JP7109186B2 - Urethane (meth)acrylate composition, active energy ray-polymerizable composition, and laminate - Google Patents

Description

The present invention provides a urethane (meth)acrylate-based composition, an active energy ray-polymerizable composition containing the urethane (meth)acrylate-based composition, and a laminate of a cured product of the active energy ray-polymerizable composition and a substrate. Regarding the body.

Image display devices such as liquid crystal displays are increasingly being used not only indoors but also outdoors. Therefore, there is a demand for a display device having a surface protective material with a high hardness that is resistant to scratches even outdoors in dusty conditions. From such a point of view, there is known a technique for preventing scratches by using a laminate in which a hard coat layer is laminated on a base material.
In addition, image display devices such as liquid crystal displays are required to have a low reflectance of light emitted from the outside in order to improve the visibility of the display surface. From this point of view, attempts have been made to increase the refractive index of the hard coat layer to reduce the reflectance of external light (Patent Document 1).

The hard coat layer is formed by curing an active energy ray-polymerizable composition containing, for example, an active energy ray-polymerizable monomer such as a polyfunctional (meth)acrylate and, if necessary, a solvent. As described above, from the viewpoint of reducing light reflectance, the hard coat layer preferably has a relatively high refractive index. Therefore, a monomer with a high refractive index is required for forming the hard coat layer. there is
In addition, if the components constituting the active energy ray-polymerizable composition have poor compatibility with each other, the transparency of the hard coat layer formed is deteriorated. is required.
Patent Documents 2 to 4 disclose a urethane (meth)acrylate composition obtained by reacting a (meth)acrylic acid ester compound of an epoxy resin obtained by adding (meth)acrylic acid to an epoxy resin with a polyisocyanate compound or the like. Examples are disclosed for use as monomers. The urethane (meth)acrylate composition is used as an active energy ray-polymerizable composition mixed with an active energy ray-polymerizable monomer, a solvent, etc., and a cured product with improved various physical properties such as heat resistance can be obtained. It has been reported.

JP 2013-142793 A JP-A-60-250023 JP-A-2005-255555 JP 2013-53249 A

However, the urethane (meth)acrylate-based compositions in these prior arts lack compatibility with various solvents contained in the active energy ray-polymerizable composition, such as alcohol-based solvents and ketone-based solvents, and urethane (meth)acrylate-based The compatibility with the active energy ray-polymerizable monomer used in combination with the composition is not sufficient, and there is room for improvement from the viewpoint of increasing the refractive index.

The present invention has been made in view of the above circumstances, and urethane ( An object of the present invention is to provide a meth)acrylate composition.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a urethane (meth)acrylate composition containing a urethane (meth)acrylate compound containing a specific structural unit and having a number average molecular weight within a certain range. and completed the following invention.
That is, the present invention provides the following [1] to [11].
[1] A structural unit derived from a (meth)acrylic acid ester compound (A) of an epoxy compound obtained by adding (meth)acrylic acid to an epoxy compound, a structural unit derived from an organic polyisocyanate compound (B), and a polyisocyanate having a hydroxyl group. A urethane (meth)acrylate composition containing a urethane (meth)acrylate compound (D) containing structural units derived from a functional (meth)acrylate (C) and having a number average molecular weight of 500 to 1,800.
[2] The urethane (meth)acrylate composition according to [1] above, which has a hydroxyl value of 70 mgKOH/g or more and 130 mg or less.
[3] (meth)acrylic acid ester compound (A) of an epoxy compound in which (meth)acrylic acid is added to an epoxy compound, an organic polyisocyanate compound (B), and a polyfunctional (meth)acrylate having a hydroxyl group (C); A urethane (meth)acrylate composition having a number average molecular weight of 500 or more and 1800 or less obtained by reacting
[4] The NCO/OH ratio, which is the molar ratio of the isocyanate groups of the component (B) to the total hydroxyl groups of the hydroxyl groups of the component (A) and the hydroxyl groups of the component (C), is 0.15 or more and 0.40 or less. , the urethane (meth)acrylate composition according to the above [3].
[5] The urethane (meth)acrylate composition according to any one of [1] to [4] above, wherein the epoxy compound is a bisphenol A type epoxy compound or a fluorene type epoxy compound.
[6] The urethane (meth)acrylate composition according to any one of [1] to [5] above, wherein the organic polyisocyanate compound (B) is an aromatic polyisocyanate.
[7] The urethane (meth) according to any one of [1] to [6] above, wherein the polyfunctional (meth)acrylate (C) contains at least one of pentaerythritol triacrylate and dipentaerythritol pentaacrylate. Acrylate-based composition.
[8] The urethane (meth)acrylate composition according to any one of the above [1] to [7], which is used for an optical member.
[9] An active energy ray-polymerizable composition containing the urethane (meth)acrylate composition according to any one of the above [1] to [8] and an active energy ray-polymerizable monomer.
[10] The active energy ray-polymerizable composition according to [9] above, which further contains a solvent.
[11] A laminate having a substrate and a hard coat layer laminated on the substrate, wherein the hard coat layer is the active energy ray-polymerizable composition according to [9] or [10] above. A laminate that is a cured product.

According to the present invention, a urethane (meta- ) acrylate-based compositions can be provided.

The urethane (meth)acrylate composition of the present invention comprises a structural unit derived from a (meth)acrylic acid ester compound (A) of an epoxy compound in which (meth)acrylic acid is added to an epoxy compound, and an organic polyisocyanate compound (B). It contains a urethane (meth)acrylate compound (D) containing a structural unit derived from and a structural unit derived from a polyfunctional (meth)acrylate (C) having a hydroxyl group, and has a number average molecular weight of 500 or more and 1800 or less.
The urethane (meth)acrylate composition can be used as one component of an active energy ray-polymerizable composition containing an active energy ray-polymerizable monomer, a solvent, and the like, as described later.
The urethane (meth)acrylate composition of the present invention will be described in detail below.

[Urethane (meth)acrylate composition]
The urethane (meth)acrylate composition of the present invention comprises a structural unit derived from the (meth)acrylic acid ester compound (A) of the epoxy compound, a structural unit derived from the organic polyisocyanate compound (B), and a polyfunctional ( It contains at least a urethane (meth)acrylate compound (D) containing structural units derived from meth)acrylate (C).
In addition, in this specification, the (meth)acrylic acid ester compound (A) of the epoxy compound may be simply referred to as the (A) component. The same applies to the organic polyisocyanate compound (B), the polyfunctional (meth)acrylate (C) having a hydroxyl group, and the urethane (meth)acrylate compound (D).
In the present specification, (meth)acrylic acid means acrylic acid or methacrylic acid, (meth)acrylate means acrylate or methacrylate, and (meth)acryloyl group means acryloyl group or methacryloyl means the base.

As will be described later, the urethane (meth)acrylate composition comprises an epoxy compound (meth)acrylic acid ester compound (A), an organic polyisocyanate compound (B), and a polyfunctional (meth)acrylate having a hydroxyl group (C). and containing at least a urethane (meth)acrylate compound (D) containing structural units derived from (A) to (C).

Component (D) is a compound obtained by reacting each of the hydroxyl groups present in component (A) and the hydroxyl groups of component (C) with the isocyanate groups of component (B). C) It is connected with each component by a urethane bond. A representative structure of component (D) is a structure having one structural unit derived from each of components (A) to (C). A structure having two or more of at least one may exist. Therefore, component (D) can exist not only as a single structure but also as a mixture of compounds having multiple different structures. The structure of component (D) depends on the reaction conditions such as the types and amounts of components (A) to (C) used and the molar ratio of isocyanate groups to hydroxyl groups.

Further, the urethane (meth)acrylate-based composition of the present invention has a structural unit derived from the component (A) and a structural unit derived from the component (B) in addition to the component (D), depending on the reaction conditions. (C) Compounds not having component-derived structural units, compounds having (B) component-derived structural units and (C) component-derived structural units and not having (A) component-derived structural units, and others, unreacted (A) ~ (C) components and the like may be included.
In other words, the urethane (meth)acrylate-based composition of the present invention is obtained by reacting components (A), (B) and (C), so that structural units derived from component (A) , a structural unit derived from the component (B), and a compound having at least one of the structural units derived from the component (C), may contain unreacted components (A) to (C), these monomers, It is a mixture of oligomers.
In the urethane (meth)acrylate-based composition of the present invention, a compound having at least one of a structural unit derived from component (A), a structural unit derived from component (B), and a structural unit derived from component (C), and an un The total amount of components (A) to (C) in the reaction is preferably 90% by mass or more, more preferably 95% by mass or more, and 100% by mass of the entire urethane (meth)acrylate composition. It is particularly preferred to have

The number average molecular weight of the urethane (meth)acrylate composition is 500 or more and 1800 or less. If the number average molecular weight of the urethane (meth)acrylate composition is less than 500, the strength of the hard coat layer formed from the urethane (meth)acrylate composition tends to decrease. On the other hand, when the number average molecular weight of the urethane (meth)acrylate composition exceeds 1800, the compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition tends to deteriorate. From the viewpoint of better compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition, the number average molecular weight of the urethane (meth)acrylate composition is preferably 600 or more. , more preferably 700 or more, still more preferably 800 or more, and preferably 1500 or less, more preferably 1400 or less, still more preferably 1200 or less.
The number average molecular weight of the urethane (meth)acrylate composition can be measured by the method described in Examples.

The hydroxyl value of the urethane (meth)acrylate composition is preferably 60 mgKOH/g or more, more preferably 70 mgKOH/g or more, still more preferably 80 mgKOH/g or more, and preferably 140 mgKOH/g or less, more preferably It is 130 mgKOH/g or less, more preferably 120 mgKOH/g or less. When the hydroxyl value of the urethane (meth)acrylate-based composition is adjusted to such a range, compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition tends to be improved.
In the present invention, the hydroxyl value of the urethane (meth)acrylate composition is the hydroxyl value required to neutralize the acetic acid bonded to the hydroxyl group when 1 g of the urethane (meth)acrylate composition is acetylated. It is the number of mg of potassium, and can be measured according to JIS K0070.

((Meth)acrylic acid ester compound (A) of epoxy compound)
The urethane (meth)acrylate compound (D) contained in the urethane (meth)acrylate composition of the present invention has a structural unit derived from the (meth)acrylic acid ester compound (A) of the epoxy compound.
The (meth)acrylic acid ester compound (A) of an epoxy compound is a compound obtained by adding (meth)acrylic acid to an epoxy compound.
Although the epoxy compound is not particularly limited, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, hydrogenated bisphenol S type epoxy compounds, biphenyl type epoxy compounds, phenol novolak type epoxy compounds, biphenol type epoxy compounds, naphthalene type epoxy compounds, fluorene type epoxy compounds and the like.
Among them, the epoxy compound is selected from the group consisting of an epoxy compound having an aromatic ring, specifically a bisphenol A type epoxy compound and a fluorene type epoxy compound, from the viewpoint of obtaining a urethane (meth)acrylate composition with a high refractive index. 1 or more is preferred.

一般式（１）において、Ｘは、直接結合、炭素数１～４のアルキレン基、又は炭素数２～４のアルキリデン基を表す。中でも、Ｘは、炭素数２～４のアルキリデン基が好ましく、イソプロピリデン基がより好ましい。
一般式（１）において、Ｒは、それぞれ独立に水素原子、炭素数１～５の直鎖若しくは分岐アルキル基、フェニル基、又はハロゲン原子を表す。ａはそれぞれ独立に０～４の整数である。中でもａは０～２の整数であることが好ましく、０であることがより好ましい。
一般式（１）においてｎは０以上の整数である。ウレタン（メタ）アクリレート系組成物の数平均分子量を低くし、活性エネルギー線重合性組成物に含有される各種溶剤及び活性エネルギー線重合性モノマーなどとの相溶性を良好とする観点から、ｎは好ましくは０～３の整数であり、より好ましくは０又は１であり、さらに好ましくは０である。 A bisphenol A type epoxy compound is a compound having a bisphenol A skeleton and an epoxy group, and is preferably a compound represented by the following general formula (1).

In general formula (1), X represents a direct bond, an alkylene group having 1 to 4 carbon atoms, or an alkylidene group having 2 to 4 carbon atoms. Among them, X is preferably an alkylidene group having 2 to 4 carbon atoms, and more preferably an isopropylidene group.
In general formula (1), each R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom. Each a is an integer of 0 to 4 independently. Among them, a is preferably an integer of 0 to 2, more preferably 0.
In general formula (1), n is an integer of 0 or more. From the viewpoint of lowering the number average molecular weight of the urethane (meth)acrylate composition and improving compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition, n is preferably It is an integer of 0 to 3, preferably 0 or 1, and still more preferably 0.

一般式（２－１）において、Ｒは、それぞれ独立に水素原子、炭素数１～５の直鎖若しくは分岐アルキル基、フェニル基、又はハロゲン原子を表す。ａはそれぞれ独立に０～４の整数である。中でもａは０～２の整数であることが好ましく、０であることがより好ましい。
一般式（２－１）においてｎは０以上の整数である。ウレタン（メタ）アクリレート系組成物の数平均分子量を低くし、活性エネルギー線重合性組成物に含有される各種溶剤及び活性エネルギー線重合性モノマーなどとの相溶性を良好とする観点から、ｎは好ましくは０～３の整数であり、より好ましくは０又は１であり、さらに好ましくは０である。 A fluorene-type epoxy compound is a compound having a fluorene skeleton and an epoxy group, and is preferably a compound represented by the following general formula (2-1) or general formula (2-2).

In general formula (2-1), each R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom. Each a is an integer of 0 to 4 independently. Among them, a is preferably an integer of 0 to 2, more preferably 0.
In general formula (2-1), n is an integer of 0 or more. From the viewpoint of lowering the number average molecular weight of the urethane (meth)acrylate composition and improving compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition, n is preferably It is an integer of 0 to 3, preferably 0 or 1, and still more preferably 0.

一般式（２－２）において、Ｒは、それぞれ独立に水素原子、炭素数１～５の直鎖若しくは分岐アルキル基、フェニル基、又はハロゲン原子を表す。ａはそれぞれ独立に０～４の整数である。中でもａは０～２の整数であることが好ましく、０であることがより好ましい。
一般式（２－２）において、ｎは０以上の整数である。好ましくは０～２０の整数であり、より好ましくは０～５の整数であり、さらに好ましくは０又は１であり、さらに好ましくは０である。

In general formula (2-2), each R independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a phenyl group, or a halogen atom. Each a is an integer of 0 to 4 independently. Among them, a is preferably an integer of 0 to 2, more preferably 0.
In general formula (2-2), n is an integer of 0 or more. It is preferably an integer of 0 to 20, more preferably an integer of 0 to 5, still more preferably 0 or 1, still more preferably 0.

Component (A) is a compound obtained by adding (meth)acrylic acid to the above epoxy compound, preferably a compound obtained by adding (meth)acrylic acid to a bisphenol A type epoxy compound or a fluorene type epoxy compound to (meth)acrylic acid. It is a compound to which an acid is added.
The compound obtained by adding (meth)acrylic acid to a bisphenol A type epoxy compound is preferably a compound obtained by adding (meth)acrylic acid to general formula (1), more preferably represented by the following formula (3). is a compound. The compound obtained by adding (meth)acrylic acid to a fluorene-type epoxy compound is preferably a compound obtained by adding (meth)acrylic acid to general formula (2-1) or general formula (2-2), more preferably It is a compound represented by the following formula (4).

(A) component may be used individually by 1 type, and may be used in combination of 2 or more type.
Component (A) can be produced by a known method. For example, a predetermined amount of epoxy compound and (meth)acrylic acid are mixed and heated to about 90 to 120°C in the presence of a polymerization inhibitor. Just heat it up.

(Organic polyisocyanate compound (B))
The urethane (meth)acrylate compound (D) contained in the urethane (meth)acrylate composition of the present invention has structural units derived from the organic polyisocyanate compound (B).
Component (B) is not particularly limited, and known components can be used. Component (B) includes, for example, aliphatic polyisocyanates such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, alicyclic polyisocyanates such as dicyclohexylmethane 4,4′-diisocyanate, aromatic polyisocyanates such as 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate; As the organic polyisocyanate compound, an isocyanurate compound obtained by cyclizing the above aliphatic polyisocyanate or aromatic polyisocyanate can also be used.
Among these, from the viewpoint of increasing the refractive index of the urethane (meth)acrylate composition, aromatic polyisocyanates are preferred, and xylylene diisocyanate is more preferred.
(B) component may be used individually by 1 type, and may be used in combination of 2 or more types.

(Polyfunctional (meth)acrylate (C) having a hydroxyl group)
The urethane (meth)acrylate compound (D) contained in the urethane (meth)acrylate composition of the present invention has structural units derived from polyfunctional (meth)acrylate (C) having hydroxyl groups.
A polyfunctional (meth)acrylate (C) having a hydroxyl group is a compound having one or more hydroxyl groups and two or more (meth)acryloyl groups, and is a compound other than the component (A) described above. . From the viewpoint of obtaining a urethane (meth)acrylate composition having good compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition, the component (C) contains one hydroxyl group. and more preferably a compound having one primary hydroxyl group. By using a polyfunctional (meth)acrylate having one hydroxyl group as the component (C), the number average molecular weight and hydroxyl value of the urethane (meth)acrylate composition can be easily adjusted to the desired range, and the compatibility is improved. Cheap.

Component (C) includes, for example, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerol di(meth)acrylate, sorbitol di(meth)acrylate, sorbitol tri (meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra (Meth)acrylate, dipentaerythritol penta(meth)acrylate and the like.
Among these, as component (C), since it has one hydroxyl group, pentaerythritol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, sorbitol penta(meth)acrylate , ditrimethylolpropane tri(meth)acrylate, and dipentaerythritol penta(meth)acrylate, and at least one of pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate It is more preferred to include one.
(C) component may be used individually by 1 type, and may be used in combination of 2 or more type.

(Urethane (meth)acrylate compound (D))
The urethane (meth)acrylate compound (D) is a compound containing structural units derived from components (A) to (C). Further, as described above, the component (D) can have various structures depending on the reaction conditions. Structure.
For example, bisphenol A diglycidyl ether acrylic acid adduct as the (meth)acrylic acid ester compound (A) of the epoxy compound, xylylene diisocyanate as the organic polyisocyanate compound (B), and pentaerythritol as the polyfunctional (meth)acrylate (C). A representative structure of the urethane (meth)acrylate compound (D) when a triacrylate is used is as follows.

The above compound corresponding to component (D) is a compound in which one of the two hydroxyl groups of bisphenol A diglycidyl ether acrylic acid adduct and each of the hydroxyl groups of pentaerythritol triacrylate have reacted with isocyanate groups of xylylene diisocyanate. and each component is linked by a urethane bond.
Although the above compound corresponding to component (D) has unreacted hydroxyl groups, it is conceivable that the hydroxyl groups may further react with isocyanate groups of another xylylene diisocyanate. That is, component (D) can have various structures depending on the amount of each component used.

The urethane (meth)acrylate-based composition of the present invention has a (meth)acrylic acid ester compound (A) of an epoxy compound in which (meth)acrylic acid is added to an epoxy compound, an organic polyisocyanate compound (B), and a hydroxyl group. Obtained by reacting with polyfunctional (meth)acrylate (C).
When these components are reacted, the molar ratio (NCO/OH ratio) of the isocyanate groups of component (B) to the total hydroxyl groups of the hydroxyl groups of component (A) and the hydroxyl groups of component (C) is preferably 0.5. 15 or more, more preferably 0.20 or more, still more preferably 0.25 or more, and preferably 0.45 or less, more preferably 0.40 or less, more preferably 0.35 or less, still more preferably 0 .30 or less.
With such an NCO/OH ratio, the number average molecular weight of the urethane (meth)acrylate composition is within the desired range, and various solvents such as alcohols and ketones contained in the active energy ray-polymerizable composition and active energy It becomes easy to obtain a urethane (meth)acrylate composition having good compatibility with a linearly polymerizable monomer or the like.
The molar ratio of the (A) component and the (C) component (the number of moles of the component (A)/the number of moles of the component (C)) when reacting each component is from the viewpoint of making it easier to obtain the urethane (meth)acrylate compound (D). from,
It is preferably 0.5 or more, more preferably 0.8 or more, and preferably 1.5 or less, more preferably 1.2 or less.

The specific method for reacting the components (A) to (C) is not particularly limited, but for example, the components (A), (C) and, if necessary, a solvent are mixed, and these ( B) The component may be added and reacted. The reaction is preferably carried out under conditions of 60° C. or higher and 110° C. or lower, preferably in the presence of additives such as catalysts and polymerization inhibitors.
As the catalyst, amine compounds such as triethylamine, piperazine and triethanolamine, organometallic compounds, and the like can be used. Examples of the organometallic compounds include organotin compounds such as dibutyltin dilaurate, tin octoate, tin laurate and dioctyltin dilaurate; organozinc compounds such as zinc 2-ethylhexanoate; organozirconium compounds such as zirconium tetraacetylacetonate; An organic bismuth compound such as ctate can be used.
As the polymerization inhibitor, hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, p-benzoquinone and the like can be used.

(Use of urethane (meth)acrylate composition)
The urethane (meth)acrylate composition of the present invention has good compatibility with various solvents and active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition. Therefore, the active energy ray-polymerizable composition containing the urethane (meth)acrylate composition of the present invention and the cured product of the composition have high transparency.
Further, the urethane (meth)acrylate composition of the present invention has a relatively high refractive index, and a specific value of the refractive index is preferably 1.50 or more, more preferably 1.51 or more, And it is preferably 1.65 or less, more preferably 1.60 or less.
Since the urethane (meth)acrylate composition has a relatively high refractive index, the refractive indexes of various materials made from the composition also increase. Therefore, the urethane (meth)acrylate composition of the present invention is preferably used as an optical member by taking advantage of such properties.
Specifically, the urethane (meth)acrylate composition of the present invention is preferably used as a material for forming a hard coat layer.

[Laminate]
The laminate of the present invention is a laminate having a substrate and a hard coat layer laminated on the substrate. The hard coat layer is preferably a cured product of an active energy ray-polymerizable composition containing at least the urethane (meth)acrylate composition of the present invention and an active energy ray-polymerizable monomer. By using the urethane (meth)acrylate-based composition of the present invention in the hard coat layer, a laminate having high transparency and capable of reducing reflection of light irradiated from external light can be obtained. is used for the image display surface of the image display device, the visibility of the display surface is improved.

The type of base material in the laminate is not particularly limited, and a metal base material, a glass base material, a resin base material, or the like can be used. Among them, a resin base material is preferable from the viewpoint of improving transparency and processability. .
Materials constituting the resin substrate include, for example, cellulose derivatives, cycloolefin resins, polymethyl methacrylate, polyvinyl alcohol, polyimides, polyarylates, polyethylene terephthalate, polysulfones, polyethersulfones, amorphous polyolefins, modified acrylic polymers, polystyrene, Epoxy resins, polycarbonates, polyesters, triacetyl cellulose, polyethylene naphthalate, cyclic olefin copolymers, polypropylene, polyethylene, polyphenyl sulfide and the like can be mentioned.
The shape of the substrate is not particularly limited, and may be appropriately selected depending on the purpose of use, such as a film shape or a plate shape. The thickness of the substrate is preferably 5 μm or more, more preferably 20 μm or more, and preferably 300 μm or less, more preferably 200 μm or less.

The hard coat layer is preferably a cured product of an active energy ray-polymerizable composition, which will be described later. The thickness of the hard coat layer may be appropriately adjusted according to the required hardness, antireflection property, etc., and may be, for example, 1 μm or less and 20 μm or less.
Further, in the laminate of the present invention, a low refractive index layer having a lower refractive index than that of the hard coat layer may be provided on the hard coat layer. Thereby, antireflection property can be improved more. From the viewpoint of further improving antireflection properties, a high refractive index layer having a higher refractive index than the hard coat layer may be provided between the hard coat layer and the low refractive index layer.

(Active energy ray-polymerizable composition)
The active energy ray-polymerizable composition contains at least the urethane (meth)acrylate-based composition of the present invention and an active energy ray-polymerizable monomer. Microparticles and the like for adjustment may be included.

Examples of active energy ray-polymerizable monomers contained in the active energy ray-polymerizable composition include radically polymerizable monomers having ethylenically unsaturated bonds such as (meth)acryloyl groups, vinyl groups, and allyl groups. . Here, the active energy ray-polymerizable monomer in the present invention includes not only monomers having only one repeating unit, but also oligomers and polymers having two or more repeating units.
The active energy ray-polymerizable monomer preferably contains a radically polymerizable monomer having a (meth)acryloyl group, and more preferably contains a polyfunctional (meth)acrylate. The urethane (meth)acrylate composition of the present invention has good compatibility with radically polymerizable monomers having (meth)acryloyl groups, and particularly good compatibility with polyfunctional (meth)acrylates. In addition, a polyfunctional (meth)acrylate means a radically polymerizable monomer having two or more (meth)acryloyl groups.
Examples of polyfunctional (meth)acrylates include diacrylates such as pentaerythritol triacrylate, ethylene glycol diacrylate, and pentaerythritol diacrylate monostearate; tri(meth)acrylates such as trimethylolpropane triacrylate and pentaerythritol triacrylate. ; pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate and the like. Pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and the like are preferable from the viewpoint of obtaining a hard coat layer with high hardness. The total amount of the active energy ray-polymerizable monomer contained in the active energy ray-polymerizable composition and the urethane (meth)acrylate-based composition of the present invention is described below with respect to the total solid content of the active energy ray-polymerizable composition. When fine particles are contained, the content is preferably 30% by mass or more and preferably 90% by mass or less. In addition, when the fine particles to be described later are not contained, the content is preferably 70% by mass or more and preferably 100% by mass or less.

The active energy ray-polymerizable composition may further contain a solvent. The solvent may be appropriately selected and used from solvents that do not react with each component in the active energy ray-polymerizable composition and that can dissolve or disperse each component. For example, alcohol solvents such as isopropyl alcohol and ethanol; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ester solvents such as ethyl acetate; halogenated hydrocarbons; aromatic hydrocarbons such as toluene and xylene; A mixed solvent of The urethane (meth)acrylate composition of the present invention has good compatibility with these various solvents, particularly good compatibility with alcohol solvents or ketone solvents. Therefore, when the active energy ray-polymerizable composition contains a solvent, it is preferable to use one or both of an alcohol-based solvent and a ketone-based solvent.
When a solvent is used, the solid content concentration of the active energy ray-polymerizable composition (the ratio of the total mass of the total solid content to the total mass of the composition) is preferably 0.1% by mass or more, and preferably 40% by mass. % by mass or less.

The active energy ray-polymerizable composition may contain fine particles from the viewpoint of increasing the hardness or adjusting the refractive index when formed into a hard coat layer. The fine particles may be inorganic fine particles or organic fine particles, but inorganic fine particles are preferable from the viewpoint of imparting hardness. Examples of inorganic fine particles include metal oxides such as silica (SiO ₂ ), aluminum oxide, zirconia, titania, zinc oxide, germanium oxide, indium oxide, tin oxide, indium tin oxide (ITO), antimony oxide, and cerium oxide. fine particles, fine particles of metal fluorides such as magnesium fluoride and sodium fluoride, and the like.

The active energy ray-polymerizable composition preferably contains a polymerization initiator for initiating the polymerization of the urethane (meth)acrylate-based composition and the active energy ray-polymerizable monomer. Among polymerization initiators, photopolymerization initiators are preferred, and examples thereof include acetophenones, benzophenones, ketals, anthraquinones, disulfide compounds, thiuram compounds, and fluoroamine compounds. More specifically, 1-hydroxy-cyclohexyl-phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzyldimethylketone, 1-(4-do Tesylphenyl)-2-hydroxy-2-methylpropan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Examples include propan-1-one, benzophenone, and the like.
When a photopolymerization initiator is used, its content is about 0.1 parts by mass or more and 20 parts by mass or less with respect to a total of 100 parts by mass of the urethane (meth)acrylate-based composition and the active energy ray-polymerizable monomer. do it.

The method for producing the laminate of the present invention is not particularly limited. , a method of forming a hard coat layer.
As a method of applying the active energy ray-polymerizable composition to form a coating film, a conventionally known coating method can be used. Examples of coating methods include spin coating, dipping, spraying, slide coating, bar coating, roll coating, meniscus coating, flexographic printing, screen printing, and bead coating. .
Ultraviolet rays, visible light, electron beams, ionizing radiation, etc. are mainly used for light irradiation of the coating film. Ultraviolet rays emitted from a light beam such as a metal halide lamp may be used.
In addition, before light irradiation, you may dry a coating film as needed. Examples of the drying method include drying under reduced pressure, drying by heating, or a combination of these drying methods.

The present invention will be described in more detail with reference to examples, but the present invention is not limited by these examples.

The measurement method and evaluation method of each physical property are as follows.
<Refractive index (solid content conversion value)>
The refractive index of a methyl ethyl ketone solution of the obtained urethane acrylate composition was measured at 25° C. using an Abbe refractive index system. The refractive index (solid conversion value) of the urethane acrylate composition was calculated from the measured values obtained, the refractive index of the solvent methyl ethyl ketone alone, the solid content weight of the urethane acrylate composition, and the weight of the solvent.

<Number average molecular weight>
The number average molecular weight (Mn) of the resulting urethane acrylate-based composition was determined by gel permeation chromatography (GPC) as a value converted to standard polystyrene. Measurement conditions are as follows.
Measuring device: GPC HLC-8220 manufactured by Tosoh Corporation
Column: Two Shodex LF-404 are connected in series Detector: Differential refractive index (RI) detector Standard polystyrene: Easical Type PS-2 polystyrene manufactured by Agilent Technologies (molecular weight range 580 to 364,000)
Sample concentration: 0.2 wt% THF solution Mobile phase: THF
Liquid sending speed: 0.35ml/min
Column temperature: 40°C
Sample injection volume: 10 μL

<Hydroxyl value>
The hydroxyl value (mgKOH/g) of the obtained urethane acrylate composition was measured according to JIS K0070.

<Compatibility>
(1) 50 parts by mass of methyl ethyl ketone was added to 50 parts by mass of the obtained urethane acrylate composition, and the mixture was sufficiently stirred to prepare a sample for evaluation of compatibility with methyl ethyl ketone.
(2) To 50 parts by mass of the obtained urethane acrylate composition, 50 parts by mass of isopropyl alcohol was blended and sufficiently stirred to prepare a sample for evaluation of compatibility with isopropyl alcohol.
(3) 50 parts by mass of pentaerythritol triacrylate was blended with 50 parts by mass of the obtained urethane acrylate composition and sufficiently stirred to prepare a compatibility evaluation sample for pentaerythritol triacrylate.
Each of the compatibility evaluation samples (1) to (3) above was evaluated according to the following evaluation criteria.
A: Transparent B: Slightly cloudy C: Cloudy or separated

（２）フルオレン型エポキシ化合物のアクリル酸エステル

The following compound was used as the (meth)acrylic acid ester compound of the epoxy compound.
(1) Acrylic acid ester of bisphenol A type epoxy compound

(2) Acrylic acid ester of fluorene-type epoxy compound

(C) The following were used as a component.
(1) Penerythritol triacrylate (mixture)
Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate Hydroxyl value: 118.0 mgKOH/g
(2) Dipentaerythritol pentaacrylate (mixture)
Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate Hydroxyl value: 95.0 mgKOH/g

[Example 1]
46.8 parts by mass of an acrylic acid ester compound of a bisphenol A type epoxy compound as component (A), 45.9 parts by mass of pentaerythritol triacrylate (mixture) as component (C), and 0.05 mass of p-methoxyphenol as an additive 0.04 parts by mass of dioctyltin dineodecanoate and 42.7 parts by mass of methyl ethyl ketone as a solvent were mixed, and the temperature was raised to 60°C. Next, 7.3 parts by mass of xylylene diisocyanate as component (B) was added dropwise over about 30 minutes, and then the temperature was raised to 75°C. A urethane acrylate containing a urethane acrylate compound (D) having structural units derived from the following components (A), (B), and (C), which is reacted until the residual isocyanate concentration is 0.1% or less. A methyl ethyl ketone solution of the system composition was obtained. Table 1 shows the evaluation results.

Structure of representative urethane acrylate compound (D) in Example 1

[Examples 2 to 5]
A methyl ethyl ketone solution of a urethane acrylate composition was obtained in the same manner as in Example 1, except that the types and amounts of each component were changed as shown in Table 1. Table 1 shows the evaluation results.
Representative structures of urethane acrylate compounds (D) having structural units derived from components (A), (B), and (C) obtained in Examples 2 to 4 are shown below.

Structure of representative urethane acrylate compound (D) in Example 2

Representative structure of urethane acrylate compound (D) in Example 3

Structure of representative urethane acrylate compound (D) in Example 4

[Comparative Example 1]
(A) 90.6 parts by mass of an acrylic acid ester compound of a bisphenol A type epoxy compound as a component, 0.05 parts by mass of p-methoxyphenol as an additive, 0.04 parts by mass of dioctyltin dineodecanoate, and methyl ethyl ketone as a solvent 42.7 parts by mass were mixed and heated to 60°C. Next, 9.4 parts by mass of xylylene diisocyanate as component (B) was added dropwise over about 30 minutes, and then the temperature was raised to 75°C. The reaction was continued until the residual isocyanate concentration became 0.1% or less to obtain a methyl ethyl ketone solution of a urethane acrylate composition. Table 1 shows the evaluation results.

[Comparative Example 2]
A methyl ethyl ketone solution of a urethane acrylate composition was obtained in the same manner as in Comparative Example 1, except that the types and amounts of each component were changed as shown in Table 1. Table 1 shows the evaluation results.

[Comparative Example 3]
95.0 parts by mass of pentaerythritol triacrylate as component (C), 0.05 parts by mass of p-methoxyphenol as an additive, 0.04 parts by mass of dioctyltin dineodecanoate, and 42.7 parts by mass of methyl ethyl ketone as a solvent. Mix and heat to 60°C. Then, 5.0 parts by mass of xylylene diisocyanate as component (B) was added dropwise over about 30 minutes, and then the temperature was raised to 75°C. The reaction was continued until the residual isocyanate concentration became 0.1% or less to obtain a methyl ethyl ketone solution of a urethane acrylate composition. Table 1 shows the evaluation results.

[Comparative Example 4]
A methyl ethyl ketone solution of a urethane acrylate composition was obtained in the same manner as in Comparative Example 3, except that the types and amounts of each component were changed as shown in Table 1. Table 1 shows the evaluation results.

From the results of Examples 1 to 5, it was found that the urethane acrylate composition of the present invention has a high refractive index and good compatibility with methyl ethyl ketone, isopropyl alcohol and pentaerythritol triacrylate.
Solvents such as methyl ethyl ketone and isopropyl alcohol and polyfunctional (meth)acrylates such as pentaerythritol triacrylate are used as one component of the active energy ray-polymerizable composition for forming the hard coat layer. Therefore, from these results, it can be seen that when the urethane acrylate-based composition of the present invention is used to prepare an active energy ray-polymerizable composition, the composition has good compatibility.
On the other hand, the urethane acrylate compositions of Comparative Examples 1 to 4, which did not satisfy the requirements of the present invention, had a low refractive index or poor compatibility, and could not achieve a good balance of physical properties as in the present invention. .

Claims (6)

(Meth)acrylic acid ester compound (A)-derived structural units of an epoxy compound obtained by adding (meth)acrylic acid to an epoxy compound, structural units derived from an organic polyisocyanate compound (B), and a polyfunctional (meth) ) containing a urethane (meth)acrylate compound (D) containing a structural unit derived from acrylate (C),
A compound having at least one of (A) component-derived structural units, (B) component-derived structural units, and (C) component-derived structural units, and the total amount of unreacted components (A) to (C) is 100% by mass,
A number average molecular weight of 500 or more and 1400 or less, a hydroxyl value of 70 mgKOH/g or more and 130 mgKOH/g or less ,
The epoxy compound is a bisphenol A type epoxy compound or a fluorene type epoxy compound,
The polyfunctional (meth)acrylate (C) includes pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, sorbitol di(meth)acrylate. , sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, di A urethane (meth)acrylate composition that is at least one selected from the group consisting of pentaerythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate . (Meth)acrylic acid ester compound (A) of epoxy compound obtained by adding (meth)acrylic acid to epoxy compound, organic polyisocyanate compound (B), and polyfunctional (meth)acrylate having hydroxyl group (C) are reacted. obtained by
A compound having at least one of (A) component-derived structural units, (B) component-derived structural units, and (C) component-derived structural units, and the total amount of unreacted components (A) to (C) is 100% by mass,
A number average molecular weight of 500 or more and 1400 or less, a hydroxyl value of 70 mgKOH/g or more and 130 mgKOH/g or less ,
The epoxy compound is a bisphenol A type epoxy compound or a fluorene type epoxy compound,
The polyfunctional (meth)acrylate (C) includes pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane di(meth)acrylate, glycerin di(meth)acrylate, sorbitol di(meth)acrylate. , sorbitol tri(meth)acrylate, sorbitol tetra(meth)acrylate, sorbitol penta(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, di A urethane (meth)acrylate composition that is at least one selected from the group consisting of pentaerythritol tetra(meth)acrylate and dipentaerythritol penta(meth)acrylate . The urethane (meth)acrylate composition according to claim 1 or 2, wherein the organic polyisocyanate compound (B) is an aromatic polyisocyanate. The urethane (meth)acrylate composition according to any one of claims 1 to 3 , wherein the polyfunctional (meth)acrylate (C) contains at least one of pentaerythritol triacrylate and dipentaerythritol pentaacrylate. The urethane (meth)acrylate composition according to any one of claims 1 to 4 , which is used for optical members. The NCO/OH ratio, which is the molar ratio of the isocyanate groups of the component (B) to the total hydroxyl groups of the hydroxyl groups of the component (A) and the hydroxyl groups of the component (C), is 0.15 or more and 0.40 or less. 2. The method for producing the urethane (meth)acrylate composition according to 2 above.