JP2006213802A - Active energy ray-curable resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable resin composition which forms a coating layer excellent in coating film physical properties, antistatic properties and optical properties. <P>SOLUTION: The active energy ray-curable resin composition comprises a urethane (meth)acrylate-based compound [I], a polymer [II] having a quaternary ammonium base, and particulates [III]. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an active energy ray-curable resin composition containing a urethane (meth) acrylate-based compound. More specifically, the present invention forms a coating layer having excellent coating film properties and antistatic properties and optical characteristics. The present invention relates to an active energy ray-curable resin composition useful for the above.

Urethane acrylate compounds have high flexibility and wear resistance, so they are often used as hard coat layers for optical films. However, when used in films, they have low electrical conductivity and are likely to accumulate static electricity. Since dust and dust are likely to adhere, antistatic ability is required. As a method for imparting antistatic ability, generally, there is a method of kneading an antistatic agent directly into a base film, but the method of kneading an antistatic agent into a base film reduces transparency. In practice, a method of applying a coating agent has been adopted. For example, an active energy ray-curable material containing a (meth) acrylate having one carboxyl group and one or more acryloyl groups and a polymer having an N, N-dialkylamino group and a quaternary ammonium base (for example, ), Or an ionizing radiation curable resin, a quaternary ammonium base-containing polymer, a sulfonic acid group-containing polymer, or a polymer charge-transfer conjugate polymer, having a molecular weight of 20,000 to 500,000. A coating composition for forming a hard coat layer comprising a polymer, a solvent having a dielectric constant of 9.0 or more and a boiling point of 80 ° C. or more and less than 180 ° C., and a solvent having a dielectric constant of 9.0 or more and a boiling point of less than 80 ° C. 2) and the like, a method of applying to the film surface as a coating agent having antistatic ability has been proposed.
JP 2002-121208 A JP 2003-268316 A

However, although the technique disclosed in Patent Document 1 can provide antistatic properties to some extent, there is a problem that the coating film obtained from the coating agent is inferior in transparency. Further, in the disclosed technique of Patent Document 2, the balance between hardness and scratch resistance required for the hard coat has not been studied in detail, and the antistatic ability has not yet been satisfactory.
On the other hand, in the optical film, in order to prevent a decrease in visibility due to reflection or reflection on the display screen, there is a high demand for imparting antiglare properties. In the cured coating film obtained from the product, the antiglare property cannot be obtained.

  In Patent Document 1, it is conceivable to add fine particles in order to impart antiglare properties. However, in such a method, when antiglare properties are imparted to a cured coating film, shiromoya occurs and the display is visually recognized. As a coating agent, it was inferior in practicality in that the property decreased.

  Accordingly, the present invention provides an active energy ray-curable resin composition useful for forming a coating layer having excellent coating film physical properties and excellent antistatic properties and optical properties under such a background. It is intended.

However, as a result of intensive studies in view of such circumstances, the present inventor contains urethane (meth) acrylate compound [I], polymer [II] having a quaternary ammonium base, and fine particles [III]. The present inventors have found that an active energy ray-curable resin composition meets the above-mentioned purpose and completed the present invention.
Among these, the urethane (meth) acrylate compound [i] is preferably a urethane (meth) acrylate compound having a quaternary ammonium base from the viewpoint of antistatic properties, and further, glossiness and display visibility (Shiromoya). ) Is also preferable.

  In the present invention, in particular, the urethane (meth) acrylate compound [i] having a quaternary ammonium base includes a polyisocyanate compound (a1) and a quaternary ammonium salt (a2) represented by the following general formula (1): When it is a urethane (meth) acrylate compound (A) obtained by reacting a hydroxyl group-containing (meth) acrylate compound (a3), or is represented by the polyisocyanate compound (b1) and the following general formula (3) When the urethane (meth) acrylate compound (B) is obtained by reacting the quaternary ammonium salt (b2) and the hydroxyl group-containing (meth) acrylate compound (b3), the effects of the present invention are remarkably exhibited. .

ここで、Ｒ₁、Ｒ₂、Ｒ₃は炭素数１〜５０のアルキル基、Ｘ₁はＣｌ、Ｂｒ、Ｒ₄ＳＯ₃（Ｒ₄はアルキル、アルキルエーテル、又はアルキルベンゼン）、ｎは１〜２００の整数である。

Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 50 carbon atoms, X ₁ is Cl, Br, R ₄ SO ₃ (R ₄ is alkyl, alkyl ether or alkylbenzene), and n is 1 to 200. Is an integer.

ここで、Ｒ₈、Ｒ₉は炭素数１〜５０のアルキル基のいずれか、Ｘ₂はＣｌ、Ｂｒ、ＲＳＯ₃（Ｒはアルキル、アルキルエーテル、又はアルキルベンゼン）、ｍ、ｎは１以上の整数、ｍ＋ｎは２〜５００である。

Here, R ₈ and R ₉ are any of alkyl groups having 1 to 50 carbon atoms, X ₂ is Cl, Br, RSO ₃ (R is alkyl, alkyl ether or alkylbenzene), m and n are integers of 1 or more. , M + n is 2 to 500.

  In the present invention, the polymer [II] having a quaternary ammonium base includes a copolymer having a quaternary ammonium base-containing unsaturated monomer as a copolymerization component, or an amino group-containing unsaturated monomer. It is preferable that it is a quaternized product of a copolymer containing as a copolymer component.

  In the present invention, it is preferable to further contain an ethylenically unsaturated monomer [V] from the viewpoint of further coating film hardness and scratch resistance.

  The active energy ray-curable resin composition of the present invention comprises a urethane (meth) acrylate compound [I], a polymer [II] having a quaternary ammonium base, and fine particles [III]. It exhibits excellent physical properties and antistatic properties and optical properties. Paints, adhesives, adhesives, adhesives, inks, protective coatings, anchor coatings, magnetic powder coating binders, sandblasts It is useful as various film forming materials such as coating films and printing materials. Among them, it is very useful to use as a coating agent for optical films.

The present invention is described in detail below.
The active energy ray-curable resin composition of the present invention comprises a urethane (meth) acrylate compound [I], a polymer [II] having a quaternary ammonium base, and fine particles [III]. By introducing a quaternary ammonium base into the polymer molecule, optical properties such as antistatic properties and antiglare properties, and hard coat performance such as coating film hardness and scratch resistance can be exhibited in a well-balanced manner. It is.
The urethane (meth) acrylate compound [I] is not particularly limited, and is obtained from a polyisocyanate compound and a hydroxyl group-containing (meth) acrylate compound, or a polyol compound, a polyisocyanate compound, and a hydroxyl group-containing (meth). Any urethane (meth) acrylate compound [i] having a quaternary ammonium base is preferable from the viewpoint of antistatic properties, and further, glossiness and display. It is also preferable from the viewpoint of visibility.
The urethane (meth) acrylate compound [i] having such a quaternary ammonium base will be described below.

  The urethane (meth) acrylate compound [i] is not particularly limited as long as it has a quaternary ammonium base, and among them, the polyisocyanate compound (a1) and the fourth compound represented by the following general formula (1) are used. The urethane (meth) acrylate compound (A) obtained by reacting the quaternary ammonium salt (a2) with the hydroxyl group-containing (meth) acrylate compound (a3) is coating film hardness, scratch resistance, antistatic property. This is more preferable.

ここで、Ｒ₁、Ｒ₂、Ｒ₃は炭素数１〜５０のアルキル基、Ｘ₁はＣｌ、Ｂｒ、Ｒ₄ＳＯ₃（Ｒ₄はアルキル、アルキルエーテル、又はアルキルベンゼン）、ｎは１〜２００の整数である。

Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 50 carbon atoms, X ₁ is Cl, Br, R ₄ SO ₃ (R ₄ is alkyl, alkyl ether or alkylbenzene), and n is 1 to 200. Is an integer.

  The polyisocyanate compound (a1) is not particularly limited, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates, among which tolylene diisocyanate, diphenylmethane diisocyanate, and hydrogenation. Diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, tetramethylxylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (Isocyanatomethyl) cyclohexane, phenylene diisocyanate, lysine diisocyanate, lysine Polyisocyanates such as reisocyanate and naphthalene diisocyanate, trimer compounds or multimer compounds of these polyisocyanates, burette type polyisocyanates, water-dispersed polyisocyanates (for example, “Aquanate 100” manufactured by Nippon Polyurethane Industry Co., Ltd.) , “Aquanate 110”, “Aquanate 200”, “Aquanate 210”, etc.), or the reaction products of these polyisocyanates and polyols.

  Examples of such polyols include, but are not limited to, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, polybutylene glycol, 1,6 -Hexanediol, neopentyl glycol, cyclohexane dimethanol, hydrogenated bisphenol A, polycaprolactone, trimethylolethane, trimethylolpropane, polytrimethylolpropane, pentaerythritol, polypentaerythritol, sorbitol, mannitol, glycerin, polyglycerin, poly Polyhydric alcohols such as tetramethylene glycol, polyethylene oxide, Polyether polyol having at least one structure of block copolymer or random copolymer of ethylene oxide / propylene oxide, polyhydric alcohol or polyether polyol and maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, Polyester-based polyols such as polyester polyols, condensates with polybasic acids such as itaconic acid, adipic acid, isophthalic acid, caprolactone-modified polyols such as caprolactone-modified polytetramethylene polyol, polyolefin-based polyols, hydrogenated polybutadiene polyols, etc. It is done.

  Furthermore, as such polyols, for example, 2,2-bis (hydroxymethyl) butyric acid, tartaric acid, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2,2-bis (hydroxymethyl) propionic acid, 2,2-bis (hydroxyethyl) propionic acid, 2,2-bis (hydroxypropyl) propionic acid, dihydroxymethylacetic acid, bis (4-hydroxyphenyl) acetic acid, 4,4-bis (4-hydroxyphenyl) pentanoic acid Also included are carboxyl group-containing polyols such as homogentisic acid, sulfonic acid group or sulfonate group-containing polyols such as sodium 1,4-butanediol sulfonate, and the like.

  When using the reaction product of polyisocyanate and polyol, for example, it may be used as a terminal isocyanate group-containing polyisocyanate obtained by reacting the polyol with the polyisocyanate. In the reaction of such polyisocyanate and polyol, for the purpose of promoting the reaction, a metal catalyst such as dibutyltin dilaurate, an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7, ethyl hexane, It is also preferable to use bismuth compounds such as bismuth acid, bismuth naphthenate, and bismuth neodecanoate.

The quaternary ammonium salt (a2) to be reacted with the polyisocyanate compound (a1) may have a structure represented by the general formula (1).
Among these, R ₁ , R ₂ , R ₃ , X ₁ , and n are as described above, and a preferable range of the number of moles of added ethylene oxide n is 1 to 100, and further 1 to 50.

Specific examples of the quaternary ammonium salt (a2) represented by the general formula (1) include dimethylalkylhydroxyethylammonium sulfonate, polyoxyethylene dimethylalkylammonium sulfonate, diethylalkylhydroxyethylammonium sulfonate. , Polyoxyethylenediethylalkylammonium sulfonate, triethylhydroxyethylammonium sulfonate, polyoxyethylenetriethylammonium sulfonate, or their R ₄ SO ₃ (R ₄ is alkyl, alkyl ether, or alkylbenzene) is chlorine And those replaced with bromine.

  The weight average molecular weight of the quaternary ammonium salt (a2) represented by the general formula (1) is preferably 130 to 9000, particularly preferably 180 to 5000, and more preferably 200 to 2000. If the weight average molecular weight is less than 130, the solubility in a solvent is lowered and the handling becomes difficult, and if it exceeds 9000, the hardness and scratch resistance of the cured coating film are remarkably inferior.

  The hydroxyl group-containing (meth) acrylate compound (a3) to be reacted with the polyisocyanate compound (a1) is not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethylacryloyl phosphate, 2- (meth) acryloyloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3- (meth) Acryloyloxypropyl (meth) acrylate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, caprolactone-modified di Pentaerythritol penta (meth) acrylate, caprolactone-modified pentaerythritol tri (meth) acrylate, ethylene oxide-modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate.

In the present invention, the method for preparing the urethane (meth) acrylate compound (A) having a quaternary ammonium base is not particularly limited.
(A) A method in which the polyisocyanate compound (a1), the quaternary ammonium salt (a2) represented by the general formula (1), and the hydroxyl group-containing (meth) acrylate compound (a3) are charged and reacted together,
(B) A method of reacting the quaternary ammonium salt (a2) represented by the general formula (1) after reacting the polyisocyanate compound (a1) and the hydroxyl group-containing (meth) acrylate compound (a3),
(C) A method of reacting the hydroxyl group-containing (meth) acrylate compound (a3) after reacting the polyisocyanate compound (a1) with the quaternary ammonium salt (a2) represented by the general formula (1),
However, the method (b) is preferable from the viewpoint of stability of reaction control and shortening of production time.

  In the method (b), after reacting the isocyanate group of the polyisocyanate compound (a1) with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a3) under the condition that the isocyanate group remains, the polyisocyanate is then reacted. The residual isocyanate group of the compound (a1) is reacted with the hydroxyl group of the quaternary ammonium salt (a2) represented by the general formula (1).

  In this reaction, for the purpose of promoting the reaction, a metal catalyst such as dibutyltin dilaurate, an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7, bismuth ethylhexanoate, It is also preferable to use a bismuth compound such as bismuth naphthenate or bismuth neodecanoate, and the reaction temperature is preferably 30 to 90 ° C, particularly 40 to 70 ° C.

  Regarding the urethane (meth) acrylate compound (A) thus obtained, the urethane (meth) acrylate compound having a structure represented by the following general formula (2) is particularly good in hardness, antistatic properties and scratch resistance. This is preferable.

ここで、Ｒ₅はポリイソシアネート系化合物（ａ１）のウレタン結合残基、Ｒ₆は上記一般式（１）で示される第４級アンモニウム塩（ａ２）のウレタン結合残基、Ｒ₇は水酸基含有（メタ）アクリレート系化合物（ａ３）のウレタン結合残基、ａは１〜５０、好ましくは１〜５の整数、ｂは１〜５０、好ましくは１〜５の整数である。
上記一般式（２）で示される構造のウレタン（メタ）アクリレート系化合物は、ポリイソシアネート系化合物（ａ１）、一般式（１）で示される第４級アンモニウム塩（ａ２）、水酸基含有（メタ）アクリレート系化合物（ａ３）の仕込み割合を調製することになり得られる。

Here, R ₅ is a urethane bond residue of the polyisocyanate compound (a1), R ₆ is a urethane bond residue of the quaternary ammonium salt (a2) represented by the general formula (1), and R ₇ contains a hydroxyl group The urethane bond residue of the (meth) acrylate compound (a3), a is an integer of 1 to 50, preferably 1 to 5, and b is an integer of 1 to 50, preferably 1 to 5.
The urethane (meth) acrylate compound having the structure represented by the general formula (2) includes a polyisocyanate compound (a1), a quaternary ammonium salt (a2) represented by the general formula (1), and a hydroxyl group-containing (meth). This can be achieved by adjusting the charge ratio of the acrylate compound (a3).

  Thus, the urethane (meth) acrylate compound (A) can be obtained. The weight average molecular weight of the obtained urethane (meth) acrylate compound (A) is preferably 500 to 30,000, more preferably 500 to It is preferably 15,000. When the weight average molecular weight is less than 500, the film-forming property is deteriorated. When the weight average molecular weight is more than 30,000, the viscosity becomes high and difficult to handle, and the hardness and scratch resistance of the cured coating film are remarkably inferior.

In addition, the weight average molecular weight of the said urethane (meth) acrylate type compound (A) is a weight average molecular weight by standard polystyrene molecular weight conversion, and is a high performance liquid chromatography (Showa Denko Co., Ltd. product "Shodex GPC system-11 type". ), Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical plate number: 10,000 plates / pack, packing material: styrene-divinylbenzene copolymer weight Measured by using three series of coalesced, filler particle size: 10 μm).
Hereinafter, the measurement of the weight average molecular weight of the urethane (meth) acrylate compound described later is measured according to the above method.

  In the present invention, the urethane (meth) acrylate compound [i] having a quaternary ammonium base is a polyisocyanate compound (b1) and a quaternary ammonium salt (b2) represented by the following general formula (3). ) And a hydroxyl group-containing (meth) acrylate-based compound (b3) are also preferably urethane (meth) acrylate-based compounds (B) obtained from the viewpoints of coating film hardness, scratch resistance, and antistatic properties.

ここで、Ｒ₈、Ｒ₉は炭素数１〜５０のアルキル基のいずれか、Ｘ₂はＣｌ、Ｂｒ、ＲＳＯ₃（Ｒはアルキル、アルキルエーテル、又はアルキルベンゼン）、ｍ、ｎは１以上の整数、ｍ＋ｎは２〜５００である。

Here, R ₈ and R ₉ are any of alkyl groups having 1 to 50 carbon atoms, X ₂ is Cl, Br, RSO ₃ (R is alkyl, alkyl ether or alkylbenzene), m and n are integers of 1 or more. , M + n is 2 to 500.

As said polyisocyanate type compound (b1), the thing similar to the said polyisocyanate type compound (a1) is mentioned.
The quaternary ammonium salt (b2) that reacts with the polyisocyanate compound (b1) may have a structure represented by the general formula (3).

Specific examples of the quaternary ammonium salt (b2) represented by the general formula (3) include polyoxyethylenedimethylammonium chloride, polyoxyethylene diethylammonium chloride, polyoxyethylene laurylmethylammonium chloride, polyoxyethylene cetylmethyl. Ammonium chloride, polyoxyethylene stearylmethylammonium chloride, or those in which these chlorines are replaced with bromine or RSO ₃ (R is alkyl, alkyl ether, or alkylbenzene) can be used.

  Among them, m and n are preferably 1 or more, particularly 1 to 300, and m + n is preferably 2 to 500, particularly 2 to 100, and more preferably 2 to 50.

  The weight average molecular weight of the quaternary ammonium salt (b2) represented by the general formula (3) is preferably 100 to 23,000, particularly preferably 100 to 10,000, and more preferably 100 to 4,000. . If the molecular weight is less than 100, the solubility in a solvent is lowered and the handling becomes difficult, and if it exceeds 23,000, the hardness and scratch resistance of the cured coating film are remarkably inferior.

  Examples of the hydroxyl group-containing (meth) acrylate compound (b3) that reacts with the polyisocyanate compound (b1) include those similar to the hydroxyl group-containing (meth) acrylate compound (b3).

In such a urethane (meth) acrylate compound (B), the isocyanate group in the polyisocyanate compound (b1) contains one hydroxyl group and a hydroxyl group in the quaternary ammonium salt (b2) represented by the general formula (3). What is obtained by forming a urethane bond with the hydroxyl group of the (meth) acrylate compound (b3) is preferable.
Among them, the urethane (meth) acrylate compound (B) is preferably a urethane (meth) acrylate compound (B1) having a structure represented by the following general formula (4) in view of hardness and scratch resistance. In the formula (4), a is preferably an integer of 1 to 50, particularly 1 to 5, and b is preferably an integer of 1 to 50, particularly 1 to 5.

ここで、Ｒ₁₀はポリイソシアネート系化合物（ｂ１）のウレタン結合残基、Ｒ₁₁は一般式（３）で示される第４級アンモニウム塩（ｂ２）のウレタン結合残基、Ｒ₁₂は水酸基含有（メタ）アクリレート系化合物（ｂ３）のウレタン結合残基、ａは１〜５０の整数、ｂは１〜５０の整数である。

Here, R ₁₀ is a urethane bond residue of the polyisocyanate compound (b1), R ₁₁ is a urethane bond residue of the quaternary ammonium salt (b2) represented by the general formula (3), and R ₁₂ contains a hydroxyl group ( The urethane bond residue of a (meth) acrylate type compound (b3), a is an integer of 1-50, b is an integer of 1-50.

  For example, when the polyisocyanate compound (b1) has two isocyanate groups, one isocyanate group forms a urethane bond with one hydroxyl group of the quaternary ammonium salt (b2), and the remaining one When the isocyanate group becomes a urethane (meth) acrylate compound (B1) that forms a urethane bond with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (b3), and the polyisocyanate compound (b1) has three isocyanate groups Then, one isocyanate group forms a urethane bond with the hydroxyl group of the quaternary ammonium salt (b2) [or the hydroxyl group-containing (meth) acrylate compound (b3)], and the remaining two isocyanate groups contain a hydroxyl group ( Hydrous acid of (meth) acrylate compound (b3) [or quaternary ammonium salt (b2)] The urethane formed a urethane bond (meth) acrylate compound (B1).

In carrying out the reaction for forming the urethane bond is not particularly limited,
(A) A method in which the polyisocyanate compound (b1), the quaternary ammonium salt (b2), and the hydroxyl group-containing (meth) acrylate compound (b3) are charged together and reacted.
(B) A method of reacting the quaternary ammonium salt (b2) after reacting the polyisocyanate compound (b1) and the hydroxyl group-containing (meth) acrylate compound (b3),
(C) A method of reacting a hydroxyl group-containing (meth) acrylate compound (b3) after reacting the polyisocyanate compound (b1) and the quaternary ammonium salt (b2),
However, the method (b) is preferable from the viewpoint of stability of reaction control and shortening of production time.

  In such a reaction, for the purpose of promoting the reaction, a metal catalyst such as dibutyltin dilaurate, an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7, bismuth ethylhexanoate, It is also preferable to use a bismuth compound such as bismuth naphthenate or bismuth neodecanoate, and the reaction temperature is preferably 30 to 90 ° C, particularly 40 to 70 ° C.

Thus, the urethane (meth) acrylate compound (B1) is obtained. The weight average molecular weight of the obtained urethane (meth) acrylate compound (B1) is preferably 100 to 100,000, and more preferably 100 to 100. Preferably it is 50,000. When the weight average molecular weight is less than 100, the film forming property is lowered. When the weight average molecular weight is more than 100,000, the viscosity becomes high and difficult to handle, and the hardness and scratch resistance of the cured coating film are remarkably inferior.
The weight average molecular weight is measured in the same manner as described above.

  In the urethane (meth) acrylate compound (B), a urethane (meth) acrylate compound (B2) having a structure represented by the following general formula (5) in which a specific quaternary ammonium base is introduced into the molecular skeleton. It is also preferable in terms of antistatic properties and scratch resistance.

ここで、Ｒ₁₃はポリイソシアネート系化合物（ｂ１）のウレタン結合残基、Ｒ₁₄、Ｒ₁₄′は上記一般式（３）で示される第４級アンモニウム塩（ｂ２）のウレタン結合残基（Ｒ₁₄、Ｒ₁₄′は同一でも異なっていてもよい。）、Ｒ₁₅は水酸基含有（メタ）アクリレート系化合物（ｂ３）のウレタン結合残基、Ｒ₁₆はＲ₁₄又はＲ₁₅のいずれか、ａは１〜５０の整数、ｂは０〜５０の整数、ｃは０〜５０の整数、ｄは０〜５０の整数、ｅは１〜３０の整数である。

Here, R ₁₃ is a urethane bond residue of the polyisocyanate compound (b1), R ₁₄ and R ₁₄ ′ are urethane bond residues (R of the quaternary ammonium salt (b2) represented by the above general formula (3). ₁₄ and R ₁₄ ′ may be the same or different.), R ₁₅ is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b3), R ₁₆ is either R ₁₄ or R ₁₅ , and a is The integer of 1-50, b is an integer of 0-50, c is an integer of 0-50, d is an integer of 0-50, e is an integer of 1-30.

  Furthermore, among the urethane (meth) acrylate compounds (B2) represented by the general formula (5), the urethane (meth) acrylate compounds having the structures represented by the following general formulas (5-1) to (5-4) A compound is more preferable in terms of hardness and scratch resistance.

In obtaining the urethane (meth) acrylate compound (B2) represented by the general formula (5), it is not particularly limited,
(A) A method in which the polyisocyanate compound (b1), the quaternary ammonium salt (b2), and the hydroxyl group-containing (meth) acrylate compound (b3) are charged together and reacted.
(B) A method of reacting the quaternary ammonium salt (b2) after reacting the polyisocyanate compound (b1) and the hydroxyl group-containing (meth) acrylate compound (b3),
(C) A method of reacting a hydroxyl group-containing (meth) acrylate compound (b3) after reacting the polyisocyanate compound (b1) and the quaternary ammonium salt (b2),
However, the method (b) is preferable from the viewpoint of stability of reaction control and shortening of production time.

  In this reaction, for the purpose of accelerating the reaction, a metal catalyst such as dibutyltin dilaurate, an amine catalyst such as 1,8-diazabicyclo [5.4.0] undecene-7, bismuth ethylhexanoate, It is also preferable to use a bismuth compound such as bismuth naphthenate or bismuth neodecanoate, and the reaction temperature is preferably 30 to 90 ° C, particularly 40 to 70 ° C.

Thus, although the urethane (meth) acrylate compound (B2) is obtained, the weight average molecular weight of the obtained urethane (meth) acrylate compound (B2) is preferably 500 to 100,000, more preferably 500 to Preferably it is 50,000. When the weight average molecular weight is less than 500, the film-forming property is lowered. When the weight average molecular weight exceeds 100,000, the viscosity becomes high and difficult to handle, and the hardness and scratch resistance of the cured coating film are remarkably inferior.
The weight average molecular weight is measured in the same manner as described above.

Next, the polymer [II] having a quaternary ammonium base will be described.
The polymer [II] having a quaternary ammonium base is not particularly limited as long as it has a quaternary ammonium base, and among them, a copolymer having a quaternary ammonium base-containing unsaturated monomer as a copolymerization component. Examples thereof include a polymer and a quaternized product of a copolymer having an amino group-containing unsaturated monomer as a copolymerization component.

  Examples of the copolymer having a quaternary ammonium base-containing unsaturated monomer as a copolymerization component include, for example, a quaternary ammonium base-containing unsaturated monomer obtained by a quaternization reaction of (meth) acrylic acid ester of amino alcohol. And a copolymer composed of a monomer and other copolymerizable unsaturated monomers. Specific examples of such amino alcohol (meth) acrylic acid esters include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, and N, N-dimethylaminopropyl (meth) acrylate. N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate, etc. In particular, N, N-dimethylaminoethyl (meth) acrylate is preferably used.

  Other copolymerizable unsaturated monomers are not particularly limited. For example, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, isobornyl (meth) ) Acrylate, dicyclopentanyl (meth) acrylate, acrylic chloride, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, vinyl chloride, ethylene, alkyl vinyl ether, (meth) acrylate In addition to rhonitrile, itaconic acid dialkyl ester, fumaric acid dialkyl ester, maleic acid dialkyl ester and the like, a monomer having a functional group may be used, and the monomer having such a functional group is not particularly limited. Carboxyl group-containing monomer containing 2 or more ethylenically unsaturated groups in one molecule, hydroxyl group-containing monomer, monomer having an ether bond, epoxy group-containing monomer, amide group, methylol group, carbonyl group And the like, and amino group-containing monomers.

  Examples of the carboxyl group-containing monomer include acrylic acid, acrylic acid dimer, methacrylic acid, crotonic acid, itaconic acid or its monoester, fumaric acid or its monoester, (anhydrous) maleic acid or its monoester, citraconic acid, Ricinoleic acid or a salt thereof (amine salt, sodium salt, potassium salt) and the like can be mentioned, and one or more are used.

  Examples of the hydroxyl group-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, ethyl carbitol acrylate, tripropylene glycol (meth) acrylate, and 1,4-butylene glycol mono (meth). Acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, glycerol mono (meth) acrylate, 2-hydroxyethyl acryloyl phosphate, 4-butylhydroxy acrylate, caprolactone-modified 2-hydroxyethyl acrylate, polyethylene glycol mono (meth) Acrylate, polypropylene glycol mono (meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-acryloyloxyethyl succinic acid, Alcohol and the like, one or two or more may be used.

  Examples of the monomer having an ether bond include 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-butoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, and methoxypolyethylene glycol (meth) ) Acrylates and the like, and one or more are used.

  Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, allyl glycidyl ether, N- (4 (2,3-epoxypropoxy) -3,5-dimethylbenzyl) acrylamide, bisphenol A diglycidyl ether mono (meta). ) Acrylates and the like, and one or more are used.

  Examples of the monomer containing an amide group, a methylol group, or a carbonyl group include acrylamide, methacrylamide, N-methylol (meth) acrylamide, butoxy N-methylol acrylamide, diacetone acrylamide, 2- (acetoacetoxy) ethyl (meth) ) Acrylate, allyl acetoacetate and the like, and one kind or two or more kinds are used.

  Examples of amino group-containing monomers include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and N, N-diethylamino. Propyl (meth) acrylate, N, N-dimethylaminobutyl (meth) acrylate, N, N-diethylaminobutyl (meth) acrylate, N, N-dihydroxyethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, Examples thereof include vinyl monomers having a tertiary amino group such as diethylaminopropyl (meth) acrylamide, and one or more are used.

  In the present invention, the proportion of the quaternary ammonium base-containing unsaturated monomer in the copolymer having a quaternary ammonium base-containing unsaturated monomer as a copolymerization component is 5 to 95% by weight, particularly 20%. It is preferably ˜70% by weight, and if it is less than 5% by weight, the antistatic property is insufficient, and if it exceeds 95% by weight, shiromoya is generated and the visibility of the display tends to be lowered.

  Examples of the quaternized product of the copolymer containing the amino group-containing unsaturated monomer of the present invention as a copolymerization component include, for example, amino group-containing unsaturated monomers and other copolymerizable unsaturated monomers. And the like obtained by quaternizing the copolymer of Examples of such amino group-containing unsaturated monomers include (meth) acrylic acid esters of the above amino alcohols, and examples of other copolymerizable unsaturated monomers include the above copolymerizable unsaturated monomers. (Excluding amino group-containing unsaturated monomers).

The ratio of the amino group-containing unsaturated monomer in the quaternized product of the copolymer having such an amino group-containing unsaturated monomer as a copolymerization component is 5 to 95% by weight, particularly 20 to 70% by weight. If it is less than 5% by weight, the antistatic property is insufficient, and if it exceeds 95% by weight, shiromoya occurs and the visibility of the display tends to be lowered.
Furthermore, in the present invention, among the polymers [II] having the quaternary ammonium base, (meth) acrylic acid ester of amino alcohol, its quaternary ammonium salt and other copolymerizable unsaturated monomers. A copolymer consisting of

  Preparation of a copolymer such as a copolymer having the above quaternary ammonium base-containing unsaturated monomer as a copolymer component, or a copolymer having an amino group-containing unsaturated monomer as a copolymer component In the presence of water, ethyl acetate, methyl ethyl ketone, isopropyl alcohol or the like alone or in a mixed solution, the polymerization can be carried out according to a known polymerization method using a radical polymerization initiator such as azobisisobutyronitrile.

  Moreover, the number average molecular weight of the obtained polymer [II] having a quaternary ammonium base is preferably 200 to 200,000, more preferably 1,000 to 100,000, and the number average molecular weight is less than 200. The antistatic property decreases with time, and if it exceeds 100,000, the compatibility with the resin is inferior, which is not preferable.

  Thus, in the present invention, urethane (meth) acrylate compound [I], preferably urethane (meth) acrylate compound [i] having a quaternary ammonium base and polymer [II] having a quaternary ammonium base, An active energy ray-curable resin composition containing fine particles [III] having an average particle size of 0.001 to 30 μm can be obtained. Content of the polymer [II] having such a quaternary ammonium base Is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 100 parts by weight, particularly 1 to 50 parts by weight based on 100 parts by weight of the urethane (meth) acrylate compound [I]. It is preferable. When the content of the polymer [II] is less than 0.1 parts by weight, the antistatic property is insufficient, and when it exceeds 300 parts by weight, shiromoya occurs and the visibility of the display is lowered, which is not preferable.

The fine particles [III] in the present invention are not particularly limited, such as organic and inorganic, but carbonates such as carbon black, silicate, calcium carbonate, clay, alumina, alumina white, mica, talc, zirconium oxide, etc. Metal particles such as zirconia, aluminum sulfate, barium sulfate, titanium oxide, tin oxide, aluminum oxide, antimony oxide, indium oxide, acrylic particles such as activated calcium fluoride, zeolite, glass fiber, polyethylene particles, polymethyl methacrylate particles , Polycarbonate particles, polystyrene particles, urethane particles, epoxy particles, silicon particles, glass particles, wax (acid, ester, saponified ester, polyethylene, polypropylene, polyethylene oxide, polypropylene oxide, (Fluorinated polyethylene, fluorinated polypropylene, amide, etc.), fluorine-containing inorganic materials such as lithium fluoride, magnesium fluoride, and calcium fluoride, fine powder silica that does not contain a dispersion medium, and silica dispersed in a dispersion medium Examples thereof include colloidal silica and silica sol, and those obtained by surface modification with a coupling agent or the like.
Such a dispersion medium is not particularly limited, for example, water, ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, ethyl cellosolve and other cellosolves, Propylene glycol ethers such as propylene glycol monomethyl ether, polyhydric alcohols such as ethylene glycol and derivatives thereof, diacetone alcohol, 2-hydroxyethyl acrylate, 2-hydroxybutyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate Acrylates and the like.
In addition, with these fine particles, acrylic particles such as polyethylene particles and polymethyl methacrylate particles, polycarbonate particles, polystyrene particles, urethane particles, epoxy particles, waxes (acid-based, ester-based) are particularly effective in further improving the antiglare property. Saponified ester type, polyethylene type, polypropylene type, polyethylene oxide type, polypropylene oxide type, fluorinated polyethylene type, fluorinated polypropylene type, amide type, etc.), fine powder silica not containing dispersion medium, silica dispersed in dispersion medium In addition, colloidal silica, silica sol, or the like whose surface is modified with a coupling agent or the like is selected.
Any of these may be used alone or in combination of two or more.

In order to obtain the active energy ray-curable resin composition of the present invention, it is preferable to further contain a photopolymerization initiator [IV].
The photopolymerization initiator [IV] is not particularly limited as long as it generates radicals by the action of light. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2- Hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylenephenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy 2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) Phenyl] -2-morpholinopropane-1, benzoin, benzoin methyl ether, benzoin Ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'- Dimethyl-4-methoxybenzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, camphorquinone, dibenzosuberone, 2-ethylanthraquinone, 4 ', 4 "-diethylisophthalophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, α-acyloxime ester, acylphosphite Examples include oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, among which benzyldimethyl ketal, 1 -Hydroxycyclohexyl phenyl ketone, benzoyl isopropyl ether, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one are preferred. Used.

  Further, triethanolamine, triisopropanolamine, 4,4'-dimethylaminobenzophenone (Michler ketone), 4,4'-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylamino as an auxiliary for the photopolymerization initiator Ethyl benzoate, ethyl 4-dimethylaminobenzoate (n-butoxy), isoamyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2,4-diisopropylthio It is also possible to use xanthone or the like together.

In the present invention, the urethane (meth) acrylate compound [I] (preferably the urethane (meth) acrylate compound [i] having a quaternary ammonium base, the polymer [II] having a quaternary ammonium base and fine particles) [III] and photopolymerization initiator [IV]
In addition, it is preferable to contain an ethylenically unsaturated monomer [V] from the viewpoint of further improving the coating film hardness and scratch resistance.
Conventionally, the moisture resistance required for use in optical applications can be improved by blending an ethylenically unsaturated monomer, but on the contrary, the antistatic property tends to be lowered. In the present invention, even if an ethylenically unsaturated monomer is added, the antistatic property is not lowered, and the effect of having excellent moisture resistance is also achieved. It becomes what has a resin composition.

  The ethylenically unsaturated monomer [V] may be any monomer having one or more ethylenically unsaturated groups in one molecule, and examples thereof include monofunctional monomers, bifunctional monomers, and trifunctional or more monomers.

  Examples of the monofunctional monomer include styrene, vinyl toluene, chlorostyrene, α-methyl styrene, methyl (meth) acrylate, ethyl (meth) acrylate, acrylonitrile, vinyl acetate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxy. Propyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 3- Chloro-2-hydroxypropyl (meth) acrylate, glycerin mono (meth) acrylate, glycidyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, isoborni (Meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, n-butyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, nonyl ( (Meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, n-stearyl (meth) acrylate, benzyl (meth) acrylate, phenol ethylene oxide modified (n = 2) (meth) acrylate, Nonylphenol propylene oxide modified (n = 2.5) (meth) acrylate, half (meth) acrylate of phthalic acid derivatives such as 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, Ryl (meth) acrylate, carbitol (meth) acrylate, benzyl (meth) acrylate, butoxyethyl (meth) acrylate, allyl (meth) acrylate, acryloylmorpholine, 2-hydroxyethylacrylamide, N-methylol (meth) acrylamide, N-vinyl pyrrolidone, 2-vinyl pyridine, 2- (meth) acryloyloxyethyl acid phosphate monoester, etc. are mentioned.

  Examples of the bifunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and dipropylene. Glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide modified bisphenol A type di (meth) acrylate, propylene oxide modified bisphenol A type Di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide modified 1,6-hexanediol di ( Acrylate), glycerin di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate Hydroxypivalic acid-modified neopentyl glycol di (meth) acrylate, isocyanuric acid ethylene oxide-modified diacrylate, 2- (meth) acryloyloxyethyl acid phosphate diester, and the like.

  Examples of the tri- or higher functional monomer include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth). ) Acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly (meth) acrylate, isocyanuric acid ethylene oxide modified triacrylate, ethylene oxide modified dipentaerythritol penta (meth) acrylate, ethylene oxide modified dipentaerythritol Hexa (meth) acrylate, ethylene oxide modified pentaerythritol tri (meth) acrylate, Chi alkylene oxide modified pentaerythritol tetra (meth) acrylate.

Other examples include a Michael adduct of acrylic acid or a 2-acryloyloxyethyl dicarboxylic acid monoester. Examples of the acrylic acid Michael adduct include acrylic acid dimer, methacrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, A methacrylic acid tetramer etc. are mentioned. The 2-acryloyloxyethyl dicarboxylic acid monoester is a carboxylic acid having a specific substituent, such as 2-acryloyloxyethyl succinic acid monoester, 2-methacryloyloxyethyl succinic acid monoester, 2-acryloyloxy. Examples thereof include ethyl phthalic acid monoester, 2-methacryloyloxyethyl phthalic acid monoester, 2-acryloyloxyethyl hexahydrophthalic acid monoester, 2-methacryloyloxyethyl hexahydrophthalic acid monoester, and the like. Furthermore, other oligoester acrylates can also be mentioned.
These ethylenically unsaturated monomers [VI] may be used alone or in combination of two or more.

  In the present invention, the urethane (meth) acrylate compound [I] (preferably the urethane (meth) acrylate compound [i] having a quaternary ammonium base) and the polymer [II] having a quaternary ammonium base, In addition to the fine particles [III], the photopolymerization initiator [IV], and the ethylenically unsaturated monomer [V], an antistatic agent [VI] can be blended in order to further improve the antistatic effect.

  Examples of the antistatic agent [VI] include quaternary ammonium salt cationic antistatic agents, aliphatic sulfonates, higher alcohol sulfates, higher alcohol alkylene oxide adduct sulfates, and higher alcohol phosphates. And anionic antistatic agents such as salts, higher alcohol alcohol alkylene oxide adduct phosphate esters, higher alcohol alkylene oxide adducts, polyalkylene glycol fatty acid esters, and the like.

In the present invention, the content of the fine particles [III] is 100 parts by weight in total of the urethane (meth) acrylate compound [I] and the polymer [II] having a quaternary ammonium base (further ethylenically unsaturated). When the monomer [V] is blended, it is preferably 0.1 to 300 parts by weight, more preferably 0.5 to 200 parts by weight based on 100 parts by weight of [I], [II] and [V]). Parts, particularly 1 to 100 parts by weight. If the content of the fine particles [III] is less than 0.1 parts by weight, the effects such as anti-glare properties due to the addition of the fine particles are insufficient, and if it exceeds 300 parts by weight, the hardness of the coating film is inferior.
Moreover, it is preferable that the average particle diameter of the said fine particle [III] is 0.001-30 micrometers from a viewpoint of the transparency of a cured coating film, and it is 0.1-25 micrometers from the point which improves anti-glare property especially. Preferably there is.

  In the present invention, the photopolymerization initiator [IV] is blended in an amount of 100 parts by weight of the urethane (meth) acrylate compound [I] (in addition, when the ethylenically unsaturated monomer [V] is blended, [I], [ V] is preferably 1 to 10 parts by weight, more preferably 1 to 8 parts by weight, and particularly preferably 1 to 5 parts by weight. If the blending amount is less than 1 part by weight, the curing rate in the case of ultraviolet curing is extremely slow, and if it exceeds 10 parts by weight, the curability is not improved and is useless.

  Moreover, as a compounding quantity of ethylenically unsaturated monomer [V], it is preferable that it is 1-1000 weight part with respect to 100 weight part of urethane (meth) acrylate type compound [I], More preferably, it is 1-500 weight. Parts, particularly preferably 5 to 300 parts by weight. If the blending amount is less than 1 part by weight, the effect of improving the coating film hardness is difficult to obtain, and if it exceeds 1000 parts by weight, the surface resistivity of the cured coating film is undesirably increased.

  The blending amount of the antistatic agent [VI] is the total amount of the urethane (meth) acrylate compound [I] and the polymer [II] having a quaternary ammonium base (further, the ethylenically unsaturated monomer [V] Is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, particularly preferably 100 parts by weight in total of [I], [II] and [V]. Is 2 to 20 parts by weight. If the blending amount is less than 1 part by weight, it is difficult to obtain the effect of improving the addition of antistatic, and if it exceeds 100 parts by weight, the coating film becomes brittle or the antistatic performance decreases with time. Absent.

  The urethane (meth) acrylate compound [I], a polymer [II] having a quaternary ammonium base, a fine particle [III], a photopolymerization initiator [IV], an ethylenically unsaturated monomer [V], and In addition to the antistatic agent [VI], fillers, electrolyte salts, dyes and pigments, oils, plasticizers, waxes, desiccants, dispersants, wetting agents, emulsifiers, gelling agents, stabilizers, Foaming agents, leveling agents, thixotropy imparting agents, antioxidants, flame retardants, fillers, reinforcing agents, matting agents, cross-linking agents, and the like can also be blended.

Thus, an active energy ray-curable resin composition comprising the urethane (meth) acrylate compound [I] of the present invention and the polymer [II] having a quaternary ammonium base and the fine particles [III] is obtained. This composition can be used by blending an organic solvent and adjusting the viscosity as necessary. Examples of the organic solvent include ethyl acetate, butyl acetate, toluene, xylene, methanol, ethanol, propanol, butanol, acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, cellosolve such as ethyl cellosolve, and propylene such as propylene glycol monomethyl ether. Examples include glycol ethers and diacetone alcohol.
These organic solvents may be used alone or in combination of two or more.

The active energy ray-curable resin composition of the present invention is cured by irradiating active energy rays after applying it to an object.
Such an object is not particularly limited. For example, polyolefin resin such as polyethylene, polypropylene, polycyclopentadiene, polycarbonate, polyester, ABS resin, acrylic resin and the like (film, sheet, cup, etc.) ), Metal, glass and the like.
In addition, the present invention is applicable to optical films such as polyethylene terephthalate films, triacetyl cellulose films, acrylic resin films, alicyclic structure-containing resin films such as “ZEONOR” manufactured by ZEON Corporation and “ARTON” manufactured by JSR Corporation, etc. Is useful.

  As such active energy rays, rays such as far ultraviolet rays, ultraviolet rays, near ultraviolet rays, infrared rays, electromagnetic waves such as X rays and γ rays, electron beams, proton rays, neutron rays, etc. can be used. Curing by ultraviolet irradiation is advantageous from the viewpoint of easy availability and price. In addition, when performing electron beam irradiation, it can harden | cure even without using photoinitiator [IV].

As a method of curing by ultraviolet irradiation, a high-pressure mercury lamp that emits light in a wavelength range of 150 to 450 nm, an ultra-high pressure mercury lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, a chemical lamp, an electrodeless discharge lamp, etc. 3000 mJ / cm ² about may be irradiated.
After the ultraviolet irradiation, heating can be performed as necessary to complete the curing.

  Thus, the active energy ray-curable resin composition of the present invention contains the urethane (meth) acrylate compound [I], the polymer [II] having a quaternary ammonium base, and the fine particles [III]. It exhibits excellent effects on coating film properties such as prevention, optical properties, coating film hardness and scratch resistance, and paints, adhesives, adhesives, adhesives, inks, protective coating agents, anchor coating agents It is useful as various film forming materials such as a magnetic powder coating binder, a sandblast coating, and a plate material. Among them, it is very useful to use as a coating agent for optical films.

Hereinafter, the present invention will be described more specifically with reference to examples.
In the examples, “%” and “parts” are based on weight unless otherwise specified.

Synthesis example of urethane (meth) acrylate compound [I] [urethane (meth) acrylate compound (A-1)]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, hexamethylene diisocyanate trimer (a1) (isocyanate group content 21.3%) 128.1 g (0.22 mol) ) And 2,6-di-tert-butylcresol 0.56 g, dibutyltin dilaurate 0.12 g, dipentaerythritol pentaacrylate (0.44 mol) (mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate acrylate) (Hydroxyl value 48 mg KOH / g) 507.5 g) (a3), methyl ethyl ketone 300.0 g was charged, reacted at 60 ° C. for 2 hours, and cooled to 45 ° C. when the residual isocyanate group reached 1.0%. In addition, dimethylalkylhydroxyethyla 64.4 g (0.22 mol) of monium sulfonate (a2) [compound represented by the following structural formula (7) (manufactured by Takemoto Yushi Co., Ltd.) (molecular weight 297.0)] was added to the reaction system at 45 ° C. The reaction was terminated at 60 ° C. for 3 hours, and when the residual isocyanate group reached 0.1%, the urethane (meth) acrylate compound (A-1) was obtained (resin concentration 70%). .

ここで、Ｒは炭素数８のアルキル基。
得られたウレタン（メタ）アクリレート系化合物（Ａ−１）の重量平均分子量は１７３０であった。

Here, R is an alkyl group having 8 carbon atoms.
The weight average molecular weight of the obtained urethane (meth) acrylate compound (A-1) was 1730.

[Urethane (meth) acrylate compound (B2-1)]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser and a nitrogen gas inlet, hexamethylene diisocyanate trimer (b1) (isocyanate group content 21.3%) 204.9 g (0.35 mol) ), 2,6-di-tert-butylcresol 1.4 g, dibutyltin dilaurate 0.02 g, pentaerythritol triacrylate (b3) (weight average molecular weight 465.64, hydroxyl value 120.5 mg KOH / g) (Osaka Organic) Chemical Industrial Co., Ltd., “Biscoat # 300”) 337.4 g (0.69 mol) and methyl ethyl ketone 300.0 g were charged and reacted at 60 ° C. for 3 hours. When the residual isocyanate group reached 1.9%, 45 After cooling to ℃, polyoxyethylene alkylmethyl ammonium salt (b2) (manufactured by Lion Corporation, “Eso” C / 25 ") (weight average molecular weight 910.50, ethylene oxide addition mole number 15) 157.68 g (0.17 mol) was added to the reaction system at 45 ° C and reacted at 50 ° C for 3 hours, The reaction was terminated when the residual isocyanate group reached 0.1%, and a urethane (meth) acrylate compound (B2-1) was obtained (resin concentration 70%).
The weight average molecular weight of the obtained urethane (meth) acrylate compound (B2-1) was 1800.

[Urethane (meth) acrylate compound [Ia]]
In a four-necked flask equipped with a thermometer, stirrer, water-cooled condenser and nitrogen gas inlet, 199.0 g (0.90 mol) of isophorone diisocyanate, 2.0 g of 2,6-di-tert-butylcresol, dibutyltin dilaurate 0.02 g was charged, and 801.0 g (1.79 mol) of pentaerythritol triacrylate (hydroxyl value 125.4 mg KOH / g) (manufactured by Osaka Organic Chemical Industry Co., Ltd., “Biscoat # 300”) at 60 ° C. or less for about 1 hour The reaction was terminated when the residual isocyanate group reached 0.3%, and urethane (meth) acrylate compound [Ia] was obtained (resin concentration 100). %).
The weight average molecular weight of the obtained urethane (meth) acrylate compound [Ia] was 1400.

Synthesis of Polymer [II] Having Quaternary Ammonium Base [Polymer Having Quaternary Ammonium Base [II-1]]
In a four-necked flask equipped with a thermometer, a stirrer, a water-cooled condenser, and a nitrogen gas inlet, 48.1 g (0.34 mol) of N, N-dimethylaminoethyl methacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “Light Ester DM”) ) And N, N-dimethylaminoethyl methacrylate quaternized product (manufactured by Kyoeisha Chemical Co., Ltd., “Light Ester DQ-100”) 158.6 g (0.48 mol), 2-ethylhexyl methacrylate 72.1 g (0.39 mol) Then, 2.38 g of azobisisobutyronitrile, 480.8 g of isopropyl alcohol, and 240.4 g of methyl ethyl ketone were charged, and after the start of stirring, the atmosphere was replaced with nitrogen, heated to 80 ° C., reacted for 8 hours, and polymer [II-1] (Resin concentration 28%) was obtained.

Fine particles [III]
[Fine particle [III-1]]
A dispersion of polyethylene fine particles (particle system is about 3 μm) “T-10P-3” (manufactured by Gifu Shellac Co., Ltd.) was used.

Example of ethylenically unsaturated monomer [V] [ethylenically unsaturated monomer [V-1]]
Pentaerythritol tetraacrylate (manufactured by Kyoeisha Chemical Co., Ltd., “Light acrylate PE-4A”) was used.
[Ethylenically unsaturated monomer [V-2]]
Dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., “Kayarad DPHA”) was used.

Examples 1-4 and Comparative Examples 1-2
[Active energy ray-curable resin composition]
The urethane (meth) acrylate compound [I] [(A-1), (B-2)] or [Ia], a polymer [II] [[II-1] having a quaternary ammonium base. ], Fine particles [III], [[III-1]], ethylenically unsaturated monomers [V] [[V-1], [V-2]], and photopolymerization initiator [IV] [1-hydroxycyclohexyl] Phenylketone (manufactured by Ciba Specialty Chemicals, "Irgacure 184")] was blended in the proportion shown in Table 1 in terms of solid content, and the resin content excluding the photopolymerization initiator with propylene glycol monomethyl ether was 20%. It diluted so that it might become, and the active energy ray hardening-type resin composition was obtained.

The obtained active energy ray-curable resin composition was placed on an easy-adhesive polyethylene terephthalate film with a bar coater no. 8 was applied so that the film thickness after drying was 5 μm, dried at 90 ° C. for 3 minutes, and then from a height of 18 cm to 5.1 m / min using a high pressure mercury lamp 80 W and one lamp. 2 passes of ultraviolet irradiation (accumulated dose 450 mJ / cm ² ) at a conveyor speed to form a cured coating film, and the following evaluation was performed.

(Adhesion)
According to the above JIS K 5600-5-6, 100 cured 1 mm grids were made on the cured coating film, adhesion tests were performed with cello tape, the peeled state of the grids was observed, and the number of remaining grids was evaluated. .

(Coating hardness)
About the cured coating film, pencil hardness was measured according to JISK5600-5-4.

(Abrasion resistance)
About the cured coating film, the degree of damage of the surface after visually reciprocating 20 times steel wool # 0000 with a load of 300 g on the surface of the cured coating film was observed. The evaluation criteria are as follows.
○ ・ ・ ・ No scratches or scratches are inconspicuous △ ・ ・ ・ Some scratches are conspicuous × ・ ・ ・ Part of the coating film is peeled off due to scratches

(Surface resistivity)
About the cured coating film, the surface resistivity (Ω / □) in a 23 ° C. × 50% RH environment was measured with a URS probe using a resistivity meter “Hiresta UP” manufactured by Mitsubishi Chemical Corporation.

(Glossiness)
The cured coating film was measured using a gloss meter “VG2000” manufactured by Nippon Denka Co., Ltd. at an incident angle of 60 degrees and a reflection angle of 60 degrees.

(Reflection)
After peeling off the polarizing plate on the outside of the liquid crystal display element (FMV-5100NL / T, 10.4 type, manufactured by Fujitsu Ltd.) and pasting together instead of easy-adhesive polyethylene terephthalate with a cured coating film, a 100 W fluorescent lamp 1 in a dark room The books were placed 4 m apart and the following evaluations were made visually.
The state of reflection of a fluorescent lamp on the surface of the cured coating film on easy-adhesive polyethylene terephthalate was observed, and the visibility was evaluated. The evaluation results were expressed in three stages of ○, Δ, and × in order from the easy to see.

(Glitter)
The microscopic area on the surface of the cured coating film on the easily-adhesive polyethylene terephthalate obtained in the same manner as described above and the state of luminance unevenness between each pixel were observed to evaluate the visibility. The evaluation results were expressed in three stages of ○, Δ, and × in order from the easy to see.

(Shiromoya)
The microscopic area on the surface of the cured coating film on the easy-adhesive polyethylene terephthalate obtained in the same manner as described above and the state of uneven whitening between the pixels were observed to evaluate the visibility. The evaluation results were expressed in three stages of ○, Δ, and × in order from the easy to see.
The evaluation results of Examples and Comparative Examples are shown in Tables 1 and 2.

( )内の数値は固形分比を、「−」は添加しなかったことを表す

Numbers in parentheses indicate solid content ratio, “-” indicates no addition

The active energy ray-curable resin composition of the present invention is excellent in coating film properties and exhibits excellent effects in antistatic properties and optical properties, such as paints, pressure-sensitive adhesives, adhesives, adhesives, and inks. It is useful as various film forming materials such as protective coating agents, anchor coating agents, magnetic powder coating binders, sandblast coatings, and plate materials. Among them, it is very useful to use as a coating agent for optical films.

Claims (15)

  An active energy ray-curable resin composition comprising a urethane (meth) acrylate compound [I], a polymer [II] having a quaternary ammonium base, and fine particles [III].   The active energy ray-curable resin composition according to claim 1, wherein the urethane (meth) acrylate compound [I] is a urethane (meth) acrylate compound [i] having a quaternary ammonium base. The urethane (meth) acrylate compound [i] having a quaternary ammonium base is a polyisocyanate compound (a1), a quaternary ammonium salt (a2) represented by the following general formula (1), and a hydroxyl group-containing (meth). The active energy ray-curable resin composition according to claim 2, which is a urethane (meth) acrylate compound (A) obtained by reacting with an acrylate compound (a3).

Here, R ₁ , R ₂ and R ₃ are alkyl groups having 1 to 50 carbon atoms, X ₁ is Cl, Br, R ₄ SO ₃ (R ₄ is alkyl, alkyl ether or alkylbenzene), and n is 1 to 200. Is an integer.   After the urethane (meth) acrylate compound (A) reacts the isocyanate group of the polyisocyanate compound (a1) with the hydroxyl group of the hydroxyl group-containing (meth) acrylate compound (a3) under the condition that the isocyanate group remains, 4. The activity according to claim 3, wherein the activity is obtained by reacting the residual isocyanate group of the polyisocyanate compound (a1) with the hydroxyl group of the quaternary ammonium salt (a2) represented by the general formula (1). Energy ray curable resin composition. The active energy ray-curable resin composition according to claim 3 or 4, wherein the urethane (meth) acrylate compound (A) is a urethane (meth) acrylate compound represented by the following general formula (2). .

Here, R ₅ is a urethane bond residue of the polyisocyanate compound (a1), R ₆ is a urethane bond residue of the quaternary ammonium salt (a2) represented by the general formula (1), and R ₇ contains a hydroxyl group The urethane bond residue of the (meth) acrylate compound (a3), a is an integer of 1 to 50, and b is an integer of 1 to 50. A urethane (meth) acrylate compound [i] having a quaternary ammonium base is a polyisocyanate compound (b1), a quaternary ammonium salt (b2) represented by the following general formula (3), and a hydroxyl group-containing (meth). The active energy ray-curable resin composition according to claim 2, which is a urethane (meth) acrylate compound (B) obtained by reacting with an acrylate compound (b3).

Here, R ₈ and R ₉ are any of alkyl groups having 1 to 50 carbon atoms, X ₂ is Cl, Br, RSO ₃ (R is alkyl, alkyl ether or alkylbenzene), m and n are integers of 1 or more. , M + n is 2 to 500. 8. The active energy ray-curable resin composition according to claim 6, wherein the urethane (meth) acrylate compound (B) is a urethane (meth) acrylate compound (B1) represented by the following general formula (4). object.

Here, R ₁₀ is a urethane bond residue of the polyisocyanate compound (b1), R ₁₁ is a urethane bond residue of the quaternary ammonium salt (b2) represented by the general formula (3), and R ₁₂ contains a hydroxyl group ( The urethane bond residue of a (meth) acrylate type compound (b3), a is an integer of 1-50, b is an integer of 1-50. 7. The active energy ray-curable resin composition according to claim 6, wherein the urethane (meth) acrylate compound (B) is a urethane (meth) acrylate compound (B2) represented by the following general formula (5). object.

Here, R ₁₃ is a urethane bond residue of the polyisocyanate compound (b1), R ₁₄ and R ₁₄ ′ are urethane bond residues (R of the quaternary ammonium salt (b2) represented by the above general formula (3). ₁₄ and R ₁₄ ′ may be the same or different.), R ₁₅ is a urethane bond residue of the hydroxyl group-containing (meth) acrylate compound (b3), R ₁₆ is either R ₁₄ or R ₁₅ , and a is The integer of 1-50, b is an integer of 0-50, c is an integer of 0-50, d is an integer of 0-50, e is an integer of 1-30.   The polymer [II] having a quaternary ammonium base is a copolymer having a quaternary ammonium base-containing unsaturated monomer as a copolymerization component or an amino group-containing unsaturated monomer as a copolymerization component. The active energy ray-curable resin composition according to claim 1, which is a quaternized product of a copolymer.   The active energy ray-curable resin according to claim 1, wherein the fine particles [III] are at least one selected from polyethylene particles, acrylic particles, polycarbonate particles, polystyrene particles, urethane particles, and silica. Composition.   11. The active energy ray-curable resin composition according to claim 1, wherein the average particle size of the fine particles [III] is 0.001 to 30 μm.   The active energy ray-curable resin composition according to claim 1, further comprising a photopolymerization initiator [IV].   The active energy ray-curable resin composition according to claim 1, further comprising an ethylenically unsaturated monomer [V]. The active energy ray-curable resin composition according to claim 1, further comprising an antistatic agent [VI]. It uses for a coating agent, The active energy ray hardening-type resin composition in any one of Claims 1-14 characterized by the above-mentioned.