JPH0463801A - Photocuring catalyst composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. acting as a highly active cationic polymn. catalyst and giving a photopolymerizable compsn. useful as a sealing material, etc., by compounding a specific pyridinium compd. with a carbonyl compd. with can undergo cleavage by irradiation with rays of light. CONSTITUTION:A compd. of formula I [wherein R<1> is H or an arom. group; Q is 1-6C linear or branched alkylene, or cycloalkylene; R<2> and R<3> are each H, cyano, alkyl, alkoxycarbonyl, or carbamoyl, or R<2> and R<3> combine with each other to form a condensed arom. or heteroarom. ring; and X is BF4, PF6, SbF6, SbF5(OH), or AsF6] (e.g. a compd. of formula II) is compound with a carbonyl compd. capable of undergoing cleavage by irradiation with rays of light (e.g. 4,4'-dichlorobenzoin or alpha-dimethoxyacetophenone) as a promoter to give the title compsn., which is compounded with a cationically polymerizable compd. (e.g. allyl glycidyl ether) to give a photopolymerizable compsn.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a photocuring catalyst composition used as a polymerization initiator for cationically polymerizable resins.

(Prior Art and its Problems) Even if a compound is cationically polymerizable, polymerization does not proceed even if it is used alone and irradiated with light. Therefore, it is common practice to use a catalyst that generates a Lewis acid upon irradiation with ultraviolet rays and acts as a cationic polymerization initiator (US Pat. No. 3,708,296, etc.). These compositions cure rather slowly and have poor continuous operation.

JP-A-57-209931 proposes that the exposure time required for curing can be considerably shortened by combining a wide range of pyridinium salts and carbonyl compounds with cationically polymerizable compounds. However, this technique has the disadvantage that the variety of nitrogen-containing rings is small and the range of application is narrow.

(Means for Solving the Problems) As a result of studies to solve the above drawbacks, the present inventors discovered that a pyridinium salt different from the pyridinium salt disclosed in JP-A-57-209931 exhibits superior effects. The present invention has been accomplished. That is, the present invention provides formula (A) in which R1 is hydrogen or an aromatic group which may have a substituent, and Q is a linear or branched alkylene group having 1 to 6 carbon atoms or a 7-chloroalkylene group. , R2 and R
3 are the same or different hydrogen or cyano group, or R2
and an aromatic ring or heteroaromatic ring to which R3 is fused, and X represents BF4, PF, , S bF a, S bF 5 (OH), or A s Fe. ] and (B) a photocuring catalyst composition containing a carbonyl compound that can be cleaved by light irradiation. Furthermore, a photopolymerizable resin composition containing this composition and a cationic polymerizable compound is provided.

Strictly speaking, the compound of component (A) used in the present invention is included in US Pat. No. 4,069,056, but specific practical data are not listed. In the present invention, it is only when this component (A) is combined with a specific carbonyl compound that (A) exerts its effect as a highly active cation catalyst that cannot be removed alone. Don't suggest it.

In formula I, R1 is preferably hydrogen or a substituted phenyl group. Q is preferably a linear or branched alkylene group having 1 to 6 carbon atoms. R'' and R
3 is preferably hydrogen, a cyan group, or a phenyl group in which both are condensed. Preferred compounds (I) are m-methylbenzyl-m-cyanopyridinium hexafluoroantimonate, 0-methylbenzyl-0-cyanopyridinium hexafluoroantimonate, 2,4-dimethylben/m-cyanopyridinium・Hexafluoroantimonite, m-methylhensyl-mcyanopyrinium, p-toluenesulfonate, 0-methylben/
Ru 0-7 Anopyrinnium p-toluenesulfonate, 2,4-dimethylben/Ru m-cyanopyridinium p-toluenesulfonate, p-nitrohensyl O-benzoylpyridinium hexafluoroantimonite, o -Nitrobenzyl-p-cyanopyridinium hexafluoroantimonite, p-methquinbenzyl-p-cyanopyridinium hexafluoroantimonite, p-methoxy7henzyru〇-chloropyridinium hexafluoroantimonite -+ -1p-t-butylbenzyl-cyanopyridinium hexafluoroantimonate, p-methylbenzyl-3-cyanoquinolinium hexafluoroantimonate, m-methylpencyl-2-cyanoquinolinium hexafluoroantimonate, 0-Methylbenzylquinolinium hexafluoroantimonite, 2,4-/methylhensylquinolinium hexafluoroantimonite, 3,4-dimethylhensylquinolinium hexafluoroantimonite , p-nitrohenol-2-nitroquinolinium hexafluoroantimobut, p-methoxyhen/-chloropyrinium hexafluoroantimobut, p-t-butylhenen-quinolinium hexafluoroantimobut Antimonite, methyl-m-cyanopyridinium hexafluoroantimonite, methyl-m
-7 Anoquinolinium hexafluoroantimonate, methyl-m-cyanopyrinnium hexafluoroantimonate, ethyl-m-cyanopyrinnium hexafluoroantimonate, p-chlorohensyl-p-
Cyanopyridinium hexafluorophosphate, p
-Nitrobenzyl-p-cyanopyridinium hexafluorophosphate.

The compound of the formula (1) is a compound of the formula (1) in which pyridine of the formula (2) (wherein R1 and R3 are the same as above) is converted into a compound of the formula (2) R'-Q-Ha(1 (Ill) (
In the formula, R1 and Q are the same as above. HaQ represents halogen. ) can be synthesized by quaternizing with a halokenated compound and exchanging the halide anion of the resulting pyridinium halide with an X- ion. That is,
A compound of formula I is obtained by reacting a pyridinium halide corresponding to the pyridinium salt of formula (1) with an alkali metal salt of X-ion.

The compound of formula (1) cleaves when the temperature rises to yield the corresponding cationic species, initiating a polymerization chain reaction of the cationically polymerizable compound.

The photolytically cleavable carbonyl compound of component (B) acts as a promoter. Examples of such compounds are benzoin and its derivatives, benzyl and its derivatives, α-di- and trisubstituted acetophenones. When this type of compound is exposed to a short wavelength light source, it splits into two lanocal fragments, one of which is anosila/cal. These radicals are capable of initiating a polymer/car chain reaction and act as radical polymerization initiators.

As component (B), the following formula % formula % [where Ar is a phenyl group, an alkyl group having 1 to 4 carbon atoms, a halokene, an alkyl group having 1 to 4 carbon atoms, a phenokyne group, an alkylthio group having 1 to 4 carbon atoms] or phenyl group substituted with phenylthio group, R4 is hydrogen, carbon number 1
-12 alkyl group, C3-15 alkoxyalkyl group, phenyl group, C1-4 alkyl group or phenyl group substituted with halogen, R5 is hydrogen,
an alkyl group having 1 to 4 carbon atoms, an allyl group, a benzyl group, or a phenyl group; R6 is defined as hydrogen or Ar; R7 is an alkyl group having 1 to 4 carbon atoms; 1 or more carbon atoms substituted with an alkoxy group
4 alkyl group, R8, R8 each independently have 1 carbon number
-8 alkyl group, -○H, alkoxy group having 1 to 4 carbon atoms, alkyl group having 1 to 8 carbon atoms substituted with a phenyl group, alkylene group having 4 to 7 carbon atoms when R8R8 are combined, RIQ is hydrogen, an alkyl group having 1 to 4 carbon atoms, a benzyl group, an allyl group, a 2-cyanoethyl group, a phenyl group, or a group represented by S:(R', R1'')
11 and R11 are methyl and phenyl groups, respectively) RI
3 is a tertiary alkyl group having 4 to 12 carbon atoms, or a phenyl group substituted at both ortho positions with an unsubstituted or alkyl group having 1 to 4 carbon atoms, or a halogen; R14 and R15 are each independently , represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a phenyl group substituted with a halogen. .

] Examples of the compound represented by formula (1) are hengeine, 4
4'-Dichlorohenzoin, α-methylhenzoin, methyl ether, ethyl ether, isopropyl ether, nibutyl ether, isobutyl ether, amyl ether, hebenzoin, octyl or dodenyl ether, benzylbenzoin-butyl ether, and 44''-α-dimethoxybenzoin-isopropyl ether.

Examples of the compound represented by formula (2) are α-dimethoxyacetophenone, α-jethoxyacetophenone, benzyldimethyl ketal, benzyl-diethyl ketal, penzyludi(2-chloroethyl)ketal, penzyludi(2-butoxyethyl)ketal, benzyl dibutyl ketal, 4,4'' dichlorobenzyl-diethyl ketal and 4,4'' dichlorobenzyl-dimethyl ketal.

An example of the compound represented by formula (3) is 1,2-benzoyl-propanol-2,2'-(4-isopropylbenzoyl)-propanol-2,2-(4-tert-butylbenzoyl)-7' opanol-2,2-(4chlorobenzoyl)-furopanol-2,2-(4methylbenzoyl)-butanol-2,2-penzoylbutanol-1,2,l-penzoylunclopenol Tanol, 1
-henzoylune clohexanol, 1-(4-isopropylbenzoyl)-cyclohexanol, 1-(4-
These are chlorobenzoyl)-cyclooctatool, α-methoxy-inbutyrophenone, α-cyanoethoxyisobutyrophenone, α-phenogynone-4-chloroa-inbutyrophenone, and α-trimethylsiloxy-isobutylphenone.

Examples of the compound represented by formula (4) are 1,3,5-trinotylbenzoyl-diphenylphosphine oxide, 2
, 6-dichlorobenzoyl diphenylphosphine oxide, 2.6-simethoxybenzoyl diphenylphosphine oxide, methyl 1.3.5-1-limethylbenzoyl diphenylphosphine oxide, bivaloyru diphenylphosphine oxide , and methyl-pivaloyl-phenylphosphinate.

The amount of cocatalyst as component (B) required for the method of the invention is:
10 to 1000 mol% based on (A), preferably 50
It is 0 to 400 mol%.

The photocuring catalyst composition of the present invention may contain a photosensitizer (C) that shifts the spectral sensitivity to a specific range. Examples of photosensitizers include acetone, benzene, acetophenone, benzophenone, naphthalene, biacetylene, aeonne, rose bengal, perylene, thioxanthone, anthraquinone. The photosensitizer (C) is present in the catalyst composition in an amount of 1 to 200 mol%, preferably 10 to 200 mol% based on (A).
It is blended in an amount of ~100 mol%.

The photocuring catalyst composition of the present invention can be easily obtained by mixing the above components. The resulting composition is combined with a cationically polymerizable compound to form a photopolymerizable resin composition.

Cationically polymerizable compounds are, for example, enzymes or sulfur-containing saturated heterocyclic compounds, especially 3-, 4- or 5-membered ring compounds and derivatives thereof. Examples of such compounds include ethylene oxide, propanediol, epichlorohydrin, styrene oxide, oquinane trimethylene oxide such as phenyl glycidyl ether or butyl glycidyl ether, 3,3-dimethyloxetane, or 3,3-dimethyloxetane, oxetanes such as methyl)-oxetane; tetrahydrofuran, or 2,3
-Oxolane such as dimethyltetrahydrofuran, trioxane, 1,3-dioxolane or 1 3 6-
Cyclic acetals like trioxane clooctane: β
- cyclic lactones and their alkyl derivatives such as propiolactone, ε-caprolactone; thiranes such as ethylene sulfide, 1°2-propylene sulfite or thioevich chlorohydrin; 1,3-propylene sulfide or 3, Examples include thietane such as 3-dimethylthietane.

The polymerizable compounds of the present invention are also ethylenically unsaturated compounds that can be polymerized by cationically active species. Such compounds include mono- and diolefins, such as isobutylene, 1-octene, butadiene, high isopropylene, styrene, allylhensen or vinylchlorohexane; vinyl ethers, such as vinyl methyl ether, vinyl isobutyl ether, ethylene glycol divinyl ether; vinyl esters. For example vinyl acetate or vinyl stearate: N-vinyl compounds such as N-vinylpyrrolidone or N-vinylcarbazole and dihydropyran derivatives such as 34-dihydro-2H-pyran-2 of 2-hydroquinemethyl-34-dihydro-2H-pyran. −
Includes carbonic acid esters, etc.

Of particular importance among the above-mentioned polymerizable compounds are epoxy compounds, especially di- and polyepoxides and epoxy resin prepolymers, such as those used for producing epoxy resins.

These curing reactions are usually performed by heating.

When the combined catalyst according to the invention is used, epoxides can be photochemically cured without the addition of chemical reactants.

The di- or polyepoxides used for this purpose are aliphatic, cycloaliphatic or aromatic. Examples of these include glycidyl ethers of aliphatic or cycloaliphatic diols or polyols, such as ethylene glyfur, propanediol-1,2, propanediol-
1,3, butanediol-1,4, diethylene glycol, glycerol, trimethylolpropane, 1,4-
dimethylol-cyclohexane or 2,2-bis(4
-Glycidyl ether of -hydroxychlorohequinyl)-propane, glycidyl ether of di- or borophene, such as resolunol, 4°4°-dihydroxydiphenylmethane, 2,2-di(4-hydroxyphenyl)-propane or glycidyl of novolak. Ether can be given. Further examples of these compounds include N-glycidyl compounds, such as digrinnor compounds of ethylene urea, 1,3-propylene urea, 5-dimethylothantoin or 4,4'-methylene-5,5'-tetramethyl-dihydantoin, or triglycidyl compounds. One example is glycidyl isocyanurate.

Commercially important gly/nor compounds are the gly/nor esters of carbonic acids, particularly socarfonic and polycarphonic acids. Examples of such compounds are ampic acid, phthalic acid,
Terephthalic acid, tetra- or hexahydrophthalic acid,
Glycidyl ether of isophthalic acid or trimellitic acid.

Examples of polyepoxides that are not glycidyl compounds are vinylchlorohexene, dicyclopentadiene sieboxide, 3-(3°, 4′-epoxycyclohexyl)-8,
9-Epoxy-2,4-dioxaspiro[5,5]-undecane, 3,4-epoxycyclohexanecarphonic acid-3',4'-epoxyhexylmethyl ester, butadiene- or isobrendiepoquine, Epoxidized linoleic acid derivatives or epoxidized polybutadiene.

Ethylenically unsaturated compounds/compounds that are capable of polyfunctional reactions under the reaction conditions and thus produce crosslinked resins can also be used. Examples of such compounds are:
Allylic acid glycidyl ether, acrylic acid- or methacrylic acid glycidyl ester, or unsaturated polyepoxy resins such as, for example, partially (meth)-acrylated epoxy resins.

The ebony/compounds can be used as a mixture with each other or with other cationically polymerizable compounds in order to modify, for example, the physical properties of the resulting resin. An example of such a mixture is a mixture of polygrinyl ether and evoquinated Soyura, which exhibits high elasticity and flexibility after cooling.

The photopolymerizable composition of the present invention comprises the above-mentioned cationic polymerizable compound 1.
0.01 to 0.00 parts by weight of the photocuring catalyst composition
It contains 10 parts by weight, preferably 0.1 to 5 parts by weight. The photopolymerizable composition of the present invention may contain other additives, such as a photosensitizer, if necessary.

(Effects of the Invention) The photocuring catalyst composition of the present invention acts as a highly active cationic polymerization catalyst. The photopolymerizable compositions obtained therewith are also very useful in applications such as protective, decorative and insulating coatings, injection compounds, wire insulation, sealants, varnishes, etc.

(Example) The present invention will be explained in more detail with reference to Examples. The invention is not limited to these examples.

Production Example 1 Benzylquinolinium hexafluoroantimonate penzyl chloride 4.1.6g<0.033mol)
and 3.87 g (0.03 mol) of quinoline were dissolved in 40 mC of methanol and heated under reflux at 80°C for 10 hours. After the reaction was completed, the solvent was distilled off, water ether was added to the residue, and unreacted substances were washed with the ether layer. Sodium hexafluoroantimonate7,74 in the aqueous layer containing chloride
g (Add 0.03mol, filter the formed precipitate,
After drying, the desired product was obtained.

Hereinafter, component A was synthesized in the same manner.

Component A p-nitrophyridinium hexafluoroantimonite IR (cm=); 3550, 3140. 1950
3150.3070,1638
゜1450 64.0 n+, p, = 153°C Hennorquinolinium hexafluoroantimonite IR (cm-'): 3070. I 580.
I 520° + 350 635 m, p, = 147-1506C Methylnor/pyrinnium fluoroantimo monomer bF8 IR (cm-'); 1645. 1570. 1
520°, p, = 153 to 154°C Examples 1 to 10 Component (A) and component (B) in Table 1, component (C
) were mixed in the ratio shown in Table 1 to obtain the photocuring catalyst composition of the present invention.

Epoxy resin (1=1 mixture of YD~8125 commercially available from Tobu Kasei Co. and ERL4206 commercially available from UCC)
The above photocuring catalyst composition was mixed with No. 19 in the proportions shown in Table 1, applied to a tin plate, and then irradiated with UV using an ultra-high pressure mercury lamp, and the total amount j/cπ2 until it became tack-free was measured. The results are shown in Table-1.

Claims (1)

[Claims] 1. Formula (A) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (1) [In the formula, R^1 is hydrogen or an aromatic group that may have a substituent, and Q is the number of carbon atoms an alkylene group or a cycloalkylene group having 1 to 6 straight or branched chains, R^2 and R^3 are the same or different and are hydrogen, a cyano group, an alkyl group, an alkoxycarbonyl group, a carbamoyl group, or R^2 and an aromatic ring or heteroaromatic ring fused with R^3, and X is BF_4, PF_6, SbF_6, Sb
Indicates F_5(OH) or AsF_6. ] A photocuring catalyst composition containing a compound represented by these and (B) a carbonyl compound that can be cleaved by light irradiation. 2. The carbonyl compound (B) has a formula: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (2), ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (3) or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (4) ) [wherein Ar is a phenyl group, an alkyl group having 1 to 4 carbon atoms, a halogen, an alkoxy group having 1 to 4 carbon atoms, a phenoxy group, an alkylthio group having 1 to 4 carbon atoms, or a phenyl group substituted with a phenylthio group, R^4 is hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkoxyalkyl group having 3 to 15 carbon atoms, a phenyl group, an alkyl group having 1 to 4 carbon atoms, or a phenyl group substituted with a halogen; R^5 is hydrogen , an alkyl group having 1 to 4 carbon atoms, an allyl group, a benzyl group, or a phenyl group, R^6 is defined as hydrogen or Ar, R^7 is an alkyl group having 1 to 4 carbon atoms, halogen or a carbon number 1 an alkyl group having 1 to 4 carbon atoms substituted with an alkoxy group of ~12, R^8 and R^9 are each independently an alkyl group having 1 to 8 carbon atoms, -OH, an alkoxy group having 1 to 4 carbon atoms; , carbon number 1- substituted with phenyl group
8 alkyl group, R^8R^9 together have 4 carbon atoms
~7 alkylene group, R^1^0 is hydrogen, carbon number 1-4
alkyl group, benzyl group, allyl group, 2-cyanoethyl group, phenyl group or S: (R^1^1)_2R^1
A group represented by ^2 (however, R^1^1 and R^1
^2 are methyl and phenyl groups, respectively) R^1^3 is a tertiary alkyl group with 4 to 12 carbon atoms, or phenyl substituted at both ortho positions with an unsubstituted or alkyl group with 1 to 4 carbon atoms or a halogen. The groups R^1^4 and R^1^5 are each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, or an alkyl group having 1 to 4 carbon atoms. , represents an alkoxy group having 1 to 4 carbon atoms or a phenyl group substituted with a halogen. ] The photocurable catalyst composition according to claim 1. 3. A photocuring catalyst composition further comprising (C) a photosensitizer. 4. A photopolymerizable resin composition containing the photocurable catalyst composition according to claim 1 and a cationically polymerizable compound.