JPH09100306A - Composition polymerizable with light/heat - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which polymerizes by the action of light and/or heat in a short time to give a cured article having satisfactory properties by compounding an ethylenic compound with a pyridinium salt and a quaternary boride salt as polymerization initiators. SOLUTION: The polymerizable composition comprises (A) an ethylenic compound, (B) a pyridinium salt represented by formula I [wherein R1 is a (substituted) alkyl; R2 to R6 each is H, a halogen, cyano, a (substituted) alkyl, a (substituted) aryl, or a heterocyclic group; and A is an anion], and (C) a quaternary boride salt represented by formula II [wherein Z<+> is a quaternary ammonium cation, a quaternary pyridinium cation, a metal cation, etc.; and R7 to R10 each is a (substituted) alkyl, a (substituted) aryl, a (substituted) aralkyl, a heterocyclic group, a halogen, etc.]. The compounds (B) and (C) as polymerization initiators are more effective than conventional initiators in polymerizing the compound (A) with light and/or heat energy. The composition is hence useful in applications such as a coating material, a (pressure-sensitive) adhesive, an ink, a photosensitive material for printing plates, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel polymerizable composition. More specifically, a compound having an ethylenically unsaturated bond is polymerized in a short time by light and / or heat to obtain, for example, paint, FRP, ink, photosensitive printing plate, photoresist, direct plate making material, hologram material, sealant, The present invention relates to a novel polymerizable composition for obtaining a cured product having good physical properties in the fields of adhesives, pressure-sensitive adhesives and the like.

[0002]

2. Description of the Related Art Conventionally, there are many examples in which a complex having an organic boron anion is used as an initiator for radical polymerization. For example, JP-A-2-4804 discloses a metal borate complex, and JP-A-62-143044 discloses a cationic dye-borate anion complex, and JP-A-2-157760.
JP-A-2-166451 and JP-A-3-704
Japanese Patent No. 3,089,058 discloses diaryl iodonium borate and the like. In all of these, it is considered that the carbon-boron bond portion of the borate anion is decomposed by the action of heat or light to generate a radical.

On the other hand, in recent years, various pyridinium compounds have been reported for the purpose of polymerization catalysts of polymerizable compositions. Chemistry Letters, 93.
On page 5 (1988), N-benzyl-p-cyanopyridinium hexafluoroantimonate was used as a cationic polymerization catalyst for styrene, and in Chemistry Letters (Chem. Lett.), Page 1861 (1989), Macro. Macromolecules, Vol. 23, p. 431 (1990) and Macromolecules (Macromolec).
Ules), 24, 2689 (1991), some N-benzylpyridinium salts have been reported as cationic polymerization catalysts of glycidyl phenyl ether.
However, the pyridinium complexes reported in these documents are all developed for the purpose of cationic polymerization catalyst.

On the other hand, a pyridinium complex whose anion part is an organic boron anion is disclosed in JP-A-7-70221, and it is described that it functions as a photo-thermal radical polymerization initiator. The problems of the above-described polymerizable composition disclosed in the prior art are listed below. First, Japanese Patent Laid-Open No. 2-
4804 metal borate complex, JP-A-62-143
The cationic dye-borate anion complex described in No. 044 has a big problem that the polymerization initiation ability is insufficient. In addition, JP-A-2-157760 and JP-A2-1
In the case of the diaryl iodonium borate described in JP-A-66451 and JP-A-3-704, they are thermally unstable,
The storage stability of the polymerizable composition may be poor. Also, in the case of the pyridinium salt of the organic boron salt disclosed in JP-A-7-70221, sufficient polymerization initiation ability is not obtained.

[0005]

An object of the present invention is to propose a radically polymerizable composition which can be polymerized by light and / or heat in a short time.
It can be used as a recording medium such as P, an adhesive, an ink, a sealant, a photosensitive printing plate requiring high sensitivity, a photoresist, a direct plate making, a hologram material and the like. Another object is to industrially provide a practical oligomer or polymer such as a paint or FRP by polymerizing a compound having an ethylenically unsaturated bond under certain conditions.

[0006]

The present inventors have reached the present invention as a result of earnest researches aimed at solving the above problems. That is, the present invention provides a compound having an ethylenically unsaturated bond, which can be polymerized in a short time by light and / or heat energy, and a pyridinium complex represented by the following general formula (1) and a general formula (2) as a polymerization initiator.
The present invention relates to a polymerizable composition containing an organic boron salt represented by

The general formula (1)

Embedded image (In the formula, R ₁ is an alkyl group which may have a substituent,
₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently
A hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group, and A ₁ ^- represents any anion)

General formula (2);

Embedded image (In the formula, Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, or a metal cation, and R ₇ , R ₈ ,
R ₉ and R ₁₀ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an allyl group which may have a substituent, or a substituent which may have a substituent. Represents an aralkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a silyl group which may have a substituent, a heterocyclic group, or a halogen atom)

First, the component represented by the general formula (1) will be described. In R ₁ of the general formula (1), the alkyl group which may have a substituent is a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a t- group.
Examples thereof include a butyl group, a sec-butyl group, a methoxyethyl group and an ethoxyethyl group.

Next, R ₂ , R ₃ , R ₄ and R of the general formula (1) are
_{In 5} and R ₆ , a halogen atom is a fluorine atom, a chlorine atom or a bromine atom, and an alkyl group which may have a substituent is a methyl group, a trichloromethyl group, a tribromomethyl group, an ethyl group or propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group and the like, the aryl group which may have a substituent is phenyl group, p-tolyl group, xylyl group, mesityl group. Examples of the heterocyclic group include a cumenyl group, a biphenyl group, a naphthyl group, a chlorophenyl group, a bromophenyl group and a fluorophenyl group (as the heterocyclic group), a heterocyclic group represented by the general formula (1). A ₁ ^- represents an arbitrary anion.

Therefore, specific examples of the compound corresponding to the present invention include N-methoxypyridinium, N-ethoxypyridinium, N-propoxypyridinium, Nn-butoxypyridinium, N-methoxy-2-picolinium as a cation moiety, N-ethoxy-2-picolinium, N-propoxy-2-picolinium, Nn-butoxy-2-picolinium, N-methoxy-3-picolinium, N-ethoxy-3-picolinium, N-propoxy-3-picolinium, N-n-butoxy-3-picolinium, N-methoxy-4-bromopyridinium, N-
Methoxy-3-bromopyridinium, N-methoxy-2
-Bromopyridinium N-ethoxy-4-bromopyridinium, N-ethoxy-3-bromopyridinium, N
-Ethoxy-2-bromopyridinium, N-methoxy-
4-chloropyridinium, N-methoxy-3-chloropyridinium, N-methoxy-2-chloropyridinium
N-ethoxy-4-chloropyridinium, N-ethoxy-3-chloropyridinium, N-ethoxy-2-chloropyridinium, N-methoxy-4-methoxypyridinium, N-methoxy-3-methoxypyridinium, N-methoxy-2 -Methoxypyridinium N-ethoxy-4
-Methoxypyridinium, N-ethoxy-3-methoxypyridinium, N-ethoxy-2-methoxypyridinium, N-methoxy-4-phenylpyridinium, N-methoxy-3-phenylpyridinium, N-methoxy-2
-Phenylpyridinium N-ethoxy-4-phenylpyridinium, N-ethoxy-3-phenylpyridinium, N-ethoxy-2-phenylpyridinium, N,
N'-dimethoxy-4,4'-bipyridinium, N,
N'-diethoxy-4,4'-bipyridinium, N,
N'-dimethoxy-2,2'-bipyridinium, N,
N'-diethoxy-2,2'-bipyridinium etc. are mentioned.

On the other hand, examples of the anion portion include halogen anions such as chlorine, bromine and iodine anions, benzenesulfonate anion, p-toluenesulfonate anion,
Sulfonate anions such as methanesulfonate anion, tetraphenylborate, n-butyltriphenylborate, n-octyltriphenylborate, n-dodecyltriphenylborate, tetra (4-tolyl) borate, tetra (4-tolyl) borate , N-butyltri (4-tolyl) borate, tetra (4-t-butylphenyl) borate, n-butyltri (4-t-butylphenyl) borate, tetraanisylborate, n-butyltrianisylborate, tetra (4) - ethoxyphenyl) borate, n- butyltri (4-ethoxyphenyl) borate, tetra (4-fluorophenyl) organic boron anion of _{^{borate, BF 4 -, PF 6 -}} , SbF 6 -
And the like.

The complex of the general formula (1) is constituted by arbitrarily combining the above-mentioned cation part and anion part, but the present invention is not limited to these examples.
Next, the component represented by the general formula (2) will be described. R
Specific examples of ₇ , R ₈ , R ₉ and R ₁₀ include phenyl group, tolyl group, t-butylphenyl group, anisyl group, ethoxyphenyl group, naphthyl group, biphenyl group, fluorophenyl group, chlorophenyl group and diethylaminophenyl. Group, phenoxyphenyl group, triphenylsilyl group, dimethylphenylsilyl group, dibutylphenylsilyl group, trimethylsilyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n Examples include -octyl group, n-dodecyl group, cyclohexyl group, cyclohexene group, methoxymethyl group, methoxyethyl group, benzyl group, vinyl group, allyl group, piperidyl group, furyl group, and halogen atom.

Specific examples of the borate anion include n-
Butyltriphenylborate, n-octyltriphenylborate, n-dodecyltriphenylborate, n-
Butyltrianisylborate, n-butyltrinaphthylborate, n-butyltri (4-tolyl) borate, n
-Butyltri (2-tolyl) borate, n-butyltri (4-ethoxyphenyl) borate, n-butyltribiphenylborate, n-butyltri (4-phenoxyphenyl) borate, n-butyltri (4-fluorophenyl) borate, n -Butyltri (4-fluoro-2-
Methyl) borate, triphenylsilyltriphenylborate, diphenylmethylsilyltriphenylborate, dimethylphenylsilyltriphenylborate, trimethylsilyltriphenylborate, tetrabenzylborate, tetracyclohexylborate, tetra-n
-Butyl borate, tetra-n-octyl borate, di-n-butyl diphenyl borate, tri-n-butylphenyl borate, tetraphenyl borate, tetraanisyl borate, tetrafluoroborate and the like can be mentioned.

Z ⁺ is an arbitrary cation, but 4
Quaternary ammonium cation, quaternary pyridinium cation,
Examples thereof include quaternary quinolinium cations, phosphonium cations, sulfonium cations, metal cations, and cations represented by the general formula (1).

Specific examples include ammonium cations such as tetramethylammonium, tetraethylammonium, tetrapropylammonium, tetrabutylammonium, tetraoctylammonium, pyridinium,
Pyridinium cations such as methylpyridinium, ethylpyridinium, butylpyridinium, quinolinium, quinolinium salts such as methylquinolinium, ethylquinolinium, butylquinolinium, tetramethylphosphonium, tetraethylphosphonium, tetrabutylphosphonium, tetraoctylphosphonium, etc. Examples thereof include phosphonium cations, sulfonium cations such as trimethylsulfonium, triethylsulfonium, tributylsulfonium, trioctylsulfonium, and metal ions such as lithium ion and sodium ion. The complex represented by the general formula (2) is constituted by arbitrarily combining the cation part and the anion part described above, but the present invention is not limited to these examples.

Further, the polymerizable composition of the present invention, when combined with various sensitizers represented by the general formula (3), enhances the activity with respect to light in the visible region to the near infrared region, It is possible to obtain a highly sensitive polymerizable composition.

[0018] Formula ^{(3); D + · A} 2 - ( wherein, D ⁺ is a cationic dye having absorption in any wavelength region of from visible light to near infrared light, A ₂ ^- is any Specific examples of D ^{+ in} the general formula (3) include cyanine, xanthene, oxazine, thiazine, diarylmethane, triarylmethane, pyrilinium, and thiapyrrinium-based cationic dyes. Representative examples of such cationic dyes include those shown in Tables 1 and 2.

[0019]

[Table 1]

[0020]

[Table 1]

[0021]

[Table 2]

Further, A ₂ ⁻ in the general formula (3) represents any anion, for example, halogen anion such as chlorine, bromine, iodine anion, benzenesulfonate anion, p-toluenesulfonate anion, methanesulfonate anion and the like. Sulfonate anion, tetraphenylborate, n-
Butyltriphenylborate, n-octyltriphenylborate, n-dodecyltriphenylborate, tetra (2-tolyl) borate, tetra (4-tolyl) borate, n-butyltri (2-tolyl) borate, n-butyltri (4) -Tolyl) borate, tetra (4-t-butylphenyl) borate, n-butyltri (4-t-butylphenyl) borate, tetraanisylborate, n
- butyl thoria Western borate, tetra (4-ethoxyphenyl) borate, n- butyltri (4-ethoxyphenyl) borate, tetra (4-fluorophenyl) organic boron anion of borate, BF ₄ ^-, PF ₆ ^-, Sb
F ₆ ^{− and the} like can be mentioned, but the present invention is not limited to these examples. Further, two or more of these cationic dyes may be used in an optional ratio as needed.

The compound having an ethylenically unsaturated bond in the polymerizable composition of the present invention may be any compound as long as it has at least one radically polymerizable ethylenically unsaturated bond in the molecule. Well, it has a chemical form such as a monomer, an oligomer or a polymer. Only one of these may be used, or a system in which two or more of them are mixed at an arbitrary ratio in order to improve target properties may be used. Examples of the compound having such an ethylenically unsaturated bond include those shown below.

Examples of the polymerizable monomer include acrylic acid or an esterified product of methacrylic acid and a monohydric alcohol. Examples thereof include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, and methacryl. Acid n-butyl, isobutyl acrylate, isobutyl methacrylate, t-butyl acrylate, t-butyl methacrylate, propyl acrylate,
Propyl methacrylate, hexyl acrylate, hexyl methacrylate, octyl acrylate, octyl methacrylate, lauryl acrylate, lauryl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, acrylic acid Stearyl, stearyl methacrylate and the like are included.

As the monomer, vinylbenzenes such as styrene, vinylstyrene, methylstyrene, chlorostyrene and divinylstyrene, vinyl ethers such as isobutyl vinyl ether, methyl vinyl ether, 2-ethylhexyl vinyl ether, acrylonitrile and methacryl. (Meth) acrylic compounds such as nitrile, acrylamide, methacrylamide, methylenebisacrylamide, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, allyl alcohol, allyl acetate, diallyl phthalate, triallyl trimellitate, etc. Other vinyl compounds such as monomers containing an allyl group can also be used.

Further, as the monomer, carboxyl group-containing monomers such as acrylic acid and methacrylic acid; 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2
A hydroxyl group-containing monomer such as hydroxypropyl methacrylate; an adduct of a polyisocyanate such as butyl isocyanate and phenyl isocyanate with the above hydroxyl group-containing monomer; and a group including N-vinylpyrrolidone, N-vinylcarbazole, N-vinylacetamide, vinylpyridines and the like. Nitrogen unsaturated monomers and the like can also be used.

Further, as the monomer, diethylene glycol diacrylate, diethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, 1,3-butanediol diacrylate,
1,3-butanediol dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 1,
6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate , Dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and other polyfunctional vinyl compounds; products obtained by reacting an adduct of polyhydric alcohol and ethylene oxide with acrylic acid and / or methacrylic acid; polyhydric alcohol and ε-caprolactone The product obtained by reacting acrylic acid and / or methacrylic acid with the adduct with and a phosphorus-containing polymerizable monomer and the like are included.

The polymerizable unsaturated polymer includes an ethylenically unsaturated group-containing resin, and specific examples include the following. Examples of the ethylenically unsaturated group-containing resin include resins obtained by condensing polyester and (meth) acrylic acid, ethylenically unsaturated group-containing polyurethane resins, ethylenically unsaturated group-containing epoxy resins, ethylenically unsaturated group-containing phosphorus epoxies. Resin, ethylenically unsaturated group-containing acrylic resin, ethylenically unsaturated group-containing silicone
Resins, melamine resins containing ethylenically unsaturated groups, and the like.

The pyridinium complex represented by the general formula (1) of the present invention is the above-mentioned compound 10 having an ethylenically unsaturated bond.
The amount is preferably 0.001 to 20.0 parts by weight, more preferably 0.01 to 10.0 parts by weight, based on 0 parts by weight, and the organoboron complex represented by the general formula (2) is similarly 0.1. 001 to 20.0 parts by weight, more preferably 0.0
By using 1 to 10 parts by weight, the object of the present invention can be achieved. If it is less than that, the polymerization may not be sufficiently performed, and the curing may be insufficiently completed. Further, it is not preferable from the economical viewpoint to use too much.

Further, by using the sensitizer represented by the general formula (3), it becomes possible to have sufficient sensitivity to light having an arbitrary wavelength in the visible light region to the near infrared light region.
The addition amount thereof is preferably 0.1 to 1000 parts by weight, more preferably 1 to 100 parts by weight, based on 100 parts by weight of the sum of the pyridinium complex represented by the general formula (1) and the organic boron complex represented by the general formula (2). Parts by weight. If it is less than that, sufficient sensitivity to the light of the target wavelength cannot be obtained, and if it is more than that, it is not preferable from the economical viewpoint.

The polymerizable composition of the present invention is mixed with a binder such as an organic high-molecular polymer to prepare a glass plate, an aluminum plate,
It can be used by coating it on other metal plates or polymer films such as polyethylene terephthalate. Polymers 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, Examples thereof include polymers and copolymers of polyvinyl esters, and more specifically, polymethacrylate, polymethylmethacrylate, polyethylmethacrylate, polyvinylcarbazole, polyvinylpyrrolidone, polyvinylbutyral, polyvinylacetate, novolac resin, phenol resin, epoxy. resin,
Examples include alkyd resins.

Further, an optional filler can be added to the polymerizable composition of the present invention. Examples of the filler here include organic substances, inorganic substances, or their composites and mixtures. Examples of the organic filler include those obtained by finely pulverizing a polymer, and examples of the inorganic filler include silica, silica-alumina, alumina, quartz, glass, calcium carbonate, kaolin, talc, mica, and aluminum sulfate. Examples thereof include powders of titanium oxide, calcium phosphate, and the like, and those obtained by coating the surfaces of the powders with a polyfunctional (meth) acrylate-based monomer or a silane coupling agent.

As the composite, there may be mentioned one obtained by mixing the above-mentioned inorganic filler with an ethylenically unsaturated compound, polymerizing and curing it, and then finely pulverizing it. In addition, 2 different fillers
There is no problem even if they are added separately or after being mixed.

The pigments and dyes used in the present invention include commercially available colors such as black pigments such as carbon black and titanium black, white pigments such as titanium white and clay, metal powders such as aluminum powder, aluminum paste and silver powder. In addition to pigments, various documents (eg "Dye Handbook" edited by the Society of Synthetic Organic Chemistry, published in 1970, "Latest Pigment Handbook")
Known materials described in Japan Pigment Technology Association, published in 1976) can be used.

The photo / thermosetting material of the present invention can be used as a solventless material and is expected to contribute to the improvement of the global environment. Of course, it can be used in a form diluted with a conventional solvent. As the solvent to be used at that time, general solvents used for applications such as conventional paints, for example, aromatic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, 2-propanol and 1-butanol, and acetone. , Ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethylene glycol dimethyl ether and triethylene glycol dimethyl ether, esters such as ethyl acetate, butyl acetate and amyl acetate, and ethylene glycol monoethers such as methyl cellosolve and ethyl cellosolve. It can be used. These solvents can be used alone or in combination of two or more. The organic solvent reduces the viscosity of the material and improves workability, adhesion of the material to the base material, and the like.

The polymerizable composition of the present invention may contain a thermal polymerization inhibitor for the purpose of preventing polymerization during storage. Specific examples of the thermal polymerization inhibitor that can be added to the polymerizable composition of the present invention include p-methoxyphenol, hydroquinone, alkyl-substituted hydroquinone, catechol, t-butylcatechol, phenothiazine and the like. The polymerization inhibitor is added in the range of 0.001 to 5 parts by weight with respect to 100 parts by weight of the compound having a radically polymerizable ethylenically unsaturated bond.
Further, for the purpose of further promoting the polymerization, the polymerizable composition of the present invention may be added with a polymerization accelerator or a chain transfer agent represented by amine, thiol, disulfide and the like.
Specific examples of the polymerization accelerator and chain transfer agent that can be added to the polymerizable composition of the present invention include N-phenylglycine,
Examples thereof include amines such as triethanolamine and N, N-diethylaniline, and thiols such as 2-mercaptobenzoxazole and 2-mercaptobenzothiazole.

The polymerizable composition of the present invention further comprises an oxygen scavenger such as phosphine, phosphonate and phosphite, a reducing agent, an antifoggant, an antifading agent, a fluorescent brightening agent, a surfactant and a coloring agent depending on the purpose. Further, a filler, a plasticizer, a flame retardant, an antioxidant, an ultraviolet absorber, a foaming agent, an antifungal agent, an antistatic agent, a magnetic substance, etc. may be used.

During the polymerization reaction, the polymerizable composition of the present invention contains light energy such as ultraviolet light, visible light, near infrared light and / or the like in a solvent inert to the compound having an ethylenically unsaturated bond. Alternatively, it is possible to obtain a desired polymer by carrying out polymerization by heating or applying heat energy with a thermal head or the like.

As used herein, ultraviolet rays and near ultraviolet rays,
The definition of visible light, near-infrared light, and infrared light is based on "Iwanami Rikagaku Jiten 4th Edition" edited by Ryogo Kubo et al. (1987, Iwanami). Therefore, the polymerizable composition of the present invention is a low pressure mercury lamp, a medium pressure mercury lamp, an ultra high pressure mercury lamp, a xenon lamp, a carbon arc lamp, a metal halide lamp, a fluorescent lamp, a halogen lamp, an argon ion laser, a helium cadmium laser, a helium neon. Laser, krypton ion laser, various semiconductor lasers, YAG laser,
The intended polymer or cured product can be obtained by applying heat energy with a light emitting diode and / or heating or a thermal head.

Therefore, in addition to paints, pressure-sensitive adhesives and adhesives, it is applied on a substrate together with a binder and the like, and various inks, various printing plate materials, photoresists, electrophotography, direct plate-making materials, hologram materials, and other photosensitive materials and It can also be used for various recording media such as microcapsules.

It is considered that when the pyridinium complex represented by the general formula (1) and the organic boron complex represented by the general formula (2) used in the present invention are mixed, a radical is generated by the mechanism shown below. First, the pyridinium complex and the organoboron complex undergo ion exchange in the system to form an ion complex composed of a pyridinium cation and an organoboron anion. Then, the pyridinium cation is excited by applying light and / or heat energy,
It is considered that the pyridinium cation and the organic boron anion are each decomposed to generate a free radical, and as a result, the radically polymerizable compound having an ethylenically unsaturated bond is polymerized very effectively.

That is, by the action of light and / or heat, the bond between the oxygen atom bonded to R ₁ of the pyridinium cation moiety of the general formula (1) and the nitrogen atom on the pyridinium ring is cleaved to generate a radical. It is considered that the radicals generated here attack and polymerize the compound having an ethylenically unsaturated bond capable of radical polymerization. JP 7
-70221 describes a compound that is polymerized by cleavage of a nitrogen atom and a carbon bond of a pyridinium cation, but an oxygen-nitrogen bond is more likely to be cleaved than a carbon-nitrogen bond. Excellent in radical generation ability.

As a combination of substituents on the organic boron anion, R ₇ is an alkyl group which may have a substituent, and R ₈ , R ₉ and R ₁₀ may have a substituent. Combinations which are good aryl groups are preferred, for example combinations where R ₇ to R ₁₀ are all aryl groups do not effectively cleave the bond between R ₇ to R ₁₀ and the boron atom and are therefore necessary for polymerization. It is considered that radicals are hard to generate. Further, the mixture of the pyridinium complex represented by the general formula (1) and the organic boron anion represented by the general formula (2) usually does not absorb at a wavelength longer than visible light, but depending on the combination, it has absorption in the visible region. It is possible to generate a decomposed radical by visible light.

Further, by combining the above-mentioned suitable sensitizers, it functions as a polymerizable composition having higher sensitivity to light in the visible to near infrared region. Although the detailed photoreaction mechanism is not clear, in the case of using a sensitizer, a sensitizer and a pyridinium cation, a sensitizer and an organoboron anion, or a sensitizer and a pyridinium cation and an organoboron anion are used. Intermolecular electron transfer or intermolecular energy transfer causes cleavage of the binding sites of both pyridinium cation and organic boron anion, resulting in the generation of free radicals, and polymerization of the compound having a radically polymerizable ethylenically unsaturated group. It is thought to cause.

[0045]

EXAMPLES The present invention will be described below in detail with reference to examples, but the present invention is not limited only to the following examples. In addition, the middle part of an example shows a weight part.

Example 1 70 parts by weight of trimethylolpropane triacrylate hexamethylene diisocyanate (urethane prepolymer Kyoeisha Chemical Co., Ltd.), PEG # 4
00 diacrylate (Kyoeisha Chemical) 30 parts by weight, N,
N'-diethoxy-4,4'-bipyridinium bis (hexafluorophosphate) 0.50 parts by weight, tetrabutylammonium n-butyltriphenylborate 0.
Sample 1 was prepared by thoroughly mixing 50 parts by weight and 30 parts by weight of acetone.

Example 2 70 parts by weight of trimethylolpropane triacrylate hexamethylene diisocyanate, 30 parts by weight of PEG # 400 diacrylate, N,
0.50 parts by weight of N'-diethoxy-4,4'-bipyridinium bis (hexafluorophosphate), tetrabutylammonium n-butyltri (4-fluoro-2-)
Methylphenyl) borate 0.50 parts by weight, acetone 3
Sample 2 was prepared by thoroughly mixing 0 parts by weight.

(Example 3) 70 parts by weight of trimethylolpropane triacrylate hexamethylene diisocyanate, 30 parts by weight of PEG # 400 diacrylate, 0.50 parts by weight of N-ethoxy-4-phenylpyridinium hexafluorophosphate, tetrabutylammonium n
-Sample 3 was prepared by thoroughly mixing 0.50 parts by weight of octyltriphenylborate and 30 parts by weight of acetone.

Example 4 70 parts by weight of trimethylolpropane triacrylate hexamethylene diisocyanate, 30 parts by weight of PEG # 400 diacrylate, 0.5 parts of N-ethoxypyridinium hexafluorophosphate.
0 parts by weight, tetrabutylammonium n-butyltri (2-tolyl) borate 0.50 parts by weight, acetone 30
Sample 4 was prepared by thoroughly mixing parts by weight.

Example 5 70 parts by weight of trimethylolpropane triacrylate hexamethylene diisocyanate, 30 parts by weight of PEG # 400 diacrylate, 0.50 parts by weight of N-ethoxypyridinium tetrafluoroborate, tetrabutylammonium n-butyltri (4) −
Sample 5 was prepared by thoroughly mixing 0.50 parts by weight of t-butylphenyl) borate and 30 parts by weight of acetone.

Example 6 0.10 parts by weight of a near-infrared light absorbing cationic dye (No. 3 in Table 1, anion part is n-butyltriphenylborate) was mixed with the composition of Example 1,
Sample 6 was prepared.

(Example 7) 0.10 parts by weight of a near-infrared light-absorbing cationic dye (No. 3 in Table 1, anion part is n-butyltriphenylborate) was mixed with the composition of Example 2,
Sample 7 was prepared.

(Example 8) 0.18 parts by weight of a near-infrared light-absorbing cationic dye (Table 1, No. 1, anion part is tetraphenylborate) was mixed with the composition of Example 3 to prepare sample 8.

(Example 9) 0.10 parts by weight of a visible light absorbing cationic dye (No. 4, anion portion of Table 2 was tetraphenylborate) was mixed with the composition of Example 4 to prepare a sample 9
Was prepared.

Example 10 Sample 10 was prepared by mixing 0.10 parts by weight of a visible light absorbing cationic dye (No. 7 in Table 2, anion part is tetotaphenyl borate) with the composition of Example 5.

(Comparative Example 1) From the composition of Example 6, N, N '
-Comparative sample 1 with the exception of diethoxy-4,4'-bipyridinium bis (hexafluorophosphate)
And

(Comparative Example 2) From the composition of Example 7, N, N '
-Comparative sample 2 with the exception of -diethoxy-4,4'-bipyridinium bis (hexafluorophosphate)
And

Comparative Example 3 Comparative Example 3 was prepared by removing N-ethoxypyridinium hexafluorophosphate from the composition of Example 9.

Comparative Example 4 N-ethoxypyridinium hexafluorophosphate was removed from the composition of Example 4,
Instead, N-methylpyridinium n-butyltriphenylborate was blended in an equimolar amount with N-ethoxypyridinium hexafluorophosphate to obtain Comparative Sample 4.

Comparative Example 5 N-ethoxypyridinium tetrafluoroborate was removed from the composition of Example 5, and N-benzylpyridinium n-butyltriphenylborate was mixed in an equimolar amount of N-ethoxypyridinium tetrafluoroborate instead. This is Comparative Sample 5.

[Polymerization test and evaluation of polymerizability of sample] Photopolymerization The prepared Samples 1 to 10 and Comparative Samples 1 to 5 were applied on an aluminum substrate with a spray gun to a thickness of about 50 μm, and under a nitrogen atmosphere, A halogen lamp with an output of 1.5 kW was irradiated for 30 seconds. The obtained coating film was peeled off, and the residual double bond was quantified with a Fourier transform infrared spectrophotometer (hereinafter abbreviated as FT-IR). The results are shown in Table 3. The smaller the amount of residual double bonds, the more the polymerization is progressing.

[0062]

[Table 3]

Thermal polymerization The prepared Samples 1 to 5 and Comparative Samples 4 and 5 were applied on an aluminum substrate with a spray gun to a thickness of about 50 μm,
It was heated at 80 ° C. for 10 minutes in the dark under a nitrogen atmosphere. The obtained coating film was peeled off, and the amount of residual double bonds was quantified by FT-IR. The results are shown in Table 4.

[0064]

[Table 4]

[0065]

The combination of the pyridinium salt represented by the general formula (1) and the quaternary boron salt represented by the general formula (2) of the present invention is a polymerization initiation of a compound having a radically polymerizable ethylenically unsaturated bond. The agents are effective as compared with conventional techniques, and they can be polymerized and cured by application of light and / or heat energy. Therefore, the present composition is a good material in the fields of paints, adhesives / adhesives, FRPs, inks, photosensitive printing plates, photoresists, direct plate making materials, hologram materials, sealants and the like.

Claims (2)

[Claims] 1. A compound having an ethylenically unsaturated bond,
A polymerizable composition comprising a pyridinium salt represented by the general formula (1) and a quaternary boron salt represented by the general formula (2). General formula (1); (In the formula, R ₁ is an alkyl group which may have a substituent,
₂ , R ₃ , R ₄ , R ₅ , and R ₆ are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or A heterocyclic group, A ₁ ^- represents an anion) General formula (2); (In the formula, Z ⁺ represents a quaternary ammonium cation, a quaternary pyridinium cation, a quaternary quinolinium cation, a phosphonium cation, or a metal cation, and R ₇ , R ₈ ,
R ₉ and R ₁₀ each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an allyl group which may have a substituent, or a substituent which may have a substituent. Represents an aralkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a silyl group which may have a substituent, a heterocyclic group, or a halogen atom) 2. A compound having an ethylenically unsaturated bond,
A pyridinium salt represented by the general formula (1), a general formula (2)
The polymerizable composition according to claim 1, comprising a quaternary boron salt represented by the formula (4) and a cationic dye represented by the general formula (3). Formula ^{(3); D + · A} 2 - ( wherein, D ⁺ is a cationic dye having absorption in any wavelength region of from visible light to near infrared light, A ₂ ^- indicates an anion )