JP6295702B2 - Reactive monomer and polymerizable composition using the same - Google Patents

Description

  The present invention relates to a molding resin, a casting resin, an optical molding resin, a sealant, a dental polymerization resin, a biocompatible material, a printing ink, a printing varnish, a paint, a photosensitive resin for a printing plate, a color proof for printing, and 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, microelectronic resist, Micromachine component 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 TECHNICAL FIELD The present invention relates to a reactive monomer for obtaining a polymer having good physical properties in the field of an agent, a composition for an image recording material using microcapsules, various devices, and a polymerizable composition using the same. .

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

  Applications using these reactive monomers are diverse and include applications listed in the technical field. In these applications, the properties that are commonly required of reactive monomers include high curability, low cure shrinkage, environmental friendliness (low migre, low sublimation, low odor), and safety (low skin irritation, Non-toxicity), handling properties (compatibility with polymerization initiators, compatibility with general-purpose monomers, compatibility with resins, solubility in solvents, low to moderate viscosity, wettability) and the like.

  On the other hand, a report using a bifunctional monomer having an amino acid skeleton for the purpose of biocompatibility, adhesion, and adhesiveness has been made (Patent Document 1, Non-Patent Document 1). In Patent Document 1, a bifunctional monomer having an amino acid skeleton is used for the pressure-sensitive adhesive, and it is used as an additive in spite of the solubility assist of acrylic acid. This is because the solubility (compatibility) is remarkably poor, and the use is limited. Furthermore, a wide range of combined effects with general-purpose monomers and initiators has not been proven.

  Further, in Non-Patent Document 1, a bifunctional monomer having an amino acid skeleton is used for the pressure-sensitive adhesive, but the monomer used in combination is also a high-functional bifunctional monomer partially having an amino acid skeleton, which is more special. A polymer is made with an initiator. Moreover, there is no description about the wide-ranging combined use effect with general-purpose initiators and monomers. Furthermore, this monomer is considered to have a very poor solubility.

  Therefore, in order to adapt to various applications, there is a need for a bifunctional monomer having an amino acid skeleton that has a combined effect with general-purpose initiators and monomers, and has high compatibility with those materials and high handling properties. It has been.

International Publication No. 96/024644 Mutation Research, Genetic Toxology (1994), 321 (4), 197-201

  An object of the present invention is to provide a reactive monomer which is rich in reactivity and excellent in handling property and safety. It is a further object of the present invention to provide a polymerizable composition that has a high curing rate with the reaction and can serve as a basis for various applications.

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, this invention relates to the reactive monomer (A) selected from the compound (1)-(20) represented by a following formula .

  The present invention also relates to a polymerizable composition comprising the above-described reactive monomer (A) and a polymerization initiator (B).

  The present invention further relates to the above-described polymerizable composition comprising a polymerizable compound (C) (excluding the reactive monomer (A)).

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

  Moreover, this invention relates to the manufacturing method of hardened | cured material which hardens the polymerizable composition of the said description by irradiating an active energy ray.

Moreover, this invention relates to the hardened | cured material obtained with the said manufacturing method.

  By this invention, the reactive monomer excellent in sclerosis | hardenability and handling property and polymerizable composition were able to be provided.

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

  First, the reactive monomer (A) of the present invention will be described. The reactive monomer (A) of the present invention, as represented by the following general formula (1), has two types of unsaturated groups polymerizable in the same molecule, and the basic skeleton has an amino acid structure ( A compound having an amino group and a carboxyl group on the same carbon).

General formula (1)

(In the formula, each of R1 to R10 independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group, an alkenyl group, an alkyloxy group, an aryl group, an aryloxy group, a heterocyclic group, or a heterocyclic group. A ring oxy group, an acyl group, a sulfanyl group, a sulfonyl group, or an amino group is represented.
R11 is a halogen atom, cyano group, nitro group, hydroxyl group, alkenyl group, alkyloxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, acyl group, sulfanyl group, sulfonyl group, or amino Represents a group.
However, R10 and R11 do not become the same substituent at the same time. )

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

  Examples of the halogen atom in R1 to R11 include, but are not limited to, a fluorine atom, an iodine atom, a bromine atom, and a chlorine atom.

The alkyl group in R1 to R10 is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms, or 2 to 18 carbon atoms and interrupted by one or more —O—. And linear, branched, monocyclic or condensed polycyclic alkyl groups. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 18 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. Group, nonyl group, decyl group, dodecyl group, octadecyl group, isopropyl group, isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group , Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group and the like, but are not limited thereto. Specific examples of the linear or branched alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include —CH ₂ —O—CH ₃ , —CH ₂ —CH. _{2 -O-CH 2 -CH 3,} -CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, - (CH 2 -CH 2 -
O) _n —CH ₃ (where n is from 1 to 8), — (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃
(Where m is 1 to 5), —CH ₂ —CH (CH ₃ ) —O—CH ₂ —CH ₃ —, —CH ₂ —CH— (OCH ₃ ) _2, etc. It is not limited to these.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 18 carbon atoms and interrupted by one or more —O— include the following, but are not limited thereto. It is not a thing.

  Examples of the alkenyl group in R1 to R11 include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms, and they have a plurality of carbon-carbon double bonds in the structure. Specific examples are vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3 -Pentenyl group, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexenyl group Examples thereof include, but are not limited to, a sadienyl group and a cyclopentadienyl group.

The alkyloxy group for R1 to R11 is a linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms, or one to one or more —O— having 2 to 18 carbon atoms. And a linear, branched, monocyclic or condensed polycyclic alkyloxy group interrupted by. Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyloxy group having 1 to 18 carbon atoms include methyloxy group, ethyloxy group, propyloxy group, butyloxy group, pentyloxy group, hexyloxy Group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyl Oxy group, tert-pentyloxy group, tert-octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boroni Group, 4-decyl cyclohexyl although group and the like, but is not limited thereto. Specific examples of the linear or branched alkyloxy group having 2 to 18 carbon atoms and interrupted by one or more —O— include —O—CH ₂ —O—CH ₃ , —O _{-CH 2 -CH 2 -O-CH 2} -CH 3, -O-CH 2 -CH 2 -CH 2 -O-CH 2 -CH 3, -O- (CH 2 -CH 2 -O) n -CH ₃ (where n is 1 to 8), —O— (CH ₂ —CH ₂ —CH ₂ —O) _m —CH ₃ (where m is 1 to 5), —O—CH ₂ — CH (CH ₃ ) —O—CH ₂ —CH ₃ —, —O—CH ₂ —
CH- (OCH ₃₎ but ₂ and the like, but is not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyloxy group having 2 to 18 carbon atoms and interrupted by one or more of -O- include the following, but are not limited thereto. It is not something.

  Examples of the aryl group in R1 to R11 include a monocyclic or condensed polycyclic aryl group having 6 to 24 carbon atoms. Specific examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 1-acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-perylenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecyl Phenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o-fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p- Rokishifeniru group, m- carboxyphenyl group, o- mercaptophenyl group, p- cyanophenyl group, m- nitrophenyl group, may be such as m- azido phenyl group include, but are not limited thereto.

Examples of the aryloxy group in R1 to R11 include a monocyclic or condensed polycyclic aryloxy group having 4 to 18 carbon atoms. Specific examples include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, and a 9-anne. Thryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1-indenyloxy group, 2-azurenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy Although groups etc. can be mentioned, it is not limited to these.

  Examples of the heterocyclic group in R1 to R11 include an aromatic or aliphatic heterocyclic group having 4 to 24 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. A 2-thienyl group, 2 -Benzothienyl group, naphtho [2,3-b] thienyl group, 3-thianthenyl group, 2-thianthrenyl group, 2-furyl group, 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group Phenoxathiinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3 -Indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolidinyl group, isoquinolyl group, quino Group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β-carbolinyl group, phenanthridinyl group, 2-acridinyl group Group, perimidinyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, 3-phenixazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, Imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group, 4-quinolinyl group Group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-phenoxathiinyl group, 3-coumarinyl group and the like, but are not limited thereto.

  Examples of the heterocyclic oxy group in R1 to R11 include a monocyclic or condensed polycyclic heterocyclic oxy group having 4 to 18 carbon atoms, including a nitrogen atom, an oxygen atom, a sulfur atom, and a phosphorus atom. 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2-carbazolyloxy group, 3-carba A zolyloxy group, a 4-carbazolyloxy group, a 9-acridinyloxy group, and the like can be mentioned, but are not limited thereto.

  As the acyl group in R1 to R11, a hydrogen atom or a carbonyl group to which a linear, branched, monocyclic or condensed polycyclic aliphatic group having 1 to 18 carbon atoms is bonded, or an alkyloxy group having 2 to 20 carbon atoms A carbonyl group substituted with a monocyclic or condensed polycyclic aryl group having 6 to 18 carbon atoms, a carbonyl group substituted with a monocyclic or condensed polycyclic aryloxy group having 6 to 18 carbon atoms, a nitrogen atom , A carbonyl group to which a monocyclic or condensed polycyclic heterocyclic group having 4 to 18 carbon atoms, including an oxygen atom, a sulfur atom, and a phosphorus atom is bonded. Specific examples include a formyl group, an acetyl group, and a propionyl group. , Butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl Group, cyclopentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, butyloxycarbonyl Group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluoyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl Group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxycal Nyl group, 2-methylsulfanylphenyloxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthrylyloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinoyl group, isonicotinoyl Although groups etc. can be mentioned, it is not limited to these.

  Examples of the sulfanyl group in R1 to R11 include linear, branched, monocyclic or condensed polycyclic alkylthio groups having 1 to 18 carbon atoms, and monocyclic or condensed polycyclic arylthio groups having 6 to 18 carbon atoms. Specific examples include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, octadecylthio, phenylthio, 1-naphthylthio, 2-naphthylthio, Examples thereof include, but are not limited to, a 9-anthrylthio group and a 9-phenanthrylthio group.

Examples of the sulfonyl group in R1 to R11 include linear, branched, monocyclic or condensed polycyclic alkylsulfonyl groups having 1 to 20 carbon atoms, and monocyclic or condensed polycyclic arylsulfonyl groups having 6 to 30 carbon atoms. Specific examples include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexylsulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group. Group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methyloxymethylsulfonyl group, phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl Group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group and the like. However, it is not limited to these.

  Examples of the amino group in R1 to R11 include an amino group, an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group.

  Here, as the alkylamino group, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group , Octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentyl Amino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantami Group, and the like, but not limited thereto.

  Dialkylamino group includes dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, Examples include, but are not limited to, piperazino groups.

  As an arylamino group, an anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4- A biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, a p-terphenylamino group, and the like are exemplified, but the invention is not limited thereto.

  Examples of the diarylamino group include, but are not limited to, a diphenylamino group, a ditolylamino group, an N-phenyl-1-naphthylamino group, and an N-phenyl-2-naphthylamino group.

  Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N-pentylanilino group, N -Ethylanilino group, N-methyl-1-naphthylamino group and the like are exemplified, but not limited thereto.

  Due to the substituents in R10 and R11, the reactive monomer of the present invention has improved asymmetry and solubility, so compatibility with general-purpose monomers, compatibility with resins, solubility in solvents, etc. are improved. It has handling properties that can be used without any problems in any application.

  Each of the substituents R1 to R11 listed above may have a substituent, and examples of such a substituent include a hydroxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkyloxy group, an aryloxy group, and an acyl group. A group, or an amino group. Here, the alkyl group, aryl group, heterocyclic group, alkyloxy group, aryloxy group, and amino group have the same meanings as described above.

  Here, R1 to 10 are preferably a hydrogen atom, an alkyl group, or an aryl group from the viewpoint of easy availability of raw materials, synthesis difficulty, influence on performance as a monomer, and the like.

  Here, R11 is preferably an alkenyl group or an aryl group from the viewpoint of easy availability of raw materials, difficulty in synthesis, influence on performance as a monomer, and the like.

  The reactive monomer (A) of the present invention is a reaction of alcohols and alkyl halides using various natural / synthetic amino acids and modified products as starting materials and a base as a catalyst, and esterification using an acid as a catalyst. Reaction, esterification reaction of carboxylic acid and alcohol using dehydrating agent, reaction using acid chloride, transesterification reaction using palladium-containing compound as described in JP-A No. 2001-220364, etc. Although it can obtain using an organic synthesis reaction, The following method etc. are mentioned among them, It is not necessarily limited to this method.

  That is, after substituting an amino group for a compound having an amino acid unit with an acid chloride corresponding to a tertiary amine, then reacting the base catalyst with the corresponding allyl halide to replace the carbonyl group. Thus, the reactive monomer of the present invention can be obtained efficiently.

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

  The polymerization initiator (B) of the present invention will be described. The polymerization initiator (B) of the present invention is a compound that generates an active species that initiates a polymerization reaction by irradiation with active energy rays or heat, and a conventionally known polymerization initiator can be used.

  Examples of the active species that initiate the polymerization reaction include radical polymerization initiators that generate radicals and cationic polymerization initiators that generate acids.

Specific examples of photo radical polymerization initiators that generate radicals by active energy rays include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzylmethyl ketal, 4- (2- Hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 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] phenyl] -2-methylpropane-1 Acetophenones such as -one; benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6 -Phosphines such as trimethylbenzoyl) -phenylphosphine oxide; Cycloalkenyl glyoxy Rick 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 N1919 (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 07 pages (19
77) various onium compounds including the iodonium compounds described in JP-A-59-1
No. 42205, an azo compound described in JP-A-1-54440, European Patent No. 109851, European Patent No. 126712, “Journal of Imaging Science (J.IMAG.SCI.)”, Vol. 30, page 174 (1986), metal allene complexes, titanocenes described in JP-A-61-151197, "COORDINATION CHEMISTRY REVIEW", Vol. 84, 85
To 277 (1988) and a transition metal complex containing a transition metal such as ruthenium described in JP-A-2-182701, an aluminate complex described in JP-A-3-209477, and JP-A-2-157760. Borate compounds described in JP-A-55-127550 and JP-A-60-202437, 2,4,5-triarylimidazole dimer, carbon tetrabromide and JP-A-59-107344. Organohalogen compounds described in JP-A-5-255347, sulfonium complexes or oxosulfonium complexes described in JP-A-5-255347, aminoketones described in JP-A-54-99185, JP-A-63-264560 and JP-A-10-29977 Compound, Japanese Patent Application Laid-Open No. 2001-264530, Japanese Patent Application Laid-Open No. 2001-261661, JP 2000-80068, JP 2001-233842, JP 2004-534797, JP 2006-342166, JP 2008-094770, JP 2009-40762, JP 2010-15025, JP 2010-. 189279, JP 2010-189280, 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, 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 100 parts by weight with respect to 100 parts by weight of the total amount of the polymerizable composition containing the polymerizable compound (C) described later that can be used in combination with the reactive monomer (A), It is preferable to contain in the range of 0.1-50 weight part.

  Examples of the thermal radical polymerization initiator that generates radicals by heat include an azo thermal polymerization initiator and an organic peroxide polymerization initiator.

  Specific examples of the azo thermal polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-. Azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate), 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane -1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, 2,2′-azobis (N-butyl-2-methylpropionamide), 2,2′-azobis ( N-cyclohexyl-2-methylpropionamide), and two or more of them may be used in combination.

  Specific examples of the organic peroxide polymerization initiator include benzoyl peroxide (BPO), lauroyl peroxide, di-t-butylperoxyhexahydroterephthalate, t-butylperoxy-2-ethylhexanoate, Di-α-cumyl peroxide (DCPO), t-butylperoxyisopropyl carbonate, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (DDBH), 2,5 , -Dimethyl-2,5-di (t-butylperoxy) hexyne-3, 1,1,3,3-tetramethylbutyl hydroperoxide, t-butyl hydroperoxide and the like. Moreover, you may use combining 2 or more types.

  The content of the azo thermal polymerization initiator and the organic peroxide polymerization initiator is 100 parts by weight of the total amount of the polymerizable composition containing a polymerizable compound (C) described later that can be used in combination with the reactive monomer (A). 0.01 parts by weight or more and 10 parts by weight or less, preferably 0.1 parts by weight or more and 5 parts by weight or less, more preferably 1 part by weight or more and 3 parts by weight or less.

Examples of the photocationic polymerization initiator that generates an acid upon irradiation with active energy rays include diazonium salts, sulfonium salts, iodonium salts, and the like. Specifically, benzenediazonium hexafluoroantimonate, benzenediazonium hexafluorophosphate, benzenediazonium. Diazonium salts such as hexafluoroborate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroborate, 4,4′-bis [bis (2
-Hydroxyethoxyphenyl) sulfonio] phenylsulfide bishexafluorophosphate, sulfonium salts such as diphenyl-4-thiophenoxyphenylsulfonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluorophosphate, bis (4-t-butyl) And iodonium salts such as phenyl) iodonium hexafluorophosphate and bis (4-t-butylphenyl) iodonium hexafluoroantimonate. Of these, iodonium salts are preferably used. These may be used alone or in combination of two or more.

Furthermore, as the above-mentioned cationic polymerization initiator, more specifically, aryldiazonium salts (for example, P-33 (manufactured by Asahi Denka Kogyo Co., Ltd.)), aryliodonium salts (for example, FC-509 (manufactured by 3M)), Arylsulfonium salts (Syracure UVI-6974, UVI
-6970, UVI-6990, UVI-6950 (Union Carbide), SP-150, SP-170 (Asahi Denka Kogyo)), allene-ion complex (for example, CG-24-61 (Ciba Geigy) )) And the like.

  The content of the cationic polymerization initiator is preferably 0 with respect to 100 parts by weight of the total amount of the polymerizable composition containing the polymerizable compound (C) described later that can be used in combination with the reactive monomer (A). .1 to 10 parts by weight, particularly preferably 1 to 5 parts by weight.

Specific examples of thermal cationic polymerization initiators that generate an acid by heat include diphenyliodonium hexafluoroarsenate, diphenyliodonium hexafluorophosphate, diphenyliodonium trifluoromethanesulfonate, triphenylsulfonium tetrafluoroborate, and tri-p. -Tolylsulfonium hexafluorophosphate, tri-p-tolylsulfonium trifluoromethanesulfonate, bis (cyclohexylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, triphenylsulfonium trifluoromethanesulfo Narate, diphenyl-4-methylphenylsulfonium trifluoromethanesulfonate, diphenyl-2,4 , 6-trimethylphenylsulfonium-p-toluenesulfonate, diphenyl-p-phenylthiophenylsulfonium hexafluorophosphate, and the like.

Further, as specific product names of the above-mentioned thermal cationic polymerization initiators, for example, diazonium salt type: AMERICURE series (American Can), ULTRASET series (Adeka), WPAG series (Wako Pure Chemical Industries)
Iodonium salt type: UVE series (manufactured by General Electric), FC series (manufactured by 3M), UV9310C (manufactured by GE Toshiba Silicone), WPI series (manufactured by Wako Pure Chemical Industries)
Sulfonium salt type: CYRACURE series (Union Carbide), UVI series (General Electric), FC series (3M), CD series (Sartomer), Optmer SP series, Optomer CP series (Adeka) ), Sun-Aid SI series (manufactured by Sanshin Chemical Industry Co., Ltd.), CI series (manufactured by Nippon Soda Co., Ltd.), WPAG series (manufactured by Wako Pure Chemical Industries, Ltd.), CPI series (manufactured by San Apro)
However, it is not limited to these.

  The content of the thermal cationic polymerization initiator is preferably 0.1 with respect to 100 parts by weight of the total amount of the polymerizable composition containing the polymerizable compound (C) described later that can be used in combination with the reactive monomer (A). 1 to 20 parts by weight, particularly preferably 1 to 5 parts by weight. If it is less than 0.1 part, curing is insufficient, and if it is more than 20 parts, coloring derived from the thermal cationic polymerization initiator and other physical properties are reduced.

  The radical polymerization initiator and the cationic polymerization initiator described above can be used in combination. As such an example, there is a production process in which a resin is firstly made with a radical polymerization initiator, optionally molded, and then secondarily cured (crosslinked) by cationic polymerization. Is not to be done.

  Moreover, in such a case, it is necessary to devise the polymerizable composition (C) described later so that desired performance can be brought out.

  The polymerizable compound (C) of the present invention will be described. As the polymerizable compound of the present invention, a radical polymerizable compound and a cationic polymerizable compound can be used in order to improve curability associated with the reaction, and these can be used in any combination.

  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 , Screw (4
-Acryloxypolyethoxyphenyl) propane, 1,9-nonanediol diacrylate, pentaerythritol diacrylate, pentaerythritol diacrylate monostearate, pentaerythritol diacrylate monobenzoate, bisphenol A diacrylate, EO-modified bisphenol A diacrylate, PO modified bisphenol A diacrylate, hydrogenated bisphenol A diacrylate, EO modified hydrogenated bisphenol A diacrylate, PO modified hydrogenated bisphenol A diacrylate, bisphenol F diacrylate, EO modified bisphenol F diacrylate, PO modified bisphenol F diacrylate , EO-modified tetrabromobisphenol A diacrylate, 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 described in Macromolecules, Vol. 15, page 1711 (1982) Preprints (Polym. Preprints), 34, 154 (1985), 5,6-benzo-2-methylene-1,3-diosepan.

  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, manufactured by Negami Kogyo Co., Ltd. 1200TPK, 6060PTM, 6060P "," Nippon Gosei Chemical Co., Ltd. "" purple light UV-6630B, 7000B, 7510B, 7461TE, 3000B, 320 " B, 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, synthetic rubber such as butadiene-acrylonitrile copolymer, and the like. 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 cationically polymerizable compound in the present invention means a compound that can be converted into a high molecular weight substance by polymerization or crosslinking reaction by the action of an acid catalyst generated by irradiation with active energy rays or heat, and the compounds shown below or a mixture thereof: This is included.

  As a typical example, a compound having a structure represented by the following general formula (2) is given as a compound having a methylol group as a formaldehyde precursor or a substituted methylol group.

General formula (2)

(However, in General formula (2), A is group shown by G or GJG,
G represents a substituted or unsubstituted arylene group or an oxygen, sulfur, or nitrogen-containing heterocyclic group.
J is a single bond, a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms, a substituted or unsubstituted arylene group, an arylalkylene group, or —O—, —S—, —SO ₂ —.
, -CO -, - COO -, - OCOO -, - CONH -, - it means SO ₂ -O- and alkylene group which may have a substituent such as having a portion of these bonds.
A may be a polymer such as a phenol resin.
Q and Q ′ each independently represent hydrogen, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group which may have a substituent, or an acyl group. r is an integer of 1 to 3, and s is an integer of 0 to 3. )

  Here, examples of the substituted or unsubstituted arylene group represented by G to J in the general formula (2) include an o-phenylene group, an m-phenylene group, a p-phenylene group, 4-methyl-1,2- Phenylene group, 4-chloro-1,2-phenylene group, 4-hydroxy-1,2-phenylene group, 2-methyl-1,4-phenylene group, p, p'-biphenylylene group, 1,2-naphthylene group 9,10-anthrylene group, 2,7-phenanthrylene group and the like.

  Examples of the oxygen-, sulfur- and nitrogen-containing heterocyclic groups include 2,5-furylene group, 2,5-thienylene group, 2,4-oxazolylene group, 2,4-thiazolylene group, 2,5-benzofurylene group, 2, 5-benzothienylene group, 2,6-pyridylene group, 5,8-quinolylene group and the like can be mentioned.

Examples of the substituted or unsubstituted alkylene group having 1 to 4 carbon atoms include methylene group, ethylene group, trimethylene group, tetramethylene group, propylene group, ethylmethylene group, chloromethylene group, dimethylmethylene group, bis (trifluoromethyl ) And a methylene group.

  Examples of the arylalkylene group include a benzylidene group, a p-tolylmethylene group, and a 2-naphthylmethylene group.

Furthermore, —O—, —S—, —SO ₂ —, —CO—, —COO—, —OCOO—, —CO
NH -, - As the alkylene group which may have a substituent such as having a portion of the SO ₂ -O- bond, a methylene dioxy group, an ethylenedioxy group, propylenedioxy group, diethylene dioxy group, Triethylenedioxy group, methylenedithio group, ethylenedithio group, propylenedithio group, diethylenedithio group, triethylenedithio group, methylenedisulfonyl group, ethylenedisulfonyl group, malonyl group, succinyl group, glutaryl group, adipoyl group,- OOC-CH ₂ -COO- group, -OOC- (CH _{2) 2} -COO- groups, -CH ₂ -OCOO-CH ₂ - _{group, -CH 2 - (OCOO-CH} 2) 2 - group, and the like .

  Examples of the alkyl group having 1 to 4 carbon atoms represented by Q and Q ′ in the general formula (2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a sec-butyl group. , Tert-butyl group and the like.

  Examples of the cycloalkyl group include a cyclopentyl group and a cyclohexyl group.

  As the aryl group which may have a substituent, a phenyl group, a p-tolyl group, a xylyl group, a mesityl group, a cumenyl group, a p-methoxyphenyl group, a biphenylyl group, a naphthyl group, an anthryl group, a phenanthryl group, p- A cyanophenyl group, a p-nitrophenyl group, a 3,5-bis (trifluoromethyl) phenyl group, a p-fluorophenyl group, a p-chlorophenyl group, a p-dimethylaminophenyl group, a p-phenylthiophenyl group, etc. Examples of the arylalkyl group include a benzyl group, a 2-naphthylmethyl group, a 9-anthrylmethyl group, a phenethyl group, a styryl group, and a cinnamyl group.

  Examples of the acyl group include an acetyl group, a hexanoyl group, a benzoyl group, a cyclohexanoyl group, a methoxalyl group, and a salicyloyl group.

  Specific examples of such cationically polymerizable compounds include various aminoplasts or phenoplasts, that is, urea-formaldehyde, melamine-formaldehyde, benzoguanamine-formaldehyde, glycoluril-formaldehyde resins and their monomers or oligomers. There is. Many of these are commercially available for applications such as paint vehicles. For example, Cymel (registered trademark) 300, 301, 303, 350, 370, 380, 1116, 1130, 1123, 1125, 1170, etc. manufactured by American Cyanamid, Inc., or Nikarak (registered trademark) Mw30 manufactured by Sanwa Chemical Co., Ltd. A typical example is a series of Mw30M, Mw30HM, Mx45, Bx4000 and the like. These may be used alone or in combination of two or more.

  Another specific example of the cationically polymerizable compound is a methylolated or alkoxydimethylated phenol derivative that can be a formaldehyde precursor. These may be used as a monomer, or may be used as a resin such as a resol resin or a benzyl ether resin.

  Furthermore, as another series of cationically polymerizable compounds, compounds having a silanol group, for example, compounds disclosed in JP-A-2-154266 and JP-A-2-173647 can be exemplified.

  Also, a mixture of polyene and polythiol, such as diallyl phthalate, diallyl isophthalate, diallyl maleate, diallyl carbonate, triallyl isocyanurate, urethane polyene produced from polyisocyanate and allyl alcohol (eg hexamethylene diisocyanate and allyl) A compound selected from, for example, a urethane compound obtained by a polycondensation reaction of alcohol, and a compound selected from, for example, trimethylolpropane trithiol glycolate, pentaerythritol-tetra-3-mercaptopropionate, etc. as polythiol These mixtures can also be exemplified as cationically polymerizable compounds.

  Moreover, the alkoxysilanes represented below can also be mentioned as a cationically polymerizable compound. Specific examples include tetraalkoxysilanes such as tetramethoxysilane and tetraethoxysilane, γ-chloropropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-glycidoxypropyl. Compounds having an alkoxysilyl group such as trimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, more specifically, Toray Dow Corning product catalog, page 59 or Shin-Etsu silicone silane "Silane coupling agent" described in the coupling agent product catalog (issued in September 1987), Toray Dow Corning product catalog, page 61 or Toshiba Silicone Corporation general catalog, page 27 (published in April 1986) Compounds having an alkoxysilyl group, known in the industry as "silane compound" described is, can be cited as alkoxysilanes.

  Furthermore, examples of the cationic polymerizable compound include a compound capable of cationic polymerization or a mixture thereof. The compound capable of cationic polymerization is, for example, an epoxy compound, an oxetane compound, a styrene, a vinyl compound, a vinyl ether, a spiro ortho ester, a bicyclo ortho ester, a spiro ortho carbonate, a cyclic ether, or a lactone. Oxazolines, aziridines, cyclosiloxanes, ketals, cyclic acid anhydrides, lactams and aryldialdehydes, episulfide groups, ethyleneimine groups, hydroxyl groups and the like. Polymerizable or crosslinkable polymers represented by acrylic, urethane, polyester, polyolefin, polyether, natural rubber, block copolymer rubber, and silicone that have these polymerizable groups in the chain. And oligomers are also included in the cationically polymerizable compound.

First, as the epoxy compound, conventionally known aromatic epoxy compounds, alicyclic epoxy compounds, aliphatic epoxy compounds, epoxide monomers, episulfite monomers, glycidylamine type epoxy resins, naphthalene type epoxies. Resin, Heterocyclic epoxy resin, Multifunctional epoxy resin, Biphenyl type epoxy resin, Glycidyl ester type epoxy resin, Alcohol type epoxy resin such as hydrogenated bisphenol A type epoxy resin, Halogenated epoxy resin such as brominated epoxy resin Rubber modified epoxy resin, urethane modified epoxy resin, epoxidized polybutadiene, epoxidized styrene-butadiene-styrene block copolymer, epoxy group-containing polyester resin, epoxy group-containing polyurethane resin, epoxy group-containing acrylic resin, etc. That. Examples of aromatic epoxy compounds include monofunctional epoxy compounds such as phenyl glycidyl ether, polyglycidyl ethers of polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof, such as bisphenol A, Bisphenol compounds such as tetrabromobisphenol A, bisphenol F, and bisphenol S, or glycidyl ethers produced by the reaction of adducts of alkylene oxides (eg, ethylene oxide, propylene oxide, butylene oxide) of bisphenol compounds with epichlorohydrin, novolak type Epoxy resins (for example, phenol novolac epoxy resin, cresol novolac epoxy resin, brominated phenol novolac epoxy resin) ), Trisphenolmethane triglycidyl ether. As the compound having an epoxy group, these epoxy resins may be liquid at room temperature or solid. Epoxy group-containing oligomers can also be preferably used, and examples thereof include bisphenol A type epoxy oligomers (for example, Epicoat 1001, 1002 manufactured by Yuka Shell Epoxy Co., Ltd.). Furthermore, addition polymers of the above epoxy group-containing monomers and oligomers may be used, and examples thereof include glycidylated polyester, glycidylated polyurethane, and glycidylated acrylic.

  Among them, photocationic polymerization is higher, and photocuring proceeds more efficiently even with a small amount of light. Therefore, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, alicyclic epoxy resin, fat A group epoxy resin or the like is preferably used. These compounds having an epoxy group may be used alone or in combination of two or more.

  Specific examples of the alicyclic epoxy resin include, for example, 1,2,8,9-diepoxy limonene, 4-vinylcyclohexene monoepoxide, vinylcyclohexene dioxide, methylated vinylcyclohexene dioxide, (3,4-epoxy). Cyclohexyl) methyl-3,4-epoxycyclohexylcarboxylate, bis- (3,4-epoxycyclohexyl) adipate, norbornene monoepoxide, limonene monoepoxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3 , 4-epoxy) cyclohexanone-meta-dioxane, bis- (3,4-epoxycyclohexylmethylene) adipate, bis- (2,3-epoxycyclopentyl) ether, (2,3-epoxy-6-methylcyclohexylmethyl) Dipate, dicyclopentadiene dioxide, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, 2,2-bis [4- (2,3-epoxy) Propoxy) cyclohexyl] hexafluoropropane, BHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin (softening point 71 ° C.), and the like, but are not limited thereto.

  Specific examples of the aliphatic epoxy resin include 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, ethylene glycol diglycidyl ether, ethylene glycol monoglycidyl ether, propylene glycol diglycidyl ether, and propylene. Glycol monoglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, neopentyl glycol monoglycidyl ether, glycerol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane diglycidyl Ether, trimethylolpropane monoglycidyl ether, trimethylolpropane triglyceride Jill ether, diglycerol triglycidyl ether, sorbitol tetraglycidyl ether, allyl glycidyl ether, 2-but-ethylhexyl glycidyl ether, and the like, but is not limited thereto.

  Specific examples of the oxetane compound include, for example, phenoxymethyl oxetane, 3,3-bis (methoxymethyl) oxetane, 3,3-bis (phenoxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3- Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane, di [1-ethyl (3-oxetanyl)] methyl ether, oxetanyl Silsesquioxane, phenol novolac oxetane, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene and the like can be mentioned, but are not limited thereto.

Examples of styrenes include, but are not limited to, styrene, α-methylstyrene, p-methylstyrene, and p-chloromethylstyrene.

  Examples of the vinyl compound include, but are not limited to, N-vinylcarbazole and N-vinylpyrrolidone.

  Examples of vinyl ethers include n- (or iso-, t-) butyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether, 1,4 butanediol divinyl ether, ethylene glycol divinyl ether, ethylene glycol monovinyl ether, triethylene glycol divinyl ether. , Tetraethylene glycol divinyl ether, propylene glycol divinyl ether, propylene glycol monovinyl ether, neopentyl glycol divinyl glycol, neopentyl glycol monovinyl glycol, glycerol divinyl ether, glycerol trivinyl ether, trimethylolpropane monovinyl ether, trimethylolpropane divinyl ether, tri Methylolpropa Trivinyl ether, diglycerol trivinyl ether, sorbitol tetravinyl ether, cyclohexanedimethanol divinyl ether, hydroxybutyl vinyl ether, dodecyl vinyl ether 2,2-bis (4-cyclohexanol) propane divinyl ether, 2,2-bis (4-cyclohexanol) Alkyl vinyl ethers such as trifluoropropane divinyl ether, alkenyl vinyl ethers such as allyl vinyl ether, ethynyl vinyl ether, alkynyl vinyl ethers such as 1-methyl-2-propenyl vinyl ether, 4-vinyl ether styrene, hydroquinone divinyl ether, phenyl vinyl ether, p- Methoxyphenyl vinyl ether, bisphenol A divinyl ether, Aryl vinyl ethers such as labromobisphenol A divinyl ether, bisphenol F divinyl ether, phenoxyethylene vinyl ether, p-bromophenoxyethylene vinyl ether, 1,4-benzenedimethanol divinyl ether, Nm-chlorophenyldiethanolamine divinyl ether, m-phenylene Examples thereof include, but are not limited to, aralkyl divinyl ethers such as bis (ethylene glycol) divinyl ether, urethane polyvinyl ether (for example, VECtomer 2010 manufactured by ALLIED-SIGNAL).

  Spiro orthoesters include 1,4,6-trioxaspiro [4.4] nonane, 2-methyl-1,4,6-trioxaspiro [4.4] nonane, 1,4,6-trio. Examples include, but are not limited to, oxaspiro [4.5] decane.

  Bicycloorthoesters include 1-phenyl-4-ethyl-2,6,7-trioxabicyclo [2.2.2] octane, 1-ethyl-4-hydroxymethyl-2,6,7-trioxa. Bicyclo [2.2.2] octane and the like are exemplified, but not limited thereto.

  Examples of spiro orthocarbonates include 1,5,7,11-tetraoxaspiro [5.5] undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5.5] undecane, and the like. Examples of such cyclic ethers include, but are not limited to.

  Examples of cyclic ethers include oxetanes such as oxetane and phenyloxetane, tetrahydrofurans such as tetrahydrofuran and 2-methyltetrahydrofuran, tetrahydropyrans such as tetrahydropyran and 3-propyltetrahydropyran, trimethylene oxide, and s-trioxane. However, it is not limited to these.

  Examples of lactones include, but are not limited to, β-propiolactone, γ-butyllactone, δ-caprolactone, δ-valerolactone, and the like.

  Examples of oxazolines include, but are not limited to, oxazoline, 2-phenyloxazoline, 2-decyloxazoline and the like.

  Examples of aziridines include, but are not limited to, aziridines and N-ethylaziridines.

Examples of cyclosiloxanes include, but are not limited to, hexamethyltrisiloxane, octamethylcyclotetrasiloxane, triphenyltrimethylcyclotrisiloxane, and the like.

  The ketals include 1,3-dioxolane, 1,3-dioxane, 2,2-dimethyl-1,3-dioxane, 2-phenyl-1,3-dioxane, 2,2-dioctyl-1,3-dioxolane. However, it is not limited to these.

  Examples of cyclic acid anhydrides include phthalic anhydride, maleic anhydride, succinic anhydride, and examples of lactams include, but are not limited to, β-propiolactam, γ-butyrolactam, and δ-caprolactam. It is not a thing.

  Aryl dialdehydes include, but are not limited to, 1,2-benzenedicarboxaldehyde, 1,2-naphthalenedialdehyde, and the like.

  The above cationic polymerizable compounds may be used alone or in combination of two or more. As said cation polymeric compound, an epoxy compound, an oxetane compound, and vinyl ether are preferable. Particularly preferred are epoxy compounds and oxetane compounds. Polymerization of epoxy compounds and oxetane compounds is relatively reactive and has a short curing time, so that the curing process can be shortened.

  Moreover, as above-mentioned, it is possible to use together with a single or 2 or more types of radically polymerizable compounds arbitrarily.

  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) and the like, but is 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 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 as the total of the reactive monomer (A) and the polymerizable compound (C) of the present invention.

  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.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited to only the following Example at all.

Example 1 Synthesis of Compound (1) After adding 18.0 g (0.15 mol) of 2-nitro-2-amino-ethanoic acid, 38 g (0.38 mol) of triethylamine, and 250 ml of dichloromethane to a reaction vessel, ice Cool and stir under bath. 17 g (0.19 mol) of acrylic acid chloride was slowly added dropwise so that the reaction temperature did not exceed 5 ° C. After completion of dropping, the mixture was stirred for 1 hour under ice greed. The reaction was stopped by adding 200 g of 5% aqueous hydrochloric acid to the reaction solution, and the layers were separated using a separatory funnel, and the organic layer was further washed with 200 g of multilayer water three times. After drying with magnesium sulfate, the solid content was removed by filtration to obtain a filtrate.
The filtrate was put into a reaction vessel, and 13 g (0.15 mol) of sodium hydrogen carbonate was added under ice greed. At this time, foaming was confirmed. After cooling and stirring in an ice bath for 30 minutes, 22 g (0.18 mol) of allyl bromide was slowly added dropwise so that the reaction temperature did not exceed 5 ° C. After completion of dropping, the mixture was returned to room temperature and stirred for 1 hour. The reaction was stopped by adding 200 g of 5% aqueous hydrochloric acid to the reaction solution, and then the layers were separated using a separatory funnel, and the organic layer was further washed with 250 g of multilayer water three times. After drying with magnesium sulfate, the solid content was removed by filtration, and then the solvent was distilled off using an evaporator, followed by concentration until the volume reached about 50 ml. The concentrated solution was purified with an alumina short column (solvent dichloromethane) to obtain 25.1 g of Compound (1) in a yield of 78%.

<Examples 2 to 20>
By reacting 2-nitro-2-amino-ethanoic acid in Example 1 in the same manner except that the compounds shown in Table 1 were used, the target compound (2-20) was obtained in the yield shown in Table 1. Obtained.

  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.

Next, known reactive monomers used in the comparative examples are shown in Table 3.

  Next, the general-purpose monomer as the polymerizable compound (C) used in the solubility test and the curability test, and the abbreviations in this patent are shown in Table 4, and further the general-purpose start as the polymerization initiator (B) used in the curability test Table 5 shows the agents.

<Examples 21 to 40, Comparative Examples 1 to 4> Solubility test for general-purpose solvents In the solvents shown in Table 6, the reactive monomers shown in Table 6 were dissolved to 35 wt%, respectively, and visually. Table 6 shows the result of confirming whether or not it was dissolved.
<Criteria>
○: Uniform dissolution confirmed Δ: Slightly turbid
X: Phase separation or sedimentation (insoluble) of insoluble matter is confirmed

  As shown in Table 6, the reactive monomer of the present invention was well dissolved in various general-purpose solvents. On the other hand, the known reactive monomer hardly dissolved (compatible). That is, the reactive monomer of the present invention can be used without any problem even in applications where a solvent is used, and the handling property is remarkably improved as compared with conventionally known reactive monomers.

<Examples 41 to 60, Comparative Examples 5 to 8> Compatibility test with general-purpose monomer The reactive monomer of the present invention with respect to 50 parts by weight of the general-purpose monomer as the polymerizable compound (C) shown in Table 7 Table 7 shows the results obtained by mixing 50 parts by weight of (A) or a known reactive monomer and stirring the mixture at 40 ° C. for 1 hour, and then checking the compatibility state visually.
<Criteria>
○: Confirmation of uniform mixing ×: Confirmation of phase separation or insoluble sedimentation

  As shown in Table 7, the reactive monomer of the present invention was well compatible with various general-purpose monomers. On the other hand, known reactive monomers were hardly compatible. That is, it was shown that the reactive monomer of the present invention can provide a polymerizable composition that can be used for various applications by freely combining with a general-purpose monomer.

<Examples 61-140, Comparative Examples 9-24> Curability Test 1
95 parts by weight of the compound shown in Table 8 as the reactive monomer (A) and 6 parts by weight of the polymerization initiator shown in Table 8 as the polymerization initiator (B) were blended to obtain a polymerizable composition.
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. The results are shown in Table 8.

  As shown in Table 8, the reactive monomer of the present invention, when used in combination with various general-purpose initiators, exhibits excellent curability and provides a polymerizable composition that can be used for various applications. It was shown that it can be done. It is considered that the known reactive monomer has poor compatibility with the initiator and the initiator does not function efficiently in the polymerizable composition.

<Examples 141-254, Comparative Examples 25-48> Curability Test 2
As shown in Table 9, 25 parts by weight of the reactive monomer (A), 75 parts by weight of the polymerizable compound (C) as a general-purpose monomer, and 8 parts by weight of Irg369 as a polymerization initiator (B) are blended as shown in Table 9. Got.
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. The results are shown in Table 9.

  As shown in Table 9, the reactive monomer of the present invention exhibited excellent curability when used in combination with a general-purpose monomer. On the other hand, known reactive monomers were not compatible with general-purpose monomers, and the test could not be performed. That is, the reactive monomer of the present invention can be used with a general-purpose monomer that could not be realized with a conventionally known reactive monomer, and can provide a polymerizable composition that can be used for various applications. It has been shown.

<Examples 255 to 334, Comparative Example 49-64> Adhesion test A cross-cut adhesion test was performed on the cured film prepared in the curability test 1 in accordance with JIS K5400. It was displayed as a fraction in number / number of all grids. It shows that adhesiveness is so good that this fraction is large. The evaluation results are shown in Table 10.

  As shown in Table 10, the polymerizable composition using the reactive monomer of the present invention is more adhesive than the polymerizable composition using a conventionally known reactive monomer by curing. It became clear that it was excellent. Conventionally known reactive monomers are often used for adhesive bonding applications, but even in such fields, the reactive monomer of the present invention has the potential to give superior performance. I was able to show.

An object of the present invention is to provide a reactive monomer that is rich in reactivity and excellent in handling properties and safety, and further has a high curing speed associated with the reaction and can be used as a basis in various applications. Is to provide. The characteristic of the reactive monomer of the present invention is that it has very high solubility / compatibility as compared with conventionally known reactive monomers having an amino acid moiety. The use is not restricted.

  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 monomer (A) selected from compounds (1) to (20) represented by the following formula:
  A polymerizable composition comprising the reactive monomer (A) according to claim 1 and a polymerization initiator (B).   The polymerizable composition according to claim 2, further comprising a polymerizable compound (C) (excluding the reactive monomer (A)).   The polymerizable composition according to claim 2 or 3, wherein the polymerization initiator (B) is a radical photopolymerization initiator. The manufacturing method of the hardened | cured material which hardens | cures the polymeric composition of Claim 4 by irradiating an active energy ray .   A cured product obtained by the production method according to claim 5.