JP2010007017A - Active energy ray-curable composition for antistatic molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an active energy ray-curable composition for moldings, excellent in curing property, and giving moldings excellent in scratch resistance, rigidity, transparency, adhesion with a substrate and antistatic property. <P>SOLUTION: The active energy ray-curable composition for antistatic moldings includes (A) an ionic liquid having one or more ethylenic unsaturated groups, (B) a (meth)acryloyl group-containing compound except (A), and (C) a photopolymerization initiator, wherein (B) includes a concentration of 3-10 mmol/g (meth)acryloyl group, the cured product formed by curing the composition has a molecular weight between crosslinking points of 60-200. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an active energy ray-curable composition for an antistatic molded article. More specifically, active energy ray curability for molded articles such as prism lenses, collimator lenses, Fresnel lenses, lenticular lenses, post-reflective lenses, holograms, and other optical lenses having a fine structure on the surface, which require antistatic properties. Relates to the composition.

Conventionally, optical lenses such as prism sheets used for liquid crystal displays and Fresnel lenses and lenticular lenses used for projection TVs are generally manufactured by injection molding or hot press molding of thermoplastic resin. In these manufacturing methods, a long time is required for heating and cooling at the time of manufacturing, so the productivity is low, and the reproducibility of the fine structure is poor and warps due to the thermal contraction of the optical lens. . In order to solve these problems, a method in which an ultraviolet curable resin composition is poured into a mold in which a transparent resin base material is set on the inner surface of a mold and is cured by irradiating with ultraviolet rays.
In recent years, with high-definition displays, optical lenses have also been required to have high-definition. For this reason, a lens with a sharp tip, a prism apex angle of 60 to 70 ° and a pitch of several tens of μm. There is a need to form an array.
However, since the lens array is easily damaged by scratches or the like, its scratch resistance has been studied, and a method of introducing a rigid structure such as a bisphenol skeleton (see, for example, Patent Document 1), surface addition by adding a fluorine compound, etc. There have been proposed a method for imparting lubricity to the surface to make it difficult to be damaged (for example, see Patent Document 2), a method for further providing a hard coat layer on the lens array (for example, see Patent Document 3), and the like.

Japanese Patent Laid-Open No. 11-240926 JP 2005-272700 A JP 11-326607 A

However, these methods have problems such as insufficient scratch resistance, poor transparency and adhesion to a substrate, complicated processes, and markedly reduced productivity.
An object of the present invention is to provide an active energy ray-curable composition for an antistatic molded article that gives a molded article having good curability and excellent scratch resistance, rigidity, transparency, antistatic properties and adhesion to a substrate. Is to provide.

  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 contains an ionic liquid (A) having one or more ethylenically unsaturated bonds, a (meth) acryloyl group-containing compound (B) excluding (A), and a photopolymerization initiator (C). In the active energy ray-curable composition for molded bodies, the cured product obtained by curing (B) having a (meth) acryloyl group concentration of 3 to 10 mmol / g and curing the composition is 60 to 200. An active energy ray-curable composition for an antistatic molded article having a molecular weight between crosslinking points of

The active energy ray-curable composition for an antistatic molded article of the present invention has the following effects.
(1) Excellent curability when irradiated with active energy rays.
(2) A cured product obtained by curing the composition is excellent in permanent antistatic properties.
(3) The cured product is excellent in scratch resistance, rigidity, transparency and adhesion to the substrate.

[Ionic liquid (A) having one or more ethylenically unsaturated groups]
The ionic liquid (A) having an ethylenically unsaturated group in the present invention (hereinafter sometimes referred to as a reactive ionic liquid) includes a monomeric ionic liquid (A1) having an ethylenically unsaturated group, ethylene The polymer type ionic liquid (A2) which has an ionic unsaturated group, and a mixture thereof are included. Here and below, the ionic liquid means a liquid composed of a cation and an anion having a melting point near room temperature.
(A1) is represented by the following general formula (1), and is an ordinary temperature molten salt having an initial conductivity of preferably 1 to 200 (more preferably 10 to 200) ms / cm, and at least one of a cation and an anion constituting the salt. Has an ethylenically unsaturated bond.

(A1X) ⁺ (A1Z) ^- (1)

[(A1X) ⁺ (hereinafter sometimes abbreviated as A1X) represents a cation, and (A1Z) ⁻ (sometimes abbreviated as A1Z in the following) represents an anion. ]

  The number of ethylenically unsaturated groups in the molecule (A1) is 1 or more, 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 group include a vinyl group, a propenyl group, and a (meth) acryloyl group. Of these, a (meth) acryloyl group is preferable from the viewpoint of active energy ray curability and copolymerization with (meth) acrylate (B) described later.
The ethylenically unsaturated group may be introduced into either A1X and / or A1Z. The combination of A1X and A1Z includes (1) A1X1 having an ethylenically unsaturated group and A1Z1 having an ethylenically unsaturated group. Combinations include (2) a combination of A1X1 and A1Z2 not having an ethylenically unsaturated group, and (3) a combination of A1X2 and A1Z1 having no ethylenically unsaturated group.

Examples of the cation (A1X) include onium cations (such as nitrogen-containing onium cations, sulfur-containing onium cations, and phosphorus-containing onium cations).
Nitrogen-containing onium cations include amidinium, guanidinium and ammonium cations; Sulfur-containing onium cations include sulfonium, thiophenium, thiomorpholinium and thioxonium cations; Phosphorus onium cations include 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 A1X1 include amidinium cation [C5-30, such as imidazolinium cation [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) acryloyloxy Ethyl-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, guanidinium cation having an imidazolinium skeleton [2-methyl-2-vinylamino-1,3,4-trimethyl] Imidazolinium, 2-dimethylamino-1,4-dimethyl-3- (meth) acryloyloxyethylimidazolinium, etc.], guanidinium cation having an imidazolium skeleton [2-methyl-2- (meth) acryloyloxy Ethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,4 -Dimethyl-3-vinylimidazolium, etc.], a guanidinium cation having a tetrahydropyrimidinium skeleton [2-methyl-2- (meth) acryloyloxyethylamino-1,3,4-trimethyl-1,4,5 , 6-tetrahydropyrimidinium, etc.]; ammonium cations [C3-50, such as (meth) acryloyloxyethyldimethylammonium, vinyldilaurylammonium]; and mixtures thereof.

  A1X2 includes an amidinium cation [C3-30, such as an 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-tetrahydropyrim Midinium, 1,2,3,5-tetramethyl-1,4,5,6-tetrahydropyrimidinium and the like], 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, eg, 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 cation 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-dimethyl Amino-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 A guanidinium cation 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-dihydropyrimidinium, etc.]] Ammonium cations [C3-50, such as methyldilaurylammonium, triethylmethylammonium]; and mixtures thereof.

  Specific examples of A1Z1 include carboxylic acid (ester) [C3-30, such as (meth) acrylic acid, 3- (meth) acryloyloxypropionic acid, mono (meth) acryloyloxyethylphthalic acid, monovinylsuccinic acid, mono (Meth) acryloyloxypropyltetrahydrophthalic acid, hydroxyl group-containing polyvalent (meth) acrylate [for example, glycerin (hereinafter abbreviated as GR) di (meth) acrylate, trimethylolpropane (hereinafter abbreviated as TMP) ethylene oxide (hereinafter abbreviated as EO) ) Adduct di (meth) acrylate, pentaerythritol (hereinafter abbreviated as PE) tri (meth) acrylate, dipentaerythritol (hereinafter abbreviated as DPE) pentaacrylate, bisphenol A type diglycidyl ether and (meth) acrylic acid Reactant] and 2 Monoester with basic acid], sulfonic acid ester [C2-30, for example, sulfonic acid monoester of (meth) acryloyloxy EO 5 mol adduct, propylene oxide of vinyl alcohol (hereinafter abbreviated as PO) 3 mol adduct sulfone Acid monoester, 2-acrylamido-2-methylpropane-1-sulfonic acid, p-vinylbenzenesulfonic acid], phosphoric acid ester [C3-30, such as mono- and di (meth) acryloyloxyethyl phosphoric acid ester, Phosphoric acid mono- and diesters of (meth) acryloyloxy EO 5 mol adduct Phosphoric mono- and diesters of (meth) acryloyloxyethyl PO3 mol adduct, phosphoric mono- and diesters of (meth) acryloyloxyethylcaprolactone 7 mol adduct And diesters, hydroxyl group-containing (Meth) acrylate [for example, GR di (meth) acrylate, di (meth) acrylate of EO adduct of TMP, PE tri (meth) acrylate, DPE pentaacrylate, bisphenol A type diglycidyl ether and (meth) acrylic acid And mono- and diesters of phosphoric acid], and mixtures thereof.

As A1Z2, organic acids (C1-30, such as carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonate ester and phosphate ester), inorganic acid [eg super strong acid (borofluoric acid, tetrafluoroboric acid, Perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid, 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.

  Of the combinations of the cation and the anion constituting the monomeric ionic liquid (A1), a cation (A1X2) having no ethylenically unsaturated group is preferable from the viewpoint of antistatic properties and mechanical properties of the cured product described later. A combination of an anion (A1Z1) having an ethylenically unsaturated group, more preferably a combination of an amidinium cation and an acid having a sulfonic acid ester, a phosphoric acid ester or a polyvalent (meth) acrylate, particularly preferably an imidazolium. A combination of a cation and an acid having a sulfonate ester, a phosphate ester or a polyvalent (meth) acrylate. Specifically, 1-ethyl-3-methylimidazolium-2-acrylamido-2-methylpropane-1-sulfonate, 1-ethyl-3-methylimidazolium mono- and di (meth) acryloyloxyethyl phosphorus Examples include acid ester salts, dibasic acid salts of 1-ethyl-3-methylimidazolium and PE tri (meth) acrylate.

  The molecular weight of the monomeric ionic liquid (A1) is preferably a molecular weight of 150 or more and a number average molecular weight [hereinafter abbreviated as Mn, measured by gel permeation chromatography (GPC) from the viewpoint of toughness and antistatic properties of the cured product. According to the method] less than 1,000, more preferably molecular weight of 180 or more and Mn of 800 or less.

  The content of the monomeric ionic liquid (A1) in the resin composition of the present invention is preferably 5 to 70%, more preferably 10 to 50% from the viewpoint of antistatic properties and toughness of the cured product.

The polymer type ionic liquid (A2) having an ethylenically unsaturated group in the present invention is represented by the following general formula (2), and the initial conductivity is preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻⁸ (further Preferably, it is a room temperature molten salt of 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ ) ms / cm, at least 1 (preferably 1 to 100) cations (A2X) ⁺ , and at least 1 (preferably 1 to 100). ) Polymer anion (A2Z) ⁻ having at least one counter anion and at least one ethylenically unsaturated group.

(A2X) ⁺ (A2Z) ^- (2)

[(A2X) ⁺ (hereinafter sometimes abbreviated as A2X) represents a cation, and (A2Z) ⁻ (hereinafter sometimes abbreviated as A2Z) represents a polymer anion. ]

[Cation (A2X)]
The cation (A2X) includes a nitrogen-containing onium cation [amidinium cation and guanidinium cation], a sulfur-containing onium cation, and a phosphorus-containing onium cation.

The following (1) to (4) are included in the amidinium cation.
(1) 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-dimethylimidazole Zolinium, 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-1, - dimethyl imidazolinium;

(2) 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-trimethylimidazolium, 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-hydroxy Ethyl-1,3-dimethylimidazolium;

(3) 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 -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-formylmethyl- , 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;

(4) Dihydropyrimidinium cation C6-20, such as 1,3-dimethyl-1,4- or -1,6-dihydropyrimidinium [these are 1,3-dimethyl-1,4 (6)- Described as dihydropyrimidinium, 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.

The following (1) to (4) are included in the guanidinium cation.
(1) Guanidinium cation having an 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-diethylimidazole Linium, 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-methylcarbooxymethyl 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;

(2) 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, 1,5,6, 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;

(3) 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 Til-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] pyrimidi , 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;

(4) 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) -dihydropyrimidinium 2-diethylamino-1,3-dimethyl-1,4 (6) -dihydropyrimidinium, 2-dimethylamino-1-ethyl-3-methyl-1,4 (6) -dihydropyrimidinium, -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-dimethyl Ruamino-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- -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) -dihydro Pyrimidinium.

  Sulfur-containing onium cations include sulfonium, thiophenium, thiomorpholinium, thioxonium cations, and the like.

  Examples of the phosphorus-containing cation include a phosphonium cation and a tetrabutylphosphonium bromide cation.

  Among these, the amidinium cation is preferable from the viewpoint of the electric conductivity of the polymer type ionic liquid, the imidazolium cation is more preferable, and the 1-ethyl-3-methylimidazolium cation is particularly preferable.

[Polymer anion (A2Z)]
The polymer anion (A2Z) in the present invention has a counter anion of the cation (A2X) and at least one ethylenically unsaturated group. The counter anion constituting (A2Z) includes an organic acid group such as a carboxyl group, a sulfate ester group, a higher alkyl ether sulfate ester group, a sulfo group, or a phosphate ester group.
(A2Z) includes those formed from a compound having a hydroxyl group and an ethylenically unsaturated group, a polyhydric alcohol, a polyisocyanate, and a polyhydric alcohol having an anionic group.

  The compound having a hydroxyl group and an ethylenically unsaturated group has at least one hydroxyl group and at least one ethylenically unsaturated group [(meth) acryloyl group, vinyl group, etc.], has a molecular weight of 44 or more, Mn5, 000 or less, for example, and mixtures thereof.

(1) Compound having hydroxyl group and (meth) acryloyl group (1-1) Alkylene oxide of (meth) acrylic acid (hereinafter abbreviated as AO, C2-4) 1 to 50 mol adduct (meth) acrylic acid-2- (1-2) (1-1) epsilon-caprolactone adduct (molecular weight 230 or more and Mn5, such as hydroxyethyl, -hydroxypropyl and -hydroxybutyl, and these AO adducts (molecular weight 160 or more and Mn 5,000 or less) 000 or less)
(Meth) acrylic acid-2-hydroxyethyl-ε-caprolactone 2-mole adduct, etc. (1-3) diol mono (meth) acrylate (Mn 300 to 5,000)
Diol [other than the polyol constituting (1-6) described later, for example, polycarbonate diol, polyethylene glycol (hereinafter abbreviated as PEG), polypropylene glycol (hereinafter abbreviated as PPG), polytetramethylene glycol among the polycarbonate polyols described later (Hereinafter abbreviated as PTMG) and polyester diol] mono (meth) acrylate

(1-4) Reaction product of epoxide and (meth) acrylic acid 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-biphenoxy-2-hydroxypropyl (meth) acrylate, etc. (1-5) (meth) Reaction product of acrylic acid and tri- or higher functional polyol and its AO adduct (molecular weight 146 or more and Mn 5,000 or less)
GR mono- and di (meth) acrylate, TMP mono- and di (meth) acrylate, PE mono-, di- and tri (meth) acrylate, diTMP mono-, di- and tri (meth) acrylate, DPE mono- (1-6) (meth) acrylic acid, butadiene polyol, isoprene polyol, hydrogenated butadiene, etc. Reaction product with at least one polyol selected from the group consisting of polyol and hydrogenated isoprene polyol (Mn 300 to 5,000)

(1-7) Mono (meth) acrylate of polyester (Mn 1,000 to 50,000)
Polyesters include diols [C2-11, such as aliphatic dihydric alcohols [ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, diethylene glycol, triethylene glycol, 1,5-pentanediol, 1, 6-hexanediol, neopentyl glycol (hereinafter abbreviated as EG, PG, BD, DEG, TEG, PD, HD, NPG), etc.], alicyclic divalent alcohol [cyclohexane-1,4-dimethanol, hydrogenation Bisphenol A etc.], and these AO adducts, dihydric phenols [AO adducts of bisphenol-A, -F, and -S etc.] and dicarboxylic acids [C4-12, such as aromatic ring-containing dicarboxylic acids (terephthalic acid) , Isophthalic acid, naphthalenedicarboxylic acid, and their acid Things like), aliphatic dicarboxylic acids (adipic acid, azelaic acid, maleic acid, fumaric acid, itaconic acid and their anhydrides, etc.) and polymers and the like obtained by condensation polymerization.

  Of these, (1-1), (1-4) and (1-5) are preferable from the viewpoint of reactivity with the polyisocyanate described later, and (1-1) and (1-5) are more preferable. It is.

(2) Compound having hydroxyl group and vinyl group (2-1) Monovinyl ether of diol (Mn 300 to 5,000)
Divinyl [monovinyl ether (2-2) (2-1) other than the polyol constituting (2-4) described later, for example, polycarbonate diol, PEG, PPG, PTMG, polyester diol among the polycarbonate polyols described later) Ε-caprolactone adduct (molecular weight 188 or more and Mn 5,000 or less)
(2-3) Reactive product of acetylene and trifunctional or higher functional polyol and its AO adduct (molecular weight of 118 or more and Mn of 5,000 or less)
GR mono- and divinyl ethers, TMP mono- and di- and trivinyl ethers, DPE mono-, di-, tri-, tetra- and pentavinyl ethers and their AO (1 to 100 mol) adducts, etc. (2-4) Reaction product of acetylene and at least one polyol selected from the group consisting of butadiene polyol, isoprene polyol, hydrogenated butadiene polyol and hydrogenated isoprene polyol (Mn 300 to 5,000)
Among these, (2-1) and (2-2) are preferable from the viewpoint of reactivity with the polyisocyanate described later, and (2-1) is more preferable.

  As the polyhydric alcohol, a low molecular polyol having two or more OH groups and having an OH equivalent (based on OH value, molecular weight per OH) of less than 250, and a polymer polyol having an OH equivalent of 250 or more, and These mixtures are mentioned.

Examples of the low molecular polyol include dihydric alcohols (C2-20 or higher), such as aliphatic dihydric alcohols [C2-12, such as (di) alkylene glycols [EG, DEG, PG, dipropylene glycol (hereinafter referred to as DPG). Abbreviation), 1,2-, 2,3-, 1,3- and 1,4-BD, 1,6-HD, NPG and 3-methylpentanediol (hereinafter abbreviated as MPD), dodecanediol and the like]], Alicyclic ring-containing dihydric alcohol [C5-10, such as 1,3-cyclopentanediol, 1,3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol], araliphatic dihydric alcohol [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 [GR, TMP, PE, DPE, sorbitol (hereinafter abbreviated as SO), 1, 2, 6-hexanetriol, erythritol, cyclohexanetriol, mannitol, xylitol, sorbitan, diglycerin and other polyglycerins etc.], saccharides and derivatives thereof [sucrose, glucose, fructose, mannose, lactose, glycosides (methylglucoside etc.)] and Polyether polyol, PTMG, polyester polyol, polycaprolactone polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol and Among the hydrogenated polyisoprene polyol, OH equivalent weight are those of less than 250.

The polymer polyol may be a polyether polyol [the above dihydric alcohol, or an AO adduct 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) adduct, Mn 500 to 20,000], PTMG (Mn 500 to 10,000), etc.], polyester polyol (Mn 500 to 20,000), Mn 200 to 10,000 poly Caprolactone polyol, polycarbonate polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol are included.
The polycarbonate polyol is a ring-opening addition / polycondensation of alkylene (C2-6) carbonate (such as ethylene and propylene carbonate) using a polyol as an initiator, polyhydric alcohol and diphenyl or dialkyl (alkyl group is C1-4) carbonate ( Dimethyl, diethyl and di-i-propyl carbonate)) or polyphosphatization of a polyhydric alcohol or polyhydric phenol (such as bisphenol A).

  Of these, polyether polyol, polyester polyol, hydrogenated polybutadiene polyol, and polyisoprene polyol are preferable from the viewpoint of flexibility of the cured product, and polyether polyol and polyester polyol are more preferable.

Examples of the polyisocyanate (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; , Crude MDI (polymethylene polyphenyl polyisocyanate) and 4,4 ′, 4 ″ -triphenylmethane Li isocyanate

(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, such as 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, from the viewpoint of light resistance, preferred are the urelated products of aliphatic PI and alicyclic PI among (2), (3) and (5). It is.

Examples of the polyhydric alcohol having an anionic group include the following, and a mixture of two or more thereof.
(1) Carboxyl group-containing polyhydric alcohol (1-1) Carboxyl group-containing diol C3-10, such as 2,2-bis (hydroxymethyl) propionic acid, glyceric acid, tartaric acid (1-2) tetravalent carboxylic acid anhydride And 1-10 mol polyadduct of the low molecular polyol as tetravalent carboxylic anhydride, C8-15, such as meso-butane-1,2,3,4-tetracarboxylic dianhydride, 1,2, Examples include 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and pyromellitic anhydride.

(2) Sulfo group-containing polyhydric alcohol Examples of the sulfo group-containing polyhydric alcohol include 1 to 10 molar polycondensates of the following sulfo group-containing polycarboxylic acid and the low-molecular polyol.
Examples of the sulfo group-containing polyvalent carboxylic acid include C4-20, for example, a sulfo group-containing aromatic dicarboxylic acid [sulfobenzene dicarboxylic 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 acids [sulfoalkanes and alkene dicarboxylic acids ( Sulfosuccinic acid, sulfoglutaric acid, sulfoadipic acid, sulfopimelic acid, sulfosuberic acid, sulfoazeleic acid, sulfosebacic acid, sulfomaleic acid, etc.)];

HOOC—CH (R ¹ ) —CH (SO ₃ H) —COOH

[Wherein R ¹ is a C1-13 hydrocarbyl (alkyl, alkenyl, cycloalkyl, aralkyl, aryl, etc.), alkoxy (C1-4, such as methoxy, ethoxy), hydroxyl, cyano, aldehyde, nitro group or halogen Represents an atom (chlorine, bromine, etc.). ]

(3) Sulfuric acid group-containing polyhydric alcohol Examples of the sulfuric acid group-containing polyhydric alcohol include 1-10 mole polycondensates of the following sulfuric acid group-containing polyvalent carboxylic acid and the low molecular polyol.
The sulfuric acid group-containing polyvalent carboxylic acid may be C4-10, for example, a hydroxycarboxylic acid [mono- and dihydroxyalkanedioic acid (tartronic acid, malic acid, tartaric acid, etc.)] sulfate ester [hydroxyl group sulfating agent (fuming sulfuric acid). And the like).
(4) Sulfamic acid group-containing polyhydric alcohol Examples of the sulfamic acid group-containing alcohol include 1 to 10 molar polycondensates of the following sulfamic acid group-containing polyvalent carboxylic acid and the low molecular polyol.
Examples of the sulfamic acid group-containing polyvalent carboxylic acid include C4-10, for example, sulfaminated products of aminodicarboxylic acids (aspartic acid, glutamic acid, etc.) (amino groups converted to sulfamic acid groups with fuming sulfuric acid or chlorosulfuric acid). .
(5) Phosphoric acid group-containing polyhydric alcohol Examples of the phosphoric acid group-containing polyhydric alcohol include 1 to 10 molar polycondensates of the following phosphoric acid group-containing polycarboxylic acid and the low-molecular polyol.
The phosphoric acid group-containing polyvalent carboxylic acid is a phosphoric acid ester of a C4-10 hydroxycarboxylic acid (the same as above) [the hydroxyl group is phosphorylated with a phosphorylating agent (phosphorus pentoxide, phosphorus oxychloride, etc.). And some of the acid groups (OH) thereof are alcohols or AO [partially alkyl ester or partially hydroxyalkyl ester formed by reacting with C2-4, for example, EO or PO].

The polymer anion (A2Z) can be produced by urethanating the above compound having a hydroxyl group and an ethylenically unsaturated group, a polyhydric alcohol, a polyisocyanate, and a polyhydric alcohol having an anionic group.
In the urethanization reaction, the equivalent ratio of NCO group to OH group (NCO / OH) is not particularly limited. 0.3 / 1 to 0.6 / 1, more preferably 0.4 / 1 to 0.5 / 1.

  The Mn of the polymer anion (A2Z) is preferably 900 to 16,000, more preferably 950 to 12,000, and particularly preferably 1,000 to 8,000 from the viewpoint of antistatic properties and handleability of the composition. .

  In the present invention, the polymer type ionic liquid (A2) comprises a methyl carbonate having the cation (A2X) (the salt is obtained by the production method described in JP-A No. 2001-316372) and a polymer having the counter anion group. It can be obtained by a salt exchange reaction with an anion (A2Z).

  Mn of the polymer type ionic liquid (A2) is preferably 1,000 to 20,000, more preferably 1,200 to 15,000, more preferably 1, from the viewpoint of antistatic properties and handleability of the composition. 500 to 10,000.

In addition, the resin composition of the present invention is an ionic liquid (D) having no ethylenically unsaturated group other than the above (A) as long as it does not inhibit the effects of the present invention (hereinafter referred to as a non-reactive ionic liquid). May be included). Specific examples of (D) include a combination of (x2) and (z2).
The content of (D) is usually 20% or less based on the total weight of (A) and (B) described later, and preferably 1 from the viewpoint of antistatic properties, its durability, and scratch resistance of the cured product described later. -10%.

  In the ionic liquid (A) having an ethylenically unsaturated group in the present invention, the monomer type ionic liquid (A1) having an ethylenically unsaturated group, the polymer type ionic liquid having an ethylenically unsaturated group ( A2) and mixtures thereof are included, and the content of (A1) based on the weight of (A) is usually 70% or less, preferably 5 to 70% from the viewpoint of antistatic properties and scratch resistance of the cured product More preferably, it is 10 to 50%, and the content of (A2) is usually 70% or less, preferably 5 to 70%, more preferably 10 to 50% from the viewpoint of antistatic property and scratch resistance of the cured product. is there. The weight ratio [(A1) / (A2)] when (A) is a mixture of (A1) and (A2) is preferably 1/99 to from the viewpoint of scratch resistance and antistatic properties of the cured product. 99/1, more preferably 5/95 to 95/5.

[(Meth) acryloyl group-containing compound (B)]
The (meth) acryloyl group-containing compound (B) excluding (A) in the present invention has an average of 3 or more (preferably 3 to 8 or more, more preferably 3 to 6) of (meth) acryloyl groups. Compound) (B1) and alicyclic ring-containing (meth) acrylate (B2) having 1 to 2 (meth) acryloyl groups on average.
Examples of (B1) include C9 or more and Mn500,000 or less, for example, the following.
(B11) poly (meth) acrylate polyvalent (trivalent to hexavalent or higher) alcohol (C3-40) and poly (meth) acrylate trihydric alcohol [TMP, GR, Tri (meth) acrylate of TMP PO3 mol adduct, TMP EO3 mol adduct, etc.], tri (meth) acrylate of tetrahydric alcohol [PE etc.], tetravalent alcohol [EO and 4 mol adduct of PE and PE, etc.] Tetra (meth) acrylate, hexavalent alcohol [di-PE, etc.] hexa (meth) acrylate, etc.

(B12) Polyester (meth) acrylate Polyvalent (2-4 valent) carboxylic acid, polyvalent (2 valent to 8 valent or more) alcohol (however, either polyvalent carboxylic acid or polyhydric alcohol is 3 Polyester (meth) acrylate having a molecular weight of 250 or more and Mn 4,000 or less having a plurality of ester bonds and a plurality of (meth) acryloyl groups obtained by an esterification reaction between a compound having a valence of 1 or more and a (meth) acryloyl group-containing compound

  Examples of polyvalent (2-4 tetravalent) carboxylic acids include aliphatic polycarboxylic acids [C3-20, such as malonic acid, maleic acid (anhydride), adipic acid, sebacic acid, succinic acid, and acid anhydrides. Product (reaction product of diPE and maleic anhydride, etc.)], alicyclic polyvalent carboxylic acid [C5-30, such as cyclohexanedicarboxylic acid, tetrahydro (anhydride) phthalic acid, methyltetrahydro (anhydride) phthalic acid] and aromatic ring Examples thereof include polyvalent carboxylic acids [C8-30, such as isophthalic acid, terephthalic acid, phthalic acid (anhydride), trimellitic acid (anhydride)].

  As the polyhydric alcohol, a low molecular polyol having two or more OH groups and having an OH equivalent (based on OH value, molecular weight per OH) of less than 250, and a polymer polyol having an OH equivalent of 250 or more, and These mixtures are mentioned.

Examples of the polyvalent (divalent to octavalent or higher) alcohol include C2 or more and Mn 20,000 or less, for example, the following, and a mixture of two or more thereof.
(1) Dihydric alcohol (C2-20 or higher), for example, C2-12 aliphatic dihydric alcohol [(di) alkylene glycol (eg, EG and the like)], C6-10 alicyclic ring-containing 2 Monohydric alcohol [1,3- and 1,4-cyclohexanediol, cyclohexanedimethanol (hereinafter abbreviated as CHDM), etc.], C8-20 aromatic ring-containing dihydric alcohol [xylylene glycol, bis (hydroxyethyl) benzene, etc.] ;
(2) Trivalent to octavalent or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [the GR, TMP, PE, polyGR, etc.], saccharides and their derivatives [ Sucrose etc.];

(3) polyether polyols such as PEG (Mn 200 to 20,000), PPG (Mn 200 to 20,000), PTMG (Mn 400 to 10,000);
(4) Polyester polyol (Mn 400 to 20,000), for example, ester of adipic acid and BD and HD, ester of maleic anhydride and NPG, ester of succinic acid and bisphenol A EO4 molar adduct; polycaprolactone Polyols (Mn 400-10,000), for example, ε-caprolactone adduct of HD, ε-caprolactone adduct of TMP;
(5) Polycarbonate polyol (Mn 500 to 10,000), for example, BD or HD polycarbonate diol, adipic acid-modified HD polycarbonate diol;
(6) Polybutadiene polyol (Mn 500 to 10,000), polyisoprene polyol (Mn 500 to 10,000) and hydrogenated products thereof;
(7) Epoxy resin (Mn 300 to 5,000), for example, a reaction product of 1,6HD diglycidyl ether and 2 mol of acetic acid, a 5 mol ring-opening polymer of bisphenol A diglycidyl ether;
(8) AO 1-50 mol adduct of (1), (2), (4)-(7) excluding (3) above, for example, AO 2-50 mol adduct of bisphenol A.

  Moreover, as a (meth) acryloyl group containing compound, C2-30, for example, (meth) acrylic acid and hydroxymethyl (meth) acrylate are mentioned.

(B13) Polyalkadiene having a (meth) acryloyl group at the side chain and / or terminal thereof Polybutadiene di (meth) acrylate (Mn500 to 500,000) or the like (B14) Epoxy compound (C3 to 6 or more) and (meta ) Reaction product with acrylic acid Examples of the epoxy compound include phenol novolac type epoxy compound, cresol novolac type epoxy compound, TMP triglycidyl ether, PE tri and / or tetraglycidyl ether, SO hepta and / or hexaglycidyl ether, methylene bis (2,7-dihydroxynaphthalene) tetraglycidyl ether.
(B15) Siloxane polymer having a (meth) acryloyl group at the side chain and / or terminal of dimethylpolysiloxane (Mn 300 to 20,000)
For example, dimethylpolysiloxane (Mn2,000, tetrafunctional) having a (meth) acryloxypropyl group in the side chain.
Among these, (B11) and (B14) are preferable from the viewpoint of scratch resistance of the cured product, and (B11) is more preferable.

The alicyclic ring-containing (meth) acrylate (B2) having 1 to 2 (meth) acryloyl groups on average in the present invention includes C11 or more and Mn 1,000 or less, for example, the following.
(B21) Mono (meth) acrylate of alicyclic monoalcohol (C8-20) Isobornyl (meth) acrylate, cyclohexyl acrylate, t-butylcyclohexyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, adamantyl (meth) acrylate, 3,5-dimethyladamantyl (meth) acrylate, etc. (B22) Di (meth) acrylate of alicyclic dihydric alcohol (C10-20) cyclohexane di (meth) acrylate, di Cyclopentane dimethylol di (meth) acrylate, norbornene dimethylol di (meth) acrylate, hydrogenated bisphenol compound and / or its AO 2-30 mol adduct di (meth) acrylate [hydrogenated bis Phenol A, the -F and -S, like the di (meth) acrylate of EO2 mol and PO4 mole adduct]
(B23) Di (meth) acrylate of hydrogenated novolak compound and / or its AO 2-30 mol adduct Each polydi (meth) acrylate of hydrogenated phenol novolac, hydrogenated cresol novolak EO 2 mol adduct, and the like.
Among these, (B22) and (B23) are preferable from the viewpoint of scratch resistance of the cured product, and (B22) is more preferable.

  The weight ratio [(B1) / (B2)] of (B1) and (B2) in (B) is preferably 30/70 to 90/10, more preferably 40/60 from the viewpoint of scratch resistance and cure shrinkage. -80/20, particularly preferably 50 / 50-75 / 25.

(B) has a (meth) acryloyl group concentration (x) of 3 to 10 (preferably 5 to 9.5, more preferably 6 to 9) mmol / g. Here, the (meth) acryloyl group concentration (x) is the concentration (mmol / g) of (meth) acryloyl groups per 1 g of (B) obtained by the following formula (1).

x = (a ₀ × c ₀ / M ₀ + a ₁ × c ₁ / M ₁ +...
+ A _i × c _i / M _i +... + A _n × c _n / M _n ) × 10 (1)

_{Wherein, a 0, a 1, ···} a i, ··· a n is the weight percent of (B) constituting the (meth) acryloyl group-containing compound components (hereinafter abbreviated as each component), c _{0, c 1, ··· c i} , ··· c n is the number of (meth) acryloyl groups in the _{components, M 0, M 1, ···} M i, ··· M n , each Represents the molecular weight of the component. ]
The (meth) acryloyl group concentration (mmol / g) of (x) is preferably 5 to 9.5, more preferably 6 to 9. When (x) is less than 3, the curability is poor, and when it exceeds 10, the shrinkage of curing increases.

The hardened | cured material formed by hardening | curing the active energy ray curable composition for molded objects of this invention has the molecular weight between 60-200 crosslinking points. Here, the molecular weight (M) between cross-linking points is Mn per cross-linking point determined by the following formula (2).

100 / M = a ₀ × 2 (c ₀ −1) / M ₀ + a ₁ × 2 (c ₁ −1) / M ₁ +.
+ a _i × 2 (c _i −1) / M _i +... + a _n × 2 (c _n −1) / M _n (2)

In the formula (2), a ₀ , a ₁ , a _i , a _n , a ₀ , c ₀ , c ₁ , c _i , c _n , M ₀ , M ₁ , M _i , and M _n are in the formula (1). Is the same.
(M) is preferably 65 to 150, more preferably 70 to 120. When the molecular weight between crosslinking points is less than 60, the impact resistance is deteriorated, and when it exceeds 200, the scratch resistance is deteriorated.

  The composition of the present invention further contains a polyfunctional (2-20) urethane (meth) acrylate (B3) excluding the (B1) and (B2) from the viewpoint of impact resistance and low curing shrinkage. preferable. (B3) is formed from a compound (b31) having a hydroxyl group and a (meth) acryloyl group and a polyisocyanate (b33).

(B31) includes C5 or more and Mn5,000 or less, for example, the following, and a mixture of two or more thereof.
(B31-1) AO (C2-4) adduct of (meth) acrylic acid (meth) acrylic acid-2-hydroxyethyl, -2-hydroxypropyl, -2-hydroxybutyl and their AO adducts (molecular weight 160) And Mn 5,000 or less), etc .;
(B31-2) ε-caprolactone adduct of (b31-1) (molecular weight 230 or more and Mn5,000 or less)
(Meth) acrylic acid-2-hydroxyethyl-ε-caprolactone 2 mol adduct, etc .;
(B31-3) Reaction product of (meth) acrylic acid and diol (Mn 300 to 5,000) Mono (meth) acrylate of diol (Mn 300 to 5,000, such as polycarbonate diol, PEG, polyester diol);
(B31-4) Reaction product of (meth) acrylic acid and epoxide C8-30, such as 3-phenoxy-2-hydroxypropyl (meth) acrylate, 3-biphenoxy-2-hydroxyprop (meth) acrylate, etc .;
(B31-5) Reaction product of (meth) acrylic acid and a tri- or higher functional polyol (molecular weight of 92 or more and Mn of 5,000 or less) GR mono- and di (meth) acrylate, TMP mono- and di (meth) acrylate PE mono-, di- and tri (meth) acrylate, diTMP mono-, di- and tri (meth) acrylate, diPE mono-, di-, tri-, tetra- and penta (meth) acrylate, and these AO adduct (number of added moles 1 to 100), etc .;
Among these, (b31-1), (b31-2) and (b31-5) are preferable from the viewpoint of scratch resistance.

Examples of the polyisocyanate (hereinafter sometimes abbreviated as PI) (b33) in the present invention include the following, and all are the same as those described above.
(B33-1) C (excluding C in the NCO group) 6-20 aromatic PI
(B33-2) C2-18 aliphatic PI
(B33-3) C4-45 alicyclic PI
(B33-4) C8-15 araliphatic PI
(B33-5) Nurateated products of (b33-1) to (b33-4) Among these, (b33-2), (b33-3), and (b) are preferable from the viewpoint of light resistance of the cured product described later. b33-5) are urelates of aliphatic PI and alicyclic PI.

  Of the combinations of the compound (b31) having a hydroxyl group and a (meth) acryloyl group and the polyisocyanate (b33), an AO (C2-4) adduct (b31-) of (meth) acrylic acid is preferable from the viewpoint of scratch resistance. 1) and / or a combination of the ε-caprolactone adduct (b31-2) of (b31-1) and the urelate of aliphatic PI and alicyclic PI in the polyisocyanate nurateated product (b33-5) is there.

  In producing the polyfunctional urethane (meth) acrylate (B3), from the viewpoint of toughness of the cured product, other polyol (b32) other than the compound (b31) having a hydroxyl group and a (meth) acryloyl group is used as a reaction component. You may make it contain as. Examples of (b32) are the same as those exemplified as the polyhydric alcohol constituting the polymer anion (A2Z) having C2 or more and Mn3,000 or less. Among these, dihydric alcohols, trihydric to octahydric or higher polyhydric alcohols and polyether polyols are preferable from the viewpoints of light resistance and toughness of the cured product.

  The Mn of the polyfunctional urethane (meth) acrylate (B3) is preferably 500 from the viewpoint of impact resistance of the cured product, more preferably 700, and the upper limit preferable from the viewpoint of handleability of the composition and scratch resistance of the cured product. 5,000, more preferably 3,000.

  The number of functional groups of (B3) is preferably 2 to 20, more preferably 3 to 15 from the viewpoint of scratch resistance and impact resistance.

  The amount of (B3) used is preferably 2 to 30%, more preferably 5 to 15%, from the viewpoint of impact resistance and scratch resistance, based on the total weight of (B1) and (B2).

  In the production of (B3) by the urethanization reaction, the equivalent ratio (NCO / OH) of the isocyanate group to the hydroxyl group is not particularly limited, but is preferably 0.1 / 1 to 1 in terms of impact resistance and storage stability. 2/1, more preferably 0.3 / 1 to 1.1 / 1, particularly preferably 0.6 / 1 to 1.05 / 1.

The conditions for the urethanization reaction in the production of (B3) are not particularly limited, and examples thereof include the following methods [1] and [2].
[1] Prepolymer method A part of the compound (b31) having a hydroxyl group and a (meth) acryloyl group and, if necessary, other polyol (b32) and all the polyisocyanate (b33) are mixed, and usually 40 to From the viewpoint of reactivity at 120 ° C. and the stability of the mixture, the reaction is preferably carried out at 60 to 100 ° C. for 2 to 20 hours to produce an NCO group-terminated urethane prepolymer, and then the remaining (b31) and (b32) are added. (B3) is produced under the same conditions, or (b31) and all of (b32) added as necessary are reacted with a part of (b33) under the same conditions as described above to produce an OH group-terminated prepolymer. And then the remaining (b33) is added and (B3) is produced under the same conditions;
[2] One-shot (collective reaction) method Compound (b31) having a hydroxyl group and a (meth) acryloyl group, other polyol (b32) added if necessary, and polyisocyanate (b33) are mixed together, and the same conditions as above To produce (B3).
Among these, the prepolymer method [1] is preferable from the viewpoint of controlling the molecular weight of (B3).

  In the urethanization reaction, if necessary, the reaction may be carried out by diluting with a solvent (ethyl acetate, methyl ethyl ketone, toluene, etc.). The amount of the solvent used is usually 5,000% or less based on the total weight of (b31), (b32) and (b33). The upper limit is preferably 1,000% from the viewpoint of the reaction rate, and from the viewpoint of handling of the mixture. A preferred lower limit is 10%.

  The urethanization reaction can be carried out at normal pressure, reduced pressure or increased pressure. The progress of the urethanization reaction can be judged, for example, by measuring the NCO% and hydroxyl value of the reaction system.

  In the production of (B3), it is preferable to use a urethanization catalyst from the viewpoint of reaction time. The urethanization catalyst includes the following organic bismuth compound (1), organic tin compound (2), organic titanium compound (3), tertiary amine or quaternary ammonium salt (4), and a mixture of two or more thereof. Is included.

(1) Organic bismuth compound (1-1) Organic bismuth carboxylate represented by the general formula Bi (COOR) ₃ , where R is a monovalent aliphatic group [C1-20, such as alkyl (methyl, ethyl, n- And i-propyl, n-, i-, sec- and t-butyl, octyl, 2-ethylhexyl, decyl and dodecyl) and alkenyl (1-, 2- and i-propenyl, 1-, 2- and 3- Butenyl) group], aromatic (aliphatic) (C6-20, such as phenyl, toluyl, xylenyl, benzyl, phenethyl and hexylphenyl) groups and alicyclic (C3-10, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl) ) Group and the like.
Among these R, a C2-12 aliphatic group and a C5-10 alicyclic group are preferable from the viewpoint of hydrolysis resistance.
(1-2) Organic bismuth alkoxide The organic bismuth alkoxide is represented by the general formula Bi (OR) ₃ , R is the same as described above, and R is preferably the same as described above from the viewpoint of hydrolysis resistance.
(1-3) A compound having a dicarbonyl group and a chelate compound of Bi The compound having a dicarbonyl group includes C4-15, for example, acetylacetone, acetylacetic acid, acetoacetoxyethyl (meth) acrylate, Chelate compounds formed from these and Bi are included.

(2) Organotin compounds Trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin maleate, stannous octoate and the like.
(3) Organic titanium compound Tetraalkyl (C = 2-12) titanate, alkylene dicarboxylic acid (C2-12) titanium and the like.
(4) Tertiary amine or quaternary ammonium salt (4-1) Tertiary amine Triethylenediamine, tetraalkyl (C1-3) alkylene (C2-6) diamine (tetramethylethylenediamine, tetramethylhexylenediamine, etc.), dia Zabicycloalkene {1,8-diazabicyclo [5,4,0] undecene-7 [DBU [manufactured by San Apro Co., Ltd., registered trademark]] etc.] and the like.
(4-2) Quaternary ammonium salt Tetraalkyl (C1-4) ammonium bromide, tetraalkyl (C1-4) ammonium perchlorate and the like.

Of these, (1) and (2) are preferable from the viewpoint of reactivity and non-coloring property, and (1) is more preferable from the viewpoint of safety and molecular weight control of (B3).
Of these, (1-1) and (1-3) are particularly preferable from the viewpoint of reactivity and stability as a catalyst, and (1-1) is particularly preferable from the viewpoint of non-coloring property.

  The use amount of the urethanization catalyst is preferably 0.0005 to 1%, more preferably 0.01 to 0.2% from the viewpoint of reactivity and transparency based on the weight of (B3).

When the above (1-1) is used as a urethanization catalyst, an organic acid may be further contained from the viewpoint of the stability of (1-1). Examples of organic acids include aliphatic carboxylic acids (C2 to C20, such as acetic acid, propionic acid, isopropionic acid, butyric acid, isovaric acid, octanoic acid, 2-ethylhexanoic acid, dodecanoic acid), and alicyclic carboxylic acids (C4). -10, such as cyclobutanoic acid, cyclopentanoic acid, cyclohexane acid), aromatic carboxylic acids (C7-15, such as benzoic acid, terephthalic acid, phthalic acid, trimellitic acid), α-unsaturated carboxylic acids [C3-10, (Meth) acrylic acid, cinnamic acid, maleic acid], 2-hydroxyethyl (meth) acrylate and polybasic acids (C2-15, such as oxalic acid, succinic acid, adipic acid, phthalic acid, trimellitic acid, and these Monoesterified products with acid anhydrides) and mixtures of two or more of these.
Of these, aliphatic and alicyclic carboxylic acids are preferred from the viewpoint of hydrolysis resistance.

  The weight ratio of the above (1-1) to the above organic acid is preferably 0.001 / 1 to 9/1, more preferably 0.01 / 1, from the viewpoint of the catalyst activity and catalyst stability of (1-1). ~ 4/1.

  In the composition of the present invention, from the viewpoint of improving the handleability by lowering the viscosity and the flexibility and adhesion of the cured product, the mono and / or the alicyclic ring-containing (meth) acrylate (B2) is excluded. Alternatively, a di (meth) acryloyl group-containing compound (B4) may be contained. These may be used alone or in combination of two or more.

Among (B4), the mono (meth) acryloyl group-containing compound (B4-1) includes C4 or more and Mn2,000 or less, for example, the following.
(1) (Meth) acrylate of aliphatic monohydric alcohol (C1-30) Lauryl (meth) acrylate, stearyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. (2) Heterocyclic ring-containing (meth) acrylate C7 15. For example, tetrafurfuryl (meth) acrylate, (meth) acryloylmorpholine, etc. (3) (Meth) acrylate of AO 1-30 mol adduct of aliphatic monohydric alcohol (C1-30) EO 2 mol adduct of lauryl alcohol (Meth) acrylate, (meth) acrylate of PO3 mol adduct of lauryl alcohol, etc. (4) [Alkyl (C1-20)] phenol (C6-30) AO 1-30 mol adduct (meth) acrylate of phenol PO3 mole adduct (meth) acrylate, nonylphenol (Meth) acrylate of EO 1 mol adduct, (meth) acrylate of phenol EO 1 mol adduct, etc. (5) (Meth) acrylate of araliphatic alcohol (C7-15) benzyl (meth) acrylate, phenylethyl (meth) (6) Hydroxyl group-containing (meth) acrylate (C5 or more and Mn2,000 or less)
Of the compound (b31) having a hydroxyl group and a (meth) acryloyl group, a monofunctional one.
Among these (B4-1), from the viewpoint of flexibility, adhesion, and toughness of the cured product, (3) to (6) are preferable, and (3), (5), and (6) are more preferable. It is.

Among (B4), the di (meth) acryloyl group-containing compound (B4-2) includes the following compounds having C8 or more and Mn5,000 or less.
(1) Di (meth) acrylate of polyoxyalkylene (alkylene is C2-4) (molecular weight 106 or more and Mn 3,000 or less) PEG (Mn400), PPG (Mn200) and PTMG (Mn650) di (meth) acrylate (2) Di (meth) acrylate of AO 2 to 30 mol adduct of bisphenol compound (C13-20) Di (meth) acrylate of EO 2 mol and PO4 mol adduct of bisphenol A, -F and -S, etc. 3) Di (meth) acrylate of aliphatic dihydric alcohol (C2-30) Each di (meth) acrylate of EG, PG, NPG and HD, etc.

  Each content of (B1) to (B4) in (B) is preferably 30 to 90%, more preferably 40 based on the weight of (B), from the viewpoint of scratch resistance and cure shrinkage. ~ 80%; (B2) is preferably 10 to 70%, more preferably 20 to 60%, from the viewpoint of curing shrinkage and scratch resistance; (B3) is usually 30% or less, preferably from the viewpoint of impact resistance and scratch resistance Is 5 to 15%; (B4) is usually 30% or less, preferably 5 to 28% from the viewpoint of the flexibility and toughness of the cured product.

  The weight ratio of (A) to (B) is preferably 5/95 to 70/30, more preferably 10/90 to 50/50, from the viewpoint of antistatic properties and scratch resistance.

[Photoinitiator (C)]
Examples of the photopolymerization initiator (C) in the present invention include hydroxybenzoyl compounds (2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, benzoin alkyl ether, etc.), benzoylformate Examples include compounds (such as methylbenzoylformate), thioxanthone compounds (such as isopropylthioxanthone), benzophenones (such as benzophenone), phosphate compounds (such as 1,3,5-trimethylbenzoyldiphenylphosphine oxide), and benzyldimethyl ketal.
Of these, hydroxybenzoyl compounds and phosphate ester compounds are preferable from the viewpoint of non-coloring properties of the cured product, and 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1-hydroxycyclohexyl are more preferable. Phenyl ketone and 1,3,5-trimethylbenzoyl diphenylphosphine oxide.

  The amount of (C) used is preferably 0.5 to 5%, more preferably 1 to 3% from the viewpoint of scratch resistance and non-coloring properties, based on the total weight of (A) and (B).

[Thermosetting catalyst (E)]
The composition of the present invention can further contain a thermosetting catalyst (E) for the purpose of improving curability within a range that does not impair the effects of the present invention.
Examples of (E) include peroxides (t-butyl peroxybenzoate, benzoyl peroxide, methyl ethyl ketone peroxide, etc.) and azo compounds (azobisisobutyronitrile, azobisisovaleronitrile, etc.). Of these, peroxides are preferable from the viewpoints of reactivity and composition stability, and t-butyl peroxybenzoate and methyl ethyl ketone peroxide are more preferable.

The amount of (E) used is usually 8% or less based on the total weight of (A) and (B), preferably 0.1 to 5%, more preferably 0.8% from the viewpoints of curability and storage stability. 5 to 1%.
When (E) is used, it is preferable to heat-treat when the composition of the present invention is cured. The heat treatment conditions are such that the heat treatment temperature is preferably 50 to 150 from the viewpoints of curability and transparency of the cured product, warpage, adhesion to the substrate when using the substrate described later, and deformation of the substrate. From the same viewpoint, the heat treatment time is preferably 1 to 60 minutes, and more preferably 5 to 30 minutes.

[Additive (F)]
If necessary, the composition of the present invention may further contain various additives (F) as long as the effects of the present invention are not impaired. (F) includes inorganic filler (F1), pigment (F2), dispersant (F3), antifoaming agent (F4), leveling agent (F5), silane coupling agent (F6), thixotropic agent ( One or more additives selected from the group consisting of (thickener) (F7), slip agent (F8), antioxidant (F9) and ultraviolet absorber (F10) are included.

  (F1) includes alumina [aluminum oxide, aluminum hydroxide, alumina white (alumina hydrate), silica alumina (a fused material of alumina and silica, alumina surface coated with silica)], zirconia, metal Carbide (tungsten carbide, titanium carbide, silicon carbide, boron carbide, etc.), 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 [precipitation (active, dry, heavy or light) carbonic acid Calcium, carbonated mug Cium, etc.], clay (kaolin clay, sericite clay, virophilite clay, montmorillonite clay, bentonite, acid 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, Examples thereof include cement, lime, calcium sulfite, molybdenum disulfide, and microballoons.

Of these, preferred are alumina, silica, silicate, carbonate, sulfate and titanium oxide, more preferably silica, calcium carbonate, Barium sulfate and titanium oxide.
(F1) 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 (F1) 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 (F1) used is usually 50% or less based on the total weight of (A) and (B), preferably from 1 to 30%, more preferably from 3 to 30% from the viewpoint of the effect of addition and the flexibility of the cured product. 25%.

Examples of the pigment (F2) include the following.
(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 lake 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 (F2) used is usually 50% or less based on the total weight of (A) and (B), preferably from 1 to 40%, more preferably from 3 to 30 from the viewpoint of the effect of addition and the flexibility of the cured product. %.

  Examples of the dispersant (F3) 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 polymeric dispersant include formalin condensate of naphthalene sulfonate [alkali metal (Na, K, etc., the same applies hereinafter) salt, ammonium salt, etc.], polystyrene sulfonate (salts are the same as above, and the same below). ), Polyacrylate, poly (2-4) carboxylic acid (maleic acid / glycerin / monoallyl ether copolymer, etc.) salt, carboxymethyl cellulose (Mn 1,000-10,000) and polyvinyl alcohol (Mn 1,000- 100,000).

The following are mentioned as a low molecular weight dispersing agent.
(1) Polyoxyalkylene type AO (C2-4) of aliphatic alcohol (C4-30), [alkyl (C1-30)] phenol, aliphatic (C4-30) amine and aliphatic (C4-30) amide 1-30 mol adducts As aliphatic alcohols, n-, i-, sec- and t-butanol, octanol, dodecanol etc .; (alkyl) phenols as phenol, methylphenol and nonylphenol etc .; as aliphatic amines , Laurylamine, methylstearylamine and the like; and aliphatic amides include stearic acid amide and the like.
(2) Polyhydric alcohol type Monomers of C4-30 fatty acids (lauric acid, stearic acid, etc .; the same shall apply hereinafter) and polyhydric (divalent to hexavalent or higher) alcohols (eg, GR, PE, SO and sorbitan). Ester Compound (3) Carboxylate Type Alkali Metal Salt of C4-30 Fatty Acid (4) Sulfate Ester Type C4-30 Fatty Alcohol (same as above, the same shall apply hereinafter) and Aliphatic Alcohol AO (C2- 4) 1-30 mol adduct sulfate alkali metal salt, etc. (5) sulfonate type [alkyl (C1-30)] sulfonic acid alkali metal salt of phenol (same as above, the same shall apply hereinafter) (6) Phosphoric ester type C4-30 fatty alcohol and AO (C2-4) 1-30 mol adduct mono- or diphosphate ester of an aliphatic alcohol [Al Li metal salts, such as quaternary ammonium salt]
(7) C1-30 aliphatic amines [primary (laurylamine, etc.), secondary (dibutylamine, etc.) and tertiary amine (dimethylstearylamine, etc.) hydrochloride, triethanolamine And C4-30 fatty acid monoester inorganic acid (hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid, etc.) (8) quaternary ammonium salt type C4-30 quaternary ammonium (butyltrimethylammonium, diethyllauryl) Inorganic acid salts of methyl ammonium, dimethyl distearyl ammonium, etc.).

  Examples of inorganic dispersants include alkali metal 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 (F3) used is usually 10% or less based on the total weight of (A) and (B), and preferably 0.05 to 5% from the viewpoint of the effect of addition and scratch resistance.

  Antifoaming agent (F4) includes lower alcohol (C1-6) (methanol, butanol, etc.), higher alcohol (C8-18) (octyl alcohol, hexadecyl alcohol, etc.), higher fatty acid (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 (F4) used is usually 3% or less based on the total weight of (A) and (B), preferably from 0.01 to 2% from the viewpoint of the effect of addition and scratch resistance.

Examples of the leveling agent (F5) include PEG type nonionic surfactants (nonylphenol EO 1 to 40 mol adducts, stearic acid EO 1 to 40 mol adducts), polyhydric alcohol type nonionic surfactants (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 [e.g. Polyether-modified silicone oil and (meth) acrylate-modified silicone oil].
The amount of (F5) used is usually 3% or less based on the total weight of (A) and (B), and preferably 0.1 to 2% from the viewpoint of the effect of addition and scratch resistance.

  Examples of the silane coupling agent (F6) include amino group-containing silane coupling agents (γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyl trimethoxysilane, etc.), ureido group-containing silane. Coupling agents (ureidopropyltriethoxysilane, etc.), vinyl group-containing silane coupling agents [vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane, etc.], methacrylate groups-containing silane coupling agents (γ-methacrylic) Loxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, etc.), epoxy group-containing silane coupling agents (γ-glycidoxypropyltrimethoxysilane, etc.), isocyanate group-containing silane coupling agents (γ- Isocyanate-propyltriethoxysilane, etc.), polymer-type silane coupling agents (polyethoxydimethylsiloxane, polyethoxydimethylsiloxane, etc.), cationic silane coupling agents [N- (N-benzyl-β-aminoethyl) -γ-amino Propyltrimethoxysilane hydrochloride, etc.].

  The amount of (F6) used is usually 10% or less based on the total weight of (A) and (B), and preferably 0.5 to 7% from the viewpoint of the effect of addition and scratch resistance.

  As thixotropic property-imparting agents (including thickeners) (F7), inorganic thixotropy-imparting agents (such as bentonite, organically treated bentonite and colloidal calcium carbonate) and organic thixotropic properties-imparting agents (hydrogenated castor oil wax, calcium stearate, Aluminum oleate, polymerized linseed oil, etc.).

  The amount of (F7) used is usually 20% or less based on the total weight of (A) and (B), and preferably 0.5 to 10% from the viewpoint of the effect of addition and scratch resistance.

  Examples of slip agents (F8) include higher fatty acid esters (such as butyl stearate), higher fatty acid amides (such as ethylene bis stearic acid amide and oleic acid amide), metal soaps (such as calcium stearate and aluminum oleate), and wax [paraffin wax. And polyolefin wax (polyethylene wax, polypropylene wax, carboxyl group-containing polyethylene wax, etc.)] and silicone (for example, dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil).

  The amount of (F8) used is usually 5% or less based on the total weight of (A) and (B), and preferably 0.01 to 2% from the viewpoint of the effect of addition and scratch resistance.

  Antioxidants (F9) 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 use amount of (F9) is usually 3% or less based on the total weight of (A) and (B), and preferably 0.005 to 2% from the viewpoint of the effect of addition and scratch resistance.

  Examples of the ultraviolet absorber (F10) 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 (F10) used is usually 3% or less based on the total weight of (A) and (B), and preferably 0.005 to 2% from the viewpoint of the effect of addition and scratch resistance.

  When the additives are the same and overlap between the above (F1) to (F10), the amount of each additive having 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.

  The total amount of (F) used is usually 60% or less based on the total weight of (A) and (B), and preferably 1 to 45% from the viewpoint of the effect of addition and scratch resistance.

  The composition of the present invention may be diluted with a solvent as necessary in order to adjust the viscosity to be suitable for coating during coating. The amount of the solvent used is usually 2,000% or less based on the weight of the composition before adding the solvent, and preferably 10 to 500% from the viewpoint of coating properties and productivity. Further, the viscosity of the coating is a temperature at the time of use (usually 5 to 60 ° C.), usually 5 to 500,000 mPa · s, and preferably 50 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, the aromatic hydrocarbon (C7 to 10, for example, toluene, xylene and ethylbenzene). Ester or ether ester (C4-10, eg ethyl acetate, butyl acetate and methoxybutyl acetate), ether (C4-10, eg diethyl ether, tetrahydrofuran, EG monoethyl ether, EG monobutyl ether, PG monomethyl ether and DEG monoethyl ether), ketones (C3-10, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone), alcohols (C1-10, such as methanol, ethanol, n- and i-propanol). n-, i-, sec- and t-butanol, 2-ethylhexyl alcohol and benzyl alcohol), amides (C3-6, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxides (C2-4, such as dimethyl) Sulfoxide), water, and a mixed solvent of two or more thereof.
Of these, esters, ketones and alcohols having a boiling point of 70 to 100 ° C. are preferred from the viewpoint of storage stability and productivity, and ethyl acetate, methyl ethyl ketone, i-propanol and mixtures thereof are more preferred.

  Although the composition of this invention is not specifically limited, For example, it can apply and shape | mold by the following method. That is, the composition of the present invention is preliminarily temperature-controlled at 20 to 50 ° C., and a dispenser or the like is placed in a mold (mold, resin mold, etc.) having a cavity (filling space) from which a molded body shape (for example, a lens array shape) is obtained. Using, coating (or filling) so that the thickness after curing is 50 to 150 μm, air the transparent substrate (including a transparent film) from above the composition coated (or filled) on the mold. Is pressed and laminated so as not to enter, and after the composition is cured by irradiating active energy rays to be described later from the transparent substrate, it is released from the mold to obtain a molded body (for example, a lens sheet). .

  Examples of the transparent substrate (including a transparent film) include those made of a resin such as methyl methacrylate (co) polymer, polyethylene terephthalate, polycarbonate, polytriacetylcellulose, and polycycloolefin.

  The active energy rays in the present invention include ultraviolet rays, electron beams, X-rays, visible rays, infrared rays and the like. Among these, ultraviolet rays are preferable from the viewpoints of curability and safety.

When the composition of the present invention is cured by ultraviolet rays, the ultraviolet ray irradiation device is not particularly limited, but various ultraviolet ray irradiation devices [for example, device name “Eye Grandage”, manufactured by Eyegraphic Co., Ltd.] can be used. Examples of the lamp to be used include a high-pressure mercury lamp and a metal halide lamp. The upper limit of the irradiation amount of ultraviolet rays (mJ / cm ² ) is preferably 10,000, more preferably 5,000 from the viewpoint of the flexibility of the cured product, and more preferably 10, from the viewpoint of the curability of the composition. Is 100.

  From the viewpoint of scratch resistance, the pencil hardness of the cured product obtained above is preferably 2H or more, more preferably 3H or more.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these. In the following examples, “part” means “part by weight” and “%” means “% by weight”.

Synthesis example 1
A reaction vessel equipped with a condenser, a stirrer, and a thermometer was charged with 20 parts of glyceric acid, 2 parts of EG, and 50 parts of methyl ethyl ketone (hereinafter abbreviated as MEK), and heated and stirred at 50 ° C. to dissolve uniformly. To this solution, 60 parts of XDI and 0.1 part of a bismuth tri (2-ethylhexanoate) solution (2-ethylhexanoic acid 50% solution, the same shall apply hereinafter) were added and reacted at 80 ° C. for 6 hours. 25 parts of hydroxyethyl acrylate was added and stirred with heating for 3 hours. After cooling, 15.7-ethyl-3-methylimidazolium monomethyl carbonate (synthetic method was according to the method described in JP-A No. 2001-316372, the same shall apply hereinafter) 25.7 parts were mixed, decarboxylated, and desolventized. As a result, a polymer type ionic liquid (A2-1) composed of 1-ethyl-3-methylimidazolium cation and urethane acrylate anion was obtained. Mn of (A2-1) was 1,300.

Synthesis example 2
In the same reaction vessel as in Synthesis Example 1, 25.5 parts of pyromellitic anhydride and 70 parts of MEK were charged, and heated and stirred at 80 ° C. to dissolve uniformly. 18.5 parts of EG was added to this solution, and the mixture was refluxed with heating and stirring for 8 hours. The mixture was allowed to cool, and 43 parts of IPDI and 0.1 part of a bismuth tri (2-ethylhexanoate) solution were mixed and reacted at 80 ° C. for 6 hours, and then 3 parts of 2-hydroxyethyl acrylate and 0.1 part of hydroquinone The mixture was heated and stirred for 3 hours to reflux. After allowing to cool, 31.8 parts of 1-ethyl-3-methylimidazolium monomethyl carbonate is mixed, decarboxylated, and solvent-removed to form a polymer type comprising 1-ethyl-3-methylimidazolium cation and urethane acrylate anion. An ionic liquid (A2-2) was obtained. Mn of (A2-2) was 15,000.

Synthesis example 3
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 titanic acid tetraisoproxide as a condensation reaction catalyst Was allowed to react at 150 ° C. for 3 hours while distilling off the water produced under nitrogen flow. Next, the temperature was gradually raised to 180 ° C., and the reaction was carried out for 10 hours while distilling off water under nitrogen flow to obtain a polyester having a hydroxyl value of 36.0 having hydroxyl groups at both ends. After allowing to cool, 8 parts of IPDI and 0.1 part of a bismuth tri (2-ethylhexanoate) solution were mixed and reacted at 80 ° C. for 6 hours, and then 3 parts of 2-hydroxyethyl acrylate and 0.1 part of hydroquinone were added. The mixture was heated and stirred for 3 hours. After allowing to cool, 42.7 parts of 1-ethyl-3-methylimidazolium monomethyl carbonate is mixed, decarboxylated and solvent-removed to form a polymer comprising 1-ethyl-3-methylimidazolium cation and urethane acrylate anion. Type ionic liquid (A2-3) was obtained. The Mn of (A2-3) was 9,100.

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- A monomeric ionic liquid (A1-1) comprising 3-methylimidazolium mono (acryloyloxyethyl) phthalate salt 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 Monomer type ionic liquid (A1-2) composed of -ethyl-3-methylimidazolium mono (methacryloyloxyethyl) phosphate ester salt was obtained.

Synthesis Example 6
2,2,2-triacryloyloxymethylethylsuccinic acid [trade name “NK ester CBX-0”, manufactured by Shin-Nakamura Chemical Co., Ltd.] and 1-ethyl-3-methylimidazolium monomethyl carbonate in equimolar amounts By mixing, 1-ethyl-3-methylimidazolium 2,2,2-triacryloyloxymethylethyl succinate (A1-3) was obtained.

Synthesis example 7
An acrylic acid EO adduct [trade name “Blemmer AE-400”, manufactured by Nippon Oil & Fats Co., Ltd., Mn400], 100 parts of HDI nurate [trade name “Coronate HDT”, Japanese polyurethane Industrial Co., Ltd.] 33.6 parts and 0.05 parts of bismuth tri (2-ethylhexanoate) as a catalyst were charged and reacted at 60 ° C. for 6 hours to obtain trifunctional urethane acrylate (B3-1). The Mn of (B3-1) was 2,470.

Synthesis example 8
In the same reaction vessel as in Synthesis Example 1, 100 parts of 2-hydroxyethyl acrylate caprolactone 4 mol adduct [trade name “Placcel FA-4D” manufactured by Daicel Chemical Industries, Ltd.] and IPDI nurate [trade name “ VESTANAT T1890 ", manufactured by Degussa Japan Co., Ltd.] 64 parts and 0.03 part of bismuth tri (2-ethylhexanoate) as a catalyst were added and reacted at 80 ° C. for 4 hours to obtain bifunctional urethane acrylate (B3-2). Obtained. The Mn of (B3-2) was 1,730.

Synthesis Example 9
In the same reaction vessel as in Synthesis Example 1, glycerin PO adduct [trade name “New Paul GP-6000”, Sanyo Chemical Industries, Ltd., Mn600] 100 parts, hydrogenated MDI [trade name “VESTANAT H12MDI”, Degussa Japan Co., Ltd.] 65.5 parts and 0.05 parts of bismuth tri (2-ethylhexanoate) as a catalyst were added and reacted at 120 ° C. for 3 hours, followed by 58 parts of 2-hydroxyethyl acrylate, 70 The mixture was reacted at ° C for 4 hours to obtain trifunctional urethane acrylate (B3-3). The Mn of (B3-3) was 1,690.

Examples 1-7
It mix | blended according to the compounding composition (part) shown in Table 1, and obtained the composition (Examples 1-7) of this invention. The viscosity of each composition at 25 ° C. was measured with a BL type viscometer [manufactured by Tokyo Keiki Co., Ltd.] (unit: mPa · s).
Next, a cured product was prepared according to the following evaluation method, the transmittance of the cured product, steel wool resistance (hereinafter abbreviated as SW resistance), pencil hardness, yellow index (hereinafter abbreviated as YI), adhesion, Warpage, foam residue, and impact resistance were evaluated. The results are shown in Table 1.

Comparative Examples 1-4
It compounded according to the compounding composition (part) shown in Table 1, and obtained the comparative composition (Comparative Examples 1-4). About each composition, it evaluated similarly to the said Example. The results are shown in Table 1.

Evaluation method (1) Transmittance (evaluation of transparency)
(I) Cured product (cured film) preparation method Periphery on glass plate ["MICRO SLIDE GLASS water plate" manufactured by Matsunami Glass Co., Ltd., length 76 mm × width 26 mm × thickness 1.3 mm] treated with a release agent The composition was filled in a spacer frame (thickness: 100 μm, width: 5 mm) set in the part, and another glass plate similar to the above was further stacked thereon to extrude air. After that, an ultraviolet irradiation device [trade name “Eye Grandage”, manufactured by Eye Graphic Co., Ltd. The irradiation lamp is a metal halide lamp. same as below. ] Was irradiated with ultraviolet rays of 1,000 mJ / cm ² to obtain a cured product (cured film, the same shall apply hereinafter).
(Ii) Transmittance measurement method In accordance with JIS K-7361-1, a total light transmittance measurement device [trade name “haze-gard dual”, manufactured by BYK Gardner Co., Ltd., and so on. ] Was used to measure the transmittance of the cured product. Units%.

(2) SW resistance (evaluation of scratch resistance)
(I) Cured product preparation method Spacer frame (thickness: 100 μm) set on the periphery of a glass plate whose surface is treated with a release agent [“GLASS PLATE”, manufactured by ASONE, vertical 200 mm × width 200 mm × thickness 5 mm] ), A PET film [trade name “A-4300”, manufactured by Toyobo Co., Ltd., vertical 200 mm × width 200 mm × thickness 0.1 mm] filled with the composition in a frame having a width of 10 mm) and further primer-treated thereon , Transparent substrate] was stacked, and air was pushed out by being sandwiched between nip rollers. Thereafter, ultraviolet rays of 1,000 mJ / cm ² were irradiated from the PET film side using an ultraviolet irradiation device. Then, the glass plate was removed and the hardened | cured material which attached PET film to the single side | surface was obtained.
(Ii) SW resistance evaluation method Using a # 0000 steel wool, rubbing the cured product 10 times with a load of 500 g, and measuring haze using a total light transmittance measuring device according to JIS K-7361-1. . Units%.

(3) Pencil hardness (evaluation of rigidity)
(I) Hardened | cured material preparation method The hardened | cured material was created by the same method as the cured | curing material preparation method of said (2) (i).
(Ii) Pencil hardness evaluation method Pencil hardness was evaluated according to JIS K5400 (temperature 23 ° C., 1 kg load).
In the evaluation of n = 5, the hardness of the hardest pencil that is not damaged when n = 4 or more was defined as the pencil hardness.

(4) YI (evaluation of non-coloring property)
(I) Hardened | cured material preparation method The hardened | cured material was created by the same method as the cured | curing material preparation method of said (2) (i).
(Ii) YI Evaluation Method According to JIS K7373, the color difference is measured at 23 ° C. with a color difference meter [trade name “color difference / cloudiness meter A-200” manufactured by Nippon Denshoku Industries Co., Ltd.], and YI is measured at D65. Asked.

(5) Adhesion test (adhesion evaluation)
(I) Hardened | cured material preparation method The hardened | cured material was created by the same method as the cured | curing material preparation method of said (2) (i).
(Ii) Adhesion evaluation method In accordance with JIS K5400, 100 vertical grids with 11 vertical and horizontal cuts at a depth that does not reach the PET film within a range of 10 mm each on the surface of the cured product. After making eyes and making the adhesive tape adhere to the surface, it was peeled off at once. At this time, the number of grids remaining without peeling from the PET film substrate was determined.

(6) Warpage (Evaluation of curing shrinkage)
(I) Hardened | cured material preparation method The hardened | cured material was created by the same method as the cured | curing material preparation method of said (2) (i).
(Ii) Warpage Evaluation Method From a portion including the center portion of the cured product (vertical 200 mm × width 200 mm), a square of 10 cm in length and width is cut out, and the center portion is removed from the base surface when the cured product surface is placed downward. The height to the concave surface was determined. The unit is mm.

(7) Foam residue (evaluation of moldability)
(I) Prism lens (optical lens) production method The temperature of the composition shown in Table 1 was adjusted to 35 ° C., and a prism lens mold (50 cm × 50 cm) that had been chrome-plated in advance using a dispenser, 10 to 150 μm. A PET film [manufactured by Toyobo Co., Ltd., A-4300, thickness 100 μm] was applied to the thickness of the above and laminated under pressure so that no air could enter from above the composition filled in the mold. . Then, after ultraviolet rays were irradiated from the PET film side to 1000 mJ / cm ² using an ultraviolet irradiation device and cured, the mold was released from the mold to obtain a prism lens (cured product).
(Ii) Bubble remaining evaluation method The state of the obtained prism lens was observed, and the remaining amount of bubbles was visually examined.
(Evaluation criteria)
○: No bubbles Δ: 1 to 5/100 cm ²
×: More than 5 / 100cm ²

(8) Falling ball test (evaluation of impact resistance)
(I) Hardened | cured material preparation method The hardened | cured material was created by the same method as the cured | curing material preparation method of said (2) (i).
(Ii) Impact resistance evaluation method About 95 g of a hard ball for ball bearings (JIS B1501 1 1/8 diameter 28) from 30 cm above the cured product which was left to stand on the surface opposite to the PET film side of the cured product. .575 mm) was allowed to fall naturally, and cracks and deformation of the cured product surface were evaluated.
(Evaluation criteria)
○: Neither cracked nor deformed ×: Cracked or deformed (9) Antistatic property (i) Surface resistance value A cured product was prepared by the same method as the cured product preparing method of (2) (i) above. A test piece (100 × 100 mm) was cut out and allowed to stand for 24 hours under the conditions of 23 ° C. and humidity 50% RH, and then a digital super insulation meter [DSM-8103, manufactured by Toa Denpa Kogyo Co., Ltd., the same applies hereinafter. ] In the atmosphere of the same conditions. The unit is Ω.
(Ii) Surface resistance value after washing with water A test piece similar to that of (i) was immersed in 1,000 ml of ion-exchanged water at 25 ° C. and allowed to stand for 24 hours. Next, the test piece was taken out and the surface of the coating film was washed with running water of 100 ml of ion exchange water at 23 ° C. × 3 times, and then dried at 80 ° C. for 3 hours in a circulating drier. After the operation of washing with water and drying was repeated three times, the test piece was allowed to stand for 24 hours at 23 ° C. and a humidity of 50% RH, and then measured with a digital superinsulator in an atmosphere of the same conditions. The unit is Ω.
(Iii) Volume resistance value A spacer having a thickness of 1 mm is set on the periphery of a glass plate (11 cm × 11 cm) whose surface is treated with a release agent, and is partitioned into 10 cm × 10 cm squares. After casting the composition of Table 1 in the square, another glass plate similar to the above is placed. After irradiating 1,000 mJ / cm ^{2 of} ultraviolet rays with an ultraviolet irradiation device, it was released from the glass plate, allowed to stand for 24 hours under the conditions of 23 ° C. and humidity 50% RH, and then in an atmosphere of the same conditions with a digital superinsulator The volume resistance value was measured. The unit is Ω · cm.

ＤＡ−６００：ジペンタエリスリトールポリアクリレート［商品名「ネオマー
ＤＡ−６００」、三洋化成工業（株）製、平均官能基数５．５］
ＰＥ−３Ａ：ペンタエリスリトールトリアクリレート［商品名「ライトアクリ レートＰＥ−３Ａ」、共栄社化学（株）製、平均官能基数３．１］
ＰＥ−４Ａ：ペンタエリスリトールテトラアクリレート［商品名「ライトアクリレートＰ Ｅ−４Ａ」、共栄社化学（株）製、平均官能基数４］
ＥＯＴＭＰ：ＥＯ変性（付加モル数３）トリメチロールプロパントリアクリレート［商品 名「ネオマーＴＡ−４０１」、三洋化成工業（株）製、平均官能基数３］
ＤＣＰＡ ：ジシクロペンタンジメチロールジアクリレート［商品名「ライトアクリレー トＤＣＰ−Ａ」、共栄社化学（株）製、平均官能基数２］
ＩＢＸＡ ：イソボルニルアクリレート［商品名「ライトアクリレートＩＢＸＡ」、共栄 社化学（株）製、平均官能基数１］
ＴＰＯ ：１，３，５−トリメチルベンゾイルジフェニルホスフィンオキシド［商品名 「ルシリンＴＰＯ」、ＢＡＳＦ（株）製］
Ｉ１８４ ：１−ヒドロキシシクロヘキシルフェニルケトン［商品名「イルガキュア１８ ４」、チバスペシャルティケミカルズ（株）製］
ＢＺ−Ａ ：ベンジルアクリレート［商品名「ビスコート１６０」、大阪有機化学（株） 製］
ＰＯ−Ａ ：フェノキシエチレングリコールアクリレート［商品名「ライトアクリレート ＰＯ−Ａ」、共栄社化学（株）製］
ＢＡ６４１：ＥＯ変性ビスフェノールＡジアクリレート［商品名「ネオマーＢＡ−６４１ 」、三洋化成工業（株）製］
ＥＭＩ・ＢＦ₄：１−エチル−３−メチルイミダゾリウム４フッ化ホウ素酸塩［試薬 、和光純薬工業（株）製］
ＴＦＳＩＬｉ：ビス（トリフルオロメタンスルホニル）イミドリチウム［試薬、和光純薬 工業（株）製］
ＫＦ−６００４：ポリエーテル変性シリコーンオイル［商品名「ＫＦ−６００４」信越化 学（株）製］

DA-600: Dipentaerythritol polyacrylate [trade name “Neomer
DA-600 ", manufactured by Sanyo Chemical Industries, Ltd., average functional group number 5.5]
PE-3A: Pentaerythritol triacrylate [trade name “Light acrylate PE-3A”, manufactured by Kyoeisha Chemical Co., Ltd., average functional group number 3.1]
PE-4A: Pentaerythritol tetraacrylate [trade name “light acrylate PE-4A”, manufactured by Kyoeisha Chemical Co., Ltd., average functional group number 4]
EOTMP: EO-modified (addition mole number 3) trimethylolpropane triacrylate [trade name “Neomer TA-401”, manufactured by Sanyo Chemical Industries, Ltd., average functional group number 3]
DCPA: dicyclopentane dimethylol diacrylate [trade name “Light acrylate DCP-A”, manufactured by Kyoeisha Chemical Co., Ltd., average functional group number 2]
IBXA: isobornyl acrylate [trade name “light acrylate IBXA”, manufactured by Kyoeisha Chemical Co., Ltd., average number of functional groups 1]
TPO: 1,3,5-trimethylbenzoyldiphenylphosphine oxide [trade name “Lucirin TPO”, manufactured by BASF Corporation]
I184: 1-hydroxycyclohexyl phenyl ketone [trade name “Irgacure 184”, manufactured by Ciba Specialty Chemicals Co., Ltd.]
BZ-A: benzyl acrylate [trade name “Biscoat 160”, manufactured by Osaka Organic Chemical Co., Ltd.]
PO-A: Phenoxyethylene glycol acrylate [trade name “Light acrylate PO-A”, manufactured by Kyoeisha Chemical Co., Ltd.]
BA641: EO-modified bisphenol A diacrylate [trade name “Neomer BA-641”, manufactured by Sanyo Chemical Industries, Ltd.]
EMI · BF ₄ : 1-ethyl-3-methylimidazolium tetrafluoroborate [reagent, manufactured by Wako Pure Chemical Industries, Ltd.]
TFSILi: bis (trifluoromethanesulfonyl) imide lithium [reagent, manufactured by Wako Pure Chemical Industries, Ltd.]
KF-6004: polyether-modified silicone oil [trade name “KF-6004” manufactured by Shin-Etsu Chemical Co., Ltd.]

  From the results in Table 1, it can be seen that the composition of the present invention is superior in scratch resistance and warpage, balance between impact resistance, adhesion to a substrate, and antistatic property as compared with a comparative composition.

  The active energy ray-curable composition for molded bodies of the present invention is excellent in curability when irradiated with active energy rays, and a cured product obtained by curing the composition has scratch resistance, rigidity, transparency, and a substrate. Optical lens (prism sheet, collimator lens, Fresnel lens, lenticular lens, post-reflective lens, hologram, etc.) having a fine structure on the surface, cell phone members (decoration of buttons, etc.) due to excellent adhesion and antistatic properties It can be widely used for applications such as members and touch panels, and is extremely useful.

Claims (12)

Ionic liquid (A) having one or more ethylenically unsaturated groups, (meth) acryloyl group-containing compound (B) excluding (A) and photopolymerization initiator (C) In the energy ray-curable composition, (B) has a (meth) acryloyl group concentration of 3 to 10 mmol / g, and a cured product obtained by curing the composition has a molecular weight between crosslinking points of 60 to 200. An active energy ray-curable composition for an antistatic molded article, comprising: The composition according to claim 1, wherein (A) comprises a cation and an anion having an ethylenically unsaturated group. The (B) comprises a compound (B1) having 3 or more (meth) acryloyl groups on average and an alicyclic ring-containing (meth) acrylate (B2) having 1 to 2 (meth) acryloyl groups on average 2. The composition according to 2. The composition according to claim 3, wherein the weight ratio of (B1) to (B2) is 30/70 to 90/10. Furthermore, the composition of Claim 3 or 4 which contains polyfunctional urethane (meth) acrylate (B3) except (B1) and (B2). The composition according to claim 5, further comprising a mono- and / or di (meth) acryloyl group-containing compound (B4) excluding (B1), (B2) and (B3). The composition according to any one of claims 1 to 6, wherein the weight ratio of (A) to (B) is 5/95 to 70/30. Furthermore, at least one additive selected from the group consisting of a filler, a pigment, a dispersant, an antifoaming agent, a leveling agent, a silane coupling agent, a thixotropic agent, a slip agent, an antioxidant, and an ultraviolet absorber. The composition according to any one of claims 1 to 7, which is contained. It is an object for optical lenses, The composition in any one of Claims 1-8. Hardened | cured material formed by hardening | curing the composition in any one of Claims 1-9. An optical lens comprising the cured product according to claim 10. The composition according to any one of claims 1 to 9 is applied to a mold having a cavity from which a molded body shape can be obtained, and a transparent substrate is pressure-laminated on the coated material, and the composition is activated from above the substrate. A method for producing an antistatic molded article, comprising curing by irradiation with energy rays.