JP6028619B2 - Reactive compound, polymerizable composition using the same, and active energy ray curable inkjet ink using the same - Google Patents

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 composition for image recording material using PUSEL, various devices, etc., it relates to a reactive compound for obtaining a polymer having good physical properties and a polymerizable composition using the same, particularly curability, The present invention relates to an active energy ray-curable ink jet ink excellent in low odor, storage stability, and 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 reactively cured with ultraviolet rays, and are environmentally friendly by reducing volatile solvents compared to conventional water-based or solvent-based non-curable inks. In recent years, attention has been paid to the fact that printing on a substrate without quick drying, odor reduction, and ink absorption is possible and the substrate selectivity is high, 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.

  Active energy ray-curable inkjet inks that combine acrylate compounds and vinyl ether compounds with different reactivity have been proposed as a method for improving the curability associated with the reaction without increasing the viscosity of the ink. There remains a problem in performance (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).

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 reactive compound that is rich in reactivity and excellent in storage stability. A further object of the present invention is to provide a polymerizable composition having an extremely high curing rate with reaction, a low odor, and excellent storage stability, and an active energy ray-curable inkjet ink using the same.

  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 relates to a reactive compound (A) represented by the following general formula (1).

General formula (1)

(In the formula, m represents an integer of 0 to 4, n represents 0 or 1, and when m is 0, n is also 0. R ₁ represents a hydrogen atom or a methyl group.)

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

  The present invention also relates to the polymerizable composition, wherein the radical polymerization initiator (B) is a photo radical polymerization 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, a reactive compound and a polymerizable composition excellent in curability, low odor, and storage stability can be provided, and the curability associated with the reaction can be maintained while maintaining the dischargeability without increasing the viscosity. It was possible to provide an active energy ray-curable inkjet ink that was improved and excellent in 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) of the present invention is represented by two (meth) acrylic groups [acrylic group and methacrylic group are collectively referred to as “(meth) acrylic group” in the same molecule. The same applies below. And a vinyl ether group. By having this basic structure, it is a compound having a normally conflicting function of being highly reactive and excellent in storage stability.

  Furthermore, having a vinyl ether group is also excellent in that it has a low viscosity as compared with a reactive compound having two to three (meth) acryl groups having a similar structure.

General formula (1)

(In the formula, m represents an integer of 0 to 4, n represents 0 or 1, and when m is 0, n is also 0. R ₁ represents a hydrogen atom or a methyl group.)

  The substituent in the general formula (1) will be described.

The substituent R ₁ in the general formula (1) represents a hydrogen atom or a methyl group.

  In the general formula (1), m is an integer from 0 to 4. When m exceeds 4, the viscosity of the reactive compound (A) of the present invention becomes too high, resulting in inconvenience during production and use.

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

  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 heteropolyacid 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 mordenite type, X type, Y type, β type, and ZSM-5 type.

  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, and therefore, the generation of by-products that can occur during the 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 (manufactured 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 which 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 esterification reaction, it is desirable to use a solvent that forms an azeotrope with water produced by this reaction, and to use 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.

  From the viewpoint of easy availability of raw materials and cost, the preferred synthesis method of the reactive compound (A) of the present invention has glycerol monovinyl ether and one or more carboxyl groups in the molecule, and has a (meth) acryl group. A reaction using an α, β-unsaturated double bond-containing compound is preferred.

  Specific examples of the α, β-unsaturated double bond-containing compound having one or more carboxyl groups in the molecule of the present invention include (meth) acrylic acid [a combination of acrylic acid and methacrylic acid "(meta ) Acrylic acid ". The same applies below. ], 2-carboxyethyl (meth) acrylate, 3-carboxypropyl (meth) acrylate, and 4-carboxybutyl (meth) acrylate.

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

  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 a radical active species that initiates a polymerization reaction by irradiation with active energy rays, and a conventionally known polymerization initiator can be used. Specifically, 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) benzyl Acetophenones such as phenyl] -2-methylpropan-1-one; benzoin, benzoin methyl ether, benzoin ethyl ether Benzoins such as benzoin isopropyl ether and benzoin isobutyl ether; phosphines such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide; Examples include glyoxylic 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, Adekaoptomer N5050 (ADEKA) Esacure 1001M (Lamberti), Japanese Examined Patent Publication Nos. 59-1281, 61-9621, and Japanese Unexamined Patent Publication No. 60-60. No. 04 triazine derivatives, organic peroxides described in JP-A-59-1504 and JP-A-61-243807, JP-B 43-23684, JP-B 44-6413, JP-B No. 47-1604 and diazonium compound described in US Pat. No. 3,567,453, organic azide compounds described in USP 2,848,328, USP 2,852,379 and USP 2,940,853, Japanese Patent Publication No. 36-22062 Ortho-quinonediazides described in Japanese Patent Publication No. 37-13109, 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, No. 1 Various onium compounds including iodonium compounds described on page 07 (1977), azo compounds described in JP-A-59-142205, JP-A-1-54440, European Patent No. 109851, and European Patent No. No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Volume 30, page 174 (1986), described in JP-A-61-151197. Transition metals containing transition metals such as ruthenium described in titanocenes, "COORDINATION CHEMISTRY REVIEW", Vol. 84, pages 85-277 (1988) and JP-A-2-182701 Complexes, aluminate complexes described in JP-A-3-209477, JP-A-2-157760 Borate compounds, 2,4,5-triarylimidazole dimers described in JP-A-55-127550 and JP-A-60-202437, carbon tetrabromide and JP-A-59-107344. Organic halogen compounds described in JP-A-5-255347, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, aminoketone compounds described in JP-A-54-99185, JP-A-63-264560, and JP-A-10-29977 JP-A-2001-264530, JP-A-2001-261761, JP-A-2000-80068, JP-A-2001-233842, JP-T-2004-534797, JP-A-2006-342166, JP-A-2008. -094770, JP2009-40762, JP2010- 5025, JP2010-189279, JP2010-189280, JP2010-526846, JP2010-527338, JP2010-527339, USP3558309 (1971), USP4202697 (1980) And oxime ester compounds described in JP-A No. 61-24558.

  Among these, Preferably, the acetophenones represented by aminoketone, phosphines, and an oxime ester compound are mentioned.

  These can be used singly or in combination, and can be arbitrarily mixed and used depending on the properties required for the reaction cured product, and the amount used when using these radical polymerization initiators (B) 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 polymerization composition containing the later-described radical polymerizable compound that can be used in combination with the reactive compound (A), It is preferably contained in the range of parts by weight.

  In the polymerizable composition of the present invention, a radical polymerizable compound can be used in order to improve the curability associated with the reaction. The radical polymerizable compound in the present invention means 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 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. Further, urethane acrylates, acrylonitrile, styrene derivatives, various unsaturated polyesters, unsaturated polyethers, unsaturated polyamides, unsaturated polyurethanes and the like can be mentioned, but the present invention is not limited to these. Below, the specific example of the radically polymerizable compound in this invention is given.

Examples of acrylates:
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.

Examples of 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.

Examples of arylates:
Allyl glycidyl ether, diallyl phthalate, triallyl trimellitate, isocyanuric acid triarylate.

Examples of acid amides:
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.

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

Examples of other vinyl 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, the cyclic compound shown below is also mentioned as a radically polymerizable compound.
Examples of three-membered ring compounds:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Vol. 17, 3169 (1979), vinylcyclopropanes, Macromolecular Chemie Rapid Communication (Makromol. Chem. Rapid Commun.), Volume 5, p. 63 (1984), 1-phenyl-2-vinylcyclopropanes, Journal of Polymer Science Polymer Chemistry Edition ( J. Polym. Sci. Polym. Chem. Ed.), 23, 1931 (1985) and Journal of Polymer Science Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed. 21), 4331 (1983), 2-phenyl-3-vinyloxiranes, Proceedings of the 50th Annual Meeting of the Chemical Society of Japan, 1564 (1985) Mounting No 2,3-vinyl oxirane.

Examples of cyclic ketene acetals:
Journal of Polymer Science Polymer Chemistry Edition (J.Polym.Sci.Polym.Chem.Ed.), Volume 20, p. 3021 (1982) and Journal of Polymer Science Polymer Letter Edition (J.Polym.Sci.Polym.Lett.Ed.), Vol. 21, 373 (1983), 2-methylene-1,3-dioxepane, polymer pre-prints (Polym. Preprints), No. 34, 152 (1985), dioxolanes, Journal of Polymer Science, Polymer Letter Edition (J. Polym. Sci. Polym. Lett. Ed.), 20, 361 (1982) 2) described in Macromolecular Chemie, 183, 1913 (1982) and Macromolecular Chem., 186, 1543 (1985). -Methylene-4-phenyl-1,3-dioxepane, 4,7-dimethyl-2-methylene-1,3-dioxepane, polymer described in Macromolecules, Vol. 15, page 1711 (1982) -5,6-benzo-2-methylene-1,3-diosepane described in Polypre. Preprints, Vol. 34, page 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.

  As the radical polymerizable compound contained in the polymerizable composition of the present invention, in addition to the above monomers, what are 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.

  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 alkyd resin, polyester resin, polyvinyl chloride, poly (meth) acrylic ester, polyepoxy resin, polyurethane resin, cellulose derivative (for example, ethyl cellulose, acetic acid). Cellulose, nitrocellulose), vinyl chloride vinyl acetate copolymer, polyamide resin, polyvinyl acetal resin, diallyl phthalate resin, silicone resin, and synthetic rubber such as butadiene-acrylonitrile copolymer. These resins can be used alone or in combination of two or more thereof.

  Furthermore, the polymerizable composition of the present invention may be used by adding a carboxyl group-containing resin shown below for the purpose of using it for image formation as a so-called alkali development type photoresist material. 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 is mentioned. These copolymers may be used alone or in combination of two or more.

  Here, as the acrylic ester, an alkyl ester having 1 to 18 carbon atoms of acrylic acid such as methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, etc. Hydroxyl group-containing acrylic esters such as hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, nitrogen-containing acrylic esters such as dimethylaminoethyl acrylate, diethylaminoethyl acrylate, glycidyl acrylate, tetrahydrofurfuryl acrylate, morpholyl Other acrylic esters such as acrylate, isobornyl acrylate, cyclohexyl acrylate, etc. That, without being limited thereto.

  Examples of the methacrylic acid ester include alkyl methacrylates having 1 to 18 carbon atoms of methacrylic acid such as methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate and the like. Hydroxyl methacrylates such as hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, etc., nitrogen-containing methacrylates such as dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, morpholy Methacrylate, isobornyl methacrylate, cyclohexyl methacrylate, etc. Of although other methacrylic acid esters can be exemplified, but the invention 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.

  The polymerizable composition of the present invention is mixed with a binder such as an organic polymer resin in order to improve film formability, and is applied to a glass plate, an aluminum plate, other metal plates, a resin film such as polyethylene terephthalate or polyethylene. Can be used.

  Further, binders that can be used by mixing with the polymerizable composition of the present invention include polyacrylates, poly-α-alkyl acrylates, polyamides, polyvinyl acetals, polyformaldehydes, polyurethanes, polycarbonates, polystyrenes. And polymers such as polyvinyl esters and copolymer resins, and more specifically, polymethacrylate, polymethyl methacrylate, polyethyl methacrylate, polyvinyl carbazole, polyvinyl pyrrolidone, polyvinyl butyral, polyvinyl acetate, novolac resin, phenol Resin, Epoxy resin, Alkyd resin, etc., supervised by Kiyoshi Akamatsu, “A new technology of photosensitive resin” (CMC, 1987) and “Chemical products of 10188”, pages 657-767 (Chemical Industry Daily, 1988) industry known organic polymer according the like.

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

  Examples of 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 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, oxonol derivatives, etc. Pigment, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin Derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, Examples include tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, and organoruthenium complexes. Other specific examples include Ogahara Shin et al., “Dye Handbook” (1986, Kodansha). ), Okawara Nobu et al., “Functional dye chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special functional materials” (1986, CMC). Although not limited to these, other dyes and sensitizers that absorb light from the ultraviolet to the near-infrared region are included, and these may be two or more in any ratio as necessary. You can use it. Among the sensitizers, thioxanthone derivatives include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone. Examples of benzophenones include benzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4,4′-dimethylbenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-bis. (Diethylamino) benzophenone and the like can be mentioned. 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 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 a polymerization reaction 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 compound (B).

  Moreover, the polymerization composition of this invention can add the polymerization accelerator represented by amine, thiol, disulfide, etc. and a chain transfer catalyst for the purpose of further promoting a polymerization reaction.

  Specific examples of the polymerization accelerator and chain transfer catalyst 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. 4414 No. 12 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 wettability 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.

  The polymerizable composition of the present invention can undergo a polymerization reaction by applying energy by heat, ultraviolet light, visible light, near infrared light, electron beam or the like in the polymerization reaction, and can obtain a desired polymer. A light source having a dominant wavelength of light emission in a wavelength region of 250 nm to 450 nm is preferable as the light source for providing the light. 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 addition, the definition of ultraviolet rays, visible light, near infrared rays, etc. in this specification is based on “Iwanami Riken Dictionary 4th Edition” (1987, Iwanami) edited by Ryogo Kubo et al.

  Therefore, various inks, ink-jet inks, overcoat varnishes, various printing plate materials, photoresists, electrophotography, direct printing plate materials, optical fibers, hologram materials, and other photosensitive materials, microcapsules, etc. It can be applied to various recording media, as well as adhesives, pressure-sensitive adhesives, adhesives, release coating agents, sealants, and various paints.

  The member to which the polymerizable composition of the present invention is applied 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, and the like. Examples of the polyolefin-based polymer include polyethylene, polypropylene, polyolefin having a cyclic or norbornene structure, and an ethylene / propylene copolymer. Examples of the polyamide polymer include nylon and aromatic polyamide.

  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 active energy ray-curable ink-jet inks used in the present invention include pigments conventionally used in ink-jet inks, such as achromatic pigments such as carbon black, titanium oxide, and calcium carbonate, or chromatic organic pigments. 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 insoluble azo pigments such as Toluidine Red, Toluidine Maroon, Hansa Yellow, Benzidine Yellow, and Pyrazolone Red, soluble azo pigments such as Ritolol Red, Helio Bordeaux, Pigment Scarlet, and Permanent Red 2B, Alizarin, Indantron Derivatives from vat dyes such as thioindigo maroon, phthalocyanine organic pigments such as phthalocyanine blue and phthalocyanine green, quinacridone organic pigments such as quinacridone red and quinacridone magenta, perylene organic pigments such as perylene red and perylene scarlet, Isoindolinone organic pigments such as indolinone yellow and isoindolinone orange, and pyranthrone organic pigments such as pyranthrone red and pyranthrone orange 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 flavanthron yellow and acylamide yellow And publicly known various pigments such as nickel azo yellow, copper azomethine yellow, perinone orange, anthrone orange, dianthraquinonyl 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 “Titanics JA-1, C, 3, 4 5 ”,“ Tai Pure R-900, 902, 960, 706, 931 ”manufactured by DuPont.

  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 dispersant include BYK Chemie's “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)”, “Disperbyk-101 (polyamino acid). Amide 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 (high Molecular 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) Acid polycarboxylic acid and silicon) ”and“ Lactimon (long-chain amine and unsaturated acid polycarboxylic acid and silicon) ” It is.

  Further, “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 polycarboxylic acid), # 7004 (polyether ester type) ”.

  Furthermore, "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)”, “Abisia” Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type), 24000GR, 32000, 33000, 39000, 41000, 53000, “Nikkor T106 (polyoxyethylene sorbitan monoo) manufactured by Nikko Chemical Co., Ltd. Over DOO), MYS-IEX (polyoxyethylene monostearate), Hexagline 4-0 (hexaglyceryl ruthenate Huwei Rate) ", Ajinomoto Fine-Techno Co., Ltd.," Ajisper PB821,822,824 ", and the like.

  The addition amount of the 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 ink-jet ink of the present invention is produced by well dispersing a pigment together with a monomer and a 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 a monomer. 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 adjusted to a high viscosity of 5 to 50 mPa · s at 25 ° C. 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 electric conductivity by the electrolyte. In this case, it is necessary to adjust the electric 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. As a result, the composition on the printing medium is quickly reaction-cured.

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

  Specific non-absorbable supports include various non-absorbable plastics and films thereof. Examples of various plastic films include PET (polyethylene terephthalate) film, OPS (biaxially oriented polystyrene) film, and OPP ( Biaxially stretched polypropylene) film, ONy (biaxially stretched nylon) film, PVC (polyvinyl chloride) film, PE (polyethylene) film, TAC (triacetylcellulose) film can be mentioned. Other plastics include, but are not limited to, polycarbonate resins, polyacrylic resins, ABS resins, polyacetal resins, PVA (polyvinyl alcohol) resins, rubbers, and the like. Metals and glasses can also be used.

  The active energy ray-curable inkjet ink obtained in the present invention can be subjected to printing and curing reaction using the same technique as in the past.

  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.

<Example 1> Synthesis of compound (1) In a reaction vessel, 20.0 g (0.17 mol) of glycerin monovinyl ether, 73.2 g (1.02 mol) of acrylic acid, and 2.9 g of dimesityl ammonium pentafluorobenzenesulfonate. (0.006 mol) and 0.05 g of hydroquinone were added and stirred at 80 ° C. for 24 hours. After completion of the reaction, the target compound (1) was obtained in a yield of 42% by distillation under reduced pressure.

Example 2 Synthesis of Compound (2) The target compound (2) was recovered by reacting in the same manner except that the acrylic acid (1.02 mol) in Example 1 was replaced with methacrylic acid (1.02 mol). Obtained at a rate of 40%.

<Example 3> Synthesis of compound (3) By reacting in the same manner except that acrylic acid (1.02 mol) in Example 1 was replaced with 2-carboxyethyl acrylate (1.02 mol), the desired compound ( 3) was obtained with a yield of 45%.

Example 4 Synthesis of Compound (4) By reacting in the same manner except that acrylic acid (1.02 mol) in Example 1 was replaced with 2-carboxyethyl methacrylate (1.02 mol), the desired compound ( 4) was obtained with a yield of 41%.

Example 5 Synthesis of Compound (5) The target compound (5) was reacted in the same manner except that the acrylic acid (1.02 mol) in Example 1 was replaced with 3-carboxypropyl acrylate (1.02 mol). 5) was obtained with a yield of 48%.

<Example 6> Synthesis of compound (6) By reacting in the same manner except that acrylic acid (1.02 mol) in Example 1 was replaced with 3-carboxypropyl methacrylate (1.02 mol), the target compound ( 6) was obtained with a yield of 47%.
<Example 7> Synthesis of compound (7) By reacting in the same manner except that acrylic acid (1.02 mol) in Example 1 was replaced with 4-carboxybutyl acrylate (1.02 mol), the desired compound ( 7) was obtained with a yield of 43%.
Example 8 Synthesis of Compound (8) By reacting in the same manner except that acrylic acid (1.02 mol) in Example 1 was replaced with 4-carboxybutyl methacrylate (1.02 mol), the target compound ( 8) was obtained with a yield of 45%.

  The structure of the obtained compound was confirmed by mass spectrometry using EI-MS (PolarisQ manufactured by Thermo). The results of mass spectrometry are shown in Table 2.

<Example 9> Preparation of polymerizable composition Formulated with 95 parts by weight of compound (1) as reactive compound (A) and 5 parts by weight of Irgacure 369 (photopolymerization initiator manufactured by BASF) as radical polymerization initiator (B) As a result, a polymerizable composition was obtained. Using the obtained polymerizable compound, a curability test and a storage stability test were performed by the following methods. The results are shown in Table 3.

<Examples 10 to 16, Comparative Examples 1 to 3>
A polymerizable composition was prepared in the same manner as in Example 9 except that the compounds shown in Table 3 were used as the reactive compound (A), and a curability test and a storage stability test were performed. The results are shown in Table 3.

<Curing test>
The prepared polymerizable composition was added to a K control coater No. After coating on a PET film so that the wet film thickness is 12 μm using 2 bars, the coated material is applied to a conveyor conveyor type ultraviolet irradiation device (high pressure mercury lamp 100 W / cm1 lamp), and the conveyor speed is 50 m. The curing reaction was carried out by irradiating with ultraviolet rays at a rate of / min. The surface of the 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>
The state of the polymerization composition after visually storing the prepared polymerizable composition at 70 ° C. for 5 days was visually observed.

Judgment method ◎: No change ×: Increased viscosity XX: Gelled

  When the reactive compound (A) of the present invention was used, it became clear that a cured product having high reaction curability and excellent storage stability was obtained. Further, when a compound having an acrylic group and a vinyl ether group, which are reactive substituents of the reactive compound (A) of the present invention, is used (Comparative Examples 1 and 2), the curability is insufficient. When these compounds were used in combination (Comparative Example 3), it was found that although the curability was improved, the storage stability was 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 exhibits high reaction curability and excellent storage stability. Therefore, it was shown that the polymerizable composition of the present invention has a very wide selectivity and 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 monomer were prepared.

[Preparation of pigment dispersion a]
The formulation of pigment dispersion a is shown in Table 4. After stirring the polymerization-reactive monomer and the polymer dispersant and confirming that the polymer dispersant was completely dissolved, the pigment was added and the resulting mill base was stirred until it became uniform with a high speed mixer or the like. Was prepared by dispersing for about 1 hour in a horizontal sand mill.

[Preparation of pigment dispersion b]
The formulation of pigment dispersion b is shown in Table 5. The pigment dispersion b was produced by the same production method as the pigment dispersion a.

[Preparation of Pigment Dispersion c]
The formulation of pigment dispersion c is shown in Table 6. After stirring the polymerization-reactive monomer and the polymer dispersant and confirming that the polymer dispersant was completely dissolved, the pigment was added and the resulting mill base was stirred until it became uniform with a high speed mixer or the like. Was dispersed for about 2 hours using a horizontal sand mill.

[Preparation of Pigment Dispersion d]
The formulation of pigment dispersion d is shown in Table 7. After stirring the polymerization-reactive monomer and the polymer dispersant and confirming that the polymer dispersant was completely dissolved, the pigment was added and the resulting mill base was stirred until it became uniform with a high speed mixer or the like. Was dispersed for about 1.5 hours in a horizontal sand mill.

Examples 17-31, Comparative Examples 4-6
(1) Curability Yellow, magenta, cyan, black ink by mixing pigment dispersion, reactive compound (A), radical polymerizable compound, radical polymerization initiator (B), sensitizer, and surface modifier. Got. Table 8 shows the composition of the inkjet ink. This inkjet ink was printed on PET with a UV-IJ printer. The coated product was irradiated with ultraviolet rays (high pressure mercury lamp 120 W / cm1 lamp) to undergo a curing reaction, and then judged by a conveyor speed at which the film was not rubbed by rubbing with a cotton cloth. The results are shown in Table 8. It should be noted that the larger the number at the conveyor speed (m / min) of the ultraviolet irradiation device, the better the curability.
(2) Storage stability The state of the inkjet inks A to R after the prepared inkjet inks A to R were stored at 70 ° C. for 5 days was visually observed. The results are shown in Table 8.

Judgment method ◎: No change ×: Increased viscosity XX: Gelled

Table 8

Table 8

  The ink-jet inks (Examples 17 to 31) using the polymerizable composition of the present invention were found to have high curability and excellent storage stability. On the other hand, when a compound having an acrylic group and a vinyl ether group, which are reactive substituents of the reactive compound (A) of the present invention, is used (Comparative Examples 4 and 5), the curability is insufficient. When these compounds were used in combination (Comparative Example 6), it was found that although the curability was improved, the storage stability was insufficient.

  It has been clarified that the photopolymerizable composition of the present invention can be used for inkjet inks having both high curability and high storage stability.

  An object of the present invention is to provide a reactive compound which is rich in reactivity and excellent in storage stability, and further, a polymerizable composition having an extremely high curing reaction rate and excellent in storage stability, and the use thereof. An active energy ray-curable inkjet ink is provided. The reactive compound of the present invention is a compound characterized by having a (meth) acryl group and a vinyl ether group in the same molecule, and by using this compound, it is excellent in reaction curability, low odor, and storage stability. It was possible to provide a polymerizable composition. Therefore, in particular, it can be expected to be used as an active energy ray-curable inkjet ink that improves curability while maintaining dischargeability without increasing viscosity and has excellent 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, stereolithography resins, sealants, dental polymerization resins, and printing inks that utilize polymerization or crosslinking reactions. , Printing varnish, paint, photosensitive resin for printing plate, color proof for printing, 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 Resists for printed circuit boards, solder resists, photoresists for semiconductors, resists for microelectronics, resists for manufacturing micromachine parts, resists for etching, microlens arrays, insulating materials, hologram materials, optical switches, waveguide materials, overcoats Agent, End coatings, 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 (6)

A reactive compound (A) represented by the following general formula (1).
General formula (1)

(In the formula, m represents an integer of 0 to 4, n represents 0 or 1, and when m is 0, n is also 0. R ₁ represents a hydrogen atom or a methyl group.)   A polymerizable composition comprising the reactive compound (A) according to claim 1 and a radical polymerization initiator (B).   The polymerizable composition according to claim 2, 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 3.   The manufacturing method of printed matter which prints the active energy ray hardening-type inkjet ink of Claim 4, and makes it harden | cure by active energy ray irradiation. A printed matter obtained by the production method according to claim 5.