JP6217208B2 - Active energy ray-curable composition - Google Patents

Description

  The present invention relates to an active energy ray-curable composition and preferably belongs to the technical field of coating agents and paints.

  Conventionally, for various substrates such as metal, glass and plastic, a protective film is formed on the substrate using a coating composition for the purpose of protecting the substrate surface or imparting aesthetics or design. The forming method is used. In particular, the plastic substrate is lightweight and excellent in impact resistance, easy moldability, and the like. However, since the surface is easily damaged and has low hardness, there is a drawback that the appearance is remarkably impaired when used as it is. For this reason, it is required to apply a so-called hard coat treatment on the surface of the plastic substrate with a coating composition to impart scratch resistance and improve surface hardness.

Conventionally, as a method for improving the surface hardness of a plastic substrate, an active energy ray curable composition comprising a (meth) acrylate having an alicyclic skeleton excellent in hardness of a cured coating film is known (Patent Document 1 and 2).
Moreover, what utilized the photocationic polymerization of cyclic ether as a coating agent is known (patent document 3).
Furthermore, as a coating agent, a method of combining 4- (meth) acryloylmorpholine and a trifunctional or higher functional (meth) acrylate having one or more hydroxyl groups is known (Patent Document 4).

JP 2003-268263 A JP 2013-49802 A JP 2007-284613 A JP 2012-111943 A

The (meth) acrylate having an alicyclic skeleton as described in Patent Documents 1 and 2 has a high glass transition point (Tg) and good hardness in many cases, but the stress at the time of active energy ray curing is high. Since it is large, there is a tendency that adhesion to a substrate is difficult to obtain. In Patent Documents 1 and 2, adhesion to a plastic substrate is not disclosed in Examples. In the method described in Patent Document 2, a reactive polymer is produced in advance using a thermal initiator. If the thermal initiator used at this time remains, the active energy ray-curable composition is stored. It may be cured by polymerization, and it cannot be said that it has sufficient stability.
In the method described in Patent Document 3, it is disclosed in Examples that adhesion and curl resistance are good as compared with a coating agent using photoradical polymerization of (meth) acrylate. However, in cationic polymerization, it is known that the humidity in the working atmosphere greatly affects the curability. In particular, since hard coating is often applied as a thin film, the influence of humidity is likely to occur, and the desired curability and performance as a coating may not be obtained in the rainy season or summer.
In the method described in Patent Document 4, good adhesion is obtained by using 4- (meth) acryloylmorpholine. However, in this method, shrinkage at the time of curing is large and curl resistance is good. It is not possible.

  The problem to be solved by the present invention is to provide an active energy ray-curable composition in which the obtained cured film is excellent in hardness, adhesion to a substrate, followability to deformation of the substrate, and curl resistance. is there.

The above object has been achieved by the means described in <1> below. It is shown below with <2>-<10> which are preferable embodiments.
<1> (A) The following (A-1) component or the following (A-2) component, and (B) the compound which has ethylenically unsaturated groups other than (A) component, (A) component And with respect to 100 weight part of total content of (B) component, content of (A) component is 40-97 weight part, and content of (B) component is 3-60 weight part An active energy ray-curable composition characterized by
(A-1) A hydroxyl group of a (meth) acrylic acid adduct of a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g or more, and a polyvalent isocyanate compound (A) a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g. Polyester (meth) acrylate-containing reaction product obtained by reacting the hydroxyl group of the (meth) acrylic acid adduct and the carboxyl group of the polyvalent carboxylic acid compound <2> (A-1) component and (A- 2) The hydroxyl value of the (meth) acrylic acid adduct of the trihydric or higher aliphatic polyhydric alcohol compound in the component is 160 to 220 mgKOH / In it, the active energy ray curable composition according to <1>,
<3> The (meth) acrylic acid adduct of the trivalent or higher aliphatic polyhydric alcohol compound in the component (A-1) and the component (A-2) is a 3-6 valent aliphatic polyhydric alcohol compound. The active energy ray-curable composition according to <1> or <2>, which is a (meth) acrylic acid adduct,
<4> The (meth) acrylic acid adduct of the trivalent or higher aliphatic polyhydric alcohol compound in the components (A-1) and (A-2) is a (meth) acrylic acid adduct of pentaerythritol. The active energy ray-curable composition according to <3>,
<5> The active energy ray-curable composition according to any one of <1> to <4>, wherein the component (A) is the component (A-2),
<6> (C) The active energy ray-curable composition according to any one of <1> to <5>, further containing a photopolymerization initiator,
<7> The active energy according to <6>, wherein the content of the component (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B). Wire curable composition,
<8> (D) The active energy ray-curable composition according to any one of <1> to <7>, further containing an organic solvent,
<9> The active energy according to <8>, wherein the content of the component (D) is 10 to 1,000 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B). Wire curable composition,
<10> The active energy ray-curable composition according to any one of <1> to <9>, which is used for a coating agent.

  ADVANTAGE OF THE INVENTION According to this invention, the cured film obtained can provide the active energy ray hardening-type composition excellent in hardness, adhesiveness with a base material, followable | trackability with respect to a deformation | transformation of a base material, and curl resistance.

Hereinafter, the present invention will be described in detail.
In the present specification, acrylate and / or methacrylate are also referred to as (meth) acrylate, acryloyl group and / or methacryloyl group as (meth) acryloyl group, and acrylic acid and / or methacrylic acid as (meth) acrylic acid. .
In the present invention, the description of “lower limit to upper limit” representing a numerical range represents “more than the lower limit and less than or equal to the upper limit”, and the description of “upper limit to lower limit” represents “the upper limit or less and less than the lower limit”. That is, it represents a numerical range including an upper limit and a lower limit.
In the present invention, “(A) (A-1) component or (A-2) component” or the like is also simply referred to as “(A) component” or the like, and “(A-1) trivalent or higher fat”. (Meth) acrylic acid adduct of an aromatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g or more, and a urethane formed by reacting the hydroxyl group of the polyvalent isocyanate compound with an isocyanato group The “(meth) acrylate-containing reaction product” or the like is also simply referred to as “(A-1) component” or the like.

(Active energy ray-curable composition)
Hereinafter, the active energy ray-curable composition of the present invention (hereinafter, also simply referred to as “the composition of the present invention”) will be described in detail.
The active energy ray-curable composition of the present invention is a compound having an ethylenically unsaturated group other than (A) the following (A-1) component or the following (A-2) component and (B) (A) component. The content of the component (A) is 40 to 97 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B), and the content of the component (B) is 3 to 60 parts by weight.
(A-1) A hydroxyl group of a (meth) acrylic acid adduct of a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g or more, and a polyvalent isocyanate compound (A) a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g. Polyester (meth) acrylate-containing reaction product obtained by reacting the hydroxyl group of the (meth) acrylic acid adduct and the carboxyl group of the polyvalent carboxylic acid compound as described above.

The active energy ray-curable composition of the present invention can be used in various applications such as coating agents such as paints described later, forming resins such as inks, nanoimprints and lens sheets, and adhesives. It can be suitably used for the agent.
Hereinafter, components (A) and (B), which are essential components, and components (C) to (E) and other components, which are optional components, contained in the composition of the present invention will be described in order.

(A) (A-1) component or (A-2) component The active energy ray-curable composition of the present invention contains (A) the following (A-1) component or the following (A-2) component, The content of the component (A) is 40 to 97 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B).
(A-1) A hydroxyl group of a (meth) acrylic acid adduct of a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g or more, and a polyvalent isocyanate compound (A) a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g. Polyester (meth) acrylate-containing reaction product obtained by reacting the hydroxyl group of the (meth) acrylic acid adduct and the carboxyl group of the polyvalent carboxylic acid compound as described above (A-1) and (A-2) In the component, “(meth) acrylic acid adduct” is synonymous with “(meth) acrylic acid ester”.
The component (A) is preferably the component (A-1) from the viewpoint of the adhesion of the resulting cured film, and the component (A-2) from the viewpoint of cost and ease of preparation of physical properties. It is preferable that

<(Meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 140 mgKOH / g or more>
A (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound used for the production of the component (A-1) and the component (A-2) having a hydroxyl value of 140 mgKOH / g or more (meta ) Acrylic acid adduct (hereinafter also referred to as “compound (A0)”) is a reaction product obtained by esterifying (meth) acrylic acid with a trihydric or higher aliphatic polyhydric alcohol compound. The product has a hydroxyl value of 140 mgKOH / g or more.

The trihydric or higher aliphatic polyhydric alcohol compound used for the production of the compound (A0) may be any trihydric or higher alcohol compound having no aromatic ring. An alcohol compound is preferable, a tetravalent to hexavalent aliphatic polyhydric alcohol compound is more preferable, and a tetravalent aliphatic polyhydric alcohol compound is particularly preferable. When it is the said aspect, the cured film obtained is excellent by hardness, adhesiveness with a base material, followability with respect to a deformation | transformation of a base material, and curl resistance.
Specific examples of trihydric or higher aliphatic polyhydric alcohol compounds include trimethylolpropane, trimethylolpropane alkylene oxide adduct, pentaerythritol, pentaerythritol alkylene oxide adduct, ditrimethylolpropane, and ditrimethylolpropane alkylene oxide. Examples include adducts, dipentaerythritol, alkylene oxide adducts of dipentaerythritol, tripentaerythritol, alkylene oxide adducts of tripentaerythritol, and isocyanurate alkylene oxide adducts. Preferred examples of the alkylene oxide of the alkylene oxide adduct include ethylene oxide and / or propylene oxide.
Among these, trimethylolpropane, alkylene oxide adduct of trimethylolpropane, pentaerythritol, alkylene oxide adduct of pentaerythritol, ditrimethylolpropane, alkylene oxide adduct of ditrimethylolpropane, alkylene of dipentaerythritol and dipentaerythritol Oxide adducts are preferred, pentaerythritol, alkylene oxide adducts of pentaerythritol, ditrimethylolpropane, alkylene oxide adducts of ditrimethylolpropane, alkylene oxide adducts of dipentaerythritol and dipentaerythritol are more preferred, pentaerythritol, ditritriol. More preferred are methylolpropane and dipentaerythritol, Pentaerythritol are particularly preferred.
Trivalent or higher aliphatic polyhydric alcohol compounds may be used singly or in combination of two or more, but are preferably used singly.

(Meth) acrylic acid used for the production of compound (A0) may be either acrylic acid or methacrylic acid, or both acrylic acid and methacrylic acid, but only acrylic acid. Is preferably used.
In addition, in the production of the compound (A0), instead of (meth) acrylic acid, (meth) acrylic acid equivalent, (meth) acrylic acid halide, (meth) acrylic anhydride, (meth) acrylic acid are used. An ester compound or the like may be used.
The amount of (meth) acrylic acid used in the production of compound (A0) is not particularly limited as long as the hydroxyl value of the obtained (meth) acrylic acid adduct is 140 mgKOH / g or more. Further, the molar amount of (meth) acrylic acid used is preferably smaller than the molar amount of the hydroxyl group of the trihydric or higher aliphatic polyhydric alcohol compound used.
The hydroxyl value of the compound (A0) is 140 mgKOH / g or more, preferably 160 mgKOH / g or more, more preferably 160 to 220 mgKOH / g, and still more preferably 170 to 220 mgKOH / g. When it is the said aspect, the cured film obtained is excellent by hardness, adhesiveness with a base material, followability with respect to a deformation | transformation of a base material, and curl resistance.
In addition, the hydroxyl value employ | adopts the value measured according to the method defined in JISK0070-1992.

The compound (A0) is composed of a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having no hydroxyl group, and a (meth) acrylic polyhydric alcohol compound of a trihydric or higher aliphatic polyhydric alcohol compound having only one hydroxyl group. ) It is preferable to contain at least an acrylic acid adduct, and a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having no hydroxyl group, a trihydric or higher aliphatic polyhydric alcohol having only one hydroxyl group. It is more preferable to contain at least a (meth) acrylic acid adduct of a compound and a (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound having only two hydroxyl groups.
In addition, in the compound (A0), a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having no hydroxyl group, and a trihydric or higher aliphatic polyhydric alcohol compound having only one hydroxyl group The total content of the (meth) acrylic acid adduct is preferably 50% by weight or more, more preferably 65% by weight or more, and further preferably 80% by weight or more.
Further, in the compound (A0), a (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound having no hydroxyl group, a trivalent or higher aliphatic polyhydric alcohol compound having only one hydroxyl group ( The total content of the (meth) acrylic acid adduct and the (meth) acrylic acid adduct of the trivalent or higher aliphatic polyhydric alcohol compound having only two hydroxyl groups is preferably 65% by weight or more, and 80 More preferably, it is more than 90% by weight.

There is no restriction | limiting in particular as a manufacturing method of a compound (A0), Although well-known esterification reaction can be used, It is preferable to use a catalyst and a stabilizer. As the catalyst, an acid catalyst can be preferably exemplified. Moreover, as a stabilizer, well-known polymerization inhibitors, such as hydroquinone monomethyl ether, can be mentioned suitably. It is also preferable to use oxygen as a stabilizer, particularly a polymerization inhibitor. For example, unnecessary polymerization of (meth) acrylic acid or (meth) acrylic acid ester can be prevented by producing the compound (A0) in an oxygen-containing atmosphere. Moreover, it is preferable that it is 1-20 volume%, and, as for content of oxygen in atmosphere, it is more preferable that it is 1-10 volume%.
Moreover, it is preferable that the manufacturing method of a compound (A0) includes the method of refine | purifying at least liquid-liquid extraction (separation). In the above embodiment, an adduct having a hydroxyl value of 140 mgKOH / g or more can be easily produced.

<(A-1) component>
The component (A-1) is a urethane (meth) acrylate-containing reaction product obtained by reacting the hydroxyl group in the compound (A0) with the isocyanato group of the polyvalent isocyanate compound.
A preferred embodiment of the compound (A0) in the component (A-1) is as described above.
Various compounds can be used as the polyvalent isocyanate compound.
The polyvalent isocyanate compound is preferably a divalent isocyanate compound, and is preferably a polyvalent aliphatic isocyanate compound.
Specific examples of preferred polyisocyanate compounds include isophorone diisocyanate, hexamethylene diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-tolylene diisocyanate, naphthalene diisocyanate, xylene diisocyanate, diphenylmethane diisocyanate and their nurate. Examples include mold trimers.
Moreover, although a polyvalent isocyanate compound may be used individually by 1 type or may use 2 or more types together, it is preferable to use individually by 1 type.

The weight average molecular weight (hereinafter also referred to as “Mw”) of the component (A-1) is preferably 800 to 100,000, more preferably 1,000 to 10,000, and 1,200. Is more preferably 5,000, and particularly preferably 1,500 to 3,000.
Mw in the present invention means a weight average molecular weight in terms of polystyrene measured by a gel permeation chromatography (GPC) method.

The component (A-1) is a urethane (meth) acrylate and a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having no hydroxyl group, that is, a trihydric or higher aliphatic polyhydric alcohol. It is preferable that at least a compound in which all hydroxyl groups of the compound are (meth) acrylated is included,
A urethane (meth) acrylate obtained by reacting a (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound having only one hydroxyl group with a polyvalent isocyanate compound, and a trivalent or higher fatty acid having no hydroxyl group More preferably, it contains at least a (meth) acrylic acid adduct of an aromatic polyhydric alcohol compound,
A (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having only two hydroxyl groups and a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having only one hydroxyl group; Urethane (meth) acrylate reacted with polyvalent isocyanate compound, (meth) acrylic acid adduct of trivalent or higher aliphatic polyhydric alcohol compound having only one hydroxyl group and polyvalent isocyanate compound It is more preferable to contain at least a (meth) acrylic acid adduct of an acrylate and a trihydric or higher aliphatic polyhydric alcohol compound having no hydroxyl group.

  Moreover, it is preferable that (A-1) component contains the urethane (meth) acrylate which has a structural unit represented by a following formula (A-1-1).

（式（Ａ−１−１）中、Ｌはｎ価の脂肪族連結基を表し、Ｒはそれぞれ独立に、アクリル基又はメタクリル基を表し、ｎは３以上の整数を表す。）

(In formula (A-1-1), L represents an n-valent aliphatic linking group, R independently represents an acrylic group or a methacryl group, and n represents an integer of 3 or more.)

L is preferably a residue obtained by removing n hydroxyl groups from an n-valent aliphatic polyhydric alcohol compound, and removes n hydroxyl groups from an n-valent aliphatic polyhydric alcohol compound having 4 to 20 carbon atoms. The residue is more preferably a residue obtained by removing n hydroxyl groups from an n-valent aliphatic polyhydric alcohol compound having 5 to 10 carbon atoms.
R is preferably all acrylic groups or all methacrylic groups.
n is preferably an integer of 3 to 6, and more preferably an integer of 4 to 6.

  Furthermore, the component (A-1) is a urethane (meth) acrylate having a structural unit represented by the formula (A-1-1) and a structural unit represented by the following formula (A-1-2). The urethane (meth) acrylate having a structural unit represented by the formula (A-1-1) and a structural unit represented by the following formula (A-1-2), and the following formula ( It is more preferable to include a urethane (meth) acrylate having no structural unit represented by A-1-2) and having a structural unit represented by the formula (A-1-1).

（式（Ａ−１−２）中、Ｌはｎ価の脂肪族連結基を表し、Ｒはそれぞれ独立に、アクリル基又はメタクリル基を表し、ｎは３以上の整数を表す。）

(In formula (A-1-2), L represents an n-valent aliphatic linking group, R independently represents an acryl group or a methacryl group, and n represents an integer of 3 or more.)

L, R, and n in Formula (A-1-2) have the same meanings as L, R, and n in Formula (A-1-1), respectively, and preferred embodiments are also the same.
The component (A-1) is a urethane (meth) acrylate having a structural unit represented by the formula (A-1-1) and a structural unit represented by the following formula (A-1-2). When it contains, it is preferable that L, R, and n in Formula (A-1-1) and L, R, and n in Formula (A-1-2) are the same.

  Moreover, it is preferable that (A-1) component contains the compound represented by a following formula (A-1-3).

（式（Ａ−１−３）中、Ｌはｎ価の脂肪族連結基を表し、Ｒはそれぞれ独立に、アクリル基又はメタクリル基を表し、ｎは３以上の整数を表す。）

(In formula (A-1-3), L represents an n-valent aliphatic linking group, R independently represents an acryl group or a methacryl group, and n represents an integer of 3 or more.)

L, R and n in the formula (A-1-3) have the same meanings as L, R and n in the formula (A-1-1), respectively, and preferred embodiments are also the same.
The component (A-1) is a urethane (meth) acrylate having a structural unit represented by the formula (A-1-1), or a structural unit represented by the formula (A-1-1). When the urethane (meth) acrylate having the structural unit represented by the formula (A-1-2) is included, L, R and n in the formula (A-1-1) and the formula (A-1-2) L, R and n in the formula (A) and L, R and n in the formula (A-1-3) are preferably the same.

  (A-1) The reaction ratio (molar ratio) between the hydroxyl group in the compound (A0) and the isocyanate group of the polyvalent isocyanate compound at the time of producing the component is hydroxyl group: isocyanato group = 1: 0.6 to 1: It is preferably 1, hydroxyl group: isocyanato group = 1: 0.8 to 1: 1, more preferably hydroxyl group: isocyanato group = 1: 0.9 to 1: 1. The hardness of the obtained cured film is more excellent as it is the said aspect.

The component (A-1) is preferably a mixture of urethane (meth) acrylate and a compound in which all the hydroxyl groups of the trivalent or higher aliphatic polyhydric alcohol compound are (meth) acrylated.
The ratio of the urethane (meth) acrylate and the compound in which all the hydroxyl groups of the trihydric or higher aliphatic polyhydric alcohol compound are (meth) acrylated may be appropriately set according to the purpose, but (A-1) The component preferably contains urethane (meth) acrylate: a compound in which all hydroxyl groups of a trivalent or higher aliphatic polyhydric alcohol compound are (meth) acrylated = 30: 70 to 98: 2 in a weight ratio of urethane ( (Meth) acrylate: Compound in which all hydroxyl groups of trivalent or higher aliphatic polyhydric alcohol compound are (meth) acrylated = 30: 70 to 95: 5 is more preferably included. The hardness and adhesiveness of the cured film obtained are more excellent in the above range.

There is no restriction | limiting in particular as a manufacturing method of (A-1) component, A well-known method can be used. For example, the addition reaction between a hydroxyl group and an isocyanato group can be carried out without a catalyst, but in order to advance the reaction efficiently, a tin-based catalyst such as dibutyltin dilaurate or an amine-based catalyst such as triethylamine may be added. Good.
Further, when the isocyanato group remains, the component (A-1) does not have an isocyanato group or a small amount of the isocyanato group is preferable from the viewpoint of hardness and stability. A compound having a hydroxyl group and two or more (meth) acryloyl groups (hereinafter also referred to as “hydroxyl group-containing polyfunctional (meth) acrylate”) may be added.

As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, which are (meth) acrylates derived from a trihydric or higher polyhydric alcohol, having two or more (meth) acryloyl groups, It is preferable that it is (meth) acrylate which has 1 or more.
Specific examples of the hydroxyl group-containing polyfunctional (meth) acrylate include trimethylolpropane di (meth) acrylate, di (meth) acrylate of trimethylolpropane alkylene oxide adduct, di- or tri (meth) acrylate of pentaerythritol, penta Di or tri (meth) acrylate of alkylene oxide adduct of erythritol, di or tri (meth) acrylate of ditrimethylolpropane, di or tri (meth) acrylate of alkylene oxide adduct of ditrimethylolpropane, dipentaerythritol di, Di, tri, tetra or penta (meth) acrylate and isocyanurate alkylene oxide of tri, tetra or penta (meth) acrylate, dipentaerythritol alkylene oxide adduct Di (meth) acrylate of adduct, dipentaerythritol di, tri, tetra, penta, hexa, or hepta (meth) acrylate, alkylene oxide adduct of tripentaerythritol di, tri, tetra, penta, hexa, or hepta Examples include di (meth) acrylates of alkylene oxide adducts of (meth) acrylate and isocyanurate.
In this case, examples of the alkylene oxide include ethylene oxide and propylene oxide.
Among them, trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, di or tri (meth) acrylate of ditrimethylolpropane and di, tri, tetra or penta (meth) acrylate of dipentaerythritol Preferably mentioned.

<(A-2) component>
The component (A-2) is a polyester (meth) acrylate-containing reaction product obtained by reacting the hydroxyl group in the compound (A0) with the carboxyl group of the polyvalent carboxylic acid compound.
A preferred embodiment of the compound (A0) in the component (A-2) is as described above.
Various compounds can be used as the polyvalent carboxylic acid compound.
The polyvalent carboxylic acid compound is preferably a divalent carboxylic acid compound, and is preferably a polyvalent aliphatic carboxylic acid compound.
Examples of the polyvalent carboxylic acid compound include fumaric acid, maleic acid, maleic anhydride, succinic acid, succinic anhydride, adipic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, sebacic acid, trimellitic acid, And isocyanuric acid. Among these, succinic acid, adipic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, and sebacic acid are mentioned.
Moreover, although a polyvalent carboxylic acid compound may be used individually by 1 type or may use 2 or more types together, it is preferable to use individually by 1 type.

  The Mw of the component (A-2) is preferably 800 to 100,000, more preferably 1,000 to 10,000, further preferably 1,200 to 5,000. , 500 to 3,000 is particularly preferable.

  The component (A-2) preferably contains at least a polyester (meth) acrylate and a (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having no hydroxyl group, and has only one hydroxyl group. Polyester (meth) acrylate obtained by reacting a (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound with a polyvalent carboxylic acid compound, and a trivalent or higher aliphatic polyhydric alcohol having no hydroxyl group More preferably, it contains at least a (meth) acrylic acid adduct of the compound, and a trivalent having only one (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound having only two hydroxyl groups and one hydroxyl group. Polyester (meth) acrylate obtained by reacting the above (meth) acrylic acid adduct of an aliphatic polyhydric alcohol compound with a polycarboxylic acid compound. Relate, a polyester (meth) acrylate obtained by reacting a (meth) acrylic acid adduct of a trivalent or higher aliphatic polyhydric alcohol compound having only one hydroxyl group and a polyvalent carboxylic acid compound, and a trivalent group having no hydroxyl group More preferably, it contains at least a (meth) acrylic acid adduct of the above aliphatic polyhydric alcohol compound.

  Moreover, it is preferable that (A-2) component contains the polyester (meth) acrylate which has a structural unit represented by a following formula (A-2-1).

（式（Ａ−２−１）中、Ｌはｎ価の脂肪族連結基を表し、Ｒはそれぞれ独立に、アクリル基又はメタクリル基を表し、ｎは３以上の整数を表す。）

(In formula (A-2-1), L represents an n-valent aliphatic linking group, R independently represents an acryl group or a methacryl group, and n represents an integer of 3 or more.)

L is preferably a residue obtained by removing n hydroxyl groups from an n-valent aliphatic polyhydric alcohol compound, and removes n hydroxyl groups from an n-valent aliphatic polyhydric alcohol compound having 4 to 20 carbon atoms. The residue is more preferably a residue obtained by removing n hydroxyl groups from an n-valent aliphatic polyhydric alcohol compound having 5 to 10 carbon atoms.
R is preferably all acrylic groups or all methacrylic groups.
n is preferably an integer of 3 to 6, and more preferably an integer of 4 to 6.

  Furthermore, the component (A-2) is a polyester (meth) acrylate having a structural unit represented by the formula (A-2-1) and a structural unit represented by the following formula (A-2-2). The polyester (meth) acrylate having a structural unit represented by the formula (A-2-1) and a structural unit represented by the following formula (A-2-2), and the following formula ( More preferably, it contains a polyester (meth) acrylate having no structural unit represented by A-2-2) and having a structural unit represented by the formula (A-2-1).

（式（Ａ−２−２）中、Ｌはｎ価の脂肪族連結基を表し、Ｒはそれぞれ独立に、アクリル基又はメタクリル基を表し、ｎは３以上の整数を表す。）

(In the formula (A-2-2), L represents an n-valent aliphatic linking group, R independently represents an acrylic group or a methacryl group, and n represents an integer of 3 or more.)

L, R, and n in formula (A-2-2) have the same meanings as L, R, and n in formula (A-2-1), respectively, and preferred embodiments are also the same.
Moreover, (A-2) component has polyester (meth) acrylate which has the structural unit represented by the said Formula (A-2-1), and the structural unit represented by following formula (A-2-2). When included, L, R and n in formula (A-2-1) are preferably the same as L, R and n in formula (A-2-2).

  Moreover, it is preferable that (A-2) component contains the compound represented by a following formula (A-2-3).

（式（Ａ−２−３）中、Ｌはｎ価の脂肪族連結基を表し、Ｒはそれぞれ独立に、アクリル基又はメタクリル基を表し、ｎは３以上の整数を表す。）

(In formula (A-2-3), L represents an n-valent aliphatic linking group, R independently represents an acrylic group or a methacryl group, and n represents an integer of 3 or more.)

L, R, and n in Formula (A-2-3) have the same meanings as L, R, and n in Formula (A-2-1), respectively, and preferred embodiments are also the same.
In addition, the component (A-2) is a polyester (meth) acrylate having a structural unit represented by the formula (A-2-1), or a structural unit represented by the formula (A-2-1). When a polyester (meth) acrylate having a structural unit represented by the formula (A-2-2) is included, L, R, and n in the formula (A-2-1) and the formula (A-2-2) L, R and n in the formula (A) are preferably the same as L, R and n in the formula (A-2-3).

  (A-2) The reaction ratio (molar ratio) between the hydroxyl group in the compound (A0) and the carboxyl group of the polyvalent carboxylic acid compound at the time of production of the component is hydroxyl group: carboxyl group = 1: 0.6-1 Is preferably 1: 1, hydroxyl group: carboxyl group = 1: 0.8 to 1: 1, more preferably hydroxyl group: carboxyl group = 1: 0.9 to 1: 1. The hardness of the obtained cured film is more excellent as it is the said aspect.

The component (A-2) is preferably a mixture of a polyester (meth) acrylate and a compound in which all hydroxyl groups of a trivalent or higher aliphatic polyhydric alcohol compound are (meth) acrylated.
The ratio of the polyester (meth) acrylate and the compound in which all the hydroxyl groups of the trihydric or higher aliphatic polyhydric alcohol compound are (meth) acrylated may be appropriately set according to the purpose, (A-2) The component preferably contains polyester (meth) acrylate: a compound in which all hydroxyl groups of a trivalent or higher aliphatic polyhydric alcohol compound are (meth) acrylated = 30: 70 to 98: 2 in a weight ratio of polyester ( (Meth) acrylate: Compound in which all hydroxyl groups of trivalent or higher aliphatic polyhydric alcohol compound are (meth) acrylated = 30: 70 to 95: 5 is more preferably included. The hardness and adhesiveness of the cured film obtained are more excellent in the above range.

There is no restriction | limiting in particular as a manufacturing method of (A-2) component, A well-known method can be used. For example, although it is synthesized by an esterification reaction, it is preferable to add a catalyst, and more preferable to add an acid catalyst in order to advance the reaction efficiently.
Examples of the acid catalyst include sulfuric acid, nitric acid, p-toluenesulfonic acid, methanesulfonic acid and the like.
Further, when the carboxyl group remains, the component (A-2) does not have a carboxyl group or a small amount of carboxyl groups is preferable from the viewpoint of hardness and stability. A hydroxyl group-containing polyfunctional (meth) acrylate may be added.
As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, and the above-mentioned compounds are preferable.

The viscosity of the component (A) at 50 ° C. is preferably 500 to 500,000 mPa · s, more preferably 1,000 to 200,000 mPa · s, and 4,000 to 150,000 mPa · s. More preferably it is.
The content of the component (A) in the active energy ray-curable composition of the present invention is 40 to 97 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B), and 55 to 55 parts by weight. The amount is preferably 96 parts by weight, more preferably 70 to 95 parts by weight, and particularly preferably 80 to 90 parts by weight. Within the above range, the cured film obtained is more excellent in curling resistance and hardness.

(B) Compound having an ethylenically unsaturated group other than (A) component The active energy ray-curable composition of the present invention contains a compound having an ethylenically unsaturated group other than (B) (A) component, The content of the component (B) is 3 to 60 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B).
The component (B) is a compound having an ethylenically unsaturated group other than the component (A).
Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a (meth) acrylamide group, a vinyl group and a (meth) allyl group, and a (meth) acryloyl group is preferred.
In the following, “monofunctional ethylenically unsaturated compound” means a compound having one ethylenically unsaturated group, and “○ functional ethylenically unsaturated compound” means ○ ethylenically unsaturated group. The “polyfunctional ethylenically unsaturated compound” means a compound having two or more ethylenically unsaturated groups. Further, for example, “monofunctional (meth) acrylate compound” means a compound having one (meth) acryloxy group.

  In the component (B), specific examples of the monofunctional ethylenically unsaturated compound include (meth) acrylic acid, Michael addition dimer of acrylic acid, ω-carboxy-polycaprolactone mono (meth) acrylate, monohydroxy phthalate Ethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, butyl carbitol (meth) acrylate, 2- Ethylhexyl carbitol (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, (meth) acrylate of phenol alkylene oxide adduct, (meta) of alkylphenol alkylene oxide adduct (meta Of alkylene oxide adduct of acrylate, cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, paracumylphenol (Meth) acrylate, orthophenylphenol (meth) acrylate, (meth) acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanemethylol (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, N- (2- (meth) acryloxyethyl) hexahydrophthalimide, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide, N, N-dimethylacrylamide, acryloylmorpholine, N-vinylpyrrolidone, N-vinylcaprolactam and the like can be mentioned.

  Specific examples of the bifunctional (meth) acrylate compound include polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and tetramethylene glycol. Di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, di (meth) acrylate of bisphenol A alkylene oxide adduct, di (meth) acrylate of bisphenol F alkylene oxide adduct, butanediol di (meth) Examples include acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth) acrylate. In addition, epoxy (meth) acrylate having a bisphenol skeleton, polyether skeleton, polyalkylene skeleton, polyester skeleton, urethane (meth) acrylate having a polyether skeleton or a polycarbonate skeleton, and polyester (meth) acrylate may also be used. Can do.

As the trifunctional or higher functional (meth) acrylate compound, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Examples include dipentaerythritol hexa (meth) acrylate and tris (2- (meth) acryloyloxyethyl) isocyanurate.
In addition to this, a polyfunctional urethane (meth) acrylate other than the component (A-1) obtained by urethanizing a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate, a polyfunctional epoxy having a novolak skeleton (meta ) Acrylate and the like, and polyfunctional polyester (meth) acrylate and the like.

(B) As a component, it is preferable that a polyfunctional ethylenically unsaturated compound is included from a viewpoint of the hardness of the cured film obtained, and it is more preferable that a polyfunctional (meth) acrylate compound is included.
The component (B) preferably contains an ethylenically unsaturated compound having a hydroxyl group from the viewpoint of adhesion of the resulting cured film to the substrate and curl resistance, and a (meth) acrylate compound having a hydroxyl group It is more preferable that a monofunctional (meth) acrylate compound having a hydroxyl group is more preferable.
Preferred examples of the ethylenically unsaturated compound having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl acrylate, and 2-hydroxy-3-phenoxypropyl (meth) acrylate. 4-hydroxybutyl acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate are particularly preferred.
The component (B) is preferably a monofunctional ethylenically unsaturated compound and / or a bifunctional ethylenically unsaturated compound.

(B) A component may contain individually by 1 type, or may contain 2 or more types.
The content of the component (B) in the active energy ray-curable composition of the present invention is 3 to 60 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). The amount is preferably 45 parts by weight, more preferably 5 to 30 parts by weight, and particularly preferably 10 to 20 parts by weight. Within the above range, the cured film obtained is more excellent in curling resistance and hardness.

(C) Photopolymerization initiator The active energy ray-curable composition of the present invention does not contain, for example, (C) a photopolymerization initiator and can be cured by an electron beam. From the viewpoint of cost, it is preferable to further contain (C) a photopolymerization initiator.
As the photopolymerization initiator in the present invention, various known photopolymerization initiators can be used.
The photopolymerization initiator is preferably a photoradical polymerization initiator.

  Specific examples of the component (C) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one. 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- ( 1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl Acetophenone compounds such as 2-methylpropan-1-one; benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4′-methyldiphenylsulfide; methylbenzoyl Α-ketoester compounds such as formate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid; 2,4,6 -Trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, etc. Phosphine oxide compounds; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanocene compounds; 1- [4- (4-benzoylphenylsulfanyl) phenyl] -2- Acetophenone / benzophenone hybrid photoinitiators such as methyl-2- (4-methylphenylsulfinyl) propan-1-one; 2- (O-benzoyloxime) -1- [4- (phenylthio)]-1,2- And oxime ester photopolymerization initiators such as octanedione; and camphorquinone.

  Among these, acetophenone compounds, benzophenone compounds, and phosphine oxide compounds are preferable, and acetophenone compounds are particularly preferable.

As the component (C), only one type may be used, or two or more types may be used in combination.
The content of the component (C) in the active energy ray-curable composition of the present invention is 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B). Is more preferable, 0.5 to 7 parts by weight is more preferable, and 1 to 5 parts by weight is particularly preferable. Within the above range, the composition is excellent in curability and the resulting cured film is excellent in scratch resistance.

(D) Organic solvent The active energy ray-curable composition of the present invention preferably further contains (D) an organic solvent from the viewpoints of applicability and handleability of the composition.
Various known organic solvents can be used as the organic solvent in the present invention.
The component (D) is preferably one that dissolves the component (A) and the component (B). When the component (C) is contained, the component (A), the component (B), and the component (C) are dissolved. Those are more preferred.

Specific examples of preferred component (D) include alcohol compounds such as methanol, ethanol, isopropanol and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene, Aromatic compounds such as toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone Is mentioned.
Among these, alkylene glycol monoether compounds and ketone compounds are preferable, and alkylene glycol monoether compounds are more preferable.

As the component (D), only one type may be used, or two or more types may be used in combination.
The content of the component (D) in the active energy ray-curable composition of the present invention is 10 to 1,000 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B). Is preferable, it is more preferable that it is 50-500 weight part, and it is further more preferable that it is 50-300 weight part. Within the above range, the composition can have a viscosity suitable for coating, and the composition can be easily applied by a known application method described later.

(E) Other component The active energy ray hardening-type composition of this invention may further contain other components other than (A) component-(D) component.
As other components, known additives can be used. For example, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, antioxidants, silane coupling agents, surface modifiers, polymers, acids Examples include generators, pigments, dyes, tackifiers, polymerization inhibitors, and the like.

<Ultraviolet absorber>
The active energy ray-curable composition of the present invention may further contain an ultraviolet absorber.
Specific 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, 3,5-triazine, 2- [4-[(2-hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyroxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2- ( 2-hydroxy-4- 1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine and other triazine ultraviolet absorbers; 2- (2H-benzotriazol-2-yl)- 4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-5- (2- ( Benzotriazole ultraviolet absorbers such as (meth) acryloyloxyethyl) phenyl] -2H-benzotriazole; benzophenone ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, ethyl-2-cyano -3,3-diphenyl acrylate, octyl-2-cyano-3,3-diphenyl Cyanoacrylate ultraviolet absorbers such as acrylate, titanium oxide particles, zinc oxide particles, and inorganic particles, and the like to absorb the ultraviolet rays or the like tin oxide particles.

An ultraviolet absorber may be used individually by 1 type, and may use 2 or more types together.
Of these, benzotriazole ultraviolet absorbers are particularly preferred.
The content of the ultraviolet absorber in the active energy ray-curable composition of the present invention is 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). Preferably, it is 0.05-5 weight part, More preferably, it is 0.1-2 weight part.

<Light stabilizer>
The active energy ray-curable composition of the present invention may further contain a light stabilizer.
As the light stabilizer, a known light stabilizer can be used. Among them, a hindered amine light stabilizer (HALS) is preferably exemplified.
Specific examples of the hindered amine light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. 2,4-bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-triazine, decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, and the like.
Examples of commercially available hindered amine light stabilizers include BASIN, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100.

A light stabilizer may be used individually by 1 type and may use 2 or more types together.
The content of the ultraviolet absorber in the active energy ray-curable composition of the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). Preferably, it is 0.05-2 parts by weight, more preferably 0.1-1 part by weight.

<Acid substance>
The active energy ray-curable composition of the present invention is excellent as a material for adhering to a substrate such as plastic, but the adhesion can be further improved by adding an acidic substance.
Examples of the acidic substance include a photoacid generator that generates an acid upon irradiation with active energy rays, sulfuric acid, nitric acid, hydrochloric acid, p-toluenesulfonic acid, methanesulfonic acid, phosphoric acid, and the like.
Among these, an inorganic acid or an organic acid is preferable, an organic sulfonic acid compound is more preferable, an aromatic sulfonic acid compound is further preferable, and p-toluenesulfonic acid is particularly preferable.
An acidic substance may be used individually by 1 type, and may use 2 or more types together.
The content of the acidic substance in the active energy ray-curable composition of the present invention is preferably 0.0001 to 5 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). 0.0001 to 1 part by weight, more preferably 0.0005 to 0.5 part by weight. Within the above range, the adhesion to the substrate is excellent, and problems such as corrosion of the substrate and decomposition of other components can be prevented.

<Inorganic particles>
The active energy ray-curable composition of the present invention may further contain inorganic particles.
As the inorganic particles, metal oxide particles are preferable.
The metal oxide particles are preferably metal oxide particles or composite metal oxide particles made of one or more metals selected from the group consisting of silicon, zirconium, titanium, antimony, tin, cerium, aluminum, zinc and indium. Can be mentioned.

The average particle diameter of the inorganic particles may be selected according to the use, but is preferably 1 to 1,000 nm, more preferably 5 to 500 nm, and particularly preferably 10 to 100 nm. Within the above range, the transparency and appearance of the cured film are good.
In the present invention, the average particle diameter of the inorganic particles means a particle diameter when assuming that the particles are true spherical particles from the specific surface area of the sample obtained by the BET method.

The inorganic particles may be surface-modified particles.
As the surface modifier, a known one can be used, and a silane coupling agent, a titanium coupling agent, and the like are preferable.
Among these, a silane coupling agent is more preferable, and a compound having an ethylenically unsaturated group and an alkoxysilyl group is particularly preferable. It is excellent in the hardness and curl resistance of the cured film obtained as it is the said aspect. Specific examples of the silane coupling agent include the same compounds as those described below.
The surface modification amount of the inorganic particles is not particularly limited, but the ratio of the surface modifier to the inorganic particles is 1.0 to 45.0% by weight based on the total weight of the surface modifier and the inorganic particles. It is preferable to have made it react with.
As a surface treating agent, only 1 type may be used or 2 or more types may be used in combination.

An inorganic particle may be used individually by 1 type, and may use 2 or more types together.
The content of inorganic particles in the active energy ray-curable composition of the present invention is preferably 25 to 400 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B), 30 More preferably, it is -200 weight part, More preferably, it is 50-150 weight part. It is excellent in transparency, adhesiveness, abrasion resistance, and curl resistance of the cured film obtained as it is the said aspect.

<Antioxidant>
The active energy ray-curable composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
Examples of the antioxidant used in the present invention include phenol-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.
As a phenolic antioxidant, hindered phenols, such as di-t-butylhydroxytoluene, can be mentioned preferably, for example. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Preferable examples of the phosphorus antioxidant include phosphines such as trialkylphosphine and triarylphosphine, trialkyl phosphite, triaryl phosphite, and the like. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.

An antioxidant may be used individually by 1 type and may use 2 or more types together.
The content of the antioxidant in the active energy ray-curable composition of the present invention is 0.01 to 5 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). Preferably, it is 0.1 to 1 part by weight. In the above embodiment, the composition is excellent in stability, and curability and adhesive strength are good.

<Silane coupling agent>
The active energy ray-curable composition of the present invention may further contain a silane coupling agent for the purpose of improving the adhesion to the substrate.
The silane coupling agent used in the present invention is not particularly limited, and a known silane coupling agent can be used.
Preferable specific examples of the silane coupling agent include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycol. Sidoxypropyltriethoxysilane, 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, 3-mercaptopropyl Chill dimethoxysilane, 3-mercaptopropyl trimethoxy silane and the like.
Moreover, the compound which has the ethylenically unsaturated group and alkoxysilyl group which were mentioned above can also be used.

A silane coupling agent may be used individually by 1 type, and may use 2 or more types together.
The content of the silane coupling agent in the active energy ray-curable composition of the present invention is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). Is preferable, and it is more preferable that it is 1-5 weight part. It is excellent in adhesiveness with a base material as it is the said range.

<Surface modifier>
The active energy ray-curable composition of the present invention may be added with a surface modifier for the purpose of increasing the leveling property at the time of application, the purpose of increasing the slipping property of the cured film and improving the scratch resistance, and the like. .
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, an antifoaming agent, a slipperiness imparting agent, and an antifouling imparting agent, and these known surface modifiers can be used. .
Of these, silicone-based surface modifiers and fluorine-based surface modifiers are preferred. Specific examples include silicone polymers and oligomers having a silicone chain and a polyalkylene oxide chain, silicone polymers and oligomers having a silicone chain and a polyester chain, and fluorine polymers having a perfluoroalkyl group and a polyalkylene oxide chain. And a fluorine-based polymer and an oligomer having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, for the purpose of increasing the slidability, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group, in the molecule may be used.

A surface modifier may be used individually by 1 type, and may use 2 or more types together.
The content of the surface modifier in the active energy ray-curable composition of the present invention is 0.01 to 1.0 part by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). Preferably there is. It is excellent in the surface smoothness of a coating film as it is the said range.

<Polymer>
The active energy ray-curable composition of the present invention may further contain a polymer other than the component (A) for the purpose of further improving the curl resistance of the resulting cured film.
Suitable polymers include (meth) acrylic polymers, and suitable constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- ( 2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In the case of a polymer copolymerized with (meth) acrylic acid, glycidyl (meth) acrylate may be added to introduce a (meth) acryloyl group into the polymer chain.
A polymer may be used individually by 1 type and may use 2 or more types together.
The polymer content in the active energy ray-curable composition of the present invention is preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the component (A) and the component (B). It is excellent in the curl resistance of the cured film obtained as it is the said range.

As a manufacturing method of the active energy ray-curable composition of the present invention, a conventional method may be used, and the essential component, and if necessary, the component (C), the component (D) and / or other components, It can be produced by stirring and mixing.
In this case, heating can be performed as necessary. What is necessary is just to set suitably as a heating temperature according to the component which the composition to be used contains, the base material which coats a composition, the intended purpose, etc., but 30 to 80 degreeC is preferable.

The active energy ray-curable composition of the present invention can be used for various applications, specifically, coating agents such as paints, forming resins such as inks, nanoimprints and lens sheets, and adhesives. Is mentioned.
A cured product obtained by curing the active energy ray-curable composition of the present invention, particularly a cured film, is excellent in hardness, adhesion to a substrate, followability to deformation of the substrate, and curl resistance. It can be preferably used as a coating agent. Furthermore, as the coating agent, a so-called hard coat coating agent based on a plastic can be preferably used.

(Hardened product and manufacturing method thereof)
The cured product of the present invention is a cured product obtained by curing the active energy ray-curable composition of the present invention.
The production method of the cured product of the present invention is not particularly limited, but it is active in the coating step of coating the active energy ray curable composition of the present invention on a substrate, and the applied active energy beam curable composition. It is preferable to include a curing step of irradiating and curing energy rays.
Moreover, in order to exhibit the effect of this invention more, it is preferable that the said hardened | cured material is a cured film. The thickness of the cured film may be selected according to the use of the substrate to be used or the substrate having the produced cured film, but is preferably 1 to 100 μm, more preferably 5 to 40 μm. preferable.

The substrate to which the composition of the present invention can be applied can be applied to various materials, and examples thereof include wood, metal, inorganic material, and plastic.
Examples of the inorganic material include mortar, concrete, and glass.
Specific examples of the plastic include polymethyl methacrylate, polyethylene terephthalate, polyvinyl chloride, polycarbonate resin, epoxy resin, and polyurethane resin.
Among these, a plastic substrate is particularly preferable.

What is necessary is just to follow a conventional method as a coating method of the composition of this invention.
Specifically, a method of applying the composition to a base material, drying it, and irradiating an active energy ray such as ultraviolet rays is preferable.
As a method for applying the composition of the present invention to the substrate, conventional methods may be used, and examples thereof include bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, and spray coating.

  What is necessary is just to set the coating method of the composition with respect to a base material, and the film thickness after drying suitably according to the objective. The drying temperature is not particularly limited as long as the applied substrate is at a temperature that does not cause a problem such as deformation.

Examples of the active energy rays for curing the composition of the present invention include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are particularly preferable. Examples of the ultraviolet irradiation device include a high pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy should be appropriately set according to the type and composition of the active energy ray. As an example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 5,000 mJ / cm ² is preferable, and 200 to 2,000 mJ / cm ² is more preferable.

A cured product obtained by curing the active energy ray-curable composition of the present invention, particularly a cured film, is excellent in hardness, adhesion to a substrate, followability to deformation of the substrate, and curl resistance. The material having the above can be used for various applications by taking advantage of this property. In particular, a material using the active energy ray-curable composition of the present invention as a coating agent is preferable.
For example, the display panel front plate, building material use, lighting equipment, mobile phone, smartphone, tablet terminal display and housing, home appliance housing, various lenses such as glasses.
Specific examples of the front plate for the display board include an electric bulletin board, a display, a signboard, an advertisement, and a sign.
Examples of using wood as a base material include woodwork products such as stairs, floors and furniture. Examples of using metal as the substrate include metal products such as kitchen panels for kitchens and stainless steel sinks.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, this invention is not limited by these Examples.
In the following, unless otherwise specified, “part” means part by weight, and “%” means percent by weight.

Synthesis example 1 (acrylic ester of pentaerythritol)
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser, and 5% by volume oxygen-containing nitrogen gas inlet, 1,000 parts (13.89 mol) of acrylic acid, pentaerythritol [manufactured by Guangei Chemical Industry Co., Ltd. 555 parts (4.08 mol), 23 parts of sulfuric acid, 0.4 part of hydroquinone monomethyl ether (hereinafter also referred to as “MEHQ”) and 744 parts of toluene are mixed together, and the reaction temperature is about 80 ° C. and 370 Torr (absolute pressure). The reaction was continued until 59% of all the hydroxyl groups in pentaerythritol had been esterified while removing the condensed water under the conditions described above.
The generated condensed water was 173 parts. After completion of the reaction, 690 parts of toluene was added.
A 20% by weight aqueous solution of sodium hydroxide corresponding to 1.1 times the molar amount of the acid content of the reaction solution to which toluene was added was added with stirring to carry out neutralization, and excess acrylic acid and sulfuric acid were removed. Removed. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer under stirring, followed by washing with water. The organic layer was separated and heated under reduced pressure to distill off toluene.
The obtained acrylic ester was 837 parts, and the hydroxyl value was 173 mgKOH / g.
As for the hydroxyl value, a sample was dissolved in acetic anhydride / pyridine (15.6 g / 250 mL), reacted at 92 ° C. for 1 hour, added with a small amount of water, further reacted for 10 minutes, and then cooled to room temperature. It was obtained by adding phenolphthalein as an indicator and titrating with a 0.5 mol / L potassium hydroxide (KOH) ethanol solution.

Synthesis Example 2 (acrylic ester of pentaerythritol)
The reaction was continued under the same conditions as in Synthesis Example 1 until 63% of all hydroxyl groups in pentaerythritol had been esterified.
The generated condensed water was 185 parts. After completion of the reaction, 690 parts of toluene was added.
A 20% by weight aqueous solution of sodium hydroxide corresponding to 1.1 times the molar amount of the acid content of the reaction solution to which toluene was added was added with stirring to carry out neutralization, and excess acrylic acid and sulfuric acid were removed. Removed. The organic layer was separated, and 10 parts of water was added to 100 parts of the organic layer under stirring, followed by washing with water. The organic layer was separated and heated under reduced pressure to distill off toluene.
The obtained acrylic ester was 865 parts, and the hydroxyl value was 163 mgKOH / g.

Production Example 1 (urethane acrylate)
Into a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a 5% by volume oxygen-containing nitrogen gas inlet, 200 parts of an acrylic ester of pentaerythritol having a hydroxyl value of 173 mgKOH / g obtained in Synthesis Example 1 , 6-di-tert-butylcresol 0.13 part, dibutyltin dilaurate 0.065 part, 61.4 parts of isophorone diisocyanate was added dropwise at 70 ° C. in about 1 hour, and reacted at 80 ° C. for 6 hours to obtain an isocyanate group. The ratio was measured by IR spectrum, and it was confirmed that the residual isocyanate group was 0.25% or less, and the reaction was terminated.
Mw of the obtained urethane acrylate containing reaction product (UA-1) was 1,762, and the viscosity at 50 ° C. was 124,700 mPa · s.
Mw was analyzed using a Waters GPC equipped with a polystyrene column, a column temperature of 40 ° C., tetrahydrofuran (THF) as an eluent, a flow rate of 0.75 mL / min, and a detector as RI. The viscosity was measured using an E-type viscometer.

Production Example 2 (urethane acrylate)
A urethanization reaction was performed in the same manner as in Production Example 1 except that 48.5 parts of hexamethylene diisocyanate was used instead of isophorone diisocyanate.
Mw of the obtained urethane acrylate containing reaction product (UA-2) was 1,778, and the viscosity at 50 ° C. was 7,000 mPa · s.

Production Example 3 (urethane acrylate)
The urethanization reaction was carried out in the same manner as in Production Example 1 except that 200 parts of the acrylic ester of pentaerythritol having a hydroxyl value of 163 mg KOH / g obtained in Synthesis Example 2 was added dropwise over 64.1 parts of isophorone diisocyanate in about 1 hour. went.
Mw of the obtained urethane acrylate containing reaction product (UA-3) was 1,675, and the viscosity at 50 ° C. was 86,900 mPa · s.

Production Example 4 (polyester acrylate)
200 parts of toluene was added to a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a 5% by volume oxygen-containing nitrogen gas inlet, and an acrylic ester of pentaerythritol having a hydroxyl value of 173 mgKOH / g obtained in Synthesis Example 1 was added. 200 parts of an acid ester, 0.1 part of 4-methoxyphenol and 4 parts of methanesulfonic acid are added, 50 parts of sebacic acid is added dropwise at 80 ° C. over about 1 hour, and the mixture is reacted for 6 hours by refluxing with toluene. The reaction was terminated after confirming that water no longer flowed out.
Mw of the obtained polyester acrylate-containing reaction product (PEA) was 1,534, and the viscosity at 50 ° C. was 4,600 mPa · s.

Production Example 5 (urethane acrylate)
To a 0.5 L separable flask equipped with a stirrer and an air blowing tube, a mixture of pentaerythritol triacrylate (PETri) and pentaerythritol tetraacrylate (PETet) [Aronix M-305 manufactured by Toagosei Co., Ltd .: hydroxyl value 100 mg KOH / g. Hereinafter, it is also referred to as “M-305”. ] 159.2 g (containing 0.3 mol of PETri and 0.2 mol of PETet), 0.092 g of 2,6-di-tert-butyl-4-methylphenol (hereinafter also referred to as “BHT”), dibutyltin dilaurate ( Hereinafter, 0.055 g is charged, and while stirring at a liquid temperature of 70 ° C. to 75 ° C., 25.2 g (0.15 mol) of hexamethylene diisocyanate (hereinafter also referred to as “HDI”). Was dripped.
After completion of the dropwise addition, the mixture was stirred at 80 ° C. for 3 hours, and the reaction was terminated by confirming that the isocyanate group had disappeared by IR (infrared absorption) analysis of the reaction product. The urethane acrylate-containing reaction product (UA- 5) was obtained.

○ Examples 1 to 7 and Comparative Examples 1 to 4
The components shown in Table 1 or Table 2 were mixed according to a conventional method, and the composition containing the component (D) was stirred at room temperature (25 ° C.) for 30 minutes. The composition containing no component (D) was dissolved in a solid photopolymerization initiator by heating in a drier previously maintained at 40 ° C. over 15 minutes to obtain an ultraviolet curable composition. The evaluation shown below was performed using the obtained composition. The evaluation results are summarized in Table 3.

When the obtained composition does not contain the (D) component, the bar coater # 4 is used, and when the (D) component is contained, the # 10 is used. A polyethylene terephthalate (PET) film U-35 (film) (Thickness: 125 μm) was applied so that the film thickness after drying would be 5 μm, and dried for 5 minutes in a dryer at 80 ° C.
The composition of Example 2 was heated to 80 ° C. and then applied at room temperature.
After drying, using a high-pressure mercury lamp equipped with a conveyor (H06-L41 manufactured by Eye Graphics Co., Ltd.), UV-A illuminance 200 mW / cm ² , irradiation energy 200 mJ / cm ² per pass, 2 passes of ultraviolet rays Irradiated.

○ Hardness evaluation In the curability test, using a bar coater # 10, after the same coating and drying process as above, using a high-pressure mercury lamp equipped with a conveyor, UV-A illuminance of 200 mW / cm ² , 1 pass Ultraviolet rays were irradiated at an irradiation energy of 200 mJ / cm ² .
About the obtained cured film, pencil hardness was measured according to JIS K5600-5-4.

○ Evaluation of adhesiveness 11 cuts at 1 mm intervals in each length and width are cut into the cured coating film with a cutter knife to form a 100 mm grid, and a cellophane tape of # 405 made by Nichiban Co., Ltd. is pasted on the grid. The cellophane tape was peeled off according to JIS K5400. A film having a residual film of 90 or more after peeling of the cellophane tape was marked with ◎, a film with 70 to 89 was marked with ◯, and a film with 69 or less was marked with x.

○ Evaluation of curl resistance The coating film formed on the PET film was cut out to 100 mm × 100 mm, the heights at which the four corners were lifted were measured, and the average value was obtained. A smaller value indicates better curl resistance.

○ Evaluation of follow-up to base material deformation (base material follow-up property) Cross-cutting is performed on the coating film formed on the PET film with a cutter, and this coating film is wound around an iron rod having a diameter of 5 mm to prevent peeling from the cross-cut portion. The presence or absence was evaluated. The case where no floating or peeling was observed at the end of the crosscut was indicated as “◯”, and the case where it was peeled off was indicated as “X”.

The numerical value in the parenthesis described below each component described in Table 1 and Table 2 indicates the content, and the unit is parts by weight.
Details of components other than those described above among the components described in Table 1 or 2 are shown below.
MT-2506: Triethylene glycol diacrylate [Aronix MT-2506 manufactured by Toagosei Co., Ltd.]
4-HBA: 4-hydroxybutyl acrylate [Osaka Organic Chemical Industry Co., Ltd. 4-HBA]
THF-MA: Tetrahydrofurfuryl methacrylate [Kyoeisha Chemical Co., Ltd. light ester THF]
P-2M: 2-methacryloyloxyethyl acid phosphate [Kyoeisha Chemical Co., Ltd. light ester P-2M]
OT-2501: Bisphenol A type epoxy diacrylate [Aronix OT-2501 manufactured by Toagosei Co., Ltd.]
M-5700: 2-hydroxy-3-phenoxypropyl acrylate [Aronix M-5700 manufactured by Toagosei Co., Ltd.]
M-140: N-acryloyloxyethyl hexahydrophthalimide [Aronix M-140 manufactured by Toagosei Co., Ltd.]
ACMO: Acryloyl morpholine [ACMO manufactured by Kojin Holdings Co., Ltd.]
M-305: Pentaerythritol tetraacrylate [Aronix M-305, manufactured by Toagosei Co., Ltd.]
HCPK: 1-hydroxycyclohexyl phenyl ketone [IRGACURE 184 manufactured by BASF]
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [BARO DAROCUR TPO]
HMPO: 2-hydroxy-2-methyl-1-phenylpropan-1-one [DAROCUR 1173 manufactured by BASF Corporation]
PGM: Propylene glycol monomethyl ether MEK: Methyl ethyl ketone T-900: Benzotriazole ultraviolet absorber [TINUVIN 900 manufactured by BASF Corporation]
T-144: Hindered amine light stabilizer [TINUVIN 144 manufactured by BASF Corporation]
PTS: p-Toluenesulfonic acid

  As shown in the Examples, the active energy ray-curable composition of the present invention is excellent in hardness, has high adhesion to the substrate, and exhibits sufficient followability even when the substrate is deformed. Also, when applied to a film, curling is small and it is suitable as a plastic paint. On the other hand, like the composition of Comparative Example 1, a composition using urethane acrylate using an acrylate having a low hydroxyl value as a raw material has high hardness, but does not provide sufficient adhesion, and is resistant to substrate deformation. It is apparent that the followability is also insufficient, and the hydroxyl value of a specific (meth) acrylate used as a raw material for the component (A) is important for obtaining desired characteristics. Further, as is clear from Comparative Example 2, the composition containing the component (A) has excellent adhesion to the substrate, but when it does not contain the component (B), it can follow the deformation of the substrate. Cannot be obtained. In addition, like the compositions of Comparative Examples 3 and 4, a composition not including the component (A) cannot satisfy desired characteristics.

Claims (8)

(A) below (A-1) Ingredients, and,
(B) a compound having an ethylenically unsaturated group other than the component (A),
With respect to 100 parts by weight of the total content of component (A) and component (B),
(A) Content of a component is 40-97 weight part,
(B) Content of component is 3-60 weight part, Active energy ray hardening-type composition characterized by the above-mentioned.
(A-1) A (meth) acrylic acid adduct of a trihydric or higher aliphatic polyhydric alcohol compound having a hydroxyl value of 170 to 220 mgKOH / g and a polyhydric group urethane obtained by reacting a isocyanate group of the isocyanate compound (meth) acrylate-containing reaction product (A-1) (meth) acrylic acid adduct of Ingredients aliphatic trivalent or more definitive polyhydric alcohol compound, a trivalent to hexavalent aliphatic polyhydric alcohol compound (meth) acrylic acid adduct The active energy ray-curable composition according to claim 1 . (A-1) (meth) acrylic acid adduct of Ingredients aliphatic trivalent or more definitive polyhydric alcohol compound is (meth) acrylic acid adduct of pentaerythritol, activity according to claim 2 Energy ray curable composition. (C) The active energy ray-curable composition according to any one of claims 1 to 3 , further comprising a photopolymerization initiator. The active energy ray-curable type according to claim 4 , wherein the content of the component (C) is 0.01 to 10 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B). Composition. (D) The active energy ray-curable composition according to any one of claims 1 to 5 , further comprising an organic solvent. The active energy ray-curable type according to claim 6 , wherein the content of the component (D) is 10 to 1,000 parts by weight with respect to 100 parts by weight of the total content of the components (A) and (B). Composition. The active energy ray-curable composition according to any one of claims 1 to 7 , which is used for a coating agent.