a glycidyl group as an essential component. Examples include those obtained by introducing a (meth)acryloyl group by further reacting an acrylic resin intermediate with a (meth)acrylate monomer (β) having a reactive functional group capable of reacting with these functional groups.

Examples of the (meth)acrylate monomer (α) having a reactive functional group include hydroxyl group-containing (meth)acrylate monomers such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate; (meth)acrylate monomers such as (meth)acrylic acid; Carboxyl group-containing (meth)acrylate monomer; Isocyanate group-containing (meth)acrylate monomer such as 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, 1,1-bis(acryloyloxymethyl)ethyl isocyanate; glycidyl (meth) Examples include glycidyl group-containing (meth)acrylate monomers such as acrylate and 4-hydroxybutyl acrylate glycidyl ether. These (meth)acrylate monomers (α) can be used alone or in combination of two or more.

In addition to the (meth)acrylate monomer (α), the acrylic resin intermediate may be one obtained by copolymerizing other polymerizable unsaturated group-containing compounds as necessary. Examples of the other polymerizable unsaturated group-containing compounds include (meth)acrylate, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate. ) Acrylic acid alkyl ester; cyclo ring-containing (meth)acrylates such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth)acrylate; phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl Examples include aromatic ring-containing (meth)acrylates such as acrylate; silyl group-containing (meth)acrylates such as 3-methacryloxypropyltrimethoxysilane; and styrene derivatives such as styrene, α-methylstyrene, and chlorostyrene. These polymerizable unsaturated group-containing compounds can be used alone or in combination of two or more. Among these, (meth)acrylic acid alkyl esters are preferred.

When the acrylic resin intermediate is obtained by copolymerizing the (meth)acrylate monomer (α) and the other polymerizable unsaturated group-containing compound, the reaction ratio of the two may be determined depending on the curability. In order to obtain an excellent (meth)acryloyl group-containing acrylic resin, the ratio of the (meth)acrylate monomer (α) to the total of both is preferably in the range of 20 to 70% by mass, more preferably in the range of 30 to 60% by mass. .

The acrylic resin intermediate can be produced in the same manner as general acrylic resins. For example, it can be produced by polymerizing various monomers at a temperature range of 60 to 150° C. in the presence of a polymerization initiator. Examples of polymerization methods include bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization. Moreover, examples of the polymerization mode include random copolymers, block copolymers, graft copolymers, and the like. When carrying out the solution polymerization method, for example, a ketone solvent such as methyl ethyl ketone or methyl isobutyl ketone, or a glycol ether solvent such as propylene glycol monomethyl ether, propylene glycol dimethyl ether, propylene glycol monopropyl ether, or propylene glycol monobutyl ether may be used. is preferred.

The (meth)acrylate monomer (β) is not particularly limited as long as it can react with the reactive functional group possessed by the (meth)acrylate monomer (α), but from the viewpoint of reactivity it should be the following combination: is preferred. That is, when the hydroxyl group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use an isocyanate group-containing (meth)acrylate as the (meth)acrylate monomer (β). When the carboxyl group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use the glycidyl group-containing (meth)acrylate as the (meth)acrylate monomer (β). When the isocyanate group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use the hydroxyl group-containing (meth)acrylate as the (meth)acrylate monomer (β). When the glycidyl group-containing (meth)acrylate is used as the (meth)acrylate monomer (α), it is preferable to use the carboxy group-containing (meth)acrylate as the (meth)acrylate monomer (β).

For example, in the case where the reaction between the acrylic resin intermediate and the (meth)acrylate monomer (β) is an esterification reaction, the reaction is carried out at a temperature range of 60 to 150° C. to esterify triphenylphosphine, etc. Examples include methods using appropriate catalysts. In addition, when the reaction is a urethanization reaction, a method of reacting while dropping the (meth)acrylate monomer (α) onto the acrylic resin intermediate at a temperature range of 50 to 120° C. can be mentioned.

The weight average molecular weight (Mw) of the (meth)acryloyl group-containing acrylic resin is preferably in the range of 5,000 to 80,000. Further, the (meth)acryloyl group equivalent is preferably in the range of 100 to 500 g/equivalent.

These other photocurable compounds (R) may be used alone, or two or more types may be used in combination. When using these other photocurable compounds (R), the urethane (meth)acrylate resin of the present invention and the other photocurable compounds (R) out of 100 parts by mass in total, The acrylate resin is preferably used in a proportion of 5 parts by mass or more, more preferably 20 parts by mass or more, and particularly preferably 80 parts by mass or more.

Examples of the organic solvent include ketone solvents such as methyl ethyl ketone, acetone, and isobutyl ketone; cyclic ether solvents such as tetrahydrofuran and dioxolane; ester solvents such as methyl acetate, ethyl acetate, and butyl acetate; aromatic solvents such as toluene and xylene; Alicyclic solvents such as cyclohexane and methylcyclohexane; alcohol solvents such as carbitol, cellosolve, methanol, isopropanol, butanol, propylene glycol monomethyl ether; alkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether, dialkylene glycol monoalkyl ether Examples include glycol ether solvents such as acetate. These organic solvents can be used alone or in combination of two or more. Further, these organic solvents are mainly used for the purpose of adjusting the viscosity of the curable composition, and it is usually preferable to adjust the nonvolatile content to be in the range of 10 to 80% by mass.

Examples of the ultraviolet absorber include 2-[4-{(2-hydroxy-3-dodecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 , 3,5-triazine, 2-[4-{(2-hydroxy-3-tridecyloxypropyl)oxy}-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, Triazine derivatives such as 3,5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2 -xanthenecarboxy-4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone, and the like. These ultraviolet absorbers can be used alone or in combination of two or more.

Examples of the antioxidant include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, and the like. These antioxidants can be used alone or in combination of two or more.

Examples of the silicone additive include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified copolymer. Dimethylpolysiloxane copolymers, polyorganosiloxanes with alkyl groups or phenyl groups such as amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes with polyether-modified acrylic groups, polydimethylsiloxanes with polyester-modified acrylic groups, etc. Can be mentioned. These silicon-based additives can be used alone or in combination of two or more.

Examples of the fluorine-based additive include the "Megaface" series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.

Examples of the silane coupling agent include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, - Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyl Methyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3 -aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1 , 3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, special aminosilane, 3- ureidopropyltriethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatepropyltriethoxysilane, allyltri Vinyl silane coupling such as chlorosilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, trichlorovinylsilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris(2-methoxyethoxy)silane, etc. agent;

Diethoxy(glycidyloxypropyl)methylsilane, 2-(3,4epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltri Epoxy-based silane coupling agents such as ethoxysilane;

Styrenic silane coupling agents such as p-styryltrimethoxysilane;

(Meta) such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. Acryloxy-based silane coupling agent;

N-2(aminoethyl)3-aminopropylmethyldimethoxysilane, N-2(aminoethyl)3-aminopropyltrimethoxysilane, N-2(aminoethyl)3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane Amino-based silane coupling such as methoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, etc. agent;

A ureido-based silane coupling agent such as 3-ureidopropyltriethoxysilane;

Chloropropyl-based silane coupling agent such as 3-chloropropyltrimethoxysilane;

Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;

Sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide;

Examples include isocyanate-based silane coupling agents such as 3-isocyanatepropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.

Examples of the phosphoric acid ester compounds include those having a (meth)acryloyl group in the molecular structure, and commercially available products include, for example, "Kayamar PM-2" and "Kayamar PM-2" manufactured by Nippon Kayaku Co., Ltd. 21", "Light Ester P-1M", "Light Ester P-2M", "Light Acrylate P-1A (N)", manufactured by Kyoeisha Chemical Co., Ltd., "SIPOMER PAM 100", "SIPOMER PAM 200", manufactured by SOLVAY, " SIPOMER PAM 300'', ``SIPOMER PAM 4000'', Osaka Organic Chemical Industry Co., Ltd. ``Viscoat #3PA'', ``Viscoat #3PMA'', Daiichi Kogyo Seiyaku Co., Ltd. ``New Frontier S-23A''; allyl ether group in the molecular structure. Examples include "SIPOMER PAM 5000" manufactured by SOLVAY, which is a phosphoric acid ester compound having the following.

Examples of the organic beads include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, and polyolefin resin beads. , polyester resin beads, polyamide resin beads, polyimide resin beads, polyfluoroethylene resin beads, polyethylene resin beads, and the like. These organic beads can be used alone or in combination of two or more. Further, the average particle size of these organic beads is preferably in the range of 1 to 10 μm.

Examples of the inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These inorganic fine particles can be used alone or in combination of two or more types. Further, the average particle diameter of these inorganic fine particles is preferably in the range of 95 to 250 nm, particularly preferably in the range of 100 to 180 nm.

When containing the above-mentioned inorganic fine particles, a dispersion aid can be used. Examples of the dispersion aid include phosphoric acid ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These dispersion aids can be used alone or in combination of two or more. In addition, commercially available products of the dispersion aid include, for example, "Kayamar PM-21" and "Kayamar PM-2" manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-2M" manufactured by Kyoeisha Chemical Co., Ltd. .

[Cured product]
The cured product of the present invention is obtained by curing the active energy ray-curable composition.

Examples of methods for curing the curable composition include a heating method and a method of irradiating active energy rays such as ultraviolet rays.

As for the heating method, curing can be performed by heating in a temperature range of 60 to 200° C. for 0.5 minutes to 60 minutes.

In addition, as a method of irradiating the active energy rays, for example, in the case of ultraviolet rays, the ultraviolet ray generation source includes a low pressure mercury lamp, a high pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a gallium lamp, a metal halide lamp, sunlight, and an LED. It can be cured by a method using an ultraviolet lamp such as.

In addition to the ultraviolet rays, ionizing radiation such as electron beams, α rays, β rays, and γ rays can also be used as the active energy rays.

The irradiation amount of the active energy ray is preferably in the range of 0.05 to 5 J/cm ² , more preferably in the range of 0.1 to 3 J/cm ² , and more preferably in the range of 0.1 to 1 J/cm ² It is particularly preferable that the range is within the range of . Note that the above-mentioned amount of ultraviolet irradiation is based on a value measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).

[Laminated film]
The laminated film of the present invention has a layer made of the cured product on a base material.

Examples of the method for producing the laminated film of the present invention include a method in which the active energy ray-curable composition is applied to at least one surface of the base material, and then active energy rays are irradiated.

Examples of the base material include a metal base material, a plastic base material, a glass base material, a paper base material, a wood base material, a fibrous base material, and the like. Among these base materials, plastic base materials are preferred because they have excellent adhesion with the active energy ray-curable composition.

The materials for the plastic base material include polyester, acrylic resin (polymethyl methacrylate, etc.), polycarbonate, acrylonitrile-butadiene-styrene copolymer (ABS resin), composite resin of ABS resin and polycarbonate, polystyrene, polyurethane, and epoxy resin. , polyvinyl chloride, polyamide, polyolefin (polyethylene, polypropylene, polycycloolefin (COP), etc.), triacetyl cellulose (TAC), polyimide, and the like.

Examples of the plastic base material include plastic molded products such as mobile phones, home appliances, automobile interior and exterior materials, and OA equipment. Furthermore, a film base material made of plastic can also be used.

Examples of methods for applying the active energy ray-curable composition include a gravure coater, roll coater, comma coater, knife coater, air knife coater, curtain coater, kiss coater, shower coater, flow coater, spin coater, and dipping. , screen printing, spraying, brushing, applicator, bar coater and the like.

The film thickness of the coating film formed using the active energy ray active energy ray curable composition can be adjusted as appropriate depending on the intended use, but is usually in the range of 0.01 to 50 μm. is preferred.

The laminated film of the present invention may have a functional film layer such as an antireflection film, a diffusion film, or a polarizing film in addition to the layer made of the base material and the cured product.

Since the laminated film of the present invention has a cured coating film with high hardness, excellent scratch resistance, flexibility, and curl resistance, it can be used as a coating layer for protecting the surface of a substrate. For example, it can be suitably used for front panels of liquid crystal displays and organic EL displays.

Furthermore, examples of articles having the laminated film of the present invention include plastic molded articles such as mobile phones, home appliance casings, automobile bumpers, and OA equipment.

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

In this example, the hydroxyl value is an actual value measured according to the neutralization titration method of JIS K 0070 (1992).

In this example, the weight average molecular weight (Mw) is a value measured using gel permeation chromatography (GPC) under the following conditions.

Measuring device: HLC-8220 manufactured by Tosoh Corporation
Column: Guard column H _XL -H manufactured by Tosoh Corporation
+TSKgel G5000HXL manufactured by Tosoh Corporation
+TSKgel G4000HXL manufactured by Tosoh Corporation
+TSKgel G3000HXL manufactured by Tosoh Corporation
+TSKgel G2000HXL manufactured by Tosoh Corporation
Detector; RI (differential refractometer)
Data processing: Tosoh Corporation SC-8010
Measurement conditions: Column temperature 40℃
Solvent Tetrahydrofuran
Flow rate 1.0ml/min Standard: Polystyrene Sample: 0.4% by mass of tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (100μl)

In this example, the NCO content is a value measured by titration of an aqueous hydrochloric acid solution after reacting an isocyanate compound with di-n-butylamine.

(Production Example 1: Production of isocyanate compound (A2-3))
84 parts by mass of hexamethylene diisocyanate ("50M-HDI" manufactured by Asahi Kasei Corporation, NCO content 49.9%) and 0.04 parts by mass of dibutyltin dilaurate were added to a four-necked flask, and the internal temperature of the flask was adjusted to 60°C. It was heated until Next, 45.3 parts by mass of butylethylpropanediol (manufactured by KH Neochem Co., Ltd.) was added in portions over about 1 hour and reacted at 85° C. for 2 hours to obtain an isocyanate compound (A2-3). The NCO content of the isocyanate compound (A2-3) was 13.7%.

(Production Example 2: Production of isocyanate compound (A2-4))
84 parts by mass of hexamethylene diisocyanate ("50M-HDI" manufactured by Asahi Kasei Corporation, NCO content 49.9%) and 0.04 parts by mass of dibutyltin dilaurate were added to a four-necked flask, and the internal temperature of the flask was adjusted to 60%. It was heated until it reached ℃. Next, 21.5 parts by mass of propylene glycol (manufactured by AGC Corporation) was added in portions over about 1 hour and reacted at 85° C. for 2 hours to obtain an isocyanate compound (A2-4). The NCO content of the isocyanate compound (A2-4) was 16.3%.

(Production Example 3: Production of isocyanate compound (A2-5))
In a four-necked flask, 97 parts by weight of 1,3-bis(isocyanatomethyl)cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals, NCO content 43.2%) and 0.04 parts by mass of dibutyltin dilaurate were added. In addition, the flask was heated until the internal temperature reached 60°C. Next, 29.4 parts by mass of neopentyl glycol (manufactured by Mitsubishi Gas Chemical Co., Ltd.) was added in portions over about 1 hour and reacted at 85° C. for 2 hours to obtain an isocyanate compound (A2-5). The NCO content of the isocyanate compound (A2-5) was 15.8%.

(Production Example 4: Production of urethane (meth)acrylate resin (1))
163 parts by mass of dipentaerythritol (meth)acrylate (B1) (hydroxyl value: 125 mgKOH/g) was charged into a four-necked flask. 0.6 parts by mass of dibutyltin dilaurate and 0.6 parts by mass of methoquinone were added, and the flask was heated until the internal temperature reached 60°C. Next, 19.1 parts of hexamethylene diisocyanate ("50M-HDI" manufactured by Asahi Kasei Corporation, NCO content 49.9%) was added in portions over about 1 hour, and then polyisocyanate of hexamethylene diisocyanate (manufactured by Asahi Kasei Corporation, NCO content 49.9%) was added in portions. 17.3 parts by mass of "Duranate A201H" (NCO content 17.2%) was added in portions and reacted at 85°C for 8 hours. It was confirmed by titration and 50.6 parts by mass of butyl acetate was added to obtain urethane (meth)acrylate resin (1). The weight average molecular weight (Mw) of this urethane (meth)acrylate resin (1) was 6,000, and the theoretical value of (meth)acryloyl group equivalent calculated from the charging ratio of raw materials was 123 g/equivalent. .

(Production Examples 5 to 9: Production of urethane (meth)acrylate resins (2) to (6))
Urethane (meth)acrylate resins (2)-( 6) was obtained.

(Production Examples 10 and 11: Production of urethane (meth)acrylate resins (C1) and (C2))
Urethane (meth)acrylate resin (C1) and ( C2) was obtained.

The abbreviations in Table 1 indicate the following.
Compound (A1-1): Hexamethylene diisocyanate (“50M-HDI” manufactured by Asahi Kasei Corporation), NCO content 49.9%
Compound (A1-2): 1,3-bis(isocyanatomethyl)cyclohexane ("Takenate 600" manufactured by Mitsui Chemicals), NCO content 43.2%
Compound (A2-1): Polyisocyanate of hexamethylene diisocyanate (“Duranate (registered trademark) A201H” manufactured by Asahi Kasei Corporation), NCO content 17.2%
Compound (A2-2): polyisocyanate of hexamethylene diisocyanate (“Duranate (registered trademark) D201” manufactured by Asahi Kasei Corporation), NCO content 15.8%
Compound (A2-3): Isocyanate compound (A2-3) obtained in Production Example 1, NCO content 13.7%
Compound (A2-4): Isocyanate compound (A2-4) obtained in Production Example 2, NCO content 16.3%
Compound (A2-5): Isocyanate compound (A2-5) obtained in Production Example 3, NCO content 15.8%
Compound (B1): polyfunctional acrylate (“Aronix MT-3545” manufactured by Toagosei Co., Ltd., containing 20 to 40% by mass of dipentaerythritol hexaacrylate), hydroxyl value 125 mgKOH/g
Compound (C1): 2-hydroxyethyl (meth)acrylate (“HEA” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
Compound (C2): Unsaturated fatty acid hydroxyalkyl ester modified ε-caprolactone (“Plaxel FA-2D” manufactured by Daicel)

(Example 1: Creation of laminated film (1))
100 parts by mass of the urethane (meth)acrylate resin (1) obtained in Production Example 4, 6.4 parts by mass of a photopolymerization initiator ("Omnirad-184" manufactured by IGM), and 128 parts by mass of methyl ethyl ketone were mixed, and active energy rays were added. A curable composition was obtained. Next, the obtained active energy ray-curable composition was applied onto a 50 μm thick polyethylene terephthalate film (hereinafter abbreviated as “PET film”) using a bar coater, and dried at 90° C. for 1 minute. Next, under a nitrogen atmosphere, 100 mJ/cm ² of ultraviolet light was irradiated using an 80 W high-pressure mercury lamp to obtain a laminated film having a cured coating film with a thickness of 10 μm on a PET film with a thickness of 50 μm.

(Examples 2 to 6: Creation of laminated films (2) to (6))
Example 1 except that the urethane (meth)acrylate resins (2) to (6) obtained in Examples 5 to 9 were used in place of the urethane (meth)acrylate resin (1) used in Production Example 4, respectively. Laminated films (2) to (6) were obtained in the same manner as above.

(Example 7: Creation of laminated film (7))
Instead of the urethane (meth)acrylate resin (1) used in Production Example 4, the urethane (meth)acrylate resin (2) obtained in Example 5 and glycerin di/triacrylate (manufactured by Toagosei Co., Ltd. "Aronix M-920" were used) A laminated film (7) was obtained in the same manner as in Example 1, except for using the same method as in Example 1.

(Comparative Examples 1 and 2: Creation of laminated films (R1) and (R2))
Example 1 except that the urethane (meth)acrylate resins (R1) and (R2) obtained in Comparative Examples 1 and 2 were used in place of the urethane (meth)acrylate resin (1) used in Production Example 4, respectively. Laminated films (R1) and (R2) were obtained in the same manner.

The following evaluations were performed using the laminated films obtained in the above Examples and Comparative Examples.

[Method of measuring coating film hardness]
In the laminated films obtained in Examples and Comparative Examples, the hardness of the cured coating film surface of the active energy ray-curable composition was measured under a load of 500 g in accordance with JIS K5600-5-4 [scratch hardness (pencil method)]. It was measured with Each hardness was measured five times, and the hardness for which no scratches were observed four or more times was defined as the hardness of the cured coating film.

[Evaluation method of scratch resistance]
In Examples and Comparative Examples, a disc-shaped indenter with a diameter of 2.4 cm was wrapped with 0.5 g of steel wool ("Bonstar #0000" manufactured by Nippon Steel Wool Co., Ltd.), and a load of 500 g was applied to the indenter. An abrasion test was conducted by making the cured coating surface of the obtained laminated film reciprocate 200 times. The haze value of the coating film before and after the abrasion test was measured using an automatic haze computer ("HZ-2" manufactured by Suga Test Instruments Co., Ltd.), and the scratch resistance was evaluated based on the difference value (dH) between them. Note that the smaller the difference value (dH), the higher the resistance to scratches.

[Flexibility evaluation method]
Using a mandrel tester ("Bending tester" manufactured by TP Giken Co., Ltd.), the laminated films obtained in the examples and comparative examples were wrapped around a test rod, and a test was conducted to visually confirm whether or not cracks occurred. The evaluation result was the minimum diameter of the test bar without cracking. The test rods used ranged in diameter from 2 mm to 12 mm in 1 mm increments.

[Evaluation method of curl resistance]
A 5 cm square coating film was cut out from the laminated films obtained in the Examples and Comparative Examples to obtain a test piece, and the lift of the four corners from the horizontal was measured for the test piece, and the average value (mm) was evaluated. The smaller the value, the smaller the curl, and the better the curl resistance.

Table 2 shows the evaluation results of the laminated films (1) to (7) produced in Examples 1 to 7 and the laminated films (R1) and (R2) produced in Comparative Examples 1 and 2.

Examples 1 to 7 shown in Table 2 are examples of laminated films using the urethane (meth)acrylate resin of the present invention, and the cured coating film of the urethane (meth)acrylate resin has excellent coating hardness. It was also confirmed that the laminated film had excellent scratch resistance, flexibility, and curl resistance.

On the other hand, Comparative Examples 1 and 2 are examples in which the acrylate compound (A2) is not used as a raw material for the urethane (meth)acrylate resin, but the cured coating film of the urethane (meth)acrylate resin has excellent coating hardness. However, it was confirmed that the laminated film using the urethane (meth)acrylate resin had extremely insufficient curl resistance.

Claims (10)

Essential reaction of an isocyanate compound (A1) that does not contain a bond derived from an isocyanate group in its molecule, an isocyanate compound (A2) that contains a bond derived from an isocyanate group in its molecule, and dipentaerythritol (meth)acrylate (B) A urethane (meth)acrylate resin used as a raw material,
A urethane (meth)acrylate resin, wherein the dipentaerythritol (meth)acrylate (B) has a hydroxyl value in a range of more than 120 mgKOH/g and less than 150 mgKOH/g. The urethane (meth)acrylate according to claim 1, wherein the NCO content of the isocyanate compound (A1) is in the range of 20 to 55%, and the NCO content of the isocyanate compound (A2) is in the range of 10 to 25%. resin. The urethane (meth) according to claim 1, wherein the equivalent ratio of the isocyanate compound (A2) to the isocyanate compound (A1) in the reaction raw material [(A1)/(A2)] is in the range of 70/30 to 95/5. acrylate resin. The urethane (meth)acrylate resin according to claim 1, further comprising a hydroxyl group-containing acrylic ester (C) other than the dipentaerythritol (meth)acrylate (B) as a reaction raw material. The urethane (meth)acrylate resin according to claim 1, wherein the dipentaerythritol (meth)acrylate (B) contains dipentaerythritol hexa(meth)acrylate. The urethane (meth)acrylate resin according to claim 1, wherein the content of the dipentaerythritol hexa(meth)acrylate in the dipentaerythritol (meth)acrylate (B) is in the range of 10 to 50% by mass. An active energy ray-curable composition comprising the urethane (meth)acrylate resin according to any one of claims 1 to 6 and a photopolymerization initiator. A cured product of the active energy ray-curable composition according to claim 7. A laminated film having a cured coating film comprising the cured product according to claim 8 on one or both sides of a base material. The laminated film according to claim 9, wherein the thickness of the base material is in the range of 50 to 80 μm, and the thickness of the cured coating film is in the range of 5 to 20 μm.