JP2015168702A - Polymerizable composition, and active energy ray-curable inkjet ink using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymerizable composition having a low viscosity, an extremely fast curing rate, and excellent low odor property and storage property, and an active energy ray-curable inkjet ink using the composition.SOLUTION: The polymerizable composition comprises a compound having a (meth)acryl group, and an allyl ether group or a vinyl ether group in the same molecule. With radicals generated by the combination of the above compound with a radical polymerization initiator, a polymerization reaction, a crosslinking reaction or the like can be reliably carried out in a short time for curing the composition, and further, a low viscosity, low odor and high storage stability can be achieved.

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 In the field of compositions for image recording materials using pusels, various devices, and the like, the present invention relates to a polymerizable composition for obtaining a polymer having good physical properties, particularly curability, low odor, storage stability, and The present invention relates to an active energy ray-curable inkjet ink having excellent ejection stability.

  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. .

  Applications using these reactive compounds are diverse, and one of them is active energy ray-curable ink.

  Conventionally, active energy ray-curable inks have been used for offset printing and silk screen printing, but the cost per colorant can be reduced by ejecting the required amount of ink droplets when necessary when printing. In recent years, demand for active energy ray-curable inks for ink jet printing has been increasing from the point that on-demand printing is possible without requiring a plate. Active energy ray curable inks for inkjet printing include ultraviolet curable inkjet inks that are cured with ultraviolet rays, and are environmentally friendly and fast due to the reduction of volatile solvents compared to conventional water-based or solvent-based non-curable inks. In recent years, it has been attracting attention because of its high dryness, odor reduction, and ink-absorptive substrate printing, and high substrate selectivity, and patents have been disclosed (Patent Documents 1 and 2).

  Ink-jet ink is also characterized in that the viscosity has a great influence on the printing stability and other image quality obtained compared to ink for other printing methods such as gravure and offset.

  In recent years, there has been a demand for an active energy ray-curable ink-jet ink that can be printed at a higher speed, that is, reactively cured in a short time, in order to improve productivity. As one of the countermeasures, a plurality of reactive acrylic groups are substituted. A reactive compound such as an acrylate compound may be used. However, the greater the number of acrylic group substitutions, the higher the viscosity of the ink, causing a problem that the ink ejection performance from the head is significantly reduced.

  As a method for improving the curability without increasing the viscosity of the ink, an active energy ray-curable inkjet ink using an acrylate compound and a vinyl ether compound having different reactivity has been proposed. (Patent Document 3).

  In order to improve storage stability, active energy ray-curable inkjet inks using reactive compounds having an acrylic group and a vinyl ether group in the same molecule have been proposed, but they are still insufficient in terms of curability. Yes (Patent Document 4).

  Further, a reactive compound having an acryl group and an allyl ether group in the same molecule includes a glycerin skeleton compound (for example, “DA-111” manufactured by Nagase ChemteX Corporation), which remains excellent although it has excellent curability. There is a problem that the viscosity increases due to —OH groups.

JP-A-6-200204 Special Table 2000-504778 Japanese Patent Laid-Open No. 9-183927 European Patent Application Publication No. 0997508

  An object of the present invention is to provide a polymerizable composition having an extremely high curing rate associated with a reaction by irradiation with active energy rays and having excellent low viscosity, low odor, and storage stability, and an active energy ray curable inkjet ink using the same. Is to provide.

  As a result of intensive studies to solve the above problems in consideration of the above problems, the present inventors have reached the present invention. That is, the present invention comprises a reactive compound (A) containing a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and a radical polymerization initiator (B). The present invention relates to a polymerizable composition.

General formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group,
R ² represents a group represented by the following general formula (3) or the following general formula (4). )

General formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group,
R ⁴ represents a group represented by the following general formula (3) or the following general formula (4). )

General formula (3)

(In the formula, R ⁵ represents an alkyl group having 1 to 10 carbon atoms. The alkyl group may be interrupted by an ether bond.)

General formula (4)

(In formula, R < ⁶ > -R < ⁸ > represents a C1-C10 alkyl group or a C1-C10 alkyloxy group each independently.)

  The present invention also relates to the polymerizable composition, wherein the radical polymerization initiator (B) is a radical photopolymerization initiator.

  The present invention also relates to an active energy ray-curable inkjet ink comprising the polymerizable composition.

  Moreover, this invention relates to the manufacturing method of printed matter which prints the said active energy ray hardening-type inkjet ink, and makes it harden | cure by active energy ray irradiation.

  Moreover, this invention relates to the printed matter obtained with the said manufacturing method.

  According to the present invention, it is possible to provide a polymerizable composition excellent in curability, low odor, and storage stability associated with a reaction by irradiation with active energy rays, and while maintaining dischargeability without increasing the viscosity. It was possible to provide an active energy ray-curable inkjet ink with improved curability and excellent storage stability.

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

  First, the reactive compound (A) of the present invention will be described.

  The reactive compound (A) is a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2).

General formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group,
R ² represents a group represented by the following general formula (3) or the following general formula (4). )

General formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group,
R ⁴ represents a group represented by the following general formula (3) or the following general formula (4). )

General formula (3)

(In the formula, R ⁵ represents an alkyl group having 1 to 10 carbon atoms. The alkyl group may be interrupted by an ether bond.)

Specific examples of the alkyl group in R ⁵ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, A methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are mentioned, More preferably, a methyl group, an ethyl group, and a propyl group are mentioned.

Specific examples of the alkyl group in R ⁵ interrupted by an ether bond include, for example, —CH ₂ —O— (CH ₂ ) _n —CH ₃ (n is an integer of 0 to 8), — ( CH is ₂ -O) _n -CH _{3 (n} is an integer of 1 to 4) -. and the like (CH ₂ is _{-CH 2 -O) n -CH 3 (} n is an integer of 1 to 3). . Preferably, n is an integer of 2 or less, more preferably n is an integer of 1 or less.

General formula (4)

(In formula, R < ⁶ > -R < ⁸ > represents a C1-C10 alkyl group or a C1-C10 alkyloxy group each independently.)

Specific examples of the alkyl group in R ^{6 to} R ⁸ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, Preferably, a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group are mentioned, More preferably, a methyl group, an ethyl group, and a propyl group are mentioned.

Specific examples of the alkyloxy group for R ^{6 to} R ⁸ include —O— (CH ₂ ) _n —CH ₃ (n is an integer of 0 to 8). Preferably, n is an integer of 4 or less, more preferably n is an integer of 2 or less.

Specific structures are shown in Table 1 below, but the structure of the reactive compound (A) of the present invention is not limited thereto.

  The reactive compound (A) of the present invention has a glycerin skeleton and a (meth) acrylic group [acrylic group and methacrylic group are collectively referred to as “(meth) acrylic group” in the same molecule. The same applies hereinafter. And an allyl ether group or vinyl ether group. By having this basic structure, it is a compound having a normally conflicting function that the viscosity of the ink does not increase while being highly reactive.

  In addition, having an allyl group or a vinyl ether group is superior in that it has a low viscosity as compared with reactive compounds such as acrylate compounds having two to three (meth) acrylic groups having a similar structure. Yes.

  Furthermore, as compared with reactive compounds such as acrylate compounds having a glycerin skeleton having one or two (meth) acrylic groups and —OH groups having a similar structure, —OH groups that contribute to an increase in viscosity are substituted by substituents. It is a compound that achieves lower viscosity by modification with.

  The reason why the reactive compound (A) of the present invention is preferable is that not only the curing rate accompanying the polymerization reaction is extremely high and low viscosity, but also excellent storage stability and the reactive compound (A) is obtained. It can also be mentioned that this reaction is easy.

  The reactive compound (A) of the present invention comprises a reaction between an alcohol catalyzed with a base and an alkyl halide or trialkylsilyl halide, an ester condensation reaction catalyzed with an acid, a carboxylic acid and an alcohol using a dehydrating agent. It can be obtained by using a general organic synthesis reaction such as an esterification reaction, an acid chloride reaction, a transesterification reaction using a palladium-containing compound described in JP-A No. 2001-220364.

  The acid catalyst that can be used in the synthesis of the reactive compound (A) of the present invention is an organic or inorganic strong acid, and is not particularly limited, but mineral acids and their partially neutralized salts, heteropoly acids, organic sulfonic acids A halogenated acetic acid, a Lewis acid, an acidic zeolite carrying an organic sulfonic acid, an activated carbon carrying an organic sulfonic acid, and the like.

  Specific examples of the mineral acid include sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, boric acid and the like.

  Specific examples of the heteropoly acid include tungstic acid, molybdic acid, tungstosilicic acid, molybdosilicic acid, tungstophosphoric acid, molybdophosphoric acid and the like.

  Specific examples of the organic sulfonic acid include methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, dimesityl ammonium pentafluorobenzenesulfonate, and the like.

  Specific examples of the halogenated acetic acid include trifluoroacetic acid and trichloroacetic acid.

  Specific examples of the Lewis acid include boron fluoride, boron chloride, aluminum chloride, tin dichloride, tin tetrachloride and the like.

  Specific examples of the acidic zeolite carrying an organic sulfonic acid include, for example, mordenite type, X type, Y type, β type, ZSM-5 type and the like.

  Of these acid catalysts, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, and activated carbon carrying an organic sulfonic acid are preferred.

  When synthesizing the reactive compound (A) of the present invention, a heat transfer method using an external heat source is usually used. As a heating means for synthesizing more efficiently, a method of induction heating by irradiation with microwaves is preferable. In the induction heating method using microwave irradiation, the desired reaction temperature can be reached in a short time, so that the generation of by-products that can occur at the time of temperature rise can be suppressed.

  Examples of the microwave include 2450 ± 50 MHz, 5800 ± 75 MHz, and 24125 ± 125 MHz, which are designated frequency bands in Japan, and preferably 2450 ± 50 MHz.

  A microwave generator that can generate a frequency used for commercial use can be used, and there is no restriction such as a single mode, a multimode, a magnetron type, or a cavity type. For example, a microwave reactor μ reactor (made by Shikoku Keiki Kogyo Co., Ltd.) having an oscillation frequency of 2450 ± 30 MHz and an output power of 760 W can be used.

  When microwave heating is used when synthesizing the reactive compound (A) of the present invention, a nonpolar solvent that does not absorb or hardly absorb microwave energy may be added.

  Here, as a solvent that does not absorb or hardly absorbs microwave energy, non-patent literature (from B. L. Hayes, Microwave Synthesis: Chemistry at the Speed of Light, CEM Publishing, Mattews NC, 2002). From the values of dielectric loss (tan δ) of various solvents at a wave frequency of 2450 MHz and 25 ° C., the ease of absorbing microwave energy for the various solvents is defined.

  Among them, a solvent having a tan δ of 0.1 or less is generally described in the following non-patent literature (C. Olive Kappe, Controlled Microwave Heating in Modern organic Synthesis) as a solvent that does not absorb or hardly absorb microwaves. Specific examples include chlorobenzene, chloroform, acetonitrile, ethyl acetate, acetone, tetrahydrofuran, dichloromethane, toluene, xylene, hexane, cyclohexane and the like.

  The reason why these solvents are preferable is that by using a nonpolar solvent that does not absorb or hardly absorb microwave energy, the absorption of microwaves of alcohol and carboxylic acid, which are reaction substrates, is not hindered and efficient. It can be mentioned that it becomes a reaction. In addition, in the ester condensation reaction, it is desirable to use a solvent that forms an azeotrope with water produced by this reaction, and an organic solvent that azeotropes water to promote dehydration.

  A solvent having a boiling point of 80 ° C. to 120 ° C. is preferable as the solvent. Specific examples include benzene, toluene, and cyclohexane, and more preferred are toluene and cyclohexane.

  The radical polymerization initiator (B) of the present invention will be described. The radical polymerization initiator (B) of the present invention is a compound that generates radicals that are active species upon irradiation with active energy rays such as ultraviolet rays, and the generated radicals promptly react with the reactive compound (A). A radical polymerization reaction can be initiated and cured.

As the radical polymerization initiator (B) 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 (BASF), Adekaoptomer N1414, Adekaoptomer N1717, Esacure1001M (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”. ) ”, Vol. 10, page 1307 (1977) Various onium compounds including onium compounds, azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, Of imaging science (J.IMAG.SCI.), Vol. 30, page 174 (1986), titanocenes described in JP-A No. 61-151197, “coordination chemistry. Review (COORDINATION CHEMISTRY REVIEW), Vol. 84, pages 85 to 277 (1988) and transition metal complexes containing transition metals such as ruthenium described in JP-A-2-182701, JP-A-3-209477 Aluminate complexes described in JP-A No. 2-157760, borate compounds described in JP-A-2-157760, JP-A No. 55 2,127-55050 and JP-A-60-202437, 2,4,5-triarylimidazole dimer, carbon tetrabromide and organic halogen compounds described in JP-A-59-107344, JP-A-5 Sulfonium complexes or oxosulfonium complexes described in JP-A-255347, aminoketone compounds described in JP-A-54-99185, JP-A-63-264560 and JP-A-10-29977, JP-A-2001-264530, JP 2001-261661, JP 2000-80068, JP 2001-233842, JP 2004-534797, JP 2006-342166, JP 2008-094770, JP 2009-40762, JP Open 2010-15025, JP 2010-18 279, JP 2010-189280 A, JP 2010-526846, JP 2010-527338, JP 2010-527339, USP 3558309 (1971), USP 4202697 (1980) and JP 61- Examples thereof include oxime ester compounds described in Japanese Patent No. 24558.

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

  These can be used alone or in combination of two or more, and can be mixed and used arbitrarily according to the properties required for the cured product. The amount used when using these radical polymerization initiators (B) is , Contained in the range of 0.01 to 200 parts by weight, and contained in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the radical polymerizable compounds described below that can be used in combination with the reactive compound (A). It is preferable.

  When the amount of the radical polymerization initiator (B) 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 cannot be obtained. . On the other hand, when the amount of the radical polymerization initiator (B) used exceeds 200 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. There is.

  In the polymerizable composition of the present invention, a radical polymerizable compound can be used in order to improve the curability by the polymerization reaction. The radical polymerizable compound in the present invention means a compound having at least one skeleton capable of radical polymerization in the molecule and other than the reactive compound (A). 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 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. Furthermore, urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes and other acrylates, methacrylates, arylates, acid amides, styrenes, etc. Vinyl compounds, radical polymerizable cyclic compounds, oligomers, prepolymers, and the like, but the present invention is not limited thereto. Below, the specific example of the radically polymerizable compound in this invention is given.

  Among radically polymerizable compounds, 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 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, tricyclodecane dimethylol Diacrylate, isocyanuric acid EO-modified diacrylate, 2-hydroxy-1,3-diacryloxypropane.

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 radically polymerizable compounds, the following compounds can be exemplified as methacrylates.

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, 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 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 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.

  Among the radical polymerizable compounds, examples of the arylate include the following compounds.

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

  Among the radical polymerizable compounds, 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.

  Among radically polymerizable compounds, 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, 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, N-vinylpyrrolidone etc.

  Said radically polymerizable compound can be easily obtained as a commercial product 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., Shin 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 Nippon Kayaku Co., Ltd. “Acrylic acid / methacrylic acid ester monomer” series manufactured by Nippon Shokubai Co., Ltd., Nippon Synthetic Chemical Industry Co., Ltd. Made in "Nichigo-UV Shiko urethane acrylate oligomer" series, Shin-Etsu vinyl acetate Co., Ltd. "carboxylic vinyl ester monomers" series include Co. Kohjin Co. "functional monomer" 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 mentioned as radically polymerizable compounds.

  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, p. 3169 (1979). Vinylcyclopropanes, 1-phenyl-2-vinylcyclopropanes described in Makromol. 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 (J .Polym.Sci.Polym.Lett.Ed.), Vol. 21, p. 4331 (1983), 2-phenyl-3-vinyloxiranes, The 50th Annual Meeting of the Chemical Society of Japan 2,3-Divinyloxiranes described in the Proceedings collection, page 1564 (1985).

  Examples of the 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 Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), Vol. 21, p. 373 (1983) Dioxolanes, Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.) Described in Polypre. Preprints, Volume 34, page 152 (1985). 20, 361 (1982), Macromolecular Chemie, Volume 183, 1913 (1982) and Macromolecular Chemie, 186, 1543 (1985) 2-methylene-4-phenyl-1,3-dioxepane, Macromolecules, 15, 1711 (1982) 4,7-dimethyl 2-Methylene-1,3-dioxepane, 5,6-benzo-2-methylene-1,3-diosepane described in Polymer Prepreprints, Vol. 34, 154 (1985).

  Further, examples of the radical polymerizable compound include those described in the following documents. For example, edited by Shinzo Yamashita et al., “Cross-linking agent handbook” (1981, Taiseisha), Kiyoto Kato edition, “UV / EB curing handbook (raw material edition)”, (1985, Polymer publication society), Radtech Research Association, 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), Radtech Study Group, “Application and Market of UV / EB Curing Technology” (2002, CMC).

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

  In the polymerizable composition of the present invention, those called oligomers and prepolymers can be used in addition to the above monomers. 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, manufactured by Negami Kogyo Co., Ltd. 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.

  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 the resin having no skeleton capable of radical polymerization in the molecule include, for example, alkyd resin, polyester resin, polyvinyl chloride, poly (meth) acrylate resin (combination of polyacrylate resin and polymethacrylate resin). Poly (meth) acrylic ester 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 ester Fat, polyvinyl amide resin, novolak resin, phenol resin, supervised by Kiyoshi Akamatsu "New Technology of Photosensitive Resin" (CMC, 1987) and "Chemical Products of 10188", pages 657-767 (Chemical Industry Daily) 1988), 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 has 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 and (meth) acrylic acid, and a vinyl monomer that can be copolymerized with these. 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.

  As the methacrylic acid ester, methyl methacrylate, ethyl methacrylate, methacrylic acid-n-propyl, isopropyl methacrylate, methacrylic acid-n-butyl, methacrylic acid-t-butyl, methacrylic acid- C1-C18 alkyl esters of methacrylic acid such as 2-ethylhexyl, hydroxyl-containing methacrylic esters such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, and hydroxybutyl methacrylate, dimethyl methacrylate Nitrogen-containing methacrylates such as aminoethyl and diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, morpholyl methacrylate, isobornyl methacrylate, cyclohexyl methacrylate It can be exemplified other methacrylic acid esters such as Le, but is not limited thereto.

  Examples of the vinyl monomer that can be copolymerized with (meth) acrylic acid ester, (meth) acrylic acid, and 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, CMC) Examples include, but are not limited to, the dyes and sensitizers described in “Special Functional Materials” (1986, CMC) edited by Tadaburo Ikemori et al. For light from the ultraviolet to the near infrared region Examples thereof include dyes and sensitizers that exhibit absorption, and two or more of these 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). Etc. It can gel, but not limited thereto.

  The use amount of the sensitizer of the present invention is preferably in the range of 0.01 to 100 parts by weight, more preferably in the range of 0.1 to 50 parts by weight with respect to 100 parts by weight of the radical polymerization initiator (B). .

  The polymerizable composition of the present invention can be used by adding a solvent as necessary for the purpose of improving the coating suitability including viscosity adjustment. The solvent that can be used by adding to the polymerizable composition of the present invention is not particularly limited, and any solvent can be used as long as it can be uniformly mixed with the polymerizable composition of the present invention. For example, known solvents such as alcohols, ketones, esters, aromatics, hydrocarbons, and halogenated hydrocarbons may be used, but the invention is not limited thereto.

  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 (B).

  Moreover, the polymerization composition of this invention can add the polymerization accelerator represented by amine, thiol, a disulfide, etc. and a chain transfer agent in order to further accelerate | stimulate superposition | polymerization.

  Specific examples of the polymerization accelerator and chain transfer agent that can be added to the polymerizable composition of the present invention include, for example, ethyl 4-dimethylaminobenzoate, 4-dimethylaminoacetophenone, N-phenylglycine, N, N-dimethyl. Aniline, N, N-diethylaniline, butylamine, dibutylamine, tributylamine, trimethylamine, triethylamine, triisopropylamine, octyldimethylamine, triethanolamine, cyclohexylamine, dicyclohexylamine, benzyldimethylamine, piperidine, piperazine, morpholine, Amines such as pyridine, phenyldiethanolamine, N, N-dimethyl-p-toluidine, N, N-dihydroxyethylaniline, 2- (dimethylamino) ethyl aniline acrylate, USP No. 44143 No. 2 and thiols described in JP-A No. 64-13144, disulfides described in JP-A-2-291561, thiones described in USP No. 3558322 and JP-A No. 64-17048, Examples thereof include O-acylthiohydroxamate and N-alkoxypyridinethiones described in JP-A-2-291560.

  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, phosphine, phosphonate, phosphite and other oxygen removers 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, irradiation of active energy rays with a light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable as a light source for applying energy. 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 Rikagaku Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

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

  The member for printing or applying the polymerizable composition of the present invention can be appropriately selected from the group consisting of glass, plastic, metal and paper. Furthermore, a composite member composed of a plurality of members can also be selected. These members 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 material 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 material 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 Oxymethylene-based polymers, polyepoxy-based polymers, and transparent polymers such as blends of the aforementioned polymers are also included. In particular, those having a low birefringence are preferably used.

  The pigment used for the active energy ray-curable inkjet ink using the polymerizable composition of the present invention will be described.

  Examples of the pigment used in the active energy ray-curable inkjet ink used in the present invention include pigments conventionally used in inkjet inks, such as achromatic pigments such as carbon black, titanium oxide, and calcium carbonate, or chromatic pigments. An organic pigment is mentioned. These may be used alone or may be a system in which two or more kinds are mixed at an arbitrary ratio in order to improve the properties for the purpose of adjusting hue and density.

  Specific organic pigments include, for example, insoluble azo pigments such as toluidine red, toluidine maroon, Hansa yellow, benzidine yellow, pyrazolone red, soluble azo pigments such as ritole red, heliobordeaux, pigment scarlet, and permanent red 2B, alizarin, Derivatives from vat dyes such as indanthrone and thioindigo maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, and perylene organic pigments such as perylene red and perylene scarlet , Isoindolinone organic pigments such as isoindolinone yellow and isoindolinone orange, and pyranthrone systems such as pyranthrone red and pyranthrone orange Machine pigments, thioindigo organic pigments, condensed azo organic pigments, benzimidazolone organic pigments, quinophthalone organic pigments such as quinophthalone yellow, isoindoline organic pigments such as isoindoline yellow, and other pigments such as Flavanthrone Yellow, Examples include various known and publicly known organic pigments such as acylamide yellow, nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianslaquinonyl red, and dioxazine violet.

  When organic pigments are exemplified by color index (C.I.) numbers, CI pigment yellows 12, 13, 14, 17, 20, 24, 74, 83, 8893, 109, 110, 117, 120, 125 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185, CI Pigment Orange 16, 36, 43, 51, 55, 59, 61, CI Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 123, 149, 168, 177, 180, 192, 202, 206, 215, 216, 217, 220, 223, 224, 226, 227, 228, 238, 240, CI Pigment Violet 19, 23, 29, 30, 37, 40, 50, C.I. Mento Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, CI Pigment Green 7, 36, CI Pigment Brown 23, 25, 26, etc. It is done.

  Specific examples of carbon black include “Special Black 350, 250, 100, 550, 5, 4, 4A, 6” “Printex U, V, 140 U, 140 V, 95, 90, 85, 80, 75, 55, manufactured by Degussa. 45, 40, P, 60, L6, L, 300, 30, 3, 35, 25, A, G ", Cabot's" REGAL 400R, 660R, 330R, 250R "," MOGUL E, L ", Mitsubishi Chemical “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.

  Specific examples of titanium oxide include “Taipeku CR-50, 50-2, 57, 80, 90, 93, 95, 953, 97, 60, 60-2, 63, 67, 58, 58- manufactured by Ishihara Sangyo Co., Ltd. 2, 85 "" Tipekes R-820, 830, 930, 550, 630, 680, 670, 580, 780, 780-2, 850, 855 "," Tipekes A-100, 220 "," Tipekes W-10 "," Tipekes " PF-740, 744 "" TTO-55 (A), 55 (B), 55 (C), 55 (D), 55 (S), 55 (N), 51 (A), 51 (C) " "TTO-S-1, 2", "TTO-M-1, 2", "Titanics JR-301, 403, 405, 600A, 605, 600E, 603, 805, 806, 701, 800, 808" manufactured by Teika "Titanic EN-1, C, 3, 4, 5 ", and a titanium oxide-based inorganic pigments such as DuPont" Taipyua R-900,902,960,706,931 ".

  Among the above pigments, quinacridone organic pigments, phthalocyanine organic pigments, benzimidazolone organic pigments, isoindolinone organic pigments, condensed azo organic pigments, quinophthalone organic pigments, isoindoline organic pigments, etc. are light-resistant. Is preferable because it is excellent. The organic pigment is preferably a fine pigment having an average particle diameter of 10 to 150 nm as measured by laser scattering. When the average particle diameter of the pigment is less than 10 nm, the light resistance is lowered due to the small particle diameter, and when it exceeds 150 nm, it is difficult to maintain stable dispersion, and the pigment is likely to precipitate.

  The organic pigment can be refined by the following method. That is, a mixture comprising at least three components of an organic pigment, a water-soluble inorganic salt that is at least 3 times the weight of the organic pigment, and a water-soluble solvent is made into a clay-like mixture, and is kneaded strongly with a kneader or the like and then refined. And stirred with a high speed mixer or the like to form a slurry. Next, filtration and washing of the slurry are repeated to remove the water-soluble inorganic salt and the water-soluble solvent. In the miniaturization step, a resin, a pigment dispersant and the like may be added.

  Examples of the water-soluble inorganic salt include sodium chloride and potassium chloride. These inorganic salts are used in the range of 3 times by weight or more, preferably 20 times by weight or less of the organic pigment. When the amount of the inorganic salt is less than 3 times by weight, a treated pigment having a desired size cannot be obtained. On the other hand, if the amount is more than 20 times by weight, the washing process in the subsequent step is great, and the substantial amount of the organic pigment is reduced.

  The water-soluble solvent is an organic solvent and a water-soluble inorganic salt that is used as a crushing aid, and is used for efficient crushing efficiently, especially if it is a solvent that dissolves in water. Although not limited, a high boiling point solvent having a boiling point of 120 to 250 ° C. is preferable from the viewpoint of safety because the temperature rises during kneading and the solvent is easily evaporated. Examples of water-soluble solvents include 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, low molecular weight Examples thereof include polypropylene glycol.

  In the present invention, the pigment is used in the active energy ray-curable inkjet ink in the range of 1 to 30% by weight in order to obtain a sufficient concentration and sufficient light resistance.

  In the present invention, it is preferable to add a pigment dispersant in order to improve the dispersibility of the pigment and the storage stability of the ink. 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 nonylphenyl ether)”, “Acetamine 24 (coconut amine acetate), 86 (stearyl amine acetate)”, “Abisia” Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000, “Nikkor T106 (polyoxy) manufactured by Nikko Chemical Co., Ltd. Ethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl tetraoleate), “Ajisper PB821, 822, 824” manufactured by Ajinomoto Fine Techno Co., etc.

  The addition amount of the pigment dispersant is not particularly limited, but it is preferably used in the range of 0.1 to 10% by weight in the active energy ray-curable inkjet ink.

  In order to further improve the dispersibility of the pigment and the storage stability of the ink, the active energy ray-curable inkjet ink of the present invention preferably contains an acidic derivative of an organic pigment when the pigment is dispersed.

  The active energy ray-curable inkjet ink of the present invention is produced by well dispersing the pigment together with the reactive compound (A), the radical polymerizable compound, and the pigment dispersant using an ordinary dispersing machine such as a sand mill. It is preferable to prepare a concentrated solution having a high pigment concentration in advance and dilute with the reactive compound (A) or the radical polymerizable compound. Sufficient dispersion is possible even with dispersion by a normal disperser. Therefore, excessive dispersion energy is not required, and a large amount of dispersion time is not required. An ink having excellent properties is prepared. The ink is preferably filtered through a filter having a pore size of 3 μm or less, and more preferably 1 μm or less.

The active energy ray-curable ink-jet ink of the present invention is preferably prepared so that the viscosity at 25 ° C is as high as 5 to 50 mPa · s. An ink having a viscosity of 5 to 50 mPa · s at 25 ° C. exhibits stable ejection characteristics, particularly from a head having a normal frequency of 4 to 10 KHz to a head having a high frequency of 10 to 50 KHz.
When the viscosity is less than 5 mPa · s, a decrease in the follow-up property of the discharge is recognized in the high-frequency head. When the viscosity exceeds 50 mPa · s, even if a mechanism for reducing the viscosity by heating is incorporated in the head, the discharge itself A drop occurs, the ejection stability becomes poor, and the ejection cannot be performed at all.

  In addition, the active energy ray-curable ink-jet ink of the present invention preferably has an electric conductivity of 10 μS / cm or less and no electrical corrosion inside the head in a piezo head. Further, in the continuous type, it is necessary to adjust the conductivity by the electrolyte. In this case, it is necessary to adjust the conductivity to 0.5 mS / cm or more.

  In order to use the active energy ray-curable ink jet ink of the present invention, the ink jet ink is first supplied to the printer head of the printer for the ink jet recording system, and discharged from the printer head onto the substrate, and then ultraviolet rays, electron beams, etc. Of active energy rays. Thereby, the polymerizable composition on the printing medium is quickly cured.

  Examples of the substrate that can be used in the present invention include non-coated paper, coated paper, and non-absorbent support.

  Specific examples of the non-absorbing support include the above-mentioned various non-absorbing plastic materials and films thereof. Particularly, various plastic films include, for example, PET film, OPS film, OPP film, ONy film, PVC. Although a film, PE film, and TAC film can be mentioned, it is not limited to these. Metals and glasses can also be used.

  The active energy ray-curable ink-jet ink obtained in the present invention can be printed or cured using the same technique as before.

  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.

<Synthesis Example 1> Reactive Compound (A): Synthesis of Compound (1) A 1-L four-necked flask was charged with 40 g of DA-111 (manufactured by Nagase ChemteX) and 300 mL of tetrahydrofuran, and a mixed solution of 120 g of acetic anhydride and 140 g of pyridine was prepared. The solution was added dropwise at room temperature over 10 minutes. Then, after stirring at the same temperature for 7 hours, chloroform 200mL and saturated saline 200mL were added to the reaction liquid mixture, and extraction was performed. The extracted organic layer was washed sequentially with 200 mL of saturated brine and 200 mL of 8% aqueous sodium hydrogen carbonate solution. The organic layer was added with 40 g of sodium sulfate and stirred, followed by filtration. The obtained solution was concentrated by a rotary evaporator to obtain 44 g of a colorless liquid.
The compound was identified by 1H-NMR (JEOL, JMTC-400 / 54 / SS) and GC / MS (Agilent Technologies, 6890N).

<Synthesis Example 2> Reactive Compound (A): Synthesis of Compound (2) In a 1 L four-necked flask, 40 g of DA-111 (manufactured by Nagase ChemteX), 130 g of imidazole and 300 mL of tetrahydrofuran were charged, and 140 g of trimethylchlorosilane was added at room temperature. Added dropwise over a period of minutes. Then, after stirring at the same temperature for 7 hours, chloroform 200mL and saturated saline 200mL were added to the reaction liquid mixture, and extraction was performed. The organic layer was added with 40 g of sodium sulfate and stirred, followed by filtration. The obtained solution was concentrated by a rotary evaporator to obtain 46 g of a colorless liquid. The compound was identified by 1H-NMR and GC / MS.

<Example 1> Preparation of polymerizable composition 95 parts by weight of the compound (1) as the reactive compound (A) and 5 parts by weight of Irgacure 369 (photopolymerization initiator manufactured by BASF) as the radical polymerization initiator (B) The polymerizable composition was obtained by blending. Using the resulting polymerizable composition, viscosity measurement, curability test and storage stability test were carried out by the following methods. The results are shown in Table 2.

<Examples 2 to 30>
A polymerizable composition was obtained in the same manner as in Example 1 except that the compounds shown in Table 2 were used as the reactive compound (A). A curability test and a storage stability test were performed using the obtained polymerizable composition. The results are shown in Table 2.

<Comparative Examples 1-4>
A polymerizable composition was obtained in the same manner as in Example 1 except that the polymerizable compounds shown in Table 3 were used instead of the reactive compound (A). A curability test and a storage stability test were performed using the obtained polymerizable composition. The results are shown in Table 3.

<Viscosity measurement>
Measurement was performed using an E-type viscometer. The active energy ray-curable ink-jet ink of the present invention is preferably prepared with a high viscosity at 25 ° C. of 5 to 50 mPa · s, and for this purpose, the viscosity of the polymerization composition needs to be 5 to 15 mPa · s. In particular, 5 to 10 mPa · s is preferable.

Determination method ◎: 5 to 10 mPa · s
○: 10 to 15 mPa · s
×:> 15 mPa · s

<Curing test>
The prepared polymerizable composition was added to a K control coater No. After coating on a PET film using 2 bars so that the wet film thickness becomes 12 μm, the coated material is applied with a belt conveyor type ultraviolet irradiation device (high pressure mercury lamp 100 W / cm1 lamp), and the conveyor speed is 50 m. Irradiation with ultraviolet rays as active energy rays was performed at / min. The surface of the reaction cured product after irradiation was rubbed with a cotton cloth, and irradiation was repeated until the film was not damaged, and the curability was determined. The smaller the number of irradiations, the better the curability.

<Storage stability test>
After the prepared polymerizable composition was stored at 70 ° C. for 5 days, the state of the polymerized composition was visually observed.

Judgment method ◎: No change ×: Increased viscosity

  It has been clarified that the polymerizable composition of the present invention can provide a cured product having low viscosity but high curability by active energy rays and excellent storage stability. Moreover, when the compound which has the acryl group which is the reactive substituent which this invention's reactive compound (A) has, and an allyl ether group or a biryl ether group is used (Comparative Examples 1, 2, and 3), it is curable. Is insufficient. Furthermore, in DA-111 (Comparative Example 4) which is a compound having the same skeleton as the reactive compound (A) and having an acrylic group and a vinyl ether group, the curability is improved, but the viscosity is high, It was found that the storage stability was also insufficient.

  As shown in the results of the above-described curability test and storage stability test, it was revealed that the polymerizable composition of the present invention has low viscosity, high curability, and excellent storage stability. Therefore, the polymerizable composition 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 inkjet ink>

  First, yellow, magenta, cyan, and black pigment dispersions composed of a pigment, a pigment dispersant, and a radical polymerizable compound were prepared.

<Preparation of pigment dispersion a>
The formulation of pigment dispersion a is shown in Table 4. After stirring the radical polymerizable compound and the polymer pigment dispersant and confirming that the polymer dispersant was completely dissolved, the pigment was added and obtained after stirring until uniform with a high speed mixer or the like. The 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 5. 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 formulation of pigment dispersion c is shown in Table 6. After stirring the radical polymerizable compound and the polymer pigment dispersant and confirming that the polymer dispersant was completely dissolved, the pigment was added and obtained after stirring until uniform with a high speed mixer or the like. The mill base was dispersed with 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 7. After stirring the radical polymerizable compound and the polymer pigment dispersant and confirming that the polymer dispersant was completely dissolved, the pigment was added and obtained after stirring until uniform with a high speed mixer or the like. The mill base was dispersed with a horizontal sand mill for about 1.5 hours to prepare a yellow pigment dispersion.

<Example 31> Preparation of inkjet ink 55.5 parts by weight of the compound (1) as the reactive compound (A), 11.4 parts by weight of the pigment dispersion a as the pigment dispersion, and 2- 25 parts by weight of phenoxyethyl acrylate, 0.1 part by weight of BYK-331 (silicon resin manufactured by BYK Chemi) as a surface conditioner, and 5 parts by weight of Irgacure 369 (photopolymerization initiator manufactured by BASF) as a radical polymerization initiator And an ink jet ink was obtained. Using the obtained ink-jet ink, viscosity measurement, curability test and storage stability test were carried out by the following methods. The results are shown in Table 8.

<Examples 32-47 and Comparative Examples 5-8>
As the reactive compound (A), an inkjet ink was prepared according to the formulation shown in Table 8. Using the obtained ink-jet ink, viscosity measurement, curability test and storage stability test were carried out by the following methods. The results are shown in Table 8.

<Viscosity measurement>
Measurement was performed using an E-type viscometer. The active energy ray-curable inkjet ink of the present invention is preferably prepared so that the viscosity at 25 ° C. is 5 to 50 mPa · s.

Determination method ◎: 5 to 50 mPa · s
×:> 50 mPa · s

<Curing test>
The prepared inkjet ink was printed on a PET film with a UV-IJ printer. This printed matter was irradiated with ultraviolet rays (high pressure mercury lamp 120 W / cm1), and then judged by a conveyor speed (m / min) at which the film was not rubbed by rubbing with a cotton cloth. The results are shown in Table 8. The conveyor speed of the ultraviolet irradiation device indicates that the larger the number, the better the curability.

<Storage stability test>
The state of the inkjet inks A to I after the prepared inkjet inks A to I were stored at 70 ° C. for 5 days was visually observed. The results are shown in Table 8.

Judgment method ◎: No change ×: Increased viscosity

Table 8

  Ink-jet inks using the polymerizable composition of the present invention (Examples 31 to 47) not only have a viscosity of 5 to 50 mPa · s showing stable ejection characteristics, but also have high curability and storage by irradiation with active energy rays. It was found to be excellent in stability. On the other hand, when the compound having an acrylic group which is a reactive substituent of the reactive compound (A) of the present invention and an allyl ether group or a biryl ether group alone (Comparative Examples 5, 6, and 7) is cured. Insufficient sex. Furthermore, DA-111 (Comparative Example 8), which is a compound having the same skeleton as the reactive compound (A) and having an acryl group and a vinyl ether group, is improved in curability but increases in viscosity and is further stable in storage. It was found that the sex was insufficient.

  It became clear that the polymerizable composition of the present invention can be used for inkjet inks that achieve both high curability and high storage stability when irradiated with active energy rays.

  An object of the present invention is to provide a polymerizable composition having a low viscosity, an extremely fast curing rate by irradiation with active energy rays, a low odor and excellent storage stability, and an active energy ray curable inkjet ink using the same. It is. The reactive compound of the present invention is a compound having an acrylic group and an allyl group in the same molecule, and by using this compound, a polymerizable composition having excellent curability, low odor, and storage stability. Was able to provide. Therefore, in particular, it can be expected to be used as an active energy ray-curable ink-jet ink that improves reaction curability while maintaining dischargeability without increasing viscosity and is excellent in storage stability.

  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 polymerizable composition comprising a reactive compound (A) containing a compound represented by the following general formula (1) and / or a compound represented by the following general formula (2), and a radical polymerization initiator (B).
General formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group,
R ² represents a group represented by the following general formula (3) or the following general formula (4). )
General formula (2)

(Wherein R ³ represents a hydrogen atom or a methyl group,
R ⁴ represents a group represented by the following general formula (3) or the following general formula (4). )
General formula (3)

(In the formula, R ⁵ represents an alkyl group having 1 to 10 carbon atoms. The alkyl group may be interrupted by an ether bond.)
General formula (4)

(In formula, R < ⁶ > -R < ⁸ > represents a C1-C10 alkyl group or a C1-C10 alkyloxy group each independently.)   2. The polymerizable composition according to claim 1, wherein the radical polymerization initiator (B) is a photo radical polymerization initiator.   An active energy ray-curable inkjet ink comprising the polymerizable composition according to claim 2.   A method for producing a printed matter, wherein the active energy ray-curable inkjet ink according to claim 3 is printed and cured by irradiation with active energy rays.   Printed matter obtained by the production method according to claim 4.