JPH083210A - Polymerizable composition and polymerizing method - Google Patents

Abstract

PURPOSE:To obtain a polymerizable compsn. excellent in safety while using an organoboron compd. which is unstable and has been difficult to industrially use by compounding a polymerizable unsatd. compd., a specific boron-based polymn. initiator, and an acidic compd. CONSTITUTION:A polymerizable compsn. contg. a polymerizable unsatd. compd., a boron-based polymn. initiator represented by the formula, and an acidic compd. In the formula, R1 to R4 are each an alkyl, aryl, allyl, aralkyl, alkenyl, alkynyl, silyl, heterocyclic, substd. alkyl, substd. aryl, etc.; and Z<+> is a sulfur cation, an oxygen cation, a carbon cation, a halogenium cation, etc. The acidic compd. is pref. an acid having an acid dissociation index (pKa value) in an aq. soln. thereof of 14 or lower. Generally, the higher the acidity, the faster the initiator decomposes and the faster the polymn. proceeds. Therefore, it is pref. that the compsn. is prepd. by using an acidic compd. having a more or less low acidity to improve the storage stability, is stored at a low temp., and is heated for accelerating the polymn. when used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a composition for polymerization by a novel polymerization initiation system and a polymerization method. More specifically, in the presence of a polymerizable unsaturated compound, a boron-based polymerization initiator is decomposed by a reaction with an acidic compound to generate a radical, and a polymerizable composition capable of being polymerized and a wavelength which the composition can absorb. It relates to a method of polymerizing by combination of light irradiation of an area and thermal energy.

[0002]

2. Description of the Related Art Conventional radical polymerization initiators are compounds that decompose by heat to generate radicals, that is, organic diazo compounds, organic peroxides, organic peracids and their esters, etc.
Alternatively, compounds that cleave molecules to generate radicals by irradiation with light such as ultraviolet rays to initiate polymerization, that is, acetophenones, thioxanthones, benzophenones, etc. are known. However, the thermal radical initiator has a problem in the thermal stability of the compound itself because of its characteristic of being decomposed by heat, so that it needs to be stored at a low temperature. There was a risk. Further, the photo-radical polymerization initiator requires an appropriate light source for initiating the polymerization, and in the case of ultraviolet polymerization, expensive equipment such as a high pressure mercury lamp is required, and also carcinogenicity by ultraviolet rays, ozone generation, etc. Danger has been pointed out.

On the other hand, as an example of using an organic boron compound as a radical polymerization initiator, an example is known in which a trialkylboron compound such as triethylboron is decomposed in the presence of oxygen to radically polymerize a polymerizable unsaturated compound. (For example, Journal of Industrial Chemistry Vol. 61, p. 728, issued in 1958). However, organoboron compounds are very unstable in air and have a risk of ignition and the like, and it is generally difficult to use them.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a polymerizable composition excellent in safety by using an organoboron compound, which has been difficult to industrially use as a polymerization initiator because the conventional compound has low stability. It is an object of the present invention to provide a polymerization method capable of efficiently causing the polymerization.

[0005]

[Means for Solving the Problems] To solve this problem, the present inventors have found that the alkyl atom on the boron atom is more stable and safer than the trialkylboron compound having three substituents on the boron atom. The method of using a tetracoordinated boron compound having four substituents such as an aryl group and an aryl group as a polymerization initiator was investigated, and a tetracoordinated boron anion was combined with a cation in a polymerizable unsaturated compound to form an ion pair. No compound,
It was found that a polymerizable composition was obtained by allowing an acidic compound to coexist, and the polymerization was initiated. Further, although the polymerization of the composition can be promoted by a heating operation, it was also found that the polymerization further proceeds efficiently when combined with light irradiation in a wavelength range that can be absorbed by the composition, and the present invention was completed. Ivy.

As an example of using a four-coordinated boron compound for polymerization, there has been known a method of initiating polymerization by light irradiation using an ion pair with a light-absorbing cationic dye (for example, JP-A-62-143044). Japanese Patent Laid-Open No. 1-111
No. 402), there is no known example of using a tetracoordinated boron compound in combination with an acidic compound as a polymerization initiator. That is, according to the present invention, a polymerizable unsaturated compound and a four-coordinated boron compound represented by the general formula (1) are represented by the general formula (1);

[0007]

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(In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, an aryl group, an allyl group, an aralkyl group, an alkenyl group, an alkynyl group, a silyl group, a heterocyclic group or a substituted alkyl group. Represents a group, a substituted aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a sulfur cation, an oxygen cation, a carbon cation, a halogenium cation, a cationic dye cation. Ion, arsenic, cobalt, palladium, chromium, titanium, tin, or a cation of various metal compounds of antimony, diazonium cation, morpholinium cation, tetrazolium cation, acridinium cation) The polymerizable composition of the present invention is obtained by combining the compounds to form a composition. .

Although the mechanism of the polymerization reaction in the present invention has not been clarified, decomposition of the 4-coordinated boron compound occurs due to the coexistence of the 4-coordinated boron compound of the general formula (1) and the acidic compound. It is presumed that a coordinated boron compound is generated, and the tri-coordinated boron compound is further decomposed by oxygen existing in the system to generate a radical, thereby initiating polymerization. A cation (Z which is a counter ion of a tetracoordinated boron compound)
⁺ ) Does not directly participate in the reaction with acidic compounds, so select it in consideration of the stability of the compound, the solubility in the solvent and the polymerizable unsaturated compound, the affinity, the availability of raw materials, the manufacturing cost, etc. Can be done. Alternatively, a cation having a structure having a special function can be selected. For example, a cation having a photosensitizing function as a counter ion of a boron anion,
It is also possible to generate a radical by an acid and a reaction by light in parallel. At that time, 200-2000n
A cation having photosensitivity in the wavelength range of m is preferable. Considering light transmittance, light safety, etc., the cation is preferably one having photosensitivity in a wavelength region of 400 nm or more, more preferably 740 nm or more.

The cation (Z ⁺ ) of the present invention includes cations of sulfur compounds such as sulfonium and oxosulfonium, oxygen cations such as flavylium and pyrylium, carbon cations such as tropylium and cyclopropylium, diazonium and tetrazolium. , Morpholinium, acridinium and other nitrogen cations, iodonium and other halogenium cations, cyanine, (poly) methine, xanthene,
Examples include various cationic dye cations such as thiazine, triarylmethane, and pyrylium, and cations of various metal compounds. Considering the solubility, stability, and photosensitivity of the polymerization initiator, sulfonium and oxosulfonium. Sulfur cations such as, pyrylium and other oxygen cations, tropylium and other carbon cations, halogenium cations,
Light absorbing dye cations, nitrogen cations such as diazonium, morpholinium, tetrazolium and the like are preferable.

Specific examples include trimethylsulfonium cation, triphenylsulfonium cation, tropylium cation, light-absorbing dye cation such as cyanine dye, diphenyliodonium cation, triphenyltin cation, triphenylantimony cation. , Tetraamine palladium cation, hexaamine chromium cation, benzenediazonium cation, substituted benzenediazonium cation (substituents are alkyl group, dialkylamino group, alkoxy group, etc.), 10a-acrididinium cation, acridine orange cation Examples include ions.

Specific examples of the light absorbing dye cation include:
For example, there are Table 1 (near infrared light absorbing dye cation) and Table 2 (visible light absorbing dye cation), and examples of boron compounds having photosensitivity in the wavelength region of 200 nm or more include US Pat. No. 3,567,453. There is a description in the issue.

[0013]

[Table 1]

[0014]

[Table 1]

[0015]

[Table 2]

Specific examples of the anion of the boron-based compound include tetraarylboron (aryl group is phenyl, substituted phenyl, naphthyl, pyridyl group, etc.), monoalkyltriphenylboron (alkyl group is n-butyl group, n-octyl group, n-dodecyl group, naphthyl group, etc.), monoalkyltrianisylboron (alkyl group is the same as above), dialkyldiphenylboron (alkyl group is the same as above), dialkyldianisylboron (alkyl group is above) Same as), tetra-n-butylboron, tri-n-butyl (triphenylsilyl) boron, tri-n-butyl (dimethylphenylsilyl) boron, n-octyldiphenyl (di-n-butylphenylsilyl) boron, dimethylphenyl (trimethylsilyl). ) Examples include boron. More specifically, the anions of boron compounds described in JP-A-6-75374 can be mentioned. The cations and anions of these boron compounds can be used in an appropriate combination, or can be used alone or in combination of two or more kinds.

The polymerizable unsaturated compound used in the present invention is any one or a mixture of a polymerizable unsaturated monomer, a polymerizable unsaturated oligomer and a polymer, and may be a compound having a polymerizable unsaturated group. These may be used alone or in combination of two or more.
As the polymerizable unsaturated monomer, JP-A-4-362935 is known.
And those described in JP-A-6-75374, and examples thereof include (meth) acrylic acid,
Esterification products of (meth) acrylic acid with various alcohols, (meth) acryl compounds such as (meth) acrylonitrile, (meth) acrylamide, and methylenebisacrylamide, vinylbenzenes such as styrene, vinyltoluene, and chlorostyrene, vinylisobutyl. ether,
Vinyl ethers such as 2-ethylhexyl vinyl ether, vinyl compounds such as vinyl acetates such as vinyl acetate, vinyl propionate and vinyl benzoate, and monomers containing an allyl group such as allyl alcohol, allyl acetate and diallyl phthalate. To be

Further, as the monomer, a hydroxyl group-containing monomer such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate, a phosphorus-containing polymerizable unsaturated monomer, an isocyanate compound such as butyl isocyanate and phenyl isocyanate, and the above-mentioned Addition products of hydroxyl group-containing monomers; addition products of phosphoric acid and the above hydroxyl group-containing monomers; nitrogen-containing unsaturated monomers such as N-vinylpyrrolidone, N-vinylcarbazole, N-vinylacetamide and vinylpyridines can also be used. Further, as the monomer, compounds having a plurality of polymerizable unsaturated groups such as diethylene glycol diacrylate, 1,6-hexanediol dimethacrylate, trimethylolpropane triacrylate, pentaerythritol trimethacrylate and pentaerythritol tetraacrylate are also included.

A product obtained by reacting an adduct of a polyhydric alcohol with ethylene oxide with acrylic acid and / or methacrylic acid; a product obtained by reacting the adduct of a polyhydric alcohol with propylene oxide with acrylic acid and / or methacrylic acid. Oligomers such as products obtained by reacting acrylic acid and / or methacrylic acid with the above-mentioned adduct of polyhydric alcohol and ε-caprolactone, and specific examples of the polymerizable unsaturated polymer Is a polyester (meth) acrylic acid condensed resin, an ethylenically unsaturated group-containing polyurethane resin, an ethylenically unsaturated group-containing epoxy resin, an ethylenically unsaturated group-containing phosphorus epoxy resin, an ethylenically unsaturated group-containing acrylic resin Resin, ethylenically unsaturated group-containing silicone resin, ethylenically unsaturated group-containing Such as Ramin resin and the like. In particular, it is disclosed in Japanese Patent Laid-Open No. 4-28722 (meta).
Acrylic functional polyorganosilsesquioxanes are preferred.

The acidic compound of the present invention is a substance known as Bronsted acid which gives a proton (hydrogen ion), for example, an inorganic acid such as sulfuric acid or hydrochloric acid, an organic acid such as acetic acid or methanesulfonic acid, a phenol or an alcohol. Hydroxyl group-containing compounds such as compounds, compounds having a mercapto group such as various thiols, or substances capable of forming a covalent bond by receiving an electron pair known as Lewis acid, for example, aluminum chloride, stannic chloride, boron trichloride, Examples thereof include boron tribromide. These acids are described in detail, for example, in Morrison Boyd, "Organic Chemistry", 3rd edition, page 43. The acidic compounds of the present invention also include solid or gaseous acidic compounds. Examples include acidic ion-exchange resins, carbon black, alumina, silica, and other substances having an acidic active site on the solid surface, and acidic gas substances such as hydrogen chloride and sulfurous acid gas.

Further, the acidic compound of the present invention also corresponds to a compound which generates an acidic compound by various actions. For example, a compound that generates an acidic compound by the action of heating, moisture in the air, the action of oxygen, etc. also corresponds to the acidic compound of the present invention. In addition, compounds that generate an acidic compound upon irradiation with light are generally known and are widely used, for example, called a cationic photopolymerization initiator, and these compounds also correspond to the acidic compound in the present invention. That is, these compounds are allowed to coexist with the boron-based polymerization initiator of the present invention, and the compound such as a photocationic polymerization initiator is decomposed by irradiation with light such as ultraviolet rays, and the boron-based polymerization initiation of the present invention is initiated by the generated acidic compound. It is also possible to decompose the agent and perform radical polymerization.

Of the polymerizable unsaturated compounds in the polymerizable composition of the present invention, for example, compounds containing a (meth) acrylic group generally contain a trace amount of an acidic component such as (meth) acrylic acid, It is described as the acid value, acid component, etc. These acid components can also be used as the acidic component of the present invention, and it is particularly preferable that the acidic component contains 0.01% by weight or more of the polymerizable unsaturated compound. That is, when an unsaturated compound containing these acid components is used, it can be used as a polymerizable composition by adding only the boron-based polymerization initiator without adding any other acidic compound. The above-mentioned (meth) acrylic compound may be subjected to a refining operation for removing the acid component in order to improve the quality at the time of commercialization, but when the composition of the present invention is produced, the refining operation is not performed but the acid component is removed. Since the composition can be produced in a state of being left to some extent, there is also an economic advantage.

Generally, even if the polymerizable unsaturated compound contains a small amount of an acidic component, the polymerization rate is extremely slow at a low temperature such as room temperature, and the composition has practical storage stability. Can be offered. In this case, generally, the polymerization can be accelerated by heating the polymerizable composition, and the polymerization can be performed at a practical polymerization rate. It is of course possible to add an acidic compound separately, if necessary, in order to accelerate the polymerization.

The acidic compound of the present invention is preferably an acid having an acid dissociation index (pKa value) of 14 or less in an aqueous solution. More preferably, the acid has a pKa value of 10 or less. Specific examples thereof include general inorganic acids and organic acids. The inorganic acids are, for example, hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, and sulfurous acid, and the organic acids are, for example, formic acid, acetic acid, propionic acid, butyric acid, oxalic acid, malonic acid. , Aliphatic carboxylic acids such as succinic acid, maleic acid, fumaric acid, acrylic acid and methacrylic acid, aromatic carboxylic acids such as benzoic acid, phthalic acid and trimellitic acid, chloroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoroacetic acid , Halogen-substituted carboxylic acids such as perfluoropropionic acid, sulfonic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, phenols, catechol, resorcinol, phloroglucinol, cresol and other phenols, thiophenols, etc. Examples thereof include mercapto compounds. Generally, the stronger the acidity, the faster the decomposition of the initiator and the faster the polymerization proceeds.Therefore, in order to increase the storage stability, the material is manufactured using an acidic compound with a slightly low acidity and stored at low temperature. A method of promoting polymerization by an operation such as heating is preferable.

The polymerization is initiated by adding the acidic compound to the composition in which the components other than the acidic compound are mixed immediately before the polymerization, or the composition is prepared by operations such as contact with air and moisture, heating, and light irradiation. A method of generating an acidic compound in a substance is also possible depending on the selection of the acidic compound. The acid dissociation index is the logarithm of the reciprocal of the acid dissociation constant, and is described in detail, for example, in "Chemical Handbook Basic Edition II", Maruzen Publishing Co., Ltd., 1984, page 339.

The polymerizable composition of the present invention can initiate polymerization at any temperature due to the effect of the acidic compound. However, considering storage stability and the like, it is stable at room temperature and promptly when necessary. It is desirable to start the polymerization. As mentioned above, it is possible to initiate the polymerization by heating a composition that is stable at room temperature, but at that time, it is possible to further accelerate the polymerization by irradiating with light in a wavelength region that the composition can absorb. Is. That is, efficient polymerization is achieved by a combination of appropriate heating and light irradiation in an appropriate wavelength range. In order to enhance the effect of light irradiation, it is preferable to add a photosensitive compound to the composition. For example, a photosensitive compound as described above may be present in the substituent or the cation moiety of the boron compound, or The photosensitive compound can be added separately. The photosensitive compound used at that time is preferably a compound having photosensitivity in the wavelength region of 200 nm to 2000 nm.

Any pigment, coloring dye or the like can be added to the polymerizable composition of the present invention. Specific examples include black pigments such as carbon black and titanium black,
White pigments such as titanium white and clay, aluminum powder, aluminum paste, various types of commercially available pigments including metal pigments such as gold powder and silver powder, and various documents (eg, "Handbook of Dyes" edited by the Society of Synthetic Organic Chemistry, Published in 1945,
Known products described in "Latest Pigment Handbook" edited by Japan Pigment Technology Association, published in 1976) can be used. Further, in the present invention, an arbitrary filler or the like can be added to the polymerization composition. Examples of the filler used herein include organic substances, inorganic substances, and 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 sulfuric acid. Examples include powders of aluminum, barium sulfate, calcium sulfate, titanium oxide, calcium phosphate, and the like, and those obtained by coating the surfaces of these powders with a polyfunctional (meth) acrylate-based monomer or a silane coupling agent. Examples of the composite include those obtained by mixing the above-mentioned inorganic filler with an ethylenically unsaturated compound, polymerizing and curing it, and then finely pulverizing it. Further, two or more different kinds of fillers may be added separately, or may be added after mixing, without any problem.

The object of the present invention can be achieved by using the polymerization initiator represented by the general formula (1) in the present invention in an amount of 0.001% by weight or more of the curable compound. If it is less than that, the polymerization may not be sufficiently performed, and the curing may be insufficiently completed. The preferred range is 0.01 to 10% by weight. To use too much is economically
Not preferred. The optimum amount of the acidic compound of the present invention varies depending on the strength of the acid, the stability of the polymerization initiator, the polymerizability of the polymerizable unsaturated compound, the desired polymerization rate, etc. 0.1 to 1000 molar equivalents are added.

The polymerizable composition of the present invention can be used as a solventless curable composition and is expected to contribute to the improvement of the global environment. Building materials, carpentry, car interiors,
It can be applied to coating materials such as exteriors and bumpers, coating fields, adhesives, printing inks, image forming materials, resists, electronic material-related fields such as printed circuit board preparation, and the like. Of course, it can be used in a form diluted with a conventional solvent,
Examples of the solvent that can be used at that time include general solvents used for conventional paints, such as aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as heptane, hexane, and pentane, acetone, and methyl ethyl ketone. , Ketones such as 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 cellsolve and ethyl cellsolve Can be used. These solvents can be used alone or in combination of two or more. These solvents also have a function of adjusting the viscosity of the material, compatibility of the composition, and improvement of workability, so that an appropriate amount can be added depending on the situation.

[0030]

EXAMPLES The present invention will be described below with reference to examples. Curing in the evaluation of the cured product means a state in which the surface of the coating film after curing and the inner surface of the coating film damaged by the cutter knife are visually observed and touched by hand, and there is no tackiness or tack at all.

(Example 1) 10 g of pentaerythritol triacrylate, 0.1 g of trimethylsulfonium n-butyltriphenylboron, and 0.1 g of trichloroacetic acid (acid dissociation index pKa = 0.65) were sufficiently mixed, and then mixed on an aluminum substrate. It was applied in a thickness of 250 μm. Polymerization started after about 1 minute and the sample was cured.

Example 2 A sample was prepared in the same manner as in Example 1 except that acetic acid (pKa = 4.76) was used instead of trichloroacetic acid. When the coated substrate is heated to 70 ° C,
Polymerization started and the sample was cured.

Example 3 A sample was prepared in the same manner as in Example 1 except that carbon black (trade name FW200, manufactured by Degussa Co., pH = 2.5 of aqueous dispersion) was used instead of trichloroacetic acid. Polymerization started immediately and the sample was cured.

Example 4 Sample 4 was prepared in the same manner as in Example 1 except that diphenyliodonium hexafluoroline (Ph ₂ I ⁺ · PF ₆ ⁻ ) which was a photocationic polymerization initiator was used instead of trichloroacetic acid. . A high pressure mercury lamp (HB-100A manufactured by Sen Special Light Source Co., Ltd.) was irradiated for 5 minutes. The acid generated by the photoreaction of the cationic polymerization initiator decomposed the boron compound, and the sample was cured.

Example 5 Sample 5 was prepared in the same manner as in Example 1 except that triethylene glycol diacrylate was used instead of pentaerythritol triacrylate. Polymerization of the coated sample started after about 5 minutes and the sample was cured.

Example 6 10 g of trimethylolpropane triacrylate (0.15% of acid component) and 0.1 g of trimethylsulfonium n-butyltriphenylboron were thoroughly mixed and applied on an aluminum substrate to a thickness of 250 μm. . When the substrate was heated to 100 ° C, polymerization started and the sample was cured.

(Example 7) 1,1,5,5-tetrakis [4- (diethylamino) phenyl] pentadienylium having near infrared absorption by changing the cation part of the boron compound to trimethylsulfonium. (Table 1, number 3)
Sample 7 was prepared in the same manner as in Example 2 except that Two halogen lamps with an output of 1500 W having a spectral distribution in the wavelength region of 400 nm or more are applied to the coated sample.
Upon irradiation for a minute, the sample cured due to the effects of photoreaction and thermal energy from the lamp.

(Example 8) Sample 8 was used in the same manner as in Example 7 except that 0.1 g of n-butyltriphenylboron, which is a dye of Table 2, No. 5, whose cation portion is visible absorbability was used.
It was created. When the coated sample was irradiated with the halogen lamp of Example 7 for 2 minutes, the sample was cured by the effect of photoreaction and heat energy from the lamp.

(Example 9) Trimethylsulfonium n-
Sample 9 was prepared in the same manner as in Example 1 except that triphenylsulfonium n-butyltriphenylboron was used instead of butyltriphenylboron. The coated sample started to polymerize after about 10 minutes, and the sample was cured.

Example 10 The sample of Example 9 was irradiated with the high pressure mercury lamp used in Example 4. Polymerization was accelerated by the photoreaction, and after about 3 minutes, the polymerization started, and the sample was cured.

(Example 11) A mixture having the same composition as in Example 2 was diluted with an equal amount of toluene and spray-coated so that 50 g / m ^{2 was} deposited on a steel plate. When this sample was heated to 80 ° C., polymerization started and it was cured.

Comparative Example 1 Trimethylsulfonium n-
Example 1 except that no butyltriphenylboron was added
Sample a was prepared in the same manner as in. The coated sample did not start to polymerize even after standing for 1 day or more, and the sample did not cure.

Comparative Example 2 Sample b was prepared in the same manner as in Example 1 except that trichloroacetic acid was not added. The coated sample did not start to polymerize even after standing for 1 day or more, and the sample did not cure.

[0044]

INDUSTRIAL APPLICABILITY According to the present invention, a composition capable of polymerizing a polymerizable unsaturated compound coexistent in a combination of a compound having a tetra-substituted boron anion structure and an acidic compound, and an efficient composition utilizing heat and light A polymerization method was provided.

Claims (5)

[Claims] 1. A polymerizable composition containing a polymerizable unsaturated compound, a boron-based polymerization initiator represented by the general formula (1), and an acidic compound. General formula (1); (In the formula, R ₁ , R ₂ , R ₃ and R ₄ are each independently an alkyl group, aryl group, allyl group, aralkyl group, alkenyl group, alkynyl group, silyl group, heterocyclic group, substituted alkyl group, substituted Represents an aryl group, a substituted allyl group, a substituted aralkyl group, a substituted alkenyl group, a substituted alkynyl group or a substituted silyl group, and Z ⁺ represents a sulfur cation, an oxygen cation, a carbon cation, a halogenium cation, a cationic dye cation, arsenic Cations of various metal compounds of cobalt, palladium, chromium, titanium, tin or antimony, diazonium cations, morpholinium cations,
Indicates a cation selected from tetrazolium cation and acridinium cation) 2. A cation (Z ⁺ ) of a boron-based polymerization initiator
The polymerizable composition according to claim 1, wherein is a cation having photosensitivity. 3. The polymerizable composition according to claim 1, wherein the acidic compound is an acidic compound contained in the polymerizable unsaturated compound in an amount of 0.01% by weight or more. 4. The polymerizable composition according to claim 1, 2 or 3, wherein the acidic compound is an acid having an acid dissociation index of 10 or less in an aqueous solution, or a compound that produces an acid. 5. The polymerization is caused by combining irradiation of light having a wavelength that can be absorbed by a component contained in the polymerizable composition and application of thermal energy to cause polymerization. A method of polymerizing the described composition.