JP2016175964A - Polymerization accelerator and polymerizable composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerization accelerator that has excellent safeness and hygienic properties with low odor and excellent adhesiveness to a substrate and significantly accelerates a rate of polymerization by active energy ray irradiation, and a polymerizable composition using the polymerization accelerator.SOLUTION: The polymerization accelerator has a nitrogen-containing heterocyclic skeleton. By using a polymerizable composition containing the above polymerization accelerator, a polymerization reaction can be accelerated by radicals produced by the combination with a radical polymerizable initiator. The composition has a low odor and exhibits excellent adhesiveness to a substrate.SELECTED DRAWING: None

Description

  The present invention includes a molding resin, a casting resin, an optical modeling resin, a sealant, a dental polymerization resin, a printing ink, a printing varnish, a paint, a printing plate photosensitive resin, a printing color proof, a color filter resist, Black matrix resist, liquid crystal photo spacer, rear projection screen material, optical fiber, plasma display rib material, dry film resist, printed circuit board resist, solder resist, semiconductor photoresist, microelectronics resist, micromachine parts manufacturing Resist, etching resist, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat agent, powder coating, adhesive, adhesive, release agent, optical recording medium, adhesive , Release coating agent, micro Composition for image recording materials using capsule, polymerization accelerator that can be used in fields such as various devices, and to a polymerizable composition using the same.

  It is known that a reactive compound represented by an acrylate compound easily undergoes a polymerization reaction by an active species generated from a polymerization initiator by heating or irradiating active energy rays to form a reaction cured product. .

  Although there are a wide variety of uses using these reactive compounds, the inhibition of curing accompanying the polymerization inhibition of the surface due to the generation of oxygen radicals is the greatest issue in any application.

  Inhibition of curing by oxygen has been studied by various research institutions, and 1) a method of physically blocking oxygen and 2) a method of using an additive are known.

  Use of an inert gas or a polyvinyl alcohol layer (Patent Document 1) is known as a method for suppressing polymerization inhibition by blocking physical oxygen. The method using an inert gas has a problem that the initial investment is large because the apparatus is large. Moreover, when using a polyvinyl alcohol layer, since the process by an alkaline solution is needed, there exists a problem that a manufacturing process will increase.

  Moreover, addition of a phosphorus compound, a sulfur compound (thiol, disulfide, etc.) (Patent Document 2), and an amine compound (Patent Document 3) is known as a method for suppressing polymerization inhibition by an additive.

  Phosphorus compounds suppress polymerization inhibition by scavenging oxygen atoms, but their effectiveness is limited to about 24 hours after addition.

  Sulfur compounds and amine compounds suppress polymerization inhibition by generating active radicals from inert radicals by hydrogen abstraction or chain transfer. Sulfur compounds typified by thiol have a bad odor, and the working environment is problematic. On the other hand, ethanolamines are frequently used as the amine compound, but the use is limited because the prepared solution is thickened.

  Among the amine compounds, nitrogen-containing heterocyclic compounds such as N-methyl-pyrrolidone and 1,3-dimethylimidazolidinone are used as a solvent for inks used for specific substrates for the purpose of improving adhesion to the substrates. There is an example (Patent Document 4). In this case, the substrate is dissolved by the nitrogen-containing heterocyclic compound such as PVC, thereby improving the adhesion. However, in this usage pattern, there is a problem that the substrate is excessively dissolved when the content is increased, and the usage amount is limited to less than about 20% by weight in the ink. On the other hand, when the amount is less than 20% by weight in such an ink, a remarkable polymerization promoting effect by the nitrogen-containing heterocyclic compound is not observed, and an increase in the content of the nitrogen-containing heterocyclic compound is required.

JP 2006-146061 A JP-A 64-13144 Patent 4818591 Patent 3888783

  An object of the present invention is to provide a polymerization accelerator using the polymerization accelerator and a polymerization accelerator that is excellent in safety and hygiene due to low odor and substrate adhesion, and that significantly accelerates the polymerization rate by irradiation with active energy rays. It is to be.

（式中、Ｘは、炭素数２〜６のアルキレン基を表し、
Ｒ¹は、アルキル基を表す。）
一般式（２）

（式中、Ｒ²は、アルキル基を表す。）
一般式（３）

（式中、Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはアルキル基を表す。） That is, the present invention relates to a polymerization accelerator (A) containing at least one compound represented by the following general formulas (1) to (3).
General formula (1)

(In the formula, X represents an alkylene group having 2 to 6 carbon atoms,
R ¹ represents an alkyl group. )
General formula (2)

(In the formula, R ² represents an alkyl group.)
General formula (3)

(In the formula, R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group.)

  The present invention also relates to a polymerizable composition comprising the polymerization accelerator (A) described above and a radical polymerizable compound (B).

  Furthermore, the present invention relates to a polymerizable composition characterized in that the polymerization accelerator (A) is contained in an amount of 20% by weight to 40% by weight in the composition.

  Moreover, this invention relates to the said polymeric composition containing a radically polymerizable initiator (C) further.

  The present invention also relates to an ink composition using the above radical polymerizable composition.

  According to the present invention, it was possible to provide a polymerizable composition that remarkably increases the polymerization rate associated with the reaction by irradiation with active energy rays, has low odor, and has excellent substrate adhesion.

  Hereinafter, embodiments of the present invention will be described in detail.

  First, the polymerization accelerator (A) used in the polymerization composition of the present invention will be described.

  The polymerization accelerator (A) is a compound represented by the following general formula (1).

（式中、Ｘは炭素数２〜６のアルキレン基を表し、
Ｒ¹は、アルキル基を表す。）
一般式（２）

（式中、Ｒ²は、アルキル基を表す。）
一般式（３）

（式中、Ｒ³およびＲ⁴は、それぞれ独立に、水素原子またはアルキル基を表す。） General formula (1)

(In the formula, X represents an alkylene group having 2 to 6 carbon atoms,
R ¹ represents an alkyl group. )
General formula (2)

(In the formula, R ² represents an alkyl group.)
General formula (3)

(In the formula, R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group.)

Here, specific examples of the alkylene group having 2 to 6 carbon atoms in X include —CH ₂ —, — (CH ₂ ) ₂ —, — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — ( CH ₂ ) ₅ —, — (CH ₂ ) ₆ —, preferably — (CH ₂ ) ₃ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₅ —, more preferably — (CH ₂ ) ₃ —, — (CH ₂ ) ₅ — may be mentioned.

Here, examples of the alkyl group in R ^{1 to} R ⁴ include linear or branched alkyl groups having 1 to 10 carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group , Decyl and the like. Of these, a methyl group, an ethyl group, an n-propyl group, and an n-butyl group are preferable, and a methyl group, an ethyl group, and an n-propyl group are more preferable.

  The specific structure is shown in Table 1 below, but the structure of the polymerization accelerator (A) of the present invention is not limited thereto.

  The polymerization accelerator (A) used in the polymerizable composition of the present invention is a compound having a nitrogen-containing heterocyclic skeleton. By having this basic structure, it has an effect of promoting polymerization by the same mechanism as that of amine, and has low odor and excellent adhesion to the substrate.

  These can be used singly or in combination, and can be mixed and used arbitrarily depending on the properties required for the cured product. The amount of use of these polymerization accelerators (A) is described below. It is preferably contained in the range of 1 to 40 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable composition containing the radical polymerizable compound (B), and contained in the range of 20 to 40 parts by weight. Is more preferable.

  When the amount of the polymerization accelerator (A) used is less than 1 part by weight, the inert radical cannot be activated sufficiently by chain transfer or hydrogen abstraction, and a desired polymerization rate cannot be obtained. On the other hand, when the amount of the polymerization accelerator (A) used exceeds 40 parts by weight, there are too many low molecular components in the polymerizable composition, which may result in insufficient properties of the cured product after the polymerization reaction. is there.

  The reason why the polymerization accelerator (A) of the present invention is preferred is that the reaction for obtaining the polymerization accelerator (A) is easy.

  The polymerization accelerator of the present invention can be obtained by using a general organic synthesis reaction such as a reaction using a base and an alkyl halide.

  As the alkyl group introducing agent, an alkyl halide is used. For example, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, n-propyl chloride, n-propyl bromide, n-propyl iodide, isopropyl chloride, isopropyl bromide, iodide Isopropyl, n-butyl chloride, n-butyl bromide, n-butyl iodide, isobutyl chloride, isobutyl bromide, isobutyl iodide, sec-butyl chloride, sec-butyl bromide, sec-butyl iodide, tert-chloride Butyl, tert-butyl bromide, tert-butyl iodide, pentyl chloride, pentyl bromide, pentyl iodide, hexyl chloride, hexyl bromide, hexyl iodide, heptyl chloride, heptyl bromide, heptyl iodide, octyl chloride, Examples include octyl bromide and octyl iodide.

  In this reaction, a base is preferably used as a reaction accelerator. For example, caustic soda, caustic potassium, magnesium hydroxide, lithium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium hydride, magnesium hydride, potassium hydride, sodium, magnesium, calcium , Potassium, sodium methylate, t-butoxypotassium, triethylemine, tributylamine, pyridine, dimethylaniline, triethylenediamine, hexamethylenetetramine, etc., among others, caustic soda, caustic potassium, sodium methylate, t-butoxypotassium, hydrogen Relatively strong bases such as sodium chloride and sodium may give better results.

  Furthermore, for the purpose of improving the reaction rate, an interfacial transfer catalyst such as tetraethylammonium halide, tetraethylammonium hydroxide, tetrabutylammonium halide, trimethylbenzylammonium halide, trimethylbenzylammonium hydroxide, etc. can be used without any problem. Only the required amount may be used.

  As the reaction solvent, any solvent may be used as long as it basically does not react with the reaction substrate, reaction reagent, product, catalyst, or the like. , Methanol, acetonitrile, THF, dioxane, glyme, diglyme, dimethylformamide, N, N′-dimethyl-ethyleneurea, dimethyl sulfoxide, sulfolane, benzene, toluene, xylene and the like.

  The radical polymerizable initiator (C) of the present invention will be described. The radical polymerizable initiator (C) of the present invention is a compound that generates radicals which are active species by irradiation with various energy, particularly active energy rays such as ultraviolet rays. The generated radical is a radical polymerizable compound (B). ) Can be quickly initiated and cured.

As the radically polymerizable initiator (C) of the present invention, a conventionally known polymerization initiator can be used. Specifically, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ) Ketone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) Butane, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) ) Acetophenones such as benzyl] phenyl} -2-methylpropan-1-one;
Benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether;
Phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Other examples include phenylglyoxylic methyl ester.

  More specifically, Irgacure 651, Irgacure 184, Darocur 1173, Irgacure 500, Irgacure 1000, Irgacure 2959, Irgacure 907, Irgacure 369, Irgacure 379, Irgacure 1700, Irgacure 149, Irgacure 149 Cure 1800, IRGACURE 1850, IRGACURE 819, IRGACURE 784, IRGACURE 261, IRGACURE OXE-01 (CGI124), CGI242 (manufactured by BASF), Adekaoptomer N1414, Adekaoptomer N1717, Esacure1001M (manufactured by Lamberti) ), Triazine derivatives described in JP-B-59-1281, JP-B-61-9621 and JP-A-60-60104 Organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B-43-23684, JP-B-44-6413, JP-B-47-1604 and US Pat. No. 3,567,453, diazonium compound publications, USP 2,848,328, USP 2,852,379 and USP 2,940,853, organic azide compounds, Japanese Patent Publication No. 36-22062, Japanese Patent Publication No. 37- Ortho-quinonediazides described in Japanese Patent Publication No. 13109, Japanese Patent Publication No. 38-18015, and Japanese Patent Publication No. 45-9610, Japanese Patent Publication No. 55-39162, Japanese Patent Publication No. 59-140203, and “Macromolecules”. ”, Volume 10, page 1307 1977), various onium compounds including the iodonium compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, and European Patent No. 126712. , "Journal of Imaging Science (J. IMAGE. SCI.)", Volume 30, page 174 (1986), titanocenes described in JP-A No. 61-151197, Transition metal complexes containing transition metals such as ruthenium described in "COORDINATION CHEMISTRY REVIEW", Vol. 84, pages 85-277 (1988) and JP-A-2-182701. Kaihei 3-209477 Aluminate complexes described in Japanese Patent Publication No. 2-157760, borate compounds described in JP-A-2-157760, 2,4,5-triarylimidazole compounds described in JP-A-55-127550 and JP-A-60-202437. Carbon tetrabromide, organic halogen compounds described in JP-A-59-107344, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, JP-A-54-99185, JP-A 63-264560 and aminoketone compounds described in JP-A-10-29977, JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, special table 2004-534797, JP 2006-342166, JP 2008 -094770, JP2009-40762, JP2010-15025, JP2010-189279, JP2010-189280, JP2010-526846, JP2010-527338, JP2010-527339, USP3558309 (1971), USP 4202697 specification (1980), and oxime ester compounds described in JP-A No. 61-24558.

  Among these, acetophenones represented by amino ketones, phosphines, and oxime ester compounds are preferably used.

  These can be used singly or in combination, and can be used arbitrarily in accordance with the properties required for the cured product, and the amount used when these radical polymerizable initiators (C) are used. Is contained in the range of 0.01 to 200 parts by weight with respect to 100 parts by weight of the total amount of the later-described radical polymerizable compound (B) that can be used in combination with the polymerization accelerator (A), and is 0.1 to 100 parts by weight. It is preferable to contain in the range.

  When the amount of the radical polymerizable initiator (C) used is less than 0.01 parts by weight, the amount of radicals which are active species generated by irradiation with active energy rays is not sufficient, and a desired curing rate can be obtained. Absent. On the other hand, when the amount of the radical polymerizable initiator (C) used exceeds 200 parts by weight, there are too many low molecular components in the polymerizable composition, and the properties of the cured product after the polymerization reaction may be insufficient. There is sex.

  The radically polymerizable compound (B) in the present invention is a compound having at least one skeleton capable of radical polymerization in the molecule. In addition, these have chemical forms of liquid or solid monomers, oligomers or polymers at normal temperature and normal pressure.

  Examples of such radically polymerizable compounds (B) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and their salts, esters, acid amides and acid anhydrides. In addition, acrylates such as urethane acrylate, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes, methacrylates, arylates, acid amides, styrene , Other vinyl compounds, radical polymerizable cyclic compounds, oligomers, prepolymers and the like, but the present invention is not limited to these. Specific examples of the radically polymerizable compound (B) in the present invention are given below.

  Among the radical polymerizable compounds (B), examples of the acrylates include the following compounds.

Examples of monofunctional alkyl acrylates:
Methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, butyl acrylate, isoamyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, isobornyl acrylate, cyclohexyl acrylate, dicyclopentenyl acrylate , Dicyclopentenyloxyethyl acrylate, benzyl acrylate.

Examples of monofunctional hydroxy acrylates:
2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxy-3-chloropropyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-allyloxypropyl acrylate, acrylic acid-2-hydroxy- 3-allyloxypropyl, 2-acryloyloxyethyl-2-hydroxypropyl phthalate.

Examples of monofunctional halogenated acrylates:
2,2,2-trifluoroethyl acrylate, 2,2,3,3-tetrafluoropropyl acrylate, 1H-hexafluoroisopropyl acrylate, 1H, 1H, 5H-octafluoropentyl acrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl acrylate, 2,6-dibromo-4-butylphenyl acrylate, 2,4,6-tribromophenoxyethyl acrylate, 2,4,6-tribromophenol 3EO addition acrylate.

Examples of monofunctional ether-containing acrylates:
2-methoxyethyl acrylate, 1,3-butylene glycol methyl ether acrylate, butoxyethyl acrylate, methoxytriethylene glycol acrylate, methoxypolyethylene glycol # 400 acrylate, methoxydipropylene glycol acrylate, methoxytripropylene glycol acrylate, methoxypolypropylene glycol acrylate, Ethoxydiethylene glycol acrylate, ethyl carbitol acrylate, 2-ethylhexyl carbitol acrylate, tetrahydrofurfuryl acrylate, phenoxyethyl acrylate, phenoxydiethylene glycol acrylate, phenoxy polyethylene glycol acrylate, cresyl polyethylene glycol acrylate, acrylic Acrylic acid 2- (vinyloxy) ethyl, p- nonyl phenoxyethyl acrylate, p- nonylphenoxy polyethylene glycol acrylate, glycidyl acrylate.

Examples of monofunctional carboxyl acrylates:
β-carboxyethyl acrylate, succinic acid monoacryloyloxyethyl ester, ω-carboxypolycaprolactone monoacrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxypropyl hydrogen phthalate, 2-acryloyloxypropyl hexahydrohydrogen phthalate, 2- Acryloyloxypropyltetrahydrophthalate.

Examples of other monofunctional acrylates:
N, N-dimethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, morpholinoethyl acrylate, trimethylsiloxyethyl acrylate, diphenyl-2-acryloyloxyethyl phosphate, 2-acryloyloxyethyl acid phosphate, caprolactone-modified-2-acryloyl Oxyethyl acid phosphate, 2-hydroxy-1-acryloxy-3-methacryloxypropane.

Examples of bifunctional acrylates:
1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol # 200 diacrylate, polyethylene glycol # 300 Diacrylate, polyethylene glycol # 400 diacrylate, polyethylene glycol # 600 diacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, tetrapropylene glycol diacrylate, polypropylene glycol # 400 diacrylate, polypropylene glycol # 700 diacrylate, neo Pentyl glycol diacrylate, ne Pentyl glycol PO modified diacrylate, hydroxypivalic acid neopentyl glycol ester diacrylate, caprolactone adduct diacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3-acryloyloxypropyl) ether Bis (4-acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO-modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate, EO modified tetrabromobisphenol A diacrylate, tricyclodecandi Methylol diacrylate, isocyanuric acid EO-modified diacrylate, 2-hydroxy-1,3-diacryloxypropane.

Examples of vinyl ether group-containing acrylic acid esters-2-vinyloxyethyl acrylate, -3-vinyloxypropyl acrylate, -1-methyl-2-vinyloxyethyl acrylate, -2-vinyloxypropyl acrylate, -4-acrylic acid-4- Vinyloxybutyl, 1-methyl-3-vinyloxypropyl acrylate, 1-vinyloxymethyl acrylate, 2-methyl-3-vinyloxypropyl acrylate, 3-methyl-3-vinyloxypropyl acrylate -1,1-dimethyl-2-vinyloxyethyl acrylate, 3-vinyloxybutyl acrylate, 1-methyl-2-vinyloxypropyl acrylate, 2-vinyloxybutyl acrylate, 4-vinyloxycyclohexyl acrylate, 5-vinyloxypentyl acrylate, acrylic 6-vinyloxyhexyl acrylate, 4-vinyloxymethylcyclohexylmethyl acrylate, 3-vinyloxymethylcyclohexylmethyl acrylate, 2-vinyloxymethylcyclohexylmethyl acrylate, p-vinyloxymethyl acrylate Phenylmethyl, acrylic acid-m-vinyloxymethylphenylmethyl, acrylic acid-o-vinyloxymethylphenylmethyl, 2- (vinyloxyethoxy) ethyl acrylate, 2- (vinyloxyisopropoxy) ethyl acrylate, 2- (vinyloxyethoxy) propyl acrylate, 2- (vinyloxyethoxy) isopropyl acrylate, 2- (vinyloxyisopropoxy) propyl acrylate, -2- (vinyloxyisopropoxy) isopropyl acrylate, Acrylic acid-2- ( Nilo ethoxy) ethyl, acrylate 2- (vinyloxyethoxy isopropoxyphenyl) ethyl, ethyl-2-acrylate (vinyloxy-isopropoxyphenyl ethoxy) -2-acrylic acid (vinyloxy-isopropoxy-isopropoxyphenyl) ethyl.

Examples of trifunctional acrylates:
Glycerin PO-modified triacrylate, trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, isocyanuric acid EO-modified triacrylate, isocyanuric acid EO-modified ε-caprolactone-modified triacrylate, 1,3 5-triacryloylhexahydro-s-triazine, pentaerythritol triacrylate, dipentaerythritol triacrylate tripropionate.

Examples of tetra- or higher functional acrylates:
Pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate monopropionate, dipentaerythritol hexaacrylate, tetramethylolmethane tetraacrylate, oligoester tetraacrylate, tris (acryloyloxy) phosphate.

  Among the radical polymerizable compounds (B), examples of the methacrylates include compounds as shown below.

Examples of monofunctional alkyl methacrylates:
Methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isoamyl methacrylate, hexyl methacrylate, 2-hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate , Dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, benzyl methacrylate.

Examples of monofunctional hydroxymethacrylates:
2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 2-hydroxy-3-chloropropyl methacrylate, 2-hydroxy-3-phenoxypropyl methacrylate, 2-hydroxy-3-allyloxypropyl methacrylate, 2-methacryloyloxyethyl-2 -Hydroxypropyl phthalate.

Examples of monofunctional halogenated methacrylates:
2,2,2-trifluoroethyl methacrylate, 2,2,3,3-tetrafluoropropyl methacrylate, 1H-hexafluoroisopropyl methacrylate, 1H, 1H, 5H-octafluoropentyl methacrylate, 1H, 1H, 2H, 2H- Heptadecafluorodecyl methacrylate, 2,6-dibromo-4-butylphenyl methacrylate, 2,4,6-tribromophenoxyethyl methacrylate, 2,4,6-tribromophenol 3EO addition methacrylate.

Examples of monofunctional ether-containing methacrylates:
2-methoxyethyl methacrylate, 1,3-butylene glycol methyl ether methacrylate, butoxyethyl methacrylate, methoxytriethylene glycol methacrylate, methoxypolyethylene glycol # 400 methacrylate, methoxydipropylene glycol methacrylate, methoxytripropylene glycol methacrylate, methoxypolypropylene glycol methacrylate, Methacrylic acid-2- (vinyloxyethoxy) ethyl, ethoxydiethylene glycol methacrylate, 2-ethylhexyl carbitol methacrylate, tetrahydrofurfuryl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, Jill polyethylene glycol methacrylate, p- nonyl phenoxyethyl methacrylate, p- nonylphenoxy polyethylene glycol methacrylate, glycidyl methacrylate.

Examples of monofunctional carboxyl-containing methacrylates:
β-carboxyethyl methacrylate, succinic acid monomethacryloyloxyethyl ester, ω-carboxypolycaprolactone monomethacrylate, 2-methacryloyloxyethyl hydrogen phthalate, 2-methacryloyloxypropyl hydrogen phthalate, 2-methacryloyloxypropyl hexahydrohydrogen phthalate, 2- Methacryloyloxypropyl tetrahydrophthalate.

Examples of other monofunctional methacrylates:
Dimethylaminomethyl methacrylate, N, N-dimethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, morpholinoethyl methacrylate, trimethylsiloxyethyl methacrylate, diphenyl-2-methacryloyloxyethyl phosphate, 2-methacryloyloxyethyl acid phosphate, caprolactone Modified-2-methacryloyloxyethyl acid phosphate and the like.

Examples of bifunctional methacrylates:
1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, polyethylene glycol # 200 dimethacrylate, polyethylene glycol # 300 Dimethacrylate, polyethylene glycol # 400 dimethacrylate, polyethylene glycol # 600 dimethacrylate, dipropylene glycol dimethacrylate, tripropylene glycol dimethacrylate, tetrapropylene glycol dimethacrylate, polypropylene glycol # 400 dimethacrylate, polypropylene glycol # 700 dimethacrylate, neopenty Glycol dimethacrylate, neopentyl glycol PO modified dimethacrylate, hydroxypivalic acid neopentyl glycol ester dimethacrylate, caprolactone adduct dimethacrylate of hydroxypivalic acid neopentyl glycol ester, 1,6-hexanediol bis (2-hydroxy-3- (Methacryloyloxypropyl) ether, 1,9-nonanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate monostearate, pentaerythritol dimethacrylate monobenzoate, 2,2-bis (4-methacryloxypolyethoxyphenyl) propane Bisphenol A dimethacrylate, EO modified bisphenol A dimethacrylate, PO modified bisphenol Nord A dimethacrylate, hydrogenated bisphenol A dimethacrylate, EO modified hydrogenated bisphenol A dimethacrylate, PO modified hydrogenated bisphenol A dimethacrylate, bisphenol F dimethacrylate, EO modified bisphenol F dimethacrylate, PO modified bisphenol F dimethacrylate, EO Modified tetrabromobisphenol A dimethacrylate, tricyclodecane dimethylol dimethacrylate, isocyanuric acid EO modified dimethacrylate, 2-hydroxy-1,3-dimethacryloxypropane.

Examples of vinyl ether group-containing methacrylic acid esters: 2-vinyloxyethyl methacrylate, 3-vinyloxypropyl methacrylate, 1-methyl-2-vinyloxymethacrylate, 2-vinyloxypropyl methacrylate, 4-vinyloxybutyl acrylate, 1-methyl-3-vinyloxypropyl methacrylate, 1-vinyloxymethyl methacrylate, 2-methyl-3-vinyloxypropyl methacrylate, methacrylic acid 3-methyl-3-vinyloxypropyl, methacrylic acid-1,1-dimethyl-2-vinyloxyethyl, methacrylic acid-3-vinyloxybutyl, methacrylic acid-1-methyl-2-vinyloxypropyl, methacrylic acid- 2-vinyloxybutyl, methacrylic acid-4-vinyloxy Cyclohexyl, methacrylic acid-5-vinyloxypentyl, methacrylic acid-6-vinyloxyhexyl, methacrylic acid-4-vinyloxymethylcyclohexylmethyl, methacrylic acid-3-vinyloxymethylcyclohexylmethyl, methacrylic acid- 2-vinyloxymethylcyclohexylmethyl, methacrylic acid-p-vinyloxymethylphenylmethyl, methacrylic acid-m-vinyloxymethylphenylmethyl, methacrylic acid-o-vinyloxymethylphenylmethyl, methacrylic acid-2- (Vinyloxyethoxy) ethyl, methacrylate-2- (vinyloxyisopropoxy) ethyl, methacrylate-2- (vinyloxyethoxy) propyl, methacrylate-2- (vinyloxyethoxy) isopropyl, methacrylate -2- (Bi Loxyisopropoxy) propyl, methacrylic acid-2- (vinyloxyisopropoxy) isopropyl, methacrylic acid-2- (vinyloxyethoxyethoxy) ethyl, methacrylic acid-2- (vinyloxyethoxyisopropoxy) ethyl, meta 2- (vinyloxyisopropoxyethoxy) ethyl acrylate, -2- (vinyloxyisopropoxyisopropoxy) ethyl methacrylate.

Examples of trifunctional methacrylates:
Glycerin PO modified trimethacrylate, trimethylolethane trimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane EO modified trimethacrylate, trimethylolpropane PO modified trimethacrylate, isocyanuric acid EO modified trimethacrylate, isocyanuric acid EO modified ε-caprolactone modified tri Methacrylate, 1,3,5-trimethacryloyl hexahydro-s-triazine, pentaerythritol trimethacrylate, dipentaerythritol trimethacrylate tripropionate.

Examples of tetrafunctional or higher methacrylates:
Pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate monopropionate, dipentaerythritol hexamethacrylate, tetramethylolmethane tetramethacrylate, oligoester tetramethacrylate, tris (methacryloyloxy) phosphate.

  Of the radically polymerizable compound (B), examples of the arylate include the following compounds.

  Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

  Among the radically polymerizable compounds (B), examples of the acid amides include the following compounds.

  Acrylamide, N-methylolacrylamide, diacetoneacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, N-isopropylacrylamide, acryloylmorpholine, methacrylamide, N-methylolmethacrylamide, diacetone methacrylamide, N, N -Dimethylmethacrylamide, N, N-diethylmethacrylamide, N-isopropylmethacrylamide, methacryloylmorpholine.

  Of the radically polymerizable compound (B), examples of styrenes include the following compounds.

  Styrene, p-hydroxystyrene, p-chlorostyrene, p-bromostyrene, p-methylstyrene, p-methoxystyrene, pt-butoxystyrene, pt-butoxycarbonylstyrene, pt-butoxycarbonyloxystyrene 2,4-diphenyl-4-methyl-1-pentene.

  Among the radical polymerizable compounds (B), examples of other vinyl compounds include the following compounds.

  Vinyl acetate, vinyl monochloroacetate, vinyl benzoate, vinyl pivalate, vinyl butyrate, vinyl laurate, divinyl adipate, vinyl methacrylate, vinyl crotonate, vinyl 2-ethylhexanoate, N-vinylcarbazole, and the like.

  Of the radically polymerizable compound (B), examples of the monofunctional N-vinyl compounds include the following compounds.

  N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide.

  Said radically polymerizable compound (B) can be easily obtained as a commercial item of the manufacturer shown below. For example, “Light acrylate”, “Light ester”, “Epoxy ester”, “Urethane acrylate” and “Highly functional oligomer” series manufactured by Kyoeisha Yushi Chemical Co., Ltd., “Nakamura Chemical Co., Ltd.” "NK Ester" and "NK Oligo" series, "Funkril" series manufactured by Hitachi Chemical Co., Ltd., "Aronix M" series manufactured by Toagosei Co., Ltd., manufactured by Daihachi Chemical Industry Co., Ltd. "Functional monomer" series, "Special acrylic monomer" series manufactured by Osaka Organic Chemical Industry Co., Ltd., "Acryester" and "Diabeam oligomer" series manufactured by Mitsubishi Rayon Co., Ltd., Nippon Kayaku Co., Ltd. "Kayarad" and "Kayamar" series manufactured by KK, "Acrylic acid / methacrylic acid ester monomer" series manufactured by Nippon Shokubai Co., Ltd., Japan "NICHIGO-UV purple urethane acrylate oligomer" series manufactured by Seikagaku Corporation, "Carboxylic acid vinyl ester monomer" series manufactured by Shin-Etsu Vinyl Acetate Co., Ltd., "functional monomer" manufactured by Kojin Co., Ltd. "Series and the like.

  Moreover, radically polymerizable cyclic compounds such as the following three-membered cyclic compounds of vinylcyclopropanes and vinyloxiranes and cyclic ketene acetals are also exemplified as the radically polymerizable compound (B).

  Examples of the three-membered ring compounds include those described in Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 17, page 3169 (1979). Vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes described in Macromolecular Chem. Rapid Commun., Vol. 5, p. 63 (1984), Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Volume 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition ( (Polym.Sci.Polym.Lett.Ed.), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 ( (1985) 2,3-divinyloxiranes.

  Examples of cyclic ketene acetals include, for example, Journal of Polymer Science Polymer Chemistry Edition (J. Polym. Sci. Polym. Chem. Ed.), Vol. 20, p. 3021 (1982) and Journal. 2-Methylene-1,3-dioxepane described in of Polymer Science Letter Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 21, p. 373 (1983). Dioxolanes described in Prepreprints, Vol. 34, page 152 (1985), Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.) , Volume 20 361 (1982), Macromolecular Chem., 183, 1913 (1982) and Macromolecular. Chem., 186, 1543 (1985). 2,7-Dimethyl-2-methylene-1,3- described in 2-methylene-4-phenyl-1,3-dioxepane, described in Macromolecules, Vol. 15, page 1711 (1982). Dioxepane, 5,6-benzo-2-methylene-1,3-diocepan described in Polymer Preprints, Vol. 34, 154 (1985).

  Furthermore, the radically polymerizable compound (B) can also include those described in the following literature. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyomi Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Meeting, Kiyoshi Akamatsu, “New Technology for Photosensitive Resins” (1987, CMC), Takeshi Endo, “Refinement of Thermosetting Polymers” (1986, CMC), Takiyama Soichiro, “Polyester Resin Handbook” (1988, Nikkan Kogyo Shimbun), edited by Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

  As the radically polymerizable compound (B) of the present invention, in addition to the above monomers, those called oligomers and prepolymers can be used. Specifically, “Ebecryl 230, 244, 245, 270, 280 / 15IB, 284, 285, 4830, 4835, 4858, 4883, 8402, 8803, 8800, 254, 264, 265, 294 / 35HD, manufactured by Daicel UCB, 1259, 1264, 4866, 9260, 8210, 1290.1290K, 5129, 2000, 2001, 2002, 2100, KRM7222, KRM7735, 4842, 210, 215, 4827, 4849, 6700, 6700-20T, 204, 205, 6602, 220, 4450, 770, IRR567, 81, 84, 83, 80, 657, 800, 805, 808, 810, 812, 1657, 1810, IRR302, 450, 670, 830, 835, 870, 1 30, 1870, 2870, IRR267, 813, IRR483, 811, 436, 438, 446, 505, 524, 525, 554W, 584, 586, 745, 767, 1701, 1755, 740 / 40TP, 600, 601, 604, 605, 607, 608, 609, 600 / 25TO, 616, 645, 648, 860, 1606, 1608, 1629, 1940, 2958, 2959, 3200, 3201, 3404, 3411, 3412, 3415, 3500, 3502, 3600, 3603, 3604, 3605, 3608, 3700, 3700-20H, 3700-20T, 3700-25R, 3701, 3701-20T, 3703, 3702, RDX63182, 6040, IRR419 ", manufactured by Sartomer CN104, CN120, CN124, CN136, CN151, CN2270, CN2271E, CN435, CN454, CN970, CN971, CN972, CN9782, CN981, CN9873, CN991, "Laromar EA81L, F87" manufactured by BASF LR8800, PE46T, LR8907, PO43F, PO77F, PE55F, LR8967, LR8981, LR8982, LR8992, LR9004, LR8956, LR8985, LR8987, UP35D, UA19T, LR9005, PO83F, PO33F, L8489, L9489 LR8996, LR9013 LR9019, PO9026V, PE9027V "manufactured by Cognis" Photomer 3005, 3015, 3016, 3072, 3982, 3215, 5010, 5429, 5430, 5432, 5662, 5806, 5930, 6008, 6010, 6019, 6184, 6210, 6217, 6230, 6891, 6892, 6893-20R, 6363, 6572, 3660 "," Art Resin UN-9000HP, 9000PEP, 9200A, 7600, 5200, 1003, 1255, 3320HA, 3320HB, 3320HC, 3320HS, 901T " 1200TPK, 6060PTM, 6060P "," Nippon Gosei Chemical Co., Ltd. "" purple light UV-6630B, 7000B, 7510B, 7461TE, 3000B, 320 " 0B, 3210EA, 3310B, 3500BA, 3520TL, 3700B, 6100B, 6640B, 1400B, 1700B, 6300B, 7550B, 7605B, 7610B, 7620EA, 7630B, 7640B, 2000B, 2010B, 2250EA, 2750B, “Kayarad” R-280, R-146, R131, R-205, EX2320, R190, R130, R-300, C-0011, TCR-1234, ZFR-1122, UX-2201, UX-2301, UX3204, UX-3301, UX-4101, UX-6101, UX-7101, MAX-5101, MAX-5100, MAX-3510, UX-4101 "and the like.

  The radically polymerizable compound (B) of the present invention may be used alone or in a mixture of two or more at an arbitrary ratio in order to improve desired properties.

  Moreover, resin can be used for the polymerizable composition of the present invention. Here, the resin means a resin having no skeleton capable of radical polymerization in the molecule. In addition, these have a liquid or solid chemical form at normal temperature and normal pressure.

  Examples of resins having no radically polymerizable skeleton in the molecule include, for example, alkyd resins, polyester resins, polyvinyl chloride, poly (meth) acrylate resins (combining polyacrylate resins and polymethacrylate resins). Poly (meth) acrylate resin, the same applies hereinafter), polyepoxy resin, polyurethane resin, cellulose derivative resin (for example, ethyl cellulose, cellulose acetate, nitrocellulose), vinyl chloride vinyl acetate copolymer resin, polyamide resin, Polyvinyl acetal resin, diallyl phthalate resin, silicone resin, butadiene-acrylonitrile copolymer resin, polyamide resin, polyformaldehyde resin, polycarbonate resin, polystyrene resin, polyvinyl ether resin, polyvinyl Steal resin, polyvinyl amide resin, novolak resin, phenol resin, supervised by Kiyoshi Akamatsu “Practical technology of new photosensitive resin” (CMC, 1987) and “Chemical products of 10188”, pages 657-767 (Chemical Industry Daily) 1988)), which are known in the industry. These resins can be used alone or in combination of two or more thereof.

  Furthermore, the polymerizable composition of the present invention contains the following carboxyl group-containing poly (meth) acrylate resin for the purpose of being used for image formation as a so-called alkali development type photoresist material. You may add and use resin. Since the carboxyl group-containing resin has solubility in an alkaline aqueous solution, if a film prepared using the polymerizable composition of the present invention is partially cured, a so-called negative resist pattern is formed due to the difference in solubility in the alkaline aqueous solution. It is possible to form. Here, the carboxyl group-containing resin is a copolymer of (meth) acrylic acid ester and (meth) acrylic acid, (meth) acrylic acid ester, (meth) acrylic acid, and a vinyl monomer copolymerizable therewith. A copolymer resin may be mentioned. These copolymer resins may be used alone or in combination of two or more.

  Here, as the acrylic ester, methyl acrylate, ethyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid-t-butyl, acrylic acid-2-ethylhexyl, etc. C1-C18 alkyl esters of acrylic acid, hydroxyl-containing acrylic esters such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, etc., nitrogen containing dimethylaminoethyl acrylate, diethylaminoethyl acrylate, etc. Acrylic esters, glycidyl acrylate, tetrahydrofurfuryl acrylate, morpholyl acrylate, isobornyl acrylate, cyclohexyl acrylate, and the like can be mentioned, but are not limited thereto. Not to.

  Examples of methacrylic acid esters include methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid-t-butyl, and methacrylic acid-2-ethylhexyl. Alkyl esters having 1 to 18 carbon atoms, hydroxyl group-containing methacrylates such as hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxybutyl methacrylate, nitrogen-containing methacrylates such as dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate Methacrylic acid esters such as glycidyl methacrylate, tetrahydrofurfuryl methacrylate, morpholyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate Can, but it is not limited thereto.

  (Meth) acrylic acid ester, (meth) acrylic acid and vinyl monomers copolymerizable therewith include tetrahydrofurfuryl acrylate, dimethylaminoethyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, 2, Examples include 2,3,3-tetrafluoropropyl acrylate, tetrahydrfurfuryl methacrylate, dimethylaminoethyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, acrylamide, and styrene.

  In order to improve the film formability, the polymerizable composition of the present invention is mixed with the resin having no skeleton capable of radical polymerization, and is a glass film, an aluminum sheet, another metal sheet, a polymer film such as polyethylene terephthalate or polyethylene. It can be used by applying to.

  In addition, the polymerizable composition of the present invention has sufficient sensitivity without using a sensitizer, but a sensitizer is used in combination for the purpose of further improving sensitivity and improving film properties after curing. Is possible.

Sensitizers that can be used in combination with the polymerizable composition of the present invention include benzophenone derivatives, unsaturated ketone derivatives typified by chalcone derivatives and dibenzalacetone, and typified by benzyl and camphorquinone. 1,2-diketone derivatives, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine Derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azurenium derivatives, squarylium derivatives Porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, Naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes Other examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CM) -), Including dyes and sensitizers described in "Special Function Materials" edited by Tadasaburo Ikemori et al. (1986, CMC), but are not limited to these. Examples thereof include dyes and sensitizers that absorb light, and two or more of them may be used in any ratio as necessary.
Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxy. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4'-dimethylbenzophenone, 4,4'-dimethoxybenzophenone, 4,4'- Examples include bis (diethylamino) benzophenone, and examples of coumarins include coumarin 1, coumarin 338, and coumarin 102. Examples of ketocoumarins include 3,3′-carbonylbis (7-diethylaminocoumarin). However, it is not limited to these.

  The amount of the sensitizer used in the present invention is preferably in the range of 0.01 to 100 parts by weight and more preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the radical polymerizable initiator (C). preferable.

  In addition, a polymerization inhibitor can be added to the polymerizable composition of the present invention for the purpose of preventing polymerization during storage.

  Specific examples of the polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, tert-butylcatechol, phenothiazine, and the like. The agent is preferably added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the radical polymerizable initiator (C).

  A surface conditioner can be added to the polymerizable composition of the present invention for the purpose of improving the adhesion to the substrate. Specific examples of the surface conditioner include BYK-300, 302, 306, 307, 310, 315, 320, 322, 323, 325, 330, 331, 333, 337, 340, 344, 370, and 375 manufactured by BYK-Chemie. 377, 350, 352, 354, 355, 356, 358N, 361N, 357, 390, 392, UV3500, UV3510, UV3570, “Tegorad-2100, 2200, 2250, 2500, 2700” manufactured by Tego Chemie. These surface conditioners may be used alone or in combination of two or more as required.

  The surface conditioner that may be used in combination in the present invention is used in the range of 0 to 5.0% by weight in the polymerizable composition.

  The polymerizable composition of the present invention is further used in accordance with the purpose, such as dyes, organic and inorganic pigments, pigment dispersants, phosphines, phosphonates, phosphites and other oxygen removing agents and reducing agents, antifoggants, antifading agents, and antihalation. Agent, optical brightener, surfactant, colorant, extender, plasticizer, flame retardant, antioxidant, dye precursor, ultraviolet absorber, foaming agent, antifungal agent, antistatic agent, magnetic substance, resin Dispersants such as type dispersants Storage stabilizers such as silane coupling agents and quaternary ammonium chlorides, plasticizers, surface tension modifiers, slipping agents, antiblocking agents, light stabilizers, leveling agents, antifoaming agents, It may be used by mixing with infrared absorbers, surfactants, thixotropic agents, antibacterial agents, fine particles such as silica, other additives imparting various properties, diluent solvents and the like.

  In the polymerization reaction, the polymerizable composition of the present invention can be polymerized by application of heat or energy by an active energy ray such as ultraviolet ray, visible ray, near infrared ray, electron beam, etc. to obtain a desired polymer. However, as a light source for applying energy, irradiation of active energy rays with a light source having a dominant wavelength of light emission in a wavelength region of 250 to 450 nm is preferable. Examples of light sources having a main wavelength of light emission in the wavelength region of 250 nm to 450 nm include ultrahigh pressure mercury lamps, high pressure mercury lamps, medium pressure mercury lamps, mercury xenon lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and pulsed light emission. Xenon lamp, deuterium lamp, fluorescent lamp, Nd-YAG triple wave laser, He-Cd laser, nitrogen laser, Xe-Cl excimer laser, Xe-F excimer laser, semiconductor-excited solid laser, 365 nm, 375 nm, 385 nm Various light sources such as an LED lamp light source having In this specification, the definition of active energy rays such as ultraviolet rays, visible light, and near infrared rays is based on “Iwanami Physical and Chemical Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, the polymerizable composition of the present invention can be printed or coated on various substrates, and various inks, inkjet inks, overcoat varnishes, various printing plate materials, photoresists, electrophotography, direct printing. It can be applied to various recording media such as plate materials, optical fibers, hologram materials, and other photosensitive materials and microcapsules, as well as adhesives, adhesives, adhesives, release coating agents, sealants, and various paints. is there.

  The substrate on which the polymerizable composition of the present invention is printed or applied can be appropriately selected from the group consisting of glass, plastic, metal and paper. Furthermore, a composite substrate composed of a plurality of substrates can also be selected. These substrates may have a flat shape such as a plate, film, or paper, or may have a three-dimensional shape. The plastic film is preferably transparent.

Examples of the plastic substrate include transparent polymers such as polyester polymers, cellulose polymers, polycarbonate polymers, and polyacrylic polymers.
Examples of the polyester polymer include polyethylene terephthalate (PET) and polyethylene naphthalate. Examples of the cellulose polymer include diacetyl cellulose and triacetyl cellulose (TAC). Examples of the polyacrylic polymer include polymethyl methacrylate.

Examples of the plastic substrate include transparent polymers such as polystyrene-based polymers, polyolefin-based polymers, polyvinyl chloride-based polymers, and polyamide-based polymers.
Examples of the polystyrene-based polymer include polystyrene, acrylonitrile / styrene copolymer polymer, and the like. Examples of the polyolefin-based polymer include polyethylene, polypropylene, a polyolefin polymer having a cyclic or norbornene structure, and an ethylene / propylene copolymer polymer. Examples of the polyamide polymer include nylon and aromatic polyamide polymer.

  Furthermore, polyimide polymer, polysulfone polymer, polyether polyether sulfone polymer, polyether ketone polymer, polyphenyl sulfide polymer, polyvinyl alcohol polymer, polyvinylidene chloride polymer, polyvinyl butyral polymer, polyarylate polymer, poly Examples thereof also include transparent polymers such as oxymethylene polymers, polyepoxy polymers, and blends of the above polymers. In particular, those having a small birefringence are preferably used.

  In order to use it as an ink composition, it is possible to add a coloring component to the polymerization composition of this invention according to the objective. A conventionally known pigment can be used as the coloring component. Further, for the purpose of obtaining a desired hue, a dye may be contained within a range in which heat resistance and weather resistance are not lowered. These may be used alone or in combination of two or more in order to obtain a desired color density and hue.

  As the pigment, for example, an organic pigment, an inorganic pigment, or carbon black (for example, acetylene black, channel black, furnace black, etc.) can be used, and two or more kinds of pigments can be mixed and used.

  Examples of organic pigments include diketopyrrolopyrrole pigments, azo pigments (eg, azo, disazo, polyazo, etc.), phthalocyanine pigments (eg, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc.), anthraquinone type Pigment (for example, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyrantrone, violanthrone, etc.), quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo pigment, iso Examples thereof include indoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.

  Examples of inorganic pigments include titanium oxide, zinc white, zinc sulfide, lead white, calcium carbonate, precipitated barium sulfate, white carbon, alumina white, kaolin clay, talc, bentonite, black iron oxide, carbon black, cadmium red, Bengara, molybdenum red, molybdate orange, chrome vermilion, yellow lead, cadmium yellow, yellow iron oxide, titanium yellow, chromium oxide, viridian, titanium cobalt green, cobalt green, cobalt chrome green, Victoria green, ultramarine blue, bitumen, cobalt Examples include blue, cerulean blue, cobalt silica blue, cobalt zinc silica blue, manganese violet, and cobalt violet.

  Examples of the carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” manufactured by Degussa, Inc., “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, 45. , 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ”,“ REGAL 400R, 660R, 330R, 250R ”,“ MOGUL E, L ”, manufactured by Mitsubishi Chemical Corporation,“ MA7, 8, 11, 77, 100, 100R, 100S, 220, 230 "" # 2700, # 2650, # 2600, # 200, # 2350, # 2300, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 900, # 850, # 750, # 650, # 52, # 50, # 47, # 45, # 4 5L, # 44, # 40, # 33, # 332, # 30, # 25, # 20, # 10, # 5, CF9, # 95, # 260 ”and the like.

  Hereinafter, pigments that can be used in the polymerization composition of the present invention are indicated by color index (CI) numbers.

  Examples of red pigments include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272 or the like can be used, but is not limited thereto.

  Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , But the invention is not limited to the like can be used 177,179,180,181,182,185,187,188,193,194,199.

  Examples of orange pigments include C.I. I. Pigment Orange 36, 43, 51, 55, 59, 61 and the like can be used, but are not limited thereto.

  Examples of the green pigment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, and 37 can be used, but are not limited thereto.

  Examples of the blue pigment include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 and the like can be used, but are not limited thereto.

  Examples of purple pigments include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and the like can be used, but are not limited thereto.

  Examples of the black pigment include C.I. I. Pigment Violet 1, 6, 7, 12, 20, 31 etc. can be used, but it is not limited to these.

  These pigments can be used by mixing two or more kinds at an arbitrary ratio.

  The amount used in the case of adding the pigment as the coloring component is 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight with respect to 100 parts by weight of the radical polymerizable compound (B).

  The particle diameter of the pigment is preferably sufficiently small with respect to the wavelength of visible light from the viewpoint of the absorption coefficient of visible light (appropriate spectrum) and transparency. That is, the pigment preferably has an average primary particle size of 0.01 μm or more and 0.3 μm or less, particularly 0.01 μm or more and 0.1 μm or less. The primary particle diameter refers to the diameter of the smallest unit pigment particle, and is measured with an electron microscope.

  The primary particle diameter of the pigment can be controlled within an appropriate range using a known dispersing device such as a sand mill, a kneader, or a two roll.

  Moreover, when adding a pigment to the polymerization composition of the present invention, a pigment derivative or a pigment dispersant can be used for the purpose of improving the dispersibility of the pigment and the storage stability of the polymerization composition.

  Here, the pigment derivative is a compound in which a substituent is introduced into an organic dye. Organic dyes include light yellow aromatic polycyclic compounds such as phthalimide, naphthalene, naphthoquinone, anthracene, and anthraquinone that are not generally called dyes.

  Examples of pigment derivatives include JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-06-06. What is described in 306301 gazette, Unexamined-Japanese-Patent No. 2001-220520, Unexamined-Japanese-Patent No. 2003-238842 etc. can be used, These can be used individually or in mixture of 2 or more types.

  Examples of the pigment dispersant include a hydroxyl group-containing carboxylic acid ester, a salt of a long chain polyaminoamide and a high molecular weight acid ester, a salt of a high molecular weight polycarboxylic acid, a salt of a long chain polyaminoamide and a polar acid ester, a high molecular weight unsaturated acid ester, Polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester, polyoxyethylene Nonylphenyl ether, stearylamine acetate, etc. can be used.

  Specific examples of the pigment dispersant include "Anti-Terra-U (polyaminoamide phosphate)", "Anti-Terra-203 / 204 (high molecular weight polycarboxylate)" manufactured by BYK Chemie, "Disperbyk-101 ( (Polyaminoamide phosphate and acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 ( Polymer copolymer) ”,“ 400 ”,“ Bykumen ”(high molecular weight unsaturated acid ester),“ BYK-P104, P105 (high molecular weight unsaturated acid polycarboxylic acid) ”,“ P104S, 240S (high molecular weight unsaturated) Saturated acid polycarboxylic acid and silicon system "," Lactimon (long chain amine and unsaturated acid poly) Recarboxylic acid and silicon) ”.

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, 766”, “Efka Polymer 100 (modified polyacrylate), 150 (aliphatic) System modified polymer), 400, 401, 402, 403, 450, 451, 452, 453 (modified polyacrylate), 745 (copper phthalocyanine system) "," Floren TG-710 (urethane oligomer) "," Flownon "manufactured by Kyoeisha Chemical Co., Ltd. “SH-290, SP-1000”, “Polyflow No. 50E, No. 300 (acrylic copolymer)”, “Disparon KS-860, 873SN, 874 (polymer dispersing agent), # 2150 (manufactured by Enomoto Kasei Co., Ltd.) Aliphatic polyvalent carboxylic acid), # 7004 (polyether ester type) ” That.

  Further, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, SN-B (aromatic sulfonic acid formalin condensate sodium salt), EP”, “Homogenol L-18 (poly) Carboxylic acid type polymer), “Emulgen 920, 930, 931, 935, 950, 985 (polyoxyethylene nonyl phenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, manufactured by Lubrizol “Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000”, “Nikkor T106 (poly) Oxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), “Ajisper PB821, 822, 824” manufactured by Ajinomoto Fine Techno Co., and the like.

  The addition amount of the pigment derivative and the pigment dispersant is not particularly limited, but is preferably 0.1 to 40 parts by weight, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the pigment. is there.

  Examples of the dye that may be contained to obtain a desired hue include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, and methine dyes. It is done.

  Examples of the azo dye include C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Examples thereof include, but are not limited to, Mordant Black 7.

  Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disper thread 60, C.I. I. Disperse Blue 56, C.I. I. Examples include, but are not limited to, Disperse Blue 60.

  Other examples of the phthalocyanine dye include C.I. I. Examples of quinoneimine dyes such as Pad Blue 5 include C.I. I. Basic Blue 3, C.I. I. Examples of quinoline dyes such as Basic Blue 9 include C.I. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are nitro dyes such as C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Examples include, but are not limited to, Disperse Yellow 42.

  The amount used in the case of adding these dyes is 0.01 to 100 parts by weight, preferably 1 to 60 parts by weight, based on 100 parts by weight of the radical polymerizable compound (B). From the viewpoint of heat resistance and weather resistance, it is not preferable that the amount used is excessive.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all. In addition, the number of the compounding amount in the table | surface in the following Examples represents a weight part.

Examples relating to the synthesis of the compounds listed in Table 1 are shown below.

<Example 1> Polymerization accelerator (A): Synthesis of compound (6) A 1 L four-necked flask was charged with 85 g of 2-pyrrolidone, 40 g of sodium hydride, and 500 mL of tetrahydrofuran and mixed. In the mixed solution, 120 g of ethyl bromide was added over 1 hour. After stirring for 1 hour, 200 mL of methanol was added little by little to deactivate the activity of unreacted sodium hydride. Diethyl ether (200 mL) was added to the reaction mixture, and the mixture was washed successively with 1% hydrochloric acid (200 mL) and saturated brine (200 mL) three times. 40 g of anhydrous sodium sulfate was added to the organic layer and stirred, followed by filtration. The obtained solution was concentrated while blowing oxygen with a rotary evaporator to obtain 100 g of a colorless transparent liquid compound (1) in a yield of 89%. The compound was identified by ¹ H-NMR (manufactured by JEOL, JMTC-400 / 54 / SS) and GC / MS (manufactured by Agilent Technologies, 6890N).

Example 2 Polymerization Accelerator (A): Synthesis of Compound (7) A 1 L four-necked flask was charged with 110 g of ε-caprolactam, 40 g of sodium hydride, and 500 mL of tetrahydrofuran and mixed. In the mixed solution, 120 g of ethyl bromide was added over 1 hour. After stirring for 1 hour, 200 mL of methanol was added little by little to deactivate the activity of unreacted sodium hydride. Diethyl ether (200 mL) was added to the reaction mixture, and the mixture was washed successively with 1% hydrochloric acid (200 mL) and saturated brine (200 mL) three times. 40 g of anhydrous sodium sulfate was added to the organic layer and stirred, followed by filtration. The obtained solution was concentrated while blowing oxygen with a rotary evaporator to obtain 120 g of a colorless transparent liquid compound (7) in a yield of 85%. The compound was identified by ¹ H-NMR and GC / MS.

<Example 3> Polymerization accelerator (A): Synthesis of compound (8) A 1 L four-necked flask was charged with 85 g of 2-oxazolidinone, 40 g of sodium hydride, and 500 mL of tetrahydrofuran and mixed. In the mixed solution, 120 g of ethyl bromide was added over 1 hour. After stirring for 1 hour, 200 mL of methanol was added little by little to deactivate the activity of unreacted sodium hydride. Diethyl ether (200 mL) was added to the reaction mixture, and the mixture was washed successively with 1% hydrochloric acid (200 mL) and saturated brine (200 mL) three times. 40 g of anhydrous sodium sulfate was added to the organic layer and stirred, followed by filtration. The obtained solution was concentrated while blowing oxygen with a rotary evaporator to obtain 95 g of a colorless transparent liquid compound (8) in a yield of 82%. The compound was identified by ¹ H-NMR and GC / MS.

<Example 4> Polymerization accelerator (A): Synthesis of compound (9) A 1 L four-necked flask was charged with 80 g of 2-imidazolidinone, 40 g of sodium hydride, and 500 mL of dimethylformamide and mixed. In the mixed solution, 250 g of ethyl bromide was added over 2 hours. After stirring for 1 hour, 200 mL of methanol was added little by little to deactivate the activity of unreacted sodium hydride. Diethyl ether (200 mL) was added to the reaction mixture, and the mixture was washed successively with 1% hydrochloric acid (200 mL) and saturated brine (200 mL) three times. 40 g of anhydrous sodium sulfate was added to the organic layer and stirred, followed by filtration. The obtained solution was concentrated while blowing oxygen with a rotary evaporator to obtain 120 g of a colorless transparent liquid compound (9) in a yield of 85%. The compound was identified by ¹ H-NMR and GC / MS.

<Example 5> Preparation of polymerizable composition 40 parts by weight of the compound (1) as a polymerization accelerator (A) and DPGDA (dipropylene glycol diacrylate) of a bifunctional acrylic ester as a radical polymerizable compound (B) Was mixed with 55 parts by weight of TPO (BASI Co., Ltd. Lucillin TPO photopolymerization initiator) as a radical polymerizable initiator (C) to obtain a polymerizable composition. Using the obtained polymerizable composition, a polymerization rate evaluation test, an adhesion test and an odor sensory test were carried out by the following methods. The results are shown in Table 2.

<Examples 6-21 and Comparative Examples 1-2>
In the same manner as in Example 5, a polymerizable composition was obtained with the formulation shown in Table 2. Using the obtained ink composition, a polymerization rate evaluation test, an adhesion test and an odor sensory test were carried out by the following methods. The results are shown in Table 2.

<Polymerization rate evaluation test>
The prepared polymerizable composition was applied onto a stainless steel plate using a K control coater so that the wet film thickness was 10 μm, thereby preparing a coating film. Using an ultra high pressure UV lamp USH-500SC (USHIO) as an active energy ray, ultraviolet irradiation is performed with time-resolved infrared spectroscopy while performing ultraviolet irradiation at an irradiation intensity of 35 mW / cm ² (in terms of 365 nm). The consumption rate of acryloyl group was observed. After 2 seconds of irradiation time, the consumption rate of acryloyl group was defined as the polymerization rate, and the calculation was performed using the following formula.
Polymerization rate [% / s] = “Consumption rate of acryloyl group after irradiation time 2 seconds” ÷ “irradiation time 2 seconds”

<Adhesion test>
The prepared polymerizable composition was applied on a PVC film (MD5 soft PVC manufactured by Metamark) using a K control coater so that the wet film thickness was 10 μm, and a coating film was prepared. The coated film was irradiated with ultraviolet rays as an active energy ray at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 100 W / cm1 lamp) to obtain a cured film. Next, the cured film was placed in a dryer and dried at 40 degrees for 1 hour. The adhesion was evaluated by a cross-cut cellophane adhesive tape peeling test. The number of cells peeled when 100 mask loss cut was put on the cured film and forcedly peeled with a cellophane adhesive tape was shown. It shows that the adhesiveness with respect to a base material is so excellent that there are few peeled-off mass numbers.

<Odor sensory test>
The prepared polymerizable composition was smelled and subjected to an odor sensory test.
Judgment method ○: Nearly odorless ×: Unique odor

  The polymerizable composition containing the polymerization accelerator (A) of the present invention is a cured product that can be polymerized remarkably in ultraviolet irradiation with active energy rays, has a low odor, and has excellent substrate adhesion. It became clear that In the polymerizable composition to which only 10 parts by weight of the polymerization accelerator (A) of the present invention was added, although remarkable substrate adhesion was exhibited, no significant polymerization acceleration was observed (Example 20). Moreover, in the polymeric composition to which the polymerization accelerator (A) is not added, the substrate adhesion is poor and the polymerization rate is slow (Comparative Example 1). On the other hand, when diethanolamine, which is a general-purpose polymerization accelerator, is used in place of the polymerization accelerator (A), the polymerization acceleration effect is exhibited, but the substrate adhesion is poor and the odor is also poor (Comparative Example 2).

  As shown in the results of the polymerization rate evaluation test, the substrate adhesion test and the odor sensory test, the polymerizable composition containing the polymerization accelerator (A) of the present invention is prominent by using an appropriate amount. It was revealed that the polymerization can be carried out rapidly, has low odor, and exhibits excellent adhesion to the substrate. Therefore, the polymerizable composition containing the polymerization accelerator (A) of the present invention has a very wide selectivity and was shown to be a polymerizable composition that can be used for various applications.

<Examples of ink composition>

  First, yellow, magenta, cyan, and black pigment dispersions comprising a pigment, a pigment dispersant, and a radical polymerizable compound (B) were prepared.

<Preparation of pigment dispersion a>
The composition of pigment dispersion a is shown in Table 3. After stirring the radical polymerizable compound (B) and the polymer pigment dispersant and confirming that the polymer dispersant is completely dissolved, the pigment is added, and after stirring until uniform with a high speed mixer or the like, The obtained mill base was dispersed in a horizontal sand mill for about 1 hour to prepare a cyanine pigment dispersion.

<Preparation of pigment dispersion b>
The formulation of pigment dispersion b is shown in Table 4. For the pigment dispersion b, a black pigment dispersion was prepared by the same production method as for the pigment dispersion a.

<Preparation of pigment dispersion c>
The composition of pigment dispersion c is shown in Table 5. After stirring the radical polymerizable compound (B) and the polymer pigment dispersant and confirming that the polymer dispersant is completely dissolved, the pigment is added, and after stirring until uniform with a high speed mixer or the like, The obtained mill base was dispersed in a horizontal sand mill for about 2 hours to prepare a magenta pigment dispersion.

<Preparation of pigment dispersion d>
The formulation of pigment dispersion d is shown in Table 6. After stirring the radical polymerizable compound (B) and the polymer pigment dispersant and confirming that the polymer dispersant is completely dissolved, the pigment is added, and after stirring until uniform with a high speed mixer or the like, The obtained mill base was dispersed in a horizontal sand mill for about 1.5 hours to prepare a yellow pigment dispersion.

<Example 22> Preparation of ink composition 30.5 parts by weight of the compound (1) as a polymerization accelerator (A), 11.4 parts by weight of a pigment dispersion a as a pigment dispersion, and a radical polymerizable compound (B ) 50 parts by weight of DPGDA, 0.1 part by weight of BYK-331 (silicon resin manufactured by BYK Chemi) as a surface conditioner, and 8 parts by weight of TPO as a radical polymerizable initiator (C), An ink composition was obtained. Using the obtained ink composition, a curability test, an adhesion test and an odor sensory test were carried out by the following methods. The results are shown in Table 7.

<Examples 23 to 45, Comparative Examples 3 to 4>
In the same manner as in Example 22, an ink composition was obtained with the formulation shown in Table 7. Using the obtained ink composition, a curability test, an adhesion test and an odor sensory test were carried out by the following methods. The results are shown in Table 7.

<Curing test>
The prepared ink composition was applied on a PVC film (MD5 soft PVC manufactured by Metamark) using a K control coater so that the wet film thickness was 10 μm, and a coating film was prepared. The coated film was irradiated with ultraviolet rays as an active energy ray at a conveyor speed of 10 m / min using a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 100 W / cm1 lamp) to obtain a cured film. Next, the cured film was placed in a dryer and dried at 40 degrees for 30 minutes. The surface of the reaction cured product after drying was rubbed with a cotton cloth, and irradiation and drying were repeated until the film was not damaged, and the curability was determined. The smaller the number of irradiations, the better the curability. The results are shown in Table 7.

Judgment method ◎: 1-3 times ○: 4-6 times ×: 7 times or more

<Adhesion test>
The adhesion was evaluated by a cross-cut cellophane adhesive tape peeling test. 100 mask loss cuts were put on the cured film, 100 mask loss cuts were put in, and the number of cells peeled off when forcibly peeling with a cellophane adhesive tape was shown. It shows that the adhesiveness with respect to a base material is so excellent that there are few peeled-off mass numbers. The results are shown in Table 7.

<Odor sensory test>
By smelling the odor of the prepared ink composition, an odor sensory test was conducted. The results are shown in Table 7. Shown in

Judgment method ○: Nearly odorless ×: Unique odor

Table 7

  The ink compositions (Examples 22 to 44) using the polymerizable composition of the present invention were found to have low odor, high curability by active energy ray irradiation, and excellent substrate adhesion.

  The ink composition to which only a small amount of the polymerization accelerator (A) was added was slightly inferior in curability as compared with the ink composition to which a large amount of the polymerization accelerator (A) was added (Example 45), but good. The substrate adhesion is shown. When the radical polymerizable compound (B) is used alone without adding the polymerization accelerator (A), the curability is insufficient and the substrate adhesion is poor (Comparative Example 3). On the other hand, when diethanolamine, which is a general-purpose polymerization accelerator, is used instead of the polymerization accelerator (A), the curability is good, but the odor is bad and the substrate adhesion is poor (Comparative Example 4).

  It became clear that the polymerizable composition of the present invention can be used for an ink composition characterized by high curability by irradiation with active energy rays, excellent substrate adhesion, and low odor.

  An object of the present invention is to provide a polymerizable composition that is excellent in safety and hygiene due to low odor and substrate adhesion, and that significantly accelerates the polymerization rate by irradiation with active energy rays, and an ink composition using the same Is to provide things. The polymerization accelerator (A) used in the polymerizable composition of the present invention comprises a compound characterized by having a nitrogen-containing heterocyclic skeleton. By adding this compound to the polymerizable composition, it was possible to provide a polymerizable composition having a remarkably fast polymerization rate, low odor, and excellent substrate adhesion. Therefore, it can be expected to be used as an active energy ray-curable ink composition that exhibits high curability, has a low odor that does not cause deterioration of the working environment, and has excellent adhesion to the substrate.

  Furthermore, use of the polymerizable composition of the present invention is not limited in various applications. Examples of applications that can be expected to increase sensitivity and improve properties according to the present invention include molding resins, casting resins, photo-molding resins, sealants, dental polymerization resins, printing inks that utilize polymerization or crosslinking reactions, Printing varnish, paint, photosensitive resin for printing plate, printing color proof, resist for color filter, resist for black matrix, photo spacer for liquid crystal, screen material for rear projection, optical fiber, rib material for plasma display, dry film resist, Resist for printed circuit board, solder resist, photoresist for semiconductor, resist for microelectronics, resist for manufacturing micromachine parts, resist for etching, microlens array, insulating material, hologram material, optical switch, waveguide material, overcoat agent Powder Computing, adhesives, pressure-sensitive adhesives, release agents, optical recording media, adhesive, release coat agent composition for image recording materials using microcapsules, and various devices and the like.

Claims (5)

A polymerization accelerator (A) comprising at least one compound represented by the following general formulas (1) to (3).
General formula (1)

(In the formula, X represents an alkylene group having 2 to 6 carbon atoms,
R ¹ represents an alkyl group. )
General formula (2)

(In the formula, R ² represents an alkyl group.)
General formula (3)

(In the formula, R ³ and R ⁴ each independently represents a hydrogen atom or an alkyl group.)   A polymerizable composition comprising the polymerization accelerator (A) according to claim 1 and a radically polymerizable compound (B).   The polymerizable composition according to claim 2, wherein the polymerization accelerator (A) is contained in an amount of 20 wt% to 40 wt% in the composition.   Furthermore, the polymeric composition of Claim 2 or Claim 3 containing a radically polymerizable initiator (C).   An ink composition using the radically polymerizable composition according to claim 4.