JP5398992B2 - Active energy ray-curable antistatic resin composition - Google Patents

Description

  The present invention relates to a composition that is cured by irradiation with active energy rays to give a cured product that exhibits excellent permanent antistatic properties. More specifically, the present invention relates to an active energy ray-curable antistatic resin composition that gives a cured product excellent in mechanical properties, permanent antistatic properties and optical properties, and is particularly useful as a coating agent.

Currently, plastics are used in large quantities in a wide range of industries, including the automobile industry and the consumer electronics industry. The reasons for this include lightness and low cost in addition to the processability and transparency of plastics. However, since plastic has a high volume resistivity, there is a problem that it is easily charged with static electricity due to friction or the like, and dust is easily attached. In addition, there is a drawback that once charged static electricity is difficult to leak. As a countermeasure for eliminating the drawback, there is a method of forming a coating layer containing an antistatic property imparting agent to impart antistatic property to the plastic surface, and the antistatic property imparting agent has high affinity with water. Ionic liquids (see, for example, Patent Document 1) and ionic liquids with low affinity for water (see, for example, Patent Document 2) have been proposed.
JP 2007-70399 A JP 2005-314332 A

However, although ionic liquids do not have vapor pressure, they do not disappear over time, but those that have a high affinity with water will disappear relatively easily in running water, although they are ionic liquids, and have antistatic properties. There was a problem of lack of long-term sustainability. In addition, ionic liquids with low affinity with water do not easily disappear with running water, but the compatibility with the coating resin is poor, so the composition becomes cloudy and the transparency of the coating layer is impaired. However, there was a problem of bleeding out over time.
An object of the present invention is to provide a resin composition that gives a cured product excellent in permanent antistatic properties and transparency without impairing mechanical properties (such as scratch resistance) and appearance.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention provides a polymer type ionic liquid (A) comprising at least one onium cation group (a) and a polymer (b) having a counter anion group selected from the group consisting of a polycondensate and a polyaddition product. , (Meth) acrylate (B) and polymerization initiator (D), or a polymer having at least one onium cation group (a) and a counter anion group selected from the group consisting of a polycondensate and a polyaddition product A polymer type ionic liquid (A) comprising (b), (meth) acrylate (B), a polymerization initiator (D) and an ionic liquid (C) having an ethylenically unsaturated bond; ) And (B) in a weight ratio of 5/95 to 80/20, and the content of (D) is 0.1 to 20 based on the total weight of (A), (B) and (C) Active energy that is% by weight Is a line-curable antistatic resin composition.

The active energy ray-curable antistatic resin composition of the present invention has the following effects.
(1) A cured product obtained by curing the composition is excellent in mechanical properties.
(2) A cured product obtained by curing the composition is excellent in permanent antistatic properties.
(3) A cured product obtained by curing the composition is excellent in transparency.

The polymer type ionic liquid (A) in the present invention comprises at least one (preferably 1 to 100) onium cation group (a) and a polymer (b) having a counter anion group. In addition and below, the ionic liquid means a liquid having a melting point near room temperature and made of ions. In the present invention, one having a cation and a counter anion constituting the ionic liquid in a polymer molecule is referred to as a polymer type ionic liquid.
The onium cation group (a) includes a nitrogen-containing onium cation [amidinium cation (a1) and guanidinium cation (a2)], a sulfur-containing onium cation (a3), and a phosphorus-containing cation (a4). .

Examples of the amidinium cation (a1) include the following.
(A11) imidazolinium cation 5 to 15 carbon atoms (hereinafter abbreviated as C), such as 1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1 , 3-dimethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, 1,2-dimethyl-3,4-diethylimidazolinium, 1-methyl-2,3,4-triethylimidazole Linium, 1,2,3,4-tetraethylimidazolinium, 1,2,3-trimethylimidazolinium, 1,3-dimethyl-2-ethylimidazolinium, 1-ethyl-2,3-dimethylimidazole Linium, 1,2,3-triethylimidazolinium, 4-cyano-1,2,3-trimethylimidazolinium, 3-cyanomethyl-1,2-dimethyli Midazolinium, 2-cyanomethyl-1,3-dimethylimidazolinium, 4-acetyl-1,2,3-trimethylimidazolinium, 3-acetylmethyl-1,2-dimethylimidazolinium, 4-methylcarbooxymethyl -1,2,3-trimethylimidazolinium, 3-methylcarbooxymethyl-1,2-dimethylimidazolinium, 4-methoxy-1,2,3-trimethylimidazolinium, 3-methoxymethyl-1, 2-dimethylimidazolinium, 4-formyl-1,2,3-trimethylimidazolinium, 3-formylmethyl-1,2-dimethylimidazolinium, 3-hydroxyethyl-1,2-dimethylimidazolinium, 4-hydroxymethyl-1,2,3-trimethylimidazolinium, 2-hydroxyethyl- , 3-dimethyl imidazolinium;

(A12) imidazolium cation C5-15, such as 1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, 1,2 , 3,4-tetramethylimidazolium, 1,3-dimethyl-2-ethylimidazolium, 1,2-dimethyl-3-ethyl-imidazolium, 1,2,3-triethylimidazolium, 1,2,3 , 4-tetraethylimidazolium, 1,3-dimethyl-2-phenylimidazolium, 1,3-dimethyl-2-benzylimidazolium, 1-benzyl-2,3-dimethyl-imidazolium, 4-cyano-1, 2,3-trimethylimidazolium, 3-cyanomethyl-1,2-dimethylimidazolium, 2-cyanomethyl-1 , 3-dimethyl-imidazolium, 4-acetyl-1,2,3-trimethylimidazolium, 3-acetylmethyl-1,2-dimethylimidazolium, 4-methylcarbooxymethyl-1,2,3-trimethylimidazole Lithium, 3-methylcarbooxymethyl-1,2-dimethylimidazolium, 4-methoxy-1,2,3-trimethylimidazolium, 3-methoxymethyl-1,2-dimethylimidazolium, 4-formyl-1, 2,3-trimethylimidazolium, 3-formylmethyl-1,2-dimethylimidazolium, 3-hydroxyethyl-1,2-dimethylimidazolium, 4-hydroxymethyl-1,2,3-trimethylimidazolium, 2 -Hydroxyethyl-1,3-dimethylimidazolium;

(A13) Tetrahydropyrimidinium cation C6-15, such as 1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyri Midinium, 1,2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium 8-methyl-1,8-diazabicyclo [5,4,0] -7-undecenium, 5-methyl-1,5-diazabicyclo [4,3,0] -5-nonenium, 4-cyano-1,2 , 3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-cyanomethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-cyanomethyl-1,3-dimethyl Til-1,4,5,6-tetrahydropyrimidinium, 4-acetyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-acetylmethyl-1,2-dimethyl -1,4,5,6-tetrahydropyrimidinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methylcarbooxymethyl-1 , 2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-methoxymethyl-1, 2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 3-formylmethi -1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4,5,6-tetrahydropyrimidinium, 4-hydroxymethyl-1 , 2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-hydroxyethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium;

(A14) Dihydropyrimidinium cation C6-20, such as 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium [these are 1,3-dimethyl-1,4 (6)- This is expressed as dihydropyrimidinium, and the same notation is used hereinafter. 1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4 (6) -dihydropyrimidinium, 1,2,3 5-tetramethyl-1,4 (6) -dihydropyrimidinium, 8-methyl-1,8-diazabicyclo [5,4,0] -7,9 (10) -undecadienium, 5-methyl- 1,5-diazabicyclo [4,3,0] -5,7 (8) -nonadienium, 4-cyano-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-cyanomethyl- 1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 2-cyanomethyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 4-acetyl-1,2,3- Trimethyl-1,4 (6) -dihydropyrimidinium, 3 Acetylmethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methylcarbooxymethyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3- Methylcarbooxymethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-methoxy-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-methoxy Methyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-formyl-1,2,3-trimethyl-1,4 (6) -dihydropyrimidinium, 3-formylmethyl-1 , 2-Dimethyl-1,4 (6) -dihydropyrimidinium, 3-hydroxyethyl-1,2-dimethyl-1,4 (6) -dihydropyrimidinium, 4-hydroxymethyl-1,2,3 Trimethyl-1,4 (6) - dihydropyrimidinium, 1,3 2-hydroxyethyl dimethyl-1,4 (6) - hydro pyrimidinium.

Examples of the guanidinium cation (a2) include the following.
(A21) Guanidinium cation having imidazolinium skeleton C8-15, such as 2-dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2 -Diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3,4-diethylimidazolinium, 2-diethylamino-1-methyl-3,4-diethylimidazolinium 2-diethylamino-1,3,4-tetraethylimidazolinium, 2-dimethylamino-1,3-dimethylimidazolinium, 2-diethylamino-1,3-dimethylimidazolinium, 2-dimethylamino-1- Ethyl-3-methylimidazolinium, 2-diethylamino-1,3-diethylimid Dazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] Imidazolinium, 1,5,6,7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolinium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1, 2a] imidazolinium, 2-dimethylamino-4-cyano-1,3-dimethylimidazolinium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolinium, 2-dimethylamino-4-acetyl-1 , 3-dimethylimidazolinium, 2-dimethylamino-3-acetylmethyl-1-methylimidazolinium, 2-dimethylamino-4-methylcarbooxime 1,3-dimethylimidazolinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methylimidazolinium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolinium, 2- Dimethylamino-3-methoxymethyl-1-methylimidazolinium, 2-dimethylamino-4-formyl-1,3-dimethylimidazolinium, 2-dimethylamino-3-formylmethyl-1-methylimidazolinium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolinium;

(A22) Guanidinium cation having imidazolium skeleton C8-15, such as 2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2-diethylamino- 1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium, 2-diethylamino-1-methyl-3,4-diethylimidazolium, 2-diethylamino-1 , 3,4-tetraethylimidazolium, 2-dimethylamino-1,3-dimethylimidazolium, 2-diethylamino-1,3-dimethylimidazolium, 2-dimethylamino-1-ethyl-3-methylimidazolium, 2 -Diethylamino-1,3-diethylimidazolium, 1,5, 6,7-tetrahydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-imide [1,2a] imidazolium, 6,7-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 1,5-dihydro-1,2-dimethyl-2H-pyrimido [1,2a] imidazolium, 2-dimethylamino -4-cyano-1,3-dimethylimidazolium, 2-dimethylamino-3-cyanomethyl-1-methylimidazolium, 2-dimethylamino-4-acetyl-1,3-dimethylimidazolinium, 2-dimethylamino -3-acetylmethyl-1-methylimidazolium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethylimidazolium 2-dimethylamino-3-methylcarbooxymethyl-1-methylimidazolium, 2-dimethylamino-4-methoxy-1,3-dimethylimidazolium, 2-dimethylamino-3-methoxymethyl-1-methylimidazolium 2-dimethylamino-4-formyl-1,3-dimethylimidazolium, 2-dimethylamino-3-formylmethyl-1-methylimidazolium, 2-dimethylamino-3-hydroxyethyl-1-methylimidazolium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethylimidazolium;

(A23) Guanidinium cation having a tetrahydropyrimidinium skeleton C10-20, such as 2-dimethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1 , 3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethyl Amino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4,5,6-tetrahydropyrimidi Ni, 2-diethylamino-1,3,4-tetraethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1,3- Dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl -1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-diethyl-1,4,5,6-tetrahydropyrimidinium, 1,3,4,6,7,8-hexahydro -1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,3,4,6 , 7,8-Hexahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,3,4,6-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrim Dinium, 2-dimethylamino-4-cyano-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-cyanomethyl-1-methyl-1,4,5,6 -Tetrahydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-acetylmethyl-1-methyl-1 , 4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3- Methylcarbooxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1 4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-formyl-1,3 -Dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3- Hydroxyethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium;

(A24) Guanidinium cation having a dihydropyrimidinium skeleton C10-20, such as 2-dimethylamino-1,3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1, 3,4-trimethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1 -Methyl-3,4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino-1-methyl-3,4-diethyl-1,4 (6) -dihydropyrimidinium, 2-diethylamino -1,3,4-tetraethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidi 2-diethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4 (6) -dihydropyrimidinium, 2 -Diethylamino-1,3-diethyl-1,4 (6) -dihydropyrimidinium, 1,6,7,8-tetrahydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6 -Dihydro-1,2-dimethyl-2H-imide [1,2a] pyrimidinium, 1,6,7,8-tetrahydro-1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 1,6-dihydro -1,2-dimethyl-2H-pyrimido [1,2a] pyrimidinium, 2-dimethylamino-4-cyano-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2- Methylamino-3-cyanomethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-acetyl-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-Dimethylamino-3-acetylmethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methylcarbooxymethyl-1,3-dimethyl-1,4 (6) -Dihydropyrimidinium, 2-dimethylamino-3-methylcarbooxymethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-4-methoxy-1,3-dimethyl-1 , 4 (6) -dihydropyrimidinium, 2-dimethylamino-3-methoxymethyl-1-methyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino -4-formyl-1,3-dimethyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-3-formylmethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium 2-dimethylamino-3-hydroxyethyl-1-methyl-1,4,5,6-tetrahydropyrimidinium, 2-dimethylamino-4-hydroxymethyl-1,3-dimethyl-1,4 (6) -Dihydropyrimidinium.

  The sulfur-containing onium cation (a3) includes sulfonium, thiophenium, thiomorpholinium, thioxonium cation, and the like.

  The phosphorus-containing cation (a4) includes a phosphonium cation and a tetrabutylphosphonium bromide cation.

  Of these, (a1) is preferable from the viewpoint of the conductivity of the polymer type ionic liquid, imidazolium cation (a12) is more preferable, and 1-ethyl-3-methylimidazolium cation is particularly preferable.

The polymer (b) in the present invention is a polymer having a counter anion group of the onium cation group (a), and from the viewpoint of the degree of freedom in composition design, the addition polymer (b1), the polycondensate (b2), and the polyadduct A polymer selected from the group consisting of (b3) is preferred.
The anionic groups constituting (b) include organic acid groups such as carboxylic acid groups, sulfate ester groups, higher alkyl ether sulfate ester groups, sulfo groups, and phosphate ester groups.

The addition polymer (b1) includes a (co) polymer of the ethylenically unsaturated group-containing monomer (b01) having at least one of the anionic groups.
(B1) can be obtained by (co) polymerizing the ethylenically unsaturated group-containing monomer (b01) having an anionic group.

Examples of (b01) include the following, and combinations thereof.
(1) Carboxylic acid group C13-30, for example, isophthalic acid, terephthalic acid, phthalic acid (anhydride), esterified product of trimellitic acid (anhydride) and hydroxyl group-containing (meth) acrylate, and (meth) acrylic acid;
(2) Those having a sulfate group C5-20, for example, a reaction product of a hydroxyl group-containing (meth) acrylate and sulfuric acid [sulfuric ester of 2-hydroxyethyl (meth) acrylate, sulfuric acid of 3-hydroxypropyl (meth) acrylate Esters, etc.];
(3) Those having a sulfo group C6-30, such as (meth) acryloylmethylbenzenesulfonic acid, (meth) acryloyloxybenzenesulfonic acid, (meth) acryloyldecylbenzenesulfonic acid, etc .;
(4) Those having a phosphate ester group C6-30, such as 2- (meth) acryloyloxyethyl acid phosphate, etc .;
Of these (b01), (1) and (3) are preferable from the viewpoint of the electric power of the polymer type ionic liquid.

  The polycondensate (b2) includes a polycondensate (polyester, polyamide, polyesteramide, polyether formed from a polyvalent carboxylic acid (b021) and a polyhydric alcohol (b022) and / or a polyvalent amine (b023). Ester, polyether ester amide, etc.) having at least one anionic group.

  The polyvalent carboxylic acid (b021) constituting (b2) is a divalent to tetravalent or higher polyvalent carboxylic acid (b0211), a sulfo group-containing polyvalent carboxylic acid (b0212), or a sulfate group-containing polyvalent carboxylic acid. Examples of the acid (b0213), sulfamic acid group-containing polyvalent carboxylic acid (b0214), phosphoric acid group-containing polyvalent carboxylic acid (b0215), and phosphonic acid group-containing polyvalent carboxylic acid (b0216) include the following.

  Among the divalent carboxylic acids in (b0211), aliphatic dicarboxylic acids (C2-15 such as oxalic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, glutaconic acid, succinic acid, adipic acid, and sebacic acid ), Azelaic acid, malonic acid, dodecenyl succinic acid and octyl succinic acid); aromatic (aliphatic) dicarboxylic acids (C8-15, such as phthalic acid, isophthalic acid, terephthalic acid, xylylene dicarboxylic acid, etc.); alicyclic dicarboxylic acids (C4-20, such as cyclohexanedicarboxylic acid); and their anhydrides, alkyl (C1-3) esters, etc .;

  Examples of trivalent carboxylic acids include aliphatic tricarboxylic acids (C7-20, such as 1,2,4-butanetricarboxylic acid, 1,2,5-hexanetricarboxylic acid, 1,3-dicarboxyl-2-methyl-2- Methylenecarboxypropane); aromatic tricarboxylic acid [C9-25, such as 1,2,4-benzenetricarboxylic acid (trimellitic acid), 2,5,7-naphthalenetricarboxylic acid, 1,2,4-naphthalenetricarboxylic acid] Alicyclic tricarboxylic acids (C9-25, such as 1,2,4-cyclohexanetricarboxylic acid); and their acid anhydrides, alkyl (C1-3) esters, and the like.

  Examples of tetravalent carboxylic acids include C9-25, such as tetra (methylenecarboxyl) methane, 1,2,7,8-octanetetracarboxylic acid, pyromellitic acid, emporic trimer acid, and acid anhydrides and alkyls thereof. (C1-3) ester etc. are mentioned.

Examples of the sulfo group-containing polyvalent (divalent or higher) carboxylic acid (b0212) include a sulfo group-containing aromatic dicarboxylic acid [sulfobenzenedicarboxylic acid and its alkyl ester [5-sulfo-ortho-, iso- and terephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, dimethyl 5-sulfoisophthalate, etc.], 4-sulfonaphthalene-2,7-dicarboxylic acid, etc.]; sulfo group-containing aliphatic dicarboxylic acid [sulfoalkane- And alkenedicarboxylic acids (sulfosuccinic acid, sulfoglutaric acid, sulfoadipic acid, sulfopimelic acid, sulfosuberic acid, sulfoazeleic acid, sulfosebacic acid, sulfomaleic acid, etc.)]; substituted sulfosuccinic acids such as the following general formula (1)
The thing etc. which are shown by are mentioned.

^{HOOC-CH (R 2) -CH} (SO 3 H) -COOH (1)

[Wherein R ² represents R ¹ or a C 1-13 hydrocarbyl (alkyl, alkenyl, cycloalkyl, aralkyl, aryl, etc.) group, R ¹ represents alkoxy (methoxy, ethoxy, etc.), hydroxyl, cyano, Represents an aldehyde or nitro group or a halogen atom (chlorine, bromine, etc.). ]

  The sulfate group-containing polyvalent carboxylic acid (b0213) is a sulfate of hydroxydicarboxylic acid [mono- and dihydroxyalkanedioic acid (tartronic acid, malic acid, tartaric acid, etc.)] [hydroxyl group sulfating agent (fuming sulfuric acid, etc.) And sulfate esterified with].

  Examples of the sulfamic acid group-containing polyvalent carboxylic acid (b0214) include sulfamic acid products of aminodicarboxylic acids (aspartic acid, glutamic acid, etc.) (amino acids converted to sulfamic acid groups with fuming sulfuric acid or chlorosulfuric acid).

  As the phosphoric acid group-containing polyvalent carboxylic acid (b0215), a phosphoric ester of hydroxydicarboxylic acid (same as above) [hydroxyl group was phosphorylated with a phosphorylating agent (phosphorus pentoxide, phosphorus oxychloride, etc.) And some of the acid groups (OH) thereof are alcohols or alkylene oxides (hereinafter abbreviated as AO) [C2-8 or more, preferably C2-4, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide. (Hereinafter abbreviated as PO)] and a partial alkyl ester or a partial hydroxyalkyl ester].

  As the phosphonic acid group-containing polyvalent carboxylic acid (b0216), a phosphonated hydroxydicarboxylic acid (same as above) [hydroxyl group was converted to phosphite with phosphorus trichloride and further isomerized to convert to a phosphonic acid group And those obtained by partial alkyl ester or partial hydroxyalkyl ester conversion of a part of the acid group (OH) in the same manner as described above.

  The polyhydric alcohol (b022) has two or more OH groups, a low molecular polyol (b0221) having an OH equivalent (based on OH value, molecular weight per OH) of less than 250, and a high OH equivalent of 250 or more. Examples thereof include molecular polyol (b0222), sulfo group-containing polyol (b0223), and mixtures thereof.

Examples of the low molecular weight polyhydric alcohol (b0221) include dihydric alcohols (C2-20 or higher) such as aliphatic dihydric alcohols [C2-12, such as (di) alkylene glycols [ethylene glycol, diethylene glycol, propylene glycol, dioxygen]. Propylene glycol, 1,2-, 2,3-, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and 3-methylpentanediol (hereinafter EG, DEG, PG, DPG, BD, HD, NPG and MPD), dodecanediol etc.], etc.], alicyclic dihydric alcohols [C5-10, such as 1,3-cyclopentanediol, 1,3- and 1,4-cyclohexane Diol, 1,4-cyclohexanedimethanol, etc.], aromatic aliphatic Esters [C8～20, for example xylylene glycol, bis (hydroxyethyl) benzene];
Trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol (hereinafter referred to as GR, TMP respectively) , PE, SO and DPE), 1,2,6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins, etc.], sugars and derivatives thereof [sucrose, glucose, fructose Mannose, lactose, glucoside (methyl glucoside, etc.) etc.], etc .;
In addition, among the polyether polyol, polytetramethylene glycol (hereinafter abbreviated as PTMG), polyester polyol, polycaprolactone, polycarbonate, polybutadiene, hydrogenated polybutadiene, polyisoprene polyol and hydrogenated polyisoprene polyol described later, the OH equivalent is less than 250. Can be mentioned.

  As the polymer polyol (b0222), a polyether polyol [the above dihydric alcohol, or an AO of a trihydric to octahydric or higher polyhydric alcohol [C2-4, such as EO, PO, 1,2- and 2, 3-butylene oxide, tetrahydrofuran (hereinafter abbreviated as THF). same as below. ] Adduct [Number average molecular weight [hereinafter abbreviated as Mn. The measurement is performed by gel permeation chromatography (GPC). ] 500-20,000], PTMG (Mn 500-10,000), etc.], Polyester polyol (Mn 500-20,000), Mn 500-10,000, polycaprolactone, polycarbonate, polybutadiene, hydrogenated polybutadiene, polyisoprene polyol And hydrogenated polyisoprene polyol.

  Examples of the sulfo group-containing polyol (b0223) include AO2 to 10 mol adducts of the sulfo group-containing polyvalent carboxylic acid (b0212) [5-sulfo-ortho-, iso- and tereophthalic acid EO2 mol adducts, etc.] It is done.

  Examples of the polyvalent amine (b023) include C2-20 diamines such as aliphatic [ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, eicosanediamine, etc.], aromatic (aliphatic) [phenylene Diamine, naphthylenediamine, xylylenediamine, etc.] and alicyclic diamines [1,3- and 1,4-cyclohexylanediamine, etc.].

In the formation of the polycondensate (b2), the equivalent ratio of COOH groups to OH groups in the reaction of the polyvalent carboxylic acid (b021) with the polyhydric alcohol (b022) and / or the polyvalent amine (b023) (COOH / OH), equivalent ratio of COOH group to NH ₂ group (COOH / NH ₂ ), or equivalent ratio of COOH group to (total of OH group and NH ₂ group) [COOH / (OH + NH ₂ )] From the viewpoint of the toughness of the polymer and the electric power of the polymer type ionic liquid, it is preferably 1.2 / 1 to 2/1, more preferably 1.5 / 1 to 2/1.

The polyadduct (b3) includes a polyurethane and / or polyurea formed from a polyhydric alcohol (b022) and / or a polyvalent amine (b023) and a polyisocyanate (b031) by a urethanation reaction, and an OH terminal or amino group. A product obtained by further reacting a polycarboxylic acid with the polyurethane or polyurea at the base end and having at least one anionic group is included.
In the urethanization reaction or the like, for example, the equivalent ratio of NCO groups to OH groups (NCO / OH) is not particularly limited, but is preferably 0.3 from the viewpoint of the toughness of the molded product described later and the temporal stability of (b3). / 1 to 0.6 / 1, more preferably 0.4 / 1 to 0.5 / 1. The same applies to the equivalent ratio of NCO groups to amino groups.

Examples of the polyisocyanate (b031) (hereinafter sometimes abbreviated as PI) include the following, and mixtures of two or more thereof.
(1) C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI
Diisocyanates (hereinafter abbreviated as DI), such as 1,3- and / or 1,4-phenylene DI, 2,4- and / or 2,6-tolylene DI (TDI), 4, 4′- and / or 2,4′-diphenylmethane DI (MDI), m- and p-isocyanatophenylsulfonyl isocyanate, 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene DI, and m- and p-isocyanatophenylsulfonyl isocyanate; and trifunctional or higher functional PI (such as triisocyanate), such as crude TDI, crude MDI (polymethylene polyphenyl polyisocyanate) and 4,4 ′, 4 ″ -triphenyl meta Triisocyanate

(2) C2-18 aliphatic PI
DI, such as ethylene DI, tetramethylene DI, hexamethylene DI (HDI), heptamethylene DI, octamethylene DI, nonamethylene DI, decamethylene DI, dodecamethylene DI, 2,2,4- and / or 2,4,4- Trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethylcaproate, 2,6-diisocyanatoethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate and Trimethylhexamethylene diisocyanate (TMDI); and trifunctional or higher functional PI (such as triisocyanate), such as 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexa Methyleneto Reisocyanates and lysine ester triisocyanates (phosgenates of reaction products of lysine and alkanolamines, such as 2-isocyanatoethyl-2,6-diisocyanatohexanoate, 2- and / or 3-isocyanatopropyl-2 , 6-Diisocyanatohexanoate)

(3) C4-45 alicyclic PI
DI, for example isophorone DI (IPDI), 2,4- and / or 2,6-methylcyclohexane DI (hydrogenated TDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexyl Silene DI, bis (2-isocyanatoethyl) -4-cyclohexylene-1,2-dicarboxylate and 2,5- and / or 2,6-norbornane DI, dimer acid DI (DDI); PI (triisocyanate etc.), for example, bicycloheptane triisocyanate (4) C8-15 araliphatic PI
m- and / or p-xylylene DI (XDI), diethylbenzene DI and α, α, α ′, α′-tetramethylxylylene DI (TMXDI)
(5) Nurateated products of the above (1) to (4) Among these (b032), preferred are (2), (3) and (5) containing aliphatic PI and alicyclic ring from the viewpoint of light resistance It is a nurateated product of PI.

  The polymer type ionic liquid (A) in the present invention has a methyl carbonate having the onium cation group (a) (the salt is obtained by the production method described in JP-A No. 2001-316372) and the counter anion group. It can be obtained by subjecting the polymer (b) to a salt exchange reaction.

  Examples of the (meth) acrylate (B) in the present invention include the following (1) to (8) and a mixture thereof.

(1) Mono (meth) acrylate (1-1) monohydric alcohol [aliphatic (C1-30), alicyclic (C6-30) and araliphatic (C7-10)] (meth) acrylate lauryl ( (Meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, etc .;
(1-2) (Meth) acrylate of monohydric alcohol [aliphatic (C1-30), alicyclic (C6-30) and araliphatic (C7-10)] AO1-30 mol adducts (1) (Meth) acrylates of AO adducts of monohydric alcohols in -1), for example (meth) acrylates of EO2 molar adducts of lauryl alcohol, (meth) acrylates of PO3 molar adducts of lauryl alcohol;
(1-3) [Alkyl (C1-20)] (meth) acrylate of phenol (C6-30) AO 1-30 mol adduct (meth) acrylate of phenol PO3 mol adduct, EO 1 mol adduct of nonylphenol (Meth) acrylate and the like;

(2) di (meth) acrylate (2-1) polyoxyalkylene (alkylene is C2-4) [molecular weight 106 or more and Mn 3,000 or less] di (meth) acrylate polyethylene glycol (hereinafter abbreviated as PEG) (Mn400 ), Polypropylene glycol (hereinafter abbreviated as PPG) (Mn200) and PTMG (Mn650) di (meth) acrylates and the like;
(2-2) AO (2 to 30 mol) adduct of dihydric phenol compound di (meth) acrylate Divalent phenol compound [C6-18, such as monocyclic phenol (catechol, resorcinol, hydroquinone, etc.), condensed polycycle AO adducts of phenol (dihydroxynaphthalene, etc.), bisphenol compounds (bisphenol A, -F, -S, etc.) [resorcinol EO 4 mol adduct di (meth) acrylate, dihydroxy naphthalene PO 4 mol adduct di (meta) ) Acrylate, bisphenol A, -F and -S, EO 2 mol, PO 4 mol each adduct, etc.] each di (meth) acrylate, etc .;
(2-3) Di (meth) acrylate of aliphatic dihydric alcohol (C2-30) Neopentyl glycol (hereinafter abbreviated as NPG) and 1,6-hexanediol (hereinafter abbreviated as 1,6-HD) Each di (meth) acrylate, etc .;
(2-4) Di (meth) acrylate of alicyclic dihydric alcohol (C6-30) Di (meth) acrylate of dimethyloltricyclodecane, di (meth) acrylate of cyclohexanedimethanol and dihydrogen bisphenol A (Meth) acrylate, etc.

(3) Poly (trivalent to hexavalent or higher) (meth) acrylate (3-1) C3-40 polyvalent (trivalent to hexavalent or higher) alcohol and poly (meth) of its AO adduct Acrylate TMP tri (meth) acrylate, GR tri (meth) acrylate, TMP EO3 mole and PO3 mole adduct tri (meth) acrylate, GR EO3 mole and PO3 mole adduct tri (meth) acrylate, PE tri (meth) acrylate, PE tetra (meth) acrylate, PE EO4 mole adduct tetra (meth) acrylate, DPE penta (meth) acrylate, DPE hexa (meth) acrylate, etc .;

(4) Polyester (meth) acrylates obtained by esterification of polyvalent (divalent to tetravalent) carboxylic acids, polyvalent (divalent to octavalent or higher) alcohols and ester-forming acryloyl group-containing compounds Polyester acrylate having an ester bond and 5 or more acryloyl groups and a molecular weight of 150 or more and Mn 4,000 or less Examples of the polyvalent carboxylic acid include aliphatic [C3-20, such as malonic acid, maleic acid (anhydride), adipine Acid, sebacic acid, succinic acid, acid anhydride reaction product (reaction product of dipentaerythritol and maleic anhydride, etc.)], alicyclic [C5-30, for example, cyclohexanedicarboxylic acid, tetrahydro (anhydride) phthalic acid, methyl Tetrahydro (anhydride) phthalic acid] and aromatic polycarboxylic acids [C8-30, such as Phthalic acid, terephthalic acid, phthalic acid (anhydride), trimellitic acid (anhydride), pyromellitic acid (anhydride)] and the like.

(5) Urethane (meth) acrylate plural obtained by urethanization reaction with poly (bifunctional to trifunctional or higher) isocyanate, polyvalent (divalent to hexavalent or higher) polyol, hydroxyl group-containing (meth) acrylate A urethane (meth) acrylate having a molecular weight of 400 or more and having an Mn of 5,000 or less and having 2 or more acryloyl groups as the polyisocyanate. As the polyisocyanate, C6-45 (excluding NCO carbon), for example, aliphatic polyisocyanate [ Hexamethylene diisocyanate (HDI), etc.], aromatic (aliphatic) polyisocyanate [2,4- and / or 2,6-tolylene diisocyanate (TDI), 1,5-naphthalene diisocyanate (NDI), xylylene diisocyanate (XDI) ), Etc.], alicyclic polyisocyanate Preparative [isophorone diisocyanate (IPDI), 4,4'-methylenebis (cyclohexyl isocyanate), etc.], other the illustrated ones, and the like.
Examples of the polyol include a molecular weight of 62 or more and Mn of 3,000 or less, such as EG, 1,4-BD, NPG, polyether polyol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, and PTMG.
Examples of the hydroxyl group-containing (meth) acrylate include C5-30, such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, PE tri (meth) acrylate, DPE penta (meth) acrylate, and the like.

(6) Epoxy (meth) acrylate Epoxy (meth) acrylate having a molecular weight of 400 or more and Mn of 5,000 or less obtained by reaction of a polyvalent (2 to 4 valent) epoxide and (meth) acrylic acid;

(7) butadiene polymer having a (meth) acryloyl group in the main chain and / or side chain, polybutadiene poly (meth) acrylate (Mn 500 to 500,000), etc.

(8) Siloxane polymer having a (meth) acryloyl group in the main chain and / or side chain of dimethylpolysiloxane [Mn 300 to 20,000, for example, dimethylpolysiloxane poly (meth) acrylate]
Said (1)-(8) may be used independently, or may use 2 or more types together. Of these (1) to (8), (2) to (6) are preferable from the viewpoint of toughness of the cured product, and (3) and (5) are more preferable.

If necessary, the composition of the present invention may further contain an ionic liquid (C) having an ethylenically unsaturated bond.
(C) is represented by the following general formula (1), and at least one of the constituent cation (c1) and anion (c2) has an ethylenically unsaturated bond, and (C) is at room temperature or lower A room temperature molten salt having a melting point and an initial conductivity of preferably 1 to 200 ms / cm (more preferably 10 to 200 ms / cm).

X + Y- (1)

[X + represents a cation, and Y- represents an anion. ]

  The number of ethylenically unsaturated bonds in the molecule (C) is preferably at least 1, and preferably 2 to 5 or more from the viewpoint of improving the permanent antistatic performance, mechanical properties and transparency of the cured product.

Examples of the ethylenically unsaturated bond include a vinyl group, a propenyl group, and a (meth) acryloyl group. Of these, a (meth) acryloyl group is preferred from the viewpoint of active energy ray curability and copolymerization with the (meth) acrylate (B).
An ethylenically unsaturated bond may be introduced into either (X +) and / or (Y-), and the combination of (X +) and (Y-) has (1) an ethylenically unsaturated bond. (X +) (x1) and a combination of (Y-) (y1) having an ethylenically unsaturated bond, (2) A combination of (x1) and (Y-) (y2) having no ethylenically unsaturated bond, (3) A combination of (X +) (x2) and (y1) having no ethylenically unsaturated bond is included.

Examples of the cation (X +) include onium cations (nitrogen-containing onium cations, sulfur-containing onium cations, phosphorus-containing onium cations, etc.), metal cations, and the like.
Nitrogen-containing onium cations include amidinium, guanidinium, and ammonium cations; sulfur-containing onium cations include sulfonium, thiophenium, thiomorpholinium, and thioxonium cations; phosphorous-containing cation includes phosphonium cation and tetrabutylphosphonium bromide Cations and the like are included respectively.
From the viewpoint of antistatic properties, preferred are onium cations, more preferred are nitrogen-containing onium cations, and particularly preferred are amidinium and ammonium cations.

  Specific examples of (x1) include amidinium cations [C5-30, such as imidazolinium cations [1-methyl-3-vinylimidazolinium, 1,2-dimethyl-3-vinylimidazolinium, 1-methyl. -3- (meth) acryloyloxyethyl imidazolinium, 1,3 dimethyl-2- (meth) acryloyloxypropyl imidazolium, etc.], imidazolium cation [1-methyl-3-vinylimidazolium, 1-methyl-3 -(Meth) acryloyloxyethylimidazolium etc.], tetrahydropyrimidinium cation [1-methyl-3-vinyl-1,4,5,6-tetrahydropyrimidinium, 1,3-dimethyl-2- (meth) Acryloyloxyethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-the Tramethyl-4- (meth) acryloyloxypropyl-1,5,6-trihydropyrimidinium and the like] and dihydropyrimidinium cation [1-methyl-3- (meth) acryloyloxyethyl, -1,4- Or -1,6-dihydropyrimidinium and the like]]; guanidinium cation [C6-30, for example, a guanidinium cation having an imidazolinium skeleton [2-methyl-2-vinylamino-1,3,4- Trimethylimidazolinium, 2-dimethylamino-1,4-dimethyl-3- (meth) acryloyloxyethylimidazolinium, etc.], guanidinium cation having an imidazolium skeleton [2-methyl-2- (meth) acryloyl Oxyethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1, 4-dimethyl-3-vinylimidazolium, etc.], guanidinium cation having a tetrahydropyrimidinium skeleton [2-methyl-2- (meth) acryloyloxyethylamino-1,3,4-trimethyl-1,4, 5,6-tetrahydropyrimidinium and the like]; ammonium cations [C3-50, such as (meth) acryloyloxyethyldimethylammonium, vinyldilaurylammonium]; and mixtures thereof.

(X2) includes amidinium cation [C3-30, such as imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium, 1,3-dimethyl-2,4-diethylimidazolinium, etc.], imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-ethyl- 3-methylimidazolium, 1,2,3-trimethylimidazolium, etc.], tetrahydropyrimidinium cation [1
, 3-Dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3-trimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,4-tetramethyl- 1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium, etc.], and dihydropyrimidinium cation [1,3- Dimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3-trimethyl-1,4- or -1,6-dihydropyrimidinium, 1,2,3,4-tetramethyl -1,4- or -1,6-dihydropyrimidinium and the like]]; guanidinium cation [C4-30, for example, a guanidinium cation having an imidazolinium skeleton [2-dimethylamino-1,3, 4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino-1-methyl-3, 4-diethylimidazolinium, etc.], guanidinium cations having an imidazolium skeleton [2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4-trimethylimidazolium, 2- Diethylamino-1,3-dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium, etc.], guanidinium cation having a tetrahydropyrimidinium skeleton [2-dimethylamino- 1,3,4-trimethyl-1,4,5,6-tetrahydropyrim Ni, 2-diethylamino-1,3,4-trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4,5,6-tetrahydro Pyrimidinium, etc.], guanidinium cations having a dihydropyrimidinium skeleton [2-dimethylamino-1,3,4-trimethyl-1,4- and -1,6-dihydropyrimidinium, 2-diethylamino- 1,3,4-trimethyl-1,4- and -1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4- and -1,6-dihydropyrimidi Ammonium cations [C3-50, such as methyldilaurylammonium, triethylmethylammonium]; and mixtures thereof. It is below.

  Specific examples of (y1) include carboxylic acid (ester) [C3-30, such as (meth) acrylic acid, 3- (meth) acryloyloxypropionic acid, mono (meth) acryloyloxyethylphthalic acid, monovinyl succinic acid. , Mono (meth) acryloyloxypropyltetrahydrophthalic acid, hydroxyl group-containing polyvalent (meth) acrylate [eg, di (meth) acrylate of TMP EO adduct, PE tri (meth) acrylate, DPE Reactants of pentaacrylate, bisphenol A type diglycidyl ether and (meth) acrylic acid, etc.] and monoesters of dibasic acids, etc.], sulfonic acid esters [C2-30, for example, (meth) acryloyloxy EO 5 mol addition Sulfonic acid monoester, vinyl alcohol PO Mole adduct sulfonic acid monoester, 2-acrylamido-2-methylpropane-1-sulfonic acid, p-vinylbenzenesulfonic acid, etc.], phosphoric acid ester [C3-30, such as mono- and di (meth) acryloyl Phosphoric acid mono- and diester of (oxy) ethyl phosphate ester, (meth) acryloyloxy EO 5 mol adduct, 7 mol addition of phosphoric acid mono- and diester of (meth) acryloyloxyethyl PO3 mol adduct, (meth) acryloyloxyethyl caprolactone Phosphoric acid mono- and diesters, hydroxyl group-containing polyvalent (meth) acrylates [eg, GR di (meth) acrylate, di (meth) acrylate of EO adduct of TMP, PE tri (meth) acrylate, DPE pentaacrylate, Bisphenol A type diglycy Mono reaction product of ether and (meth) acrylic acid] and phosphoric acid - and diesters], and mixtures thereof.

Examples of (y2) include organic acids (C1-30, such as carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonate ester and phosphate ester), inorganic acid [such as super strong acid (borofluoric acid, boron tetrafluoride). Acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid, etc.), phosphoric acid and boric acid].
Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl [C1-12] benzenesulfonic acid (for example, p-toluenesulfonic acid) ions, and poly (n = 1 to 25). Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.
Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid (eg methanesulfonic acid, dodecanesulfonic acid), poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (eg trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfone) Acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid.
Examples of the protonic acid used in combination with the Lewis acid include hydrogen halide (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof.
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

Among the combinations of the ionic liquid (C) composed of the cation and the anion, from the viewpoint of antistatic properties, the cation (X +) (x2) having no ethylenically unsaturated bond and the ethylenically unsaturated bond are preferable. A combination of an anion (Y-) (y1) having a hydrogen atom, a combination of an amidinium cation having no ethylenically unsaturated bond and a sulfonate ester or a phosphate ester, particularly preferably an ethylenically unsaturated bond. A combination of an imidazolium cation and a sulfonic acid or a phosphate ester, such as 1-ethyl-3-methylimidazolium-2-acrylamido-2-methylpropane-1-sulfonate, 1-ethyl -3-methylimidazolium mono- and di (meth) acryloyloxyethyl phosphate Ether salts.
From the viewpoint of mechanical properties, the most preferable combination is a combination of an imidazolium cation and an acid having a polyvalent (meth) acrylate. Specifically, 1-ethyl-3-methylimidazolium and PE tri (meta) ) Ester salt of acrylate dibasic acid or phosphoric acid.

Moreover, the resin composition of this invention can contain ionic liquids (C ') other than (A) and (C) as needed in the range which does not inhibit the effect of this invention. Specific examples of (C ′) include a combination of (x2) and (y2) described above.
When (C ′) is contained, the amount used is usually 200% or less based on the weight of (C), and preferably 10 to 100% from the viewpoint of antistatic properties and its sustainability.

As the polymerization initiator (D), hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate compounds (methylbenzoyl) Formate), thioxanthone compounds (isopropylthioxanthone, etc.), benzophenone compounds (benzophenone, etc.), phosphate ester compounds (1,3,5-trimethylbenzoyldiphenylphosphine oxide, etc.), benzyldimethyl ketal, and the like.
Among these, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone and 1,3,5-trimethylbenzoyldiphenylphosphine oxide are preferable from the viewpoint of preventing coloring of the cured product. is there.

  The amount of (D) used is preferably from 0.1 to 20%, more preferably from the viewpoint of reactivity and hardness of the cured product, based on the total weight of (A), (B) and (C) described later. 0.3 to 10%.

If necessary, the composition of the present invention may further contain various other additives (E) used in the paint as long as the effects of the present invention are not impaired. In (E), inorganic filler (E1), organic filler (E2), organic pigment (E3), dispersant (E4), antifoaming agent (E5), leveling agent (E6), silane coupling agent (E7), thixotropic agent (thickener) (E8), slip agent (E9), antioxidant (E10) ultraviolet absorber (E11) and antistatic agent (E12) are included.
The total use amount of (E) is usually 60% or less based on the total weight of the composition of the present invention, and preferably 0.5 to 50% from the viewpoint of addition effect and industrial viewpoint.

  As the inorganic filler (E1), alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (a fused material of alumina and silica, silica coated on the surface of alumina, etc.)], Zirconia, tungsten carbide, titanium carbide, silicon carbide, boron carbide, diamond, carbon black (channel black, furnace black, thermal black, acetylene black, etc.), silica (fine powdered silicic acid, hydrous silicic acid, diatom, colloidal silica, etc.) , Silicate (fine powdered magnesium silicate, talc, soapstone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc.), carbonate [precipitate (active, dry, heavy or light) calcium carbonate, Magnesium carbonate Etc.], clay (kaolinic clay, sericite clay, vilophyllite clay, montmorillonite clay, bentonite, acidic clay, etc.), sulfate [aluminum sulfate (sulfate band, satin white, etc.), barium sulfate (barite powder) , Precipitated barium sulfate, lithopone, etc.), magnesium sulfate, calcium sulfate (stone koji) (anhydrous koji, hemihydrate koji, etc.)], lead white, mica powder, zinc white, titanium oxide, activated calcium fluoride, cement Lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, lock fiber, microballoon and the like.

Of these, from the viewpoint of scratch resistance and composition of the cured product (film), and suppression of coloring of the cured product, alumina, silica, silicate, carbonate, sulfate, and titanium oxide are preferable, and silica is more preferable. Calcium carbonate, barium sulfate and titanium oxide.
(E1) may be used in combination of two or more, or two or more may be combined (for example, titanium oxide is fused to silica). The shape of (D1) is not particularly limited, and may be, for example, an indefinite shape, a spherical shape, a hollow shape, a porous shape, a petal shape, an aggregated shape, or a granular shape.
The amount of (E1) used is usually 50% or less based on the total weight of the composition of the present invention, preferably from 5 to 30%, more preferably from 10 to 25 from the viewpoints of heat resistance and flexibility of the cured product. %.

Examples of the organic filler (E2) include beads of acrylic, styrene, silicone, polyurethane, acrylic urethane, benzoguanamine, and polyethylene resins. Of these, silicone resin beads are preferred from the viewpoint of heat resistance.
Moreover, the number average particle diameter (μm) of (E2) is preferably 1 to 30, more preferably 3 to 20, from the viewpoints of light transmittance and coatability of the cured product.
The amount of (E2) used is usually 50% or less based on the total weight of the composition of the present invention, preferably 5 to 40%, more preferably 10 to 35, from the viewpoints of heat resistance and coating properties of the cured product. %.

Examples of the organic pigment (E3) include the following (1) to (4).
(1) Azo pigments Insoluble monoazo pigments (toluidine red, permanent carmine FB, fast yellow G, etc.), insoluble disazo pigments (disazo yellow AAA, disazo orange PMP, etc.), azo lakes (soluble azo pigments) (lake red C, brilliant carmine 6B) Etc.), condensed azo pigments, chelate azo pigments, etc .;
(2) Polycyclic pigments: phthalocyanine blue, indanthrone blue, quinacridone red, dioxazine violet, etc .;
(3) Dyeing lakes Basic dyes (Victoria Pure Blue BO lake, etc.), acidic dyes (alkali blue toner, etc.), etc .;
(4) Others Azine pigments (aniline black, etc.), daylight fluorescent pigments, nitroso pigments, nitro pigments, natural pigments, etc.
The amount of (E3) used is usually 5% or less based on the total weight of the composition of the present invention, preferably 0.5 to 4%, more preferably 1 from the viewpoint of colorability and flexibility of the cured product. ~ 3%.

  Examples of (E4) include organic dispersants [polymer dispersants (Mn 2,000 to 500,000) and low molecular dispersants (molecular weight of 100 or more and less than Mn 2,000)] and inorganic dispersants.

  Examples of the polymer dispersant include naphthalene sulfonate [alkali metal (lithium, sodium, potassium, etc.) salt, quaternary ammonium salt, and the following salts. ] Formalin condensate, polystyrene sulfonate, polyacrylate, poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salt, carboxymethyl cellulose (Mn 2,000 to 10,000) ) And polyvinyl alcohol (Mn 2,000 to 100,000).

Examples of the low molecular weight dispersant include the following (1) to (8).
(1) Polyoxyalkylene type AO [C2-4, aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide For example, EO, PO] 1-30 mol adduct, etc .;
N-, i-, sec- and t-butanol, octanol, dodecanol and the like as the aliphatic alcohol; phenol, methylphenol and nonylphenol as the (alkyl) phenol; laurylamine and methylstearyl as the aliphatic amine Examples of the aliphatic amides include stearic acid amides.
(2) Polyhydric alcohol type Monoester compound of C4-30 fatty acid (lauric acid, stearic acid, etc.) and polyhydric (divalent-6 hexavalent or higher) alcohol [eg, GR, PE, SO) and sorbitan], etc. ;
(3) Carboxylate type C4-30 fatty acid (same as above) alkali metal (same as above) salt and the like;
(4) Sulfate ester type C4-30 aliphatic alcohol (same as above) and sulfate alcohol alkali metal (same as above) salts of aliphatic alcohol AO (C2-4) 1-30 mol adduct, etc .;

(5) Sulfonate type [Alkyl (C1-30)] Phenol (same as above) sulfonate alkali metal (same as above) salt and the like;
(6) Phosphate ester type C4-30 fatty alcohol (same as above) and aliphatic alcohol AO (C2-4) 1-30 mol adduct mono or diphosphate salt [alkali metal The same) salt, quaternary ammonium salt, etc.];
(7) Primary to tertiary amine salt type C4-30 aliphatic amine [primary amine (such as laurylamine), secondary amine (such as dibutylamine) and tertiary amine (such as dimethylstearylamine)] hydrochloride, tri Inorganic acid (hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.) salt of monoester of ethanolamine and C4-30 fatty acid (same as above);
(8) Quaternary ammonium salt type Inorganic acid (same as above) salts of C4-30 quaternary ammonium (butyltrimethylammonium, diethyllaurylmethylammonium, dimethyldistearylammonium, etc.).

Examples of the inorganic dispersant include alkali metal (same as above) salts of polyphosphoric acid and phosphoric acid-based dispersants (phosphoric acid, monoalkyl phosphoric acid ester, dialkyl phosphoric acid ester and the like).
The amount of (E4) used is usually 5% or less based on the total weight of the composition of the present invention, preferably 0 from the viewpoints of dispersibility such as (E1) to (E3) and the flexibility of the cured product. 0.05-3%.

Antifoaming agents (E5) include lower alcohols (C1-6) (methanol, butanol, etc.), higher alcohols (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acids (C10-20) (oleic acid) , Stearic acid, etc.), higher fatty acid esters (C11-30) (glycerin monolaurate, etc.), phosphate esters (tributyl phosphate, etc.), metal soaps (calcium stearate, aluminum stearate, etc.), polyethers [PEG (Mn200- 10,000), PPG (Mn 200 to 10,000), etc.], silicone (dimethylsilicone oil, alkyl-modified silicone oil, fluorosilicone oil, etc.) and mineral oil (silica powder dispersed in mineral oil), etc. Can be mentioned.
The amount of (E5) used is usually 3% or less based on the total weight of the composition of the present invention, preferably 0.01 to from the viewpoints of defoaming properties during production of the cured product and light transmittance of the cured product. 2%.

As the leveling agent (E6), PEG type nonionic surfactant (nonylphenol EO 1 to 40 mol adduct, stearic acid EO 1 to 40 mol adduct, etc.), polyhydric alcohol type nonionic surfactant (sorbitan palmitic acid monoester) Sorbitan stearic acid monoester, sorbitan stearic acid triester, etc.), fluorine-containing surfactant (perfluoroalkyl EO 1-50 mol adduct, perfluoroalkyl carboxylate, perfluoroalkyl betaine, etc.), modified silicone oil [above Other than (E5), for example, polyether-modified silicone oil and (meth) acrylate-modified silicone oil].
The amount of (E6) used is usually 3% or less based on the total weight of the composition of the present invention, preferably from 0.1 to 2 in terms of leveling properties during coating of the composition and light transmittance of the cured product. %.

Examples of the silane coupling agent (E7) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane, etc.), ureido group-containing silane. Coupling agents (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], (meth) acrylate group-containing silane coupling agents [ γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, etc.], epoxy group-containing silane coupling agent (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane Coupling agent (γ-isocyanatopropyltriethoxysilane, etc.), polymer type silane coupling agent (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), cationic type silane coupling agent [N- (N-benzyl-β-aminoethyl) ) -Γ-aminopropyltrimethoxysilane hydrochloride, etc.].
The amount of (E7) used is usually 5% or less based on the total weight of the composition of the present invention, preferably 0.5 to 3% from the viewpoint of adhesion of the cured product to the substrate and light transmittance. is there.

Thixotropy imparting agent (thickening agent) (E8) includes inorganic thixotropic imparting agents [bentonite, organically treated bentonite (surface wax coating treated bentonite, etc.) and ultrafine surface treated calcium carbonate (colloidal calcium carbonate, etc.)] and Examples include organic thixotropic property-imparting agents (hydrogenated castor oil wax, calcium stearate, aluminum oleate, polymerized linseed oil, etc.).
The amount of (E8) used is usually 10% or less based on the total weight of the composition of the present invention, preferably from the viewpoint of dispersibility such as (E1) to (E3) and the flexibility of the cured product. 5 to 5%.

As the slip agent (E9), higher fatty acid esters (C11-30, such as butyl stearate), higher fatty acids (C10-20, such as oleic acid, stearic acid) amide (ethylene bis stearamide, oleic amide, etc.), Metal soap (calcium stearate, aluminum oleate, etc.), wax [paraffin wax, polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)] and silicone (eg dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone) Oil).
The amount of (E9) used is usually 5% or less based on the total weight of the composition of the present invention, preferably 0.01 from the viewpoint of blocking resistance of composition components such as fine particles and light transmittance of the cured product. ~ 2%.

Antioxidants (E10) include hindered phenol compounds [triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis. [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 3,5-di- t-butyl-4-hydroxybenzylphosphonate diethyl ester] and amine compounds (n-butylamine, triethylamine, diethylaminomethyl methacrylate, etc.).
The amount of (E10) used is usually 3% or less based on the total weight of the composition of the present invention, preferably 0.005 to 2% from the viewpoint of the antioxidant effect and low colorability.

Examples of the ultraviolet absorber (E11) include benzotriazole compounds [2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (3,5-di-t-butyl-2-hydroxyphenyl) benzotriazole, 2 -(3,5-di-t-butyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, etc.], triazine compounds [ 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol], benzophenone (such as 2-hydroxy-4-n-octyloxybenzophenone), An oxalic acid anilide compound (2-ethoxy-2'-ethyl oxalic acid bisanilide etc.) is mentioned.
The amount of (E11) used is usually 3% or less based on the total weight of the composition of the present invention, and preferably 0.005 to 2% from the viewpoint of weather resistance and light transmittance.

  Examples of the antistatic agent (E12) include a cationic antistatic agent (E121), an anionic antistatic agent (E122), and a nonionic antistatic agent (E123).

Examples of (E121) include amidinium salts, guanidinium salts and quaternary ammonium salts excluding the above (C) and (C ′). Examples of the anion constituting the salt include methyl- and ethyl carbonate anions.
Of (E121), from the viewpoint of low colorability, amidinium alkyl (C1-3) carbonate and guanidinium alkyl (C1-3) carbonate are preferred, and imidazolinium methyl carbonate and imidazo are more preferred. It is a guanidinium methyl carbonate having a rhinium skeleton.

As (E122), sulfonic acid (polyethylene sulfonic acid, lauryl sulfonic acid, etc.) salt, sulfate ester (lauryl alcohol sulfate ester, lauryl alcohol EO 3 mol adduct sulfate ester, etc.) salt, phosphate ester (octyl alcohol phosphate ester, Lauryl alcohol EO 3 mol adduct phosphate ester, etc.) and the like. Examples of the cation constituting the salt include alkali metal (lithium, sodium, potassium, etc.) ions.
Of (E122), sulfonate is preferable from the viewpoint of antistatic properties.

  (E123) EO adducts of higher alcohols (C8-24, such as oleyl alcohol, lauryl alcohol and stearyl alcohol), PEG fatty acid esters, polyhydric alcohols (C2-20, such as GR, PE, SO and sorbitan) Fatty acid esters and the like can be mentioned, and from the viewpoint of antistatic properties, polyhydric alcohol fatty acid esters are preferable.

  The amount of (E12) used is usually 30% or less based on the total weight of the composition of the present invention, and preferably 10 to 25% from the viewpoint of antistatic properties and light transmittance of the cured product.

  When the additive is the same and overlaps between (E1) to (E12) above, the amount of each additive exerting the corresponding additive effect is not used regardless of the effect as the other additive, Considering that the effects as other additives can be obtained at the same time, the amount used is adjusted according to the purpose of use.

In order to adjust the viscosity of the present invention to a viscosity suitable for coating, the composition diluted with a solvent can be used as necessary.
The amount of the solvent used is usually 2,000% or less based on the total weight of the composition, and preferably 10 to 500% from the viewpoint of handling properties (workability) and the surface hardness of the cured product. The viscosity of the diluted composition is usually 5 to 500,000 mPa · s at the temperature during use (usually 5 to 60 ° C.), and preferably 10 to 10,000 mPa · s from the viewpoint of stable coating.

The solvent is not particularly limited as long as it dissolves the resin component in the composition of the present invention. Specifically, aromatic hydrocarbons (C7-10, eg toluene, xylene and ethylbenzene), esters or ether esters (C4-10, eg ethyl acetate, butyl acetate and methoxybutyl acetate), ethers [C4-10, eg Diethyl ether, THF, monoethyl- and monobutyl ether of EG, monomethyl ether of PG and monoethyl ether of DEG], ketone (C3-10, eg acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone), alcohol (C1-10, such as methanol, ethanol, n- and i-propanol, n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol and benzyl alcohol), amides ( 3-6, such as dimethylformamide, dimethylacetamide, N- methylpyrrolidone), sulfoxides (C2-4, such as dimethyl sulfoxide), water, and a mixed solvent of two or more thereof.
Of these solvents, ketones and alcohols are preferable from the viewpoint of the drying process time, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferable.

The composition of the present invention is diluted with a solvent if necessary, applied to at least a part of at least one side of the substrate, and dried if necessary, and then irradiated with active energy rays (ultraviolet rays, electron beams, X-rays, etc.). Thus, a coating having a cured product (film) on at least a part of at least one side of the substrate can be obtained.
For the coating, a commonly used apparatus such as a coating machine [bar coater, gravure coater, roll coater (size press roll coater, gate roll coater, etc.), air knife coater, spin coater, blade coater, etc.] can be used. The coating film thickness is usually 0.5 to 300 μm as the film thickness after curing and drying, and the preferable upper limit is 250 μm from the viewpoint of drying property and curability, and the preferable lower limit is from the viewpoint of wear resistance, solvent resistance, and contamination resistance. Is 1 μm.

  When the composition of the present invention is used after being diluted with a solvent, it is preferably dried after coating. Examples of the drying method include hot air drying (such as a dryer). The drying temperature is usually 10 to 200 ° C., the upper limit is preferably 150 ° C. from the viewpoint of the smoothness and appearance of the coating film, and the lower limit is preferably 30 ° C. from the viewpoint of the drying speed.

  When the composition of the present invention is cured by ultraviolet irradiation, a known ultraviolet irradiation device [for example, trade name “Eye Grandage”, manufactured by Eyegraphic Co., Ltd.] can be used. The irradiation amount of ultraviolet rays (mJ / cm 2) is usually 10 to 10,000, and the preferable lower limit is 100 from the viewpoint of the curability of the composition, and the preferable upper limit is 5,000 from the viewpoint of the flexibility of the cured product.

  When the composition of the present invention is cured by electron beam irradiation, a known electron beam irradiation apparatus [for example, trade name “Electron Beam”, manufactured by Iwasaki Electric Co., Ltd.] can be used. The irradiation amount (Mrad) of the electron beam is usually 0.5 to 20, and the preferable lower limit is 1 from the viewpoint of the curability of the composition. The flexibility of the cured product and the damage of the cured product (film) or the substrate are avoided. From the viewpoint of the above, the preferred upper limit is 15.

  The composition of the present invention is usually cured by active energy rays (ultraviolet rays, electron beams, X-rays, etc.), but can be cured by heat when it contains a thermal polymerization initiator (B2). In the case of curing with heat, the heat treatment is usually performed in an oven at 50 to 200 ° C., preferably from 80 to 180 ° C. from the viewpoint of curability and low colorability, for 1 minute to 20 hours.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited by these. In the following, unless otherwise specified, “part” means “part by weight” and “%” means “% by weight”.
Examples 1, 4, 6, 7, and 9 to 13 are reference examples.

Synthesis example 1
Polyacrylic acid [trade name “polyacrylic acid 5,000”, manufactured by Wako Pure Chemical Industries, Ltd., 39.2 parts of Mn 5,000 ”and 1-ethyl-3-methylimidazolium monomethyl carbonate (the synthesis method is special According to the method described in Japanese Patent Application Laid-Open No. 2001-316372. The same applies hereinafter.) 96.5 parts are mixed and decarboxylated to obtain poly (1-ethyl-3-methylimidazolium) acrylate (A -1) 100 parts were obtained.

Synthesis example 2
In a reaction vessel equipped with a cooling tube, a stirrer and a nitrogen introduction tube, 11.9 parts of 1,4-BD, 58.3 parts of 5-sulfoisophthalic acid, 1.5 parts of tetraisopropoxide titanate as a condensation reaction catalyst. The reaction was carried out for 3 hours at 150 ° C. while distilling off the water produced under a nitrogen stream. Next, while the temperature was gradually raised to 180 ° C., the reaction was carried out for 10 hours while distilling off water under a nitrogen stream to obtain a polyester having both terminal hydroxyl groups and a hydroxyl value of 36.0 (). After allowing to cool, 42.7 parts of 1-ethyl-3-methylimidazolium monomethyl carbonate was added and mixed to obtain 100 parts of (1-ethyl-3-methylimidazolium) polyester (A-2).

Synthesis example 3
In a reaction vessel equipped with a condenser, a stirrer, and a thermometer, 52.7 parts of an EO2 molar adduct of 5-sulfoisophthalic acid, 31.5 parts of IPDI, and a bismuth tri (2-ethylhexanoate) solution (2-ethylhexane) Acid 50% solution) 0.1 part was mixed and reacted at 80 ° C. for 6 hours. After allowing to cool, 27.7 parts of 1-ethyl-3-methylimidazolium monomethyl carbonate was mixed and decarboxylated to obtain 100 parts of (1-ethyl-3-methylimidazolium) polyurethane (A-3). .

Synthesis example 4
Mono (acryloyloxyethyl) phthalate [trade name “Aronix M-5400”, manufactured by Toa Gosei Co., Ltd.] and 1-ethyl-3-methylimidazolium monomethyl carbonate were mixed in equimolar amounts to give 1-ethyl-3. -Methylimidazolium mono (acryloyloxyethyl) phthalate salt (C-1) was obtained.

Synthesis example 5
By mixing equimolar amounts of mono (methacryloyloxyethyl) phosphate [trade name “light ester P-1M” manufactured by Kyoeisha Chemical Co., Ltd.] and 1-ethyl-3-methylimidazolium monomethyl carbonate Ethyl-3-methylimidazolium mono (methacryloyloxyethyl) phosphate ester salt (C-2) was obtained.

Examples 1-10, Comparative Examples 1-3
According to the composition shown in Table 1, the mixture was stirred with a disperser to obtain coating compositions of Examples 1 to 10 and Comparative Examples 1 to 3. According to the following coating preparation method, the composition was applied to a film substrate to prepare a coating. The blending components in the table are as follows. In all of the examples and comparative examples, the components were mixed and mixed uniformly to prepare a composition.

TMPT: TMP trimethacrylate [trade name “TMPT”, Shin-Nakamura Chemical Co., Ltd. (
Co., Ltd., average functional group number 3.1]
DA-600: DPE polyacrylate [trade name “Neomer DA-600”, Sanyo Chemical Industries
Industry Co., Ltd., average functional group number 5.5]
UA-306H: urethane triacrylate of PE triacrylate and hexamethylene diisocyanate
Chryrate [trade name “UA-306H”, manufactured by Kyoeisha Chemical Co., Ltd., average sensory
Radix 6]
DCPA: Tricyclodecane dimethanol diacrylate [Brand name "Light acrylate"
DCP-A ", manufactured by Kyoeisha Chemical Co., Ltd.]
EMI · BF ₄ : 1-ethyl-3-methylimidazolium tetrafluoroborate [reagent, sum
Made by Kojun Pharmaceutical Co., Ltd.]
BB: dodecyltrimethylammonium chloride [trade name “cation BB”,
Nippon Oil & Fats Co., Ltd.]
TFSILi: Bis (trifluoromethanesulfonyl) imide lithium [reagent, Wako Pure Chemical Industries, Ltd.
Industrial Co., Ltd.]
I184: 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 1
84 ", manufactured by Ciba Specialty Chemicals Co., Ltd.]
TPO: 2,4,6-trimethylbenzoyldiphenylphosphine oxide [Product
Name “Lucirin TPO”, manufactured by BASF Japan Ltd.]
Aerosil: Silica fine particles [trade name “Aerosil 200”, manufactured by Nippon Aerosil Co., Ltd.,
Volume average particle size 0.012 μm]
BYK-333: Polyether-modified organopolysiloxane [trade name “Disperby
k-333, manufactured by Big Chemie Japan Co., Ltd.]

<Coating preparation method>
The composition of Table 1 is diluted with methyl ethyl ketone and adjusted to a non-volatile content of 30%. PET film with a thickness of 100 μm [trade name “Cosmo Shine A4300”, manufactured by Toyobo Co., Ltd.] Using a bar coater on one side of the base material, it was applied so that the film thickness after drying and curing was 5 μm, and at 60 ° C. After drying for 3 minutes, an ultraviolet ray irradiation device [model number “VPS / I600”, manufactured by Fusion UV Systems Co., Ltd.] is used to irradiate ultraviolet rays at 300 mJ / cm ² to create a coating having a cured film on the surface of the base film. did. The coating was evaluated for performance by the following method. The evaluation results are shown in Table 1.

<Performance evaluation method>
(1) Transparency (haze)
Based on JIS-K7105, a haze is measured using a total light transmittance measuring apparatus [trade name “haze-gard-dual” manufactured by BYK Gardner Co., Ltd.]. Units%.
(2) Scratch resistance Using steel wool # 0000, the coating film surface of the coating was subjected to 30 reciprocal scratches at a load of 250 g / cm ² , and the appearance was evaluated visually according to the following criteria.

○ No scratches.
Δ: Some scratches are observed.
X Many scratches are observed, and the surface is whitened.
(3) Pencil hardness Pencil hardness is measured according to JIS K-5400.
(4) Antistatic properties [conforms to ASTM D257 (established in 1984)]
(4-1) Surface resistance After leaving a test piece (100 × 100 mm) cut out from the coating for 24 hours under conditions of 23 ° C. and humidity 50% RH, a digital superinsulator [DSM-8103, Toa Denpa Kogyo Co., Ltd. ) Made the same below. ] Under the same conditions. The unit is Ω. (4-2) Surface resistance after washing with water A test piece similar to (4-1) is immersed in 1,000 ml of ion-exchanged water at 25 ° C. and left to stand for 24 hours. Next, the test piece is taken out, and the surface of the coating film is washed away with flowing water of 100 ml of ion exchange water at 25 ° C. × 3 times, and then dried at 80 ° C. for 3 hours in a circulating drier. After the operation of washing and drying was repeated three times, the test piece was allowed to stand for 24 hours under the conditions of 23 ° C. and humidity 50% RH, and then measured under an atmosphere of the same condition using a superinsulator. The unit is Ω.

Examples 11-13, Comparative Examples 4-5
Mixing and stirring were performed with a disperser in accordance with the composition shown in Table 2, and the molding compositions of Examples 11 to 13 and Comparative Examples 4 to 5 were obtained. The composition was molded according to the molding method described below. The blending components in the table are as follows. In all of the examples and comparative examples, the components were mixed and mixed uniformly to prepare a composition.

ML-200: Lauryl phosphate [trade name “Phosphanol ML-200”, manufactured by Toho Chemical Industry Co., Ltd.]

<Molded article preparation method>
A 1 mm thick spacer is placed on the edge of a glass plate (11 cm × 11 cm) whose surface has been treated with a release agent, and is partitioned into 10 cm × 10 cm squares. After casting the composition of Table 2 in the square, the same glass plate is mounted. After irradiating the ultraviolet rays with 1,000 mJ / cm ² with an ultraviolet irradiation device, the mold was released from the glass plate to obtain a molded product. The molded product was evaluated for performance by the following method. The results are shown in Table 2.

<Performance evaluation method>
(1) Transparency (transmittance)
Based on JIS-K7361-1, the total light transmittance is measured using a total light transmittance measuring device. Units%.
(2) Compressive elastic modulus The compressive elastic modulus is measured with a Vickers hardness meter [Fischer hardness meter: manufactured by Fischer Co., Ltd.] at a load of 100 mN. The unit is MPa.
(3) Antistatic properties [conforms to ASTM D257 (established in 1984)]
(3-1) Surface resistance and surface resistance after washing with water The surface resistance and the surface resistance after washing with water are measured in the same manner as in (4) above.
(3-2) Volume Resistance The molded product is allowed to stand for 24 hours under the conditions of 23 ° C. and humidity 50% RH, and then the volume resistance is measured with a digital superinsulator. The unit is Ω · cm.

  The cured film obtained by applying the active energy ray-curable antistatic resin composition of the present invention to a substrate and curing it is excellent in antistatic durability, scratch resistance, transparency, and the like. It can be used widely and suitably in fields where surface hardness and prevention of dust adhesion are required, such as flat panel displays and touch panels.

Claims (6)

Polymer type ionic liquid (A), (meth) acrylate (a) comprising at least one onium cation group (a) and a polymer (b) having a counter anion group selected from the group consisting of a polycondensate and a polyadduct. B) and a polymerization initiator (D), or a polymer comprising at least one onium cation group (a) and a polymer (b) having a counter anion group selected from the group consisting of a polycondensate and a polyaddition product Type ionic liquid (A), (meth) acrylate (B), polymerization initiator (D) and ionic liquid (C) having an ethylenically unsaturated bond, and (A) and (B) Active energy having a weight ratio of 5/95 to 80/20 and a content of (D) of 0.1 to 20% by weight based on the total weight of (A), (B) and (C) Wire-curing antistatic properties Fat composition. The composition according to claim 1, further comprising an ionic liquid other than (A) and (C). Further, one or more additives selected from the group consisting of fillers, dispersants, antifoaming agents, leveling agents, silane coupling agents, thixotropic agents, slip agents, antioxidants and ultraviolet absorbers. The composition according to claim 1 or 2, comprising The cured film formed by apply | coating the composition in any one of Claims 1-3 to at least one part of at least one side of a base material, and making it harden | cure. The coating which has the cured film of Claim 4 in at least one part of at least one side of a base material. A method for producing a coating, comprising applying the composition according to any one of claims 1 to 3 to at least a part of at least one side of a base material and irradiating the composition with active energy rays.