JP2002241474A - Photocurable resin composition containing aromatic sulfonium compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photo-cation-curable resin composition excellent in transparency and storage stability, and generating no benzene from a photo-cationic- polymerization initiator component, even when the cured film obtained by photo- irradiation is heat treated further. SOLUTION: This photo-cation-curable resin composition is obtained by compounding a cationically polymerizable compound with a photo-cationic- polymerization initiator which is a synthesized triallyl sulfonium salt having a specific structure wherein all the benzene rings in the structure are directly bonded to carbon atoms as substituents.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cationic photopolymerization initiator (A) which is a triallylsulfonium compound, and a photocurable resin containing the same and one or more cationically polymerizable compounds (B). The present invention relates to a composition, and a cured product obtained by irradiating the photocurable resin composition with an active energy ray.

[0002]

2. Description of the Related Art Photocurable resin compositions have been actively studied in the fields of printing inks, paints, coatings, liquid resist inks, etc. from the demands of energy saving, space saving, and pollution-free properties, and are used industrially. Most of these use the photoradical polymerization of unsaturated double bonds. In recent years, industrial application of a method of photocationically polymerizing an epoxy resin by containing a photocationic polymerization initiator has been studied. The method of photocationically polymerizing a cationically polymerizable substance such as an epoxy resin by irradiating an active energy ray such as an ultraviolet ray or an electron beam is compared with a method of photoradical polymerization of an acrylate compound or the like by irradiation of an active energy ray. The curing shrinkage is small, and it is not affected by oxygen during curing.
It has various features that are advantageous when compared with a method of curing by photoradical polymerization. When the cationically polymerizable substance is subjected to photocationic polymerization by irradiating an active energy ray such as an ultraviolet ray or an electron beam, a photocationic polymerization initiator that generates an acid upon irradiation with the active energy ray is blended. As photocationic polymerization initiators, onium salts represented by aromatic diazonium salts, iodonium salts, sulfonium salts, phosphonium salts, selenonium salts, and the like, and metal arene complexes are already known, and these are mixed with a cationic polymerizable substance. US Pat. No. 4,690,054 discloses that when irradiated with an active energy ray, the Bronsted acid or Lewis acid generated by the irradiation with the active energy ray acts on the cationic polymerizable substance to induce polymerization.
No. 4,450,360, No. 4,576,999, No. 4,640,967, Canadian Patent No. 127274646, and European Patent No. 203829. Also, Advances in Polymer S
science 62, Initiators-Pory
Reactions-Optical Activ
ty, p1 to p48, Springer-Verlag
(1984), Latest UV curing technology, edited by Technical Information Association, p.
29 (1991). In particular,
Some triallylsulfonium salts are commercially available as industrially useful cationic photopolymerization initiators.

[0003]

However, the cationic photocurable resin composition generally has a lower curing speed than the photoradical curable resin composition containing an acrylate compound and the like, and is more curable from the market. There is a need for a photocationically curable resin composition having an excellent composition. The reason why the curing speed is not improved is that the cationic photopolymerization initiator itself has poor solubility in the cationically polymerizable compound. In the case of a commercially available photocationic polymerization initiator having a triallylsulfonium salt as a basic structure, for example, a structure such as a phenylthio group or a phenyl group bonded to a sulfur atom serving as a sulfonium cation may be used. It has a benzene ring having only a substituent bonded to a sulfur atom. When such a structure has a benzene ring having only a substituent having only a bond with a sulfur atom, the solubility of the cationic photopolymerization initiator itself in the cationically polymerizable compound tends to decrease. Therefore, when stored in a dark place for a long time in a cationic polymerizable compound,
In some cases, storage stability is poor, for example, a crystallized product due to the cationic photopolymerization initiator component is generated and precipitated. In addition, a resin composition containing a cationic photopolymerization initiator having a benzene ring having only a substituent directly bonded to a sulfur atom in a structure may be cured by irradiating an active energy ray with the active energy ray. And then heat-treated to obtain a sufficient cured film, the benzene is released due to the breakage of the relatively weak bond between the carbon atom and the sulfur atom in the structure of the cationic photopolymerization initiator. there's a possibility that.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have been characterized in that all benzene rings in the structure are directly bonded to carbon atoms as substituents. Synthesize triallylsulfonium salt and use it as a photo-cationic polymerization initiator to improve the solubility of the photo-cationic polymerization initiator itself in the cationically polymerizable compound. It is excellent in curability by irradiation with radiation, and even when a heat treatment is performed on the obtained cured film, it is possible to obtain a cationic photocurable resin composition that does not generate benzene from the photocationic polymerization initiator component of the cured product. Successful.
That is, the present invention provides [1] the following formula (1)

[0005]

Embedded image

Wherein R _{1 to} R ₅ are each a hydrogen atom, C
_{2- C18} linear or branched alkyl group, trifluoromethyl group, pentafluoroethyl group, cyclohexyl group, cyclohexylmethyl group, benzyl group, 2-hydroxyethyl group, 2-methoxyethyl group, 2-ethoxyethyl represents any substituent selected from the group consisting of groups or cyano groups, X is selected from the group consisting of linear or branched alkyl group, a trifluoromethyl group or pentafluoroethyl group of C ₁ -C ₁₈ Y represents any substituent, and Y represents an atomic group that can be a monovalent anion. However, all of R _{1 to} R ₅ do not simultaneously represent a hydrogen atom. A) a cationic cationic polymerization initiator (A), which is a triallylsulfonium compound represented by the following formula:
A photocurable resin composition containing at least one kind or two or more cationically polymerizable compounds (B), wherein in formula (1), any one of R _{1 to} R ₅ is trifluoromethyl a group, X is C ₁ -C straight or branched alkyl group of _4, the optical cationic polymerization initiator is any substituent selected from the group consisting of a trifluoromethyl group or a pentafluoroethyl group (a The photocurable resin composition according to [1], wherein in the formula (1), the anion part represented by Y ⁻ is SbF ₆ ⁻ or PF ₆ ^−. The photocurable resin composition according to [1] or [2], comprising a cationic polymerization initiator (A); [4] the one or more cationically polymerizable compounds (B) At least one of them is more than one in one molecule. The photocurable resin composition according to any one of [1] to [3], which is a compound having an xy group, and [5] the cationic cationic polymerization initiator (A) is added in an amount of: The photocurable composition according to any one of [1] to [4], wherein the content is 0.1 to 10% by weight based on the one or more cationically polymerizable compounds (B). Resin composition, [6] [1] to [5]
A cured product obtained by curing the photocurable resin composition according to any one of the above.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The cationic photopolymerization initiator (A) represented by the above formula (1) of the present invention is obtained by reacting a compound having a cation portion of the above formula (1) with an alkali metal salt of an anion portion. Obtainable. The compound having a cation moiety of the formula (1) is a benzene derivative represented by the following formula (2)

[0008]

Embedded image

(Wherein R _{1 to} R ₅ have the same meanings as in formula (1)) and a reaction for producing a known triallylsulfonium salt using a diphenylsulfoxide derivative, for example, JP-A-7- No. 82244 and JP-A-7-8
The compound can be synthesized using the method described in JP-A-2245.

[0010] In benzene derivative represented by the formula used here (2), specific examples of straight-chain or branched alkyl group of C ₂ -C _{1 8,} for example, an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, n-hexyl group, isohexyl group, n-heptyl group, isoheptyl group, n-octyl group, Isooctyl group, 2-ethylhexyl group, n-nonyl group, isononyl group, n-decyl group, isodecyl group, n-lauryl group, isolauryl group, n-stearyl group, isostearyl group, and the like. To an alkyl group having 1 to 4 carbon atoms. However, an alkyl group having 5 or more carbon atoms may be preferable depending on the cationically polymerizable compound to be dissolved.

Specific examples of the benzene derivative represented by the formula (2) which can be used in the reaction include, for example, ethylbenzene, o-diethylbenzene, m-diethylbenzene,
-Diethylbenzene, 1,2,3-triethylbenzene, 1,2,4-triethylbenzene, 1,2,3,5
-Tetraethylbenzene, 1,2,4,5-tetraethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, te
rt-butylbenzene, n-pentylbenzene, isopentylbenzene, n-hexylbenzene, isohexylbenzene, n-heptylbenzene, isoheptylbenzene, n-octylbenzene, isooctylbenzene, 2
-Ethylhexylbenzene, n-decylbenzene, isodecylbenzene, n-laurylbenzene, isolaurylbenzene, n-stearylbenzene, isostearylbenzene, trifluoromethylbenzene, pentafluoroethylbenzene, cyclohexylbenzene, cyclohexylphenylmethane, diphenylmethane, ( Examples thereof include (2-hydroxyethyl) benzene, (2-methoxyethyl) benzene, (2-ethoxyethyl) benzene, and benzonitrile.

Among the substituents (X in the formula (1)) in the diphenylsulfoxide compound to be reacted with the compound represented by the formula (2), the straight-chain or branched alkyl group having 1 to 18 carbon atoms includes: A methyl group and the aforementioned R _{1 to} R ₅
And an alkyl group having 1 to 4 carbon atoms is preferable from the viewpoint of molecular weight. However, an alkyl group having 5 or more carbon atoms may be preferred depending on the cationically polymerizable compound to be dissolved.

Specific examples of the diphenylsulfoxide compound which can be used when reacting with the compound represented by the formula (2) include, for example, 4,4'-dimethyldiphenylsulfoxide, 4,4'-diethyldiphenylsulfoxide, 4,4'-di-n-propyldiphenylsulfoxide, 4,4'-diisopropyldiphenylsulfoxide, 4,4'-di-n-butyldiphenylsulfoxide, 4,4'-diisobutyldiphenylsulfoxide,
4,4′-di-tert-butyldiphenylsulfoxide, 4,4′-di-n-pentyldiphenylsulfoxide, 4,4′-diisopentyldiphenylsulfoxide, 4,4′-di-n-hexyldiphenylsulfoxide, 4,4′-diisohexyldiphenylsulfoxide, 4,4′-di-n-heptyldiphenylsulfoxide, 4,4′-diisoheptyldiphenylsulfoxide, 4,4′-di-n-octyldiphenylsulfoxide, 4, 4'-diisooctyldiphenylsulfoxide, 4,4'-di (2-ethylhexyl) diphenylsulfoxide, 4,4'-di-n-decyldiphenylsulfoxide, 4,4'-diisodecyldiphenylsulfoxide, 4,4'- Di-n-lauryldiphenylsulfoxide, 4,4'-diisolauryldiphenyls Hoxide, 4,4'-di-n-stearyldiphenylsulfoxide, 4,4'-diisostearyldiphenylsulfoxide, 4,4'-di (trifluoromethyl) diphenylsulfoxide, 4,4'-di (pentafluoroethyl )
Diphenyl sulfoxide and the like can be mentioned.

The reaction between the compound represented by the formula (2) and the diphenylsulfoxide compound is carried out in an acid solvent using a condensing agent. Specific examples of the acid solvent that can be used include, for example, methanesulfonic acid, ethanesulfonic acid, and trifluoromethanesulfonic acid. Specific examples of the condensing agent that can be used include, for example, diphosphorus pentoxide, acetic anhydride, polyphosphoric acid, concentrated sulfuric acid, and the like. The amount of the acid solvent used is usually 1 to 10 parts by weight per 1 part by weight of the condensing agent.
It is preferable to use 0 parts, more preferably 5 to 10 parts. The amount of the condensing agent to be used is generally preferably 0.5 to 10.0 mol, more preferably 0.9 to 1.5 mol, per 1 mol of the diphenylsulfoxide compound. The reaction temperature is usually preferably from 10 to 100 ° C, more preferably from 20 to 60 ° C. The reaction time is usually preferably from 0.5 to 60 hours, more preferably from 2 to 6 hours.

The cationic photopolymerization initiator (A) of the present invention comprises:
After completion of the condensation reaction, the obtained condensation reaction solution is diluted by pouring it into water, and an alkaline alkali metal such as lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate or potassium carbonate is diluted. It can be obtained by adjusting the pH to 5 to 7 by using the salt as it is or as an aqueous solution, reacting with an alkali metal salt having Y- in the above formula (1) as an anion part, and performing salt exchange. In the salt exchange, the condensation reaction solution may be dropped into an aqueous solution of an alkali metal salt, or the condensation reaction solution may be further diluted with water as needed, and a solid of the alkali metal salt may be added thereto.

The alkali metal salt which can be used in the salt exchange
As a specific example, for example, LiSbF ₆, NaSbF₆, KS
bF₆, LiSbF_FiveOH, NaSbF_FiveOH, KSbF_FiveOH,
LiSbF_Four(OH)_Two, NaSbF_Four(OH)_Two, KSbF
_Four(OH)_Two, LiAsF₆, NaAsF₆, KAsF₆, LiAs
F_FiveOH, NaAsF_FiveOH, KAsF_FiveOH, LiAsF
_Four(OH)_Two, NaAsF_Four(OH)_Two, KAsF_Four(O
H)_Two, LiPF₆, NaPF₆, KPF₆, LiPF_FiveOH,
NaPF_FiveOH, KPF_FiveOH, LiPF_Four(OH)_Two, Na
PF _Four(OH)_Two, KPF_Four(OH)_Two, LiBF_Four, NaB
F_Four, KBF_Four, LiSbCl₆, NaSbCl₆, KSbCl₆,
LiAsCl₆, NaAsCl₆, KAsCl₆, LiPCl₆, Na
PCl₆, KPCl₆, LiBCl_Four, NaBCl_Four, KBCl_Four,
LiSbBr₆, NaSbBr₆, KSbBr₆, LiAsBr₆, Na
AsBr₆, KAsBr₆, LiPBr₆, NaPBr₆, KPB
r₆, LiBBr_Four, NaBBr_Four, KBr_Four, LiClO_Four, Na
ClO_Four, KClO_Four, CF_ThreeSO_ThreeLi, CF_ThreeSO_ThreeNa, C
F_ThreeSO_ThreeK, CH_ThreeSO_ThreeLi, CH_ThreeSO_ThreeNa, CH_ThreeS
O_ThreeK, lithium p-toluenesulfonate, p-tolue
Sodium sulfonate, potassium p-toluenesulfonate
And tetrakis (pentafluorophenyl) borate
Titanium, tetrakis (pentafluorophenyl) borate
Sodium, tetrakis (pentafluorophenyl) pho
Potassium borate, tetrakis (4-fluorophenyl) pho
Lithium oxalate, tetrakis (4-fluorophenyl) pho
Sodium oxalate, tetrakis (4-fluorophenyl)
Potassium borate and the like can be mentioned. These al
Curing performance of cationic photopolymerization initiator among potassium metal salts
If more emphasis is placed on price and availability
Is KSbF₆Is preferred and safety is more important
Is KPF₆Is preferred. Benze represented by the above formula (2)
Reaction solution of a diphenyl sulfoxide derivative with a diphenyl sulfoxide derivative
When the solution is added dropwise to the aqueous solution of the alkali metal salt
The temperature is usually preferably from 0 to 80 ° C, more preferably
10 to 40 ° C. The concentration of the aqueous solution of the alkali metal salt
The degree is usually preferably 1 to 30% by weight, more preferably 5 to 30% by weight.
-10% by weight. The aqueous solution of the alkali metal salt
The amount is 0.5 to 30 times the volume of the condensation reaction solution by volume.
Is preferred, and more preferably 2 to 5 times. Dripping
After completion, stir for about 1 hour, filter, wash with water, and dry
The optical click according to the present invention represented by the above formula (1)
An on-polymerization initiator (A) can be obtained.

Specific examples of the photo-cationic polymerization initiator (A) of the present invention thus obtained include, for example, (4-ethylphenyl) di (4-toluyl) sulfonium hexafluoroantimonate, Phosphoric acid (4-ethylphenyl) di (4-toluyl) sulfonium, tetrafluoroborate (4-ethylphenyl) di (4-toluyl) sulfonium, perchloric acid (4-ethylphenyl) di (4- Toluyl) sulfonium, trifluoromethanesulfonic acid (4-ethylphenyl) di (4-tolyl) sulfonium, methanesulfonic acid (4-ethylphenyl) di (4-
Toluyl) sulfonium, p-toluenesulfonic acid (4
-Ethylphenyl) di (4-toluyl) sulfonium,
(4-ethylphenyl) di (4-toluyl) sulfonium tetrakis (pentafluorophenyl) borate, (4-ethylphenyl) di (4-toluyl) sulfonium tetrakis (4-fluorophenyl) borate, antimony hexafluoride (4-Isopropylphenyl) di (4-toluyl) sulfonium, hexafluorophosphate (4-isopropylphenyl) di (4-toluyl) sulfonium, tetrafluoroborate (4-isopropylphenyl) di (4-toluyl) Sulfonium, trifluoromethanesulfonic acid (4
-Isopropylphenyl) di (4-toluyl) sulfonium, tetrakis (pentafluorophenyl) borate (4-isopropylphenyl) di (4-toluyl) sulfonium, antimony hexafluoro (4-n-butylphenyl) di (4 -Toluyl) sulfonium, hexafluorophosphate (4-n-butylphenyl) di (4-toluyl) sulfonium, tetrafluoroborate (4-n-butylphenyl)
Di (4-toluyl) sulfonium, trifluoromethanesulfonic acid (4-n-butylphenyl) di (4-toluyl) sulfonium, p-toluenesulfonic acid (4-n-
Butylphenyl) di (4-toluyl) sulfonium, tetrakis (pentafluorophenyl) borate (4-n-
Butylphenyl) di (4-toluyl) sulfonium, (4-n-hexylphenyl) di (4-toluyl) sulfonium hexamonate antimonate, hexafluorophosphoric acid (4-
n-hexylphenyl) di (4-tolyl) sulfonium, (4-n-hexylphenyl) di (4-toluyl) sulfonium tetraborate, trifluoromethanesulfonic acid (4-n-hexylphenyl) di (4- (Toluyl) sulfonium, tetrakis (pentafluorophenyl) borate (4-n-hexylphenyl) di (4-toluyl) sulfonium, antimony hexafluoride (4-n-
Octylphenyl) di (4-toluyl) sulfonium,
Hexafluorophosphoric acid (4-n-octylphenyl) di (4-
Toluyl) sulfonium, (4-n-octylphenyl) di (4-tolyl) sulfonium trifluoromethanesulfonate, (4- (2-ethylhexyl) phenyl) di (4-toluyl) sulfonium hexafluoroantimonate, hexafluoride (4- (2-ethylhexyl) phenyl) di (4-toluyl) sulfonium phosphate, (4- (2-ethylhexyl) phenyl) di (4-toluyl) sulfonium trifluoromethanesulfonate, antimony hexafluoride (4- n-laurylphenyl) di (4-toluyl) sulfonium, hexafluorophosphate (4-n-laurylphenyl) di (4-toluyl) sulfonium, trifluoromethanesulfonic acid (4-n-laurylphenyl) di (4- Toluyl) sulfonium, antimony hexafluoride (4-n-stearyl) Enyl) di (4-toluyl) sulfonium, (4-n-stearylphenyl) di (4-tolyl) sulfonium hexafluorophosphate, (4-n-stearylphenyl) di (4-toluyl) sulfonium trifluoromethanesulfonate (3-trifluoromethylphenyl) di (4-toluyl) sulfonium hexafluoroantimonate, (3-trifluoromethylphenyl) di (4-toluyl) sulfonium hexafluorophosphate, tetrafluoroboric acid (3 -Trifluoromethylphenyl) di (4-toluyl) sulfonium, (3-trifluoromethylphenyl) di (4-toluyl) sulfonium perchlorate, trifluoromethanesulfonic acid (3-trifluoromethylphenyl) di (4-toluyl) ) Sulfonium, methanesulfonic acid (3-trifluoromethylphene) Le) di (4-toluyl) sulfonium, p- toluenesulfonic acid (3-trifluoromethylphenyl) di (4-toluyl) sulfonium tetrakis (pentafluorophenyl) borate (3-trifluoromethylphenyl) di (4
-Toluyl) sulfonium, tetrakis (4-fluorophenyl) borate (3-trifluoromethylphenyl)
Di (4-toluyl) sulfonium, (3-pentafluoroethylphenyl) difluoro (4-toluyl) sulfonium antimonate hexafluoride, (3-pentafluoroethylphenyl) di (4-toluyl) sulfonium hexafluorophosphate, (3-pentafluoroethylphenyl) difluoroborate tetra (3-toluyl) sulfonium, trifluoromethanesulfonic acid (3-pentafluoroethylphenyl)
Di (4-toluyl) sulfonium, tetrakis (pentafluorophenyl) borate (3-pentafluoroethylphenyl) di (4-toluyl) sulfonium, tetrakis (4-fluorophenyl) borate (3-pentafluoroethylphenyl) di (4-toluyl) sulfonium,
Hexafluoroantimonate (4-cyclohexylphenyl)
Di (4-toluyl) sulfonium, hexafluorophosphoric acid (4
-Cyclohexylphenyl) di (4-toluyl) sulfonium, (4-cyclohexylmethylphenyl) di (4-toluyl) sulfonium hexafluoroantimonate, (4-cyclohexylmethylphenyl) di (4-toluyl) phosphate hexafluorophosphate Sulfonium, (4-benzylphenyl) di (4-toluyl) sulfonium antimonate hexafluoride, (4-benzylphenyl) difluorophosphate (4-benzylphenyl) di (4
-Toluyl) sulfonium, antimony hexafluoride (4
-(2-hydroxyethyl) phenyl) di (4-toluyl) sulfonium, (4- (2-hydroxyethyl) phenyl) di (4-toluyl) sulfonium hexafluorophosphate, antimonic hexafluoride (4- ( 2-methoxyethyl) phenyl) di (4-toluyl) sulfonium, (4- (2-methoxyethyl) phenyl) di (4-toluyl) sulfonium hexafluorophosphate, antimonic hexafluoride (4- (2- (Ethoxyethyl) phenyl) di (4-toluyl) sulfonium, (4- (2-ethoxyethyl) phenyl) di (4-toluyl) sulfonium hexafluorophosphate, (4-cyanophenyl) dimonate hexafluoroantimonate ( 4-toluyl) sulfonium, hexafluorophosphoric acid (4-
(Cyanophenyl) di (4-toluyl) sulfonium, tri (4-ethylphenyl) sulfonium hexafluoroantimonate, tri (4-ethylphenyl) sulfonium hexafluorophosphate, (4-n-butyl antimonate hexafluoride) Phenyl) di (4-ethylphenyl) sulfonium, hexafluorophosphoric acid (4-n-butylphenyl) di (4-ethylphenyl) sulfonium,
-Ethylphenyl) 4-n-octylphenylsulfonium, di (4-ethylphenyl) hexafluorophosphate 4-n
-Octylphenylsulfonium, di (4-ethylphenyl) 4-n-laurylphenylsulfonium hexafluoroantimonate, di (4-ethylphenyl) 4-n-laurylphenylsulfonium hexafluorophosphate, antimonic hexafluoride Di (4-ethylphenyl) 4-n-stearylphenylsulfonium, di (4-ethylphenyl) 4-n-stearylphenyl) sulfonium hexafluorophosphate, di (4-ethylphenyl) hexamonate antimonate
3-trifluoromethylphenylsulfonium, di (4-ethylphenyl) hexafluorophosphate 3-trifluoromethylphenylsulfonium, di (4-ethylphenyl) hexafluoroantimonate 3-pentafluoroethylphenylsulfonium, hexafluorophosphate Di (4-ethylphenyl) phosphoric acid 3-pentafluoroethylphenylsulfonium, di (4-ethylphenyl) hexafluoroantimonate 4
-(2-methoxyethyl) phenylsulfonium, di (4-ethylphenyl) hexafluorophosphate 4- (2-methoxyethyl) phenylsulfonium, di (4-ethylphenyl) hexafluoroantimonate 4-cyanophenylsulfonium , Di (4-ethylphenyl) hexafluorophosphate 4-
Cyanophenylsulfonium, di (4-isopropylphenyl) hexafluoroantimonate 4-tolylsulfonium, di (4-isopropylphenyl) hexafluorophosphate 4
-Toluylsulfonium, antimony hexafluoride (3-
(Trifluoromethylphenyl) di (4-isopropylphenyl) sulfonium, hexafluorophosphoric acid (3-trifluoromethylphenyl) di (4-isopropylphenyl)
Sulfonium, tri (4-n-butylphenyl) sulfonium hexamonate antimonate
-N-butylphenyl) sulfonium, di (4-n-butylphenyl) hexafluoroantimonate 3-trifluoromethylphenylsulfonium,
n-butylphenyl) 3-trifluoromethylphenylsulfonium, tri (4-ter) antimonate hexafluoride
t-butylphenyl) sulfonium, tri (4-tert-butylphenyl) sulfonium hexafluorophosphate, di (4-tert-butylphenyl) hexafluoroantimonate 4-trifluoromethylphenylsulfonium, hexafluorophosphoric acid Di (4-tert-butylphenyl) 3-
Trifluoromethylphenylsulfonium, di (4-n-hexylphenyl) hexafluoroantimonate 3-trifluoromethylphenylsulfonium, di (4-n-hexylphenyl) hexafluorophosphate 3-trifluoromethylphenylsulfonium, (3-trifluoromethylphenyl) di (4-n-octylphenyl) sulfonium hexamonate antimonate, (3-trifluoromethylphenyl) di (4-n-octylphenyl) sulfonium hexafluorophosphate, hexafluorophosphate (4-ethylphenyl) di (4-n-laurylphenyl) sulfonium fluorinated antimonate, (4-ethylphenyl) di (4-n-laurylphenyl) sulfonium hexafluorophosphate, and di (4 -N-laurylphenyl) 3-trifluoromethylphenylsulfoni Arm, hexafluorophosphate di (4-n-lauryl phenyl) 3-trifluoromethylphenyl sulfonium hexafluoride antimonate (4-ethylphenyl) di (4-n-stearyl phenyl) sulfonium,
Hexafluorophosphoric acid (4-ethylphenyl) di (4-n-stearylphenyl) sulfonium, hexafluoroantimonate di (4-n-stearylphenyl) 3-trifluoromethylphenylsulfonium, hexafluorophosphoric acid diphosphate (4-
n-stearylphenyl) 3-trifluoromethylphenylsulfonium, (4-ethylphenyl) hexafluoroantimonate di (4-trifluoromethylphenyl) sulfonium, hexafluorophosphoric acid (4-ethylphenyl) di (4- Trifluoromethylphenyl) sulfonium, (3-trifluoromethylphenyl) di (4-trifluoromethylphenyl) sulfonium hexamonate antimonate, hexafluorophosphoric acid (3-trifluoromethylphenyl) di (4-trifluoro Methylphenyl) sulfonium, trifluoromethanesulfonic acid (3-trifluoromethylphenyl) di (4-trifluoromethylphenyl) sulfonium, tetrakis (pentafluorophenyl) borate (3-trifluoromethylphenyl) di (4
-Trifluoromethylphenyl) sulfonium, (4-ethylphenyl) hexafluoroantimonate di (4-pentafluoroethylphenyl) sulfonium, hexafluorophosphoric acid (4-ethylphenyl) di (4-pentafluoroethylphenyl) Sulfonium, di (4-pentafluoroethylphenyl) hexafluoroantimonate 3-trifluoromethylphenylsulfonium,
-Pentafluoroethylphenyl) 3-trifluoromethylphenylsulfonium, di (4-pentafluoroethylphenyl) 3-trifluoromethylphenylsulfonium trifluoromethanesulfonate, di (4-pentafluoroethyl) tetrakis (pentafluorophenyl) borate Phenyl) 3-trifluoromethylphenylsulfonium and the like.

Preferred examples of the cationic photopolymerization initiator (A) of the present invention include, for example, (3-trifluoromethylphenyl) antimonate hexafluoride.
Di (4-toluyl) sulfonium, hexafluorophosphoric acid (3
-Trifluoromethylphenyl) di (4-toluyl) sulfonium, di (4-n-butylphenyl) hexafluoroantimonate 3-trifluoromethylphenylsulfonium, di (4-n-butylphenyl) phosphate hexafluoride 3-
Trifluoromethylphenylsulfonium, di (4-tert-butylphenyl) hexafluoroantimonate 3-trifluoromethylphenylsulfonium, di (4-tert-butylphenyl) hexafluorophosphate 3-trifluoromethylphenylsulfonium, (3-trifluoromethylphenyl) di (4-trifluoromethylphenyl) sulfonium hexamonate antimonate, (3-trifluoromethylphenyl) di (4-trifluoromethylphenyl) sulfonium hexafluorophosphate, etc. are exemplified. be able to.

Next, the photocurable resin composition of the present invention will be described. The photocurable resin composition of the present invention contains the cationic photopolymerization initiator (A) and the cationically polymerizable compound (B) of the present invention. Examples of the cationic polymerizable compound (B) include a compound (a) having an epoxy group, a vinyl compound (b), a dicycloorthoester compound (c), a spiroorthocarbonate compound (d), and a compound having an oxetane ring ( e) and the like. These may be used alone or in combination of two or more. Among (a) to (e), the compound having an epoxy group of (a) and the compound having an oxetane ring of (e) are particularly preferably used.

Compound (a) having usable epoxy group
Specific examples of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate, 2- (3,4-epoxycyclohexyl-5,5
-Spiro-3,4-epoxy) cyclohexanone-meta-dioxane, bis- (2,3-epoxycyclopentyl) ether, limonenedioxide, 4-vinylcyclohexene dioxide, phenylglycidyl ether, bisphenol A type epoxy resin, bisphenol F Bisphenol-type epoxy resin such as epoxy resin, hydrogenated bisphenol-A epoxy resin, brominated bisphenol-A epoxy resin, phenol-novolak-type epoxy resin, cresol-novolak-type epoxy resin,
Novolak-type epoxy resins such as brominated phenol-novolak-type epoxy resins, polyglycidyl ethers of polyhydric alcohols, and the like.

Specific examples of the vinyl compound (b) that can be used include styrenes such as styrene, α-methylstyrene and p-chloromethylstyrene; n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether, hydroxybutyl vinyl ether and the like. Alkyl vinyl ethers; allyl vinyl ether, 1
Alkenyl vinyl ethers such as octahydronaphthyl vinyl ether; alkynyl vinyl ethers such as ethynyl vinyl ether and 1-methyl-2-propenyl vinyl ether; aryl vinyl ethers such as phenyl vinyl ether and p-methoxyphenyl vinyl ether; butanediol divinyl ether and triethylene glycol Alkyl divinyl ethers such as divinyl ether and cyclohexanediol divinyl ether;
Aralkyl divinyl ethers such as 4-benzenedimethanol divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether; and aryl divinyl ethers such as hydroquinone divinyl ether and resorcinol divinyl ether.

Specific examples of the dicycloorthoester compound (c) that can be used include, for example, 1-phenyl-4-
Ethyl 2,6,7-trioxabicyclo [2,2,2]
Octane, 1-ethyl-4-hydroxymethyl-2,
6,7-trioxabicyclo [2,2,2] octane and the like can be mentioned. Specific examples of the spiro orthocarbonate compound (d) that can be used include, for example, 1,5,7,1
1-tetraoxaspiro [5,5] undecane, 3,9
-Dibenzyl-1,5,7,11-tetraoxaspiro [5,5] undecane and the like, 1,4,6-trioxaspiro [4,4] nonane, 1,4,6-trioxaspiro [4,4 5] decane and the like, and as the compound (e) having an oxetane ring, for example, 3,3-dimethyloxetane, 3,3-bis (chloromethyl) oxetane,
-Hydroxymethyloxetane, 3-methyl-3-oxetanemethanol, 3-methyl-3-methoxymethyloxetane, 3-ethyl-3-phenoxymethyloxetane, resorcinol bis (3-methyl-3-oxetanylethyl) ether, m- Xylylene bis (3-ethyl-3-oxetanyl ethyl ether) and the like can be mentioned. These may be used alone or in combination of two or more.

The proportion of each component constituting the photocurable resin composition of the present invention is 100% of the cationically polymerizable compound (B).
The cationic photopolymerization initiator (A) is usually preferably 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight, relative to parts by weight.

By adding a photosensitizer to the photocurable resin composition of the present invention, the sensitivity to active energy rays can be improved, and the photocurable resin composition having a higher curing speed can be obtained. Things. Specific examples of the photosensitizer that can be used here include, for example, naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, naphthacene derivatives, chrysene derivatives, perylene derivatives, pentacene derivatives, acridine derivatives, benzothiazole derivatives, benzoin derivatives, and fluorene derivatives ,
Naphthoquinone derivative, anthraquinone derivative, xanthene derivative, xanthone derivative, thioxanthene derivative,
Thioxanthone derivative, coumarin derivative, ketocoumarin derivative, cyanine derivative, acridine derivative, azine derivative, thiazine derivative, oxazine derivative, indoline derivative, azulene derivative, triallylmethane derivative, phthalocyanine derivative, spiropyran derivative, spirooxazine derivative, thiospiropyran derivative, organic Ruthenium complexes and the like are preferable, and among them, preferred are naphthalene derivatives, anthracene derivatives, phenanthrene derivatives, chrysene derivatives, perylene derivatives, and acridine derivatives, among which substituted alkyl groups having 1 to 4 carbon atoms are particularly preferred. 9, which may have
10-dialkoxyanthracene derivative or 9.1
A 0-di (alkoxyalkoxy) anthracene derivative is preferred.

Specific examples of the 9,10-dialkoxyanthracene derivative or the 9,10-di (alkoxyalkoxy) anthracene derivative which may have an alkyl group having 1 to 4 carbon atoms as a substituent include, for example, 10-
Dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 2-tert-butyl-9,10
-Dimethoxyanthracene, 2,3-dimethyl-9,1
0-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 2-tert-butyl-9,10-diethoxyanthracene, 2,3-dimethyl-9,10-di Ethoxyanthracene, 9,10-di (n-propoxy) anthracene, 2-ethyl-9,10-di (n-propoxy) anthracene, 9,10-diisopropoxyanthracene, 2-ethyl-9,10-diiso Propoxyanthracene, 9,10-di (2-methoxyethoxy) anthracene, 2-ethyl-9,10-di (2-methoxyethoxy) anthracene, 2-tert-butyl-9,1
0-di (2-methoxyethoxy) anthracene, 2,3
-Dimethyl-9,10-di (2-methoxyethoxy) anthracene, 9,10-di (n-butoxy) anthracene, 2-ethyl-9,10-di (n-butoxy) anthracene, 9,10-di ( 2-ethoxyethoxy) anthracene, 2-ethyl-9,10-di (2-ethoxyethoxy) anthracene, 9,10-dibenzyloxyanthracene, 2-ethyl-9,10-dibenzyloxyanthracene, 2-tert- Butyl-9,10-dibenzyloxyanthracene, 2,3-dimethyl-9,10
-Dibenzyloxyanthracene, 9,10-di (2-
(Carboxyethoxy) anthracene, 2-ethyl-9,
Examples thereof include 10-di (2-carboxyethoxy) anthracene.

The photocurable resin composition of the present invention further comprises a solvent or an antifoaming agent for dilution as long as the curability is not impaired.
Various additives such as a leveling agent, a thickener, a flame retardant, an antioxidant, a light stabilizer, a filler, an antistatic agent, a flow regulator, and a coupling agent can be mixed.

The photocurable resin composition of the present invention can be obtained by uniformly mixing the above-mentioned components at a predetermined ratio, and is easily made into a cured product by irradiating active energy rays such as ultraviolet rays. be able to. For curing, the photocurable resin composition of the present invention is usually made into a thickness of about 0.01 to 1 mm, and then irradiated with an active energy ray. Any suitable active energy ray may be used as long as it has an energy that induces the decomposition of the cationic photopolymerization initiator, and is preferably a high-pressure mercury lamp, a low-pressure mercury lamp, a xenon lamp, a metal halide lamp, a germicidal lamp, or a laser. Examples include electromagnetic energy of light having a wavelength of 2000 to 7000 angstroms, light energy rays such as electron beams, X-rays, and ultraviolet rays. The irradiation time of the active energy ray depends on its intensity, but usually about 0.1 to 10 seconds is sufficient. However, it is preferable to take more time for a relatively thick coating film. After 0.1 to several minutes after the irradiation of the active energy ray, most of the photocurable resin compositions are cured by photocationic polymerization and photoradical polymerization and dried to the touch. Depending on the type and the mixing ratio, the photocurable resin composition is irradiated with an active energy ray at 30 to 100 ° C.
By heating to a certain degree, the polymerization reaction can be effectively promoted, and the curing rate can be further improved. Further, the cured product obtained by irradiating the active energy ray may be further heated at 50 to 250 ° C. for the purpose of completing the curing by polymerization. When performing the heat treatment, in consideration of the heat resistance of the substrate on which the photocurable resin composition is applied and the obtained cured product, etc., when performing the heat treatment at a high temperature of 100 ° C. or more, the heat treatment should be performed in a short time as possible. Is preferred.

Specific applications of the photocurable resin composition of the present invention include paints, coatings, inks, resists, liquid resists, adhesives, molding materials, putties, glass fiber impregnating agents, fillers, and optics. For example, the substrate applicable as a coating agent includes metal, wood, rubber, plastic, glass, and ceramic products.

[0029]

The present invention will be described more specifically below with reference to examples. However, the present invention is not limited to these examples.

Synthesis Example of Photocationic Polymerization Initiator (A) Example 1 A 100 ml separable flask was charged with 60.6 g of methanesulfonic acid, and 7.2 g of trifluoromethylbenzene and 4,4'-dimethyl were stirred. 11.4 g of diphenylsulfoxide was added, and the mixture was kept at 20 ° C.
And stirred. To this mixture, 9.2 g of acetic anhydride was added dropwise while paying attention to heat generation. After the total amount of acetic anhydride was dropped, 10
Stir for about a minute and then raise the temperature.
Stirred for hours. After cooling the reaction solution to 20-25 ° C, 1 l
To 350 ml of water in a beaker with stirring,
Further, a 25% aqueous solution of sodium hydroxide is added to the solution at a pH of 5
Add until ~ 7. After neutralization, the water obtained by diluting the reaction solution was left in a cool and dark place on ice for 1 hour, and the supernatant was removed by decantation. Then, 500 ml of water was added and the mixture was vigorously stirred to dissolve the residue. After the solution became a uniform light brown transparent liquid, 9.8 g of potassium hexafluorophosphate, which had been pulverized in advance, was added, and the mixture was stirred for 1 hour as it was, and the precipitated white crystals were separated by filtration. The obtained crystals were washed with 1 l of water, further recrystallized from ethanol, purified and air-dried for 24 hours, and then vacuum-dried at 40 ° C. to obtain the desired hexafluorophosphoric acid (3-triphosphoric acid). 17.4 g of fluoromethylphenyl) di (4-toluyl) sulfonium
(69.9% yield). The obtained (3-trifluoromethylphenyl) di (4-toluyl) sulfonium hexafluorophosphate was a white to milky white powder, and had a melting point of 118 to 121 ° C. Table 1 shows the results of elemental analysis of the obtained product.

Table 1 Element Actual value (% by weight) Calculated value (% by weight) C 50.12 50.00 H 3.58 3.60 S 6.35 6.36

Example 2 In the same manner as in Example 1, the target antimony hexafluoride was obtained by using 14.5 g of potassium hexafluoroantimonate instead of 9.8 g of potassium hexafluorophosphate. 17.9 g of (3-trifluoromethylphenyl) di (4-toluyl) sulfonium
(61.1% yield). The obtained (3-trifluoromethylphenyl) di (4-toluyl) sulfonium hexafluoroantimonate was a white to milky white powder, and had a melting point of 110 to 113 ° C. Table 2 shows the results of elemental analysis of the obtained product.

Table 2 Element Actual value (% by weight) Calculated value (% by weight) C 42.43 42.38 H 3.05 3.05 S 5.41 5.39

Examples of Resin Compositions Examples 3 and 4: The resin compositions were blended according to the blending compositions shown in Table 3 (the numerical values are parts by weight) and mixed and dissolved. The composition shown in Table 3 was prepared by dissolving 2 parts by weight of the photocationic polymerization initiator synthesized in advance in Examples 1 and 2 in 2 parts by weight of γ-butyrolactone, and compounding the cationically polymerizable compound with this. It was prepared by heating and dissolving. The cured films of these blended compositions were obtained by applying the blended compositions prepared according to Table 3 to an aluminum test panel to a thickness of 5 μm, and then irradiating ultraviolet rays from a distance of 8 cm with a high-pressure mercury lamp (80 W / cm). Was. The cured film thus obtained was tested for dryness to the touch, transparency, storage stability and gloss of the cured coating film as follows. The test results are also shown in Table 3.

Dryness to the touch: When irradiated with a finger, gauze or the like, the amount of ultraviolet irradiation until the surface is not damaged is defined as m
It was expressed in J / cm ² .

Transparency: The composition was placed in a transparent container such as a test tube and visually determined.・ ・ ・: No turbidity or precipitate.

Storage stability: The resin composition was stored at 40 ° C. for 3 months, and the stability was examined.・ ・ ・: There is no change in viscosity and no crystallized product is generated.

Gloss: The surface of the cured coating film was visually determined after irradiating ultraviolet rays until the finger was dry.・ ・ ・: Good gloss.

Table 3 Example 3 4 Product obtained in Example 1 2 Product obtained in Example 2 2 γ-butyrolactone 22 Celloxide 2021 * 1 80 80 EHPE-3150 * 2 20 20 Dryness to touch 65 25 Transparency ○ ○ Storage stability ○ ○ Gloss ○ ○

Note) * 1: Alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd. * 2: Alicyclic epoxy resin manufactured by Daicel Chemical Industries, Ltd.

Examples 5 and 6, Comparative Example 1 Resin compositions were blended according to the blending compositions (the numerical values are parts by weight) shown in Table 4 and mixed and dissolved. The composition shown in Table 4 was prepared by previously dissolving 3 parts by weight of the photocationic polymerization initiator in 3 parts by weight of γ-butyrolactone, blending the cationically polymerizable compound with the compound, and heating and dissolving. . The cured films of these blended compositions were coated with a blended composition prepared according to Table 4 on a PET film cut into 70 mm × 60 mm with a bar coater, and irradiated with ultraviolet light at a dose of 100 mJ from a distance of 8 cm with a high pressure mercury lamp (80 W / cm). / Cm ² and cured. After curing, the PET film with the cured film was put into a 100 ml glass vial bottle, which was sufficiently airtight, so that the film surfaces were not overlapped as much as possible, sealed, and then heated in an electric furnace at 110 ° C. After cooling, the gas in the vial
The benzene was sampled and quantified by gas chromatography. Note benzene certain amount of a certain concentration is quantified when benzene and analyzed by gas chromatography, after obtaining the concentration of benzene in the calibration curve, displaying the detected amount of benzene in mg per cured film 1 m ^2. The test results are shown in Table 4.

Table 4 Example Comparative Example 5 6 1 Product obtained in Example 3 3 Product obtained in Example 2 3 Triallylsulfonium compound * 3 3 γ-butyrolactone 3 3 3 UVR-6110 * 4 50 50 50 UVR-6128 * 5 50 50 50 Weight of cured film (mg) 65.2 68.9 63.2 Initiator content (mg) 1.85 1.95 1.79 Application area (cm ² ) 42 42 42 Detection amount of benzene (mg / m ² ) Not detected Not detected 0.6

Note) * 3: Diphenylsulfonium hexafluorophosphate (4-phenylthiophenyl) * 4: Alicyclic epoxy resin manufactured by Union Carbide * 5: Alicyclic epoxy resin manufactured by Union Carbide

It should be noted that the hexafluorophosphoric acid (4-
(Phenylthiophenyl) diphenylsulfonium was prepared in the same manner as in Example 1, except that 9.2 g of diphenylsulfide was used instead of 7.2 g of trifluoromethylbenzene, and 4,4′-dimethyldiphenylsulfoxide was used.
By using 10.0 g of diphenylsulfoxide instead of 4 g, 20.5 g of the desired hexafluorophosphate (4-phenylthiophenyl) diphenylsulfonium
(80.4% yield). The obtained (4-phenylthiophenyl) diphenylsulfonium hexafluorophosphate is a white to milky white powder having a melting point of 116 to 118 ° C.
Met. Table 5 shows the results of elemental analysis of the obtained product.

Table 5 Element Actual measured value (% by weight) Calculated value (% by weight) C 55.86 55.79 H 3.78 3.72 S 12.38 12.42

[0046]

The triallylsulfonium salt obtained in the present invention can be used as a photocationic polymerization initiator when photopolymerizing a cationically polymerizable substance. Further, the photocurable resin composition containing the triallylsulfonium salt obtained in the present invention has excellent storage stability and can be photocured by irradiation with active energy rays. In addition, the cured film obtained by irradiating the resin composition of the present invention with light does not generate harmful benzene from the photocationic polymerization initiator component of the cured product even when subjected to further heat treatment.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4H006 AB40 AB49 4J005 AA07 BB01 BB02 4J011 QA08 QA09 QA19 QA20 QA34 SA62 SA63 SA64 SA72 SA74 SA78 SA83 SA84 SA85 SA87 UA01 UA02 UA08 VA01 WA01 WA02 WA06 WA07 4J0A08 AD08 AJ16 GA03 GA23 HA01 HA02 HA03 JA01 JA06 JA07 JA09 JA11

Claims (6)

[Claims] (1) The following formula (1): (Wherein, R _{1 to} R ₅ are each a hydrogen atom, a C _{2 to} C ₁₈ linear or branched alkyl group, a trifluoromethyl group,
X represents a substituent selected from the group consisting of a pentafluoroethyl group, a cyclohexyl group, a cyclohexylmethyl group, a benzyl group, a 2-hydroxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group and a cyano group; Represents a substituent selected from the group consisting of a C ₁ -C ₁₈ linear or branched alkyl group, a trifluoromethyl group and a pentafluoroethyl group;
Represents an atomic group that can be a monovalent anion. Where R
All ₁ to R ₅ do not simultaneously represent hydrogen atoms. )
A cationic photopolymerization initiator (A), which is a triallylsulfonium compound represented by the formula: and a photocuring characteristic, comprising one or more cationic polymerizable compounds (B) Resin composition. 2. In the formula (1), any one of R _{1 to} R ₅
One is a trifluoromethyl group, a cationic photopolymerization X is a linear or branched alkyl group, or a substituent selected from the group consisting of a trifluoromethyl group or a pentafluoroethyl group of C ₁ -C ₄ The photocurable resin composition according to claim 1, further comprising an initiator (A). 3. In the formula (1), Y^-Anio represented by
Part is SbF₆ ^-Or PF ₆ ^-Of cationic photopolymerization
The composition according to claim 1, comprising an agent (A).
The photocurable resin composition according to claim 2. 4. A method according to claim 1, wherein at least one of said one or more cationically polymerizable compounds (B) is a compound having one or more epoxy groups in one molecule. 4. The photo-curable resin composition according to any one of claims 1 to 3. 5. The amount of the cationic photopolymerization initiator (A) is:
One or more cationically polymerizable compounds (B)
The photocurable resin composition according to any one of claims 1 to 4, wherein the content is 0.1 to 10% by weight based on the weight of the composition. 6. A cured product obtained by curing the photocurable resin composition according to any one of claims 1 to 5.