JPH11322944A - Active-energy-ray-curable composition and its cured item - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an active-energy-ray-curable compsn. which is excellent in curability and gives a cured item excellent in physical properties by incorporating a cationically polymerizable substance, a sulfonium salt having a benzophenone structure and/or a thioxanthone structure as a cationic photopolymn. initiator, and a sensitizer into the same. SOLUTION: This compsn. contains a cationically polymerizable substance such as an epoxy compd., a vinyl compd., a dicycloorthoester compd., a spiroorthocarbonate compd., or a compd. having an oxetane ring (e.g. 3,4- epoxycyclohexylmethyl 3,4-epoxycycolhexanecarboxylate), a sulfonium salt having a benzophenone structure and/or a thioxanthone structure (e.g. 4- diphenylsulfonio-4'-phenylcarbonyldiphenyl sulfide hexafluorophosphate) as a cationic photopolymn. initiator, and a sensitizer (e.g. 2-ethyl-9,10- dimethoxyanthracene).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an active energy ray-curable composition, and more particularly, to an active energy ray-curable composition which can be easily cured by irradiation with an active energy ray and cationic polymerization to obtain a cured product. Composition.

[0002]

2. Description of the Related Art Ultraviolet-curable compositions have been actively studied and industrialized in the fields of printing inks, paints, coatings, liquid resist inks, etc. due to demands for energy saving, space saving, and pollution-free properties. Most of the industrialized products utilize a double bond radical polymerization reaction. Recently, an industrial application of a method of photopolymerizing an epoxy resin by containing a photocationic polymerization initiator has been studied. The method of cationically 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 has a smaller curing shrinkage than the method of radically polymerizing by irradiating an active energy ray such as an acrylate compound. It has various features such as being unaffected by oxygen during curing and curing. However, a cationically polymerizable substance has a lower curing rate than a radically polymerizable substance such as an acrylate compound, and the market demands a cationically polymerizable composition having more excellent curability.

[0003]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides a cationically polymerizable composition having high activity (curability) with active energy rays such as ultraviolet rays and electron beams. It is intended to be.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and found that a photocationic polymerization initiator which is a sulfonium salt having a benzophenone structure and / or a thioxanthone structure is used in combination with a sensitizer. In particular, it has been found that an active energy ray-curable composition having better curability can be obtained by using a specific sensitizer in combination, and the present invention has been completed. That is, the present invention
(1) An active energy ray comprising a cationic polymerizable substance (A), a cationic photopolymerization initiator (B) which is a sulfonium salt having a benzophenone structure and / or a thioxanthone structure, and a sensitizer (C). The curable composition, (2) the active energy ray-curable composition according to (1), wherein the sensitizer (C) is an anthracene compound, and (3) the anthracene compound is 2-ethyl-9,10-dimethoxyanthracene. The active energy ray-curable composition according to (2). (4) The active energy ray-curable composition according to (1), wherein the sensitizer (C) is a perylene compound, and (5) the pigment according to any one of (1) to (4), which contains a pigment (D). The present invention relates to an active energy ray-curable composition, (6) a cured product of the active energy ray-curable composition according to any one of (1) to (5).

The cationically polymerizable substance (A) used in the present invention
Examples thereof include a compound (a) having an epoxy group, a vinyl compound (b), a dicycloorthoester compound (c), a spiroorthocarbonate compound (d), and a compound (e) having an oxetane ring. These may be used alone or in combination of two or more. Of the compounds (a) to (e), the compound (a) having an epoxy group and the compound (e) having an oxetane ring are particularly preferably used.

The compound (a) having an epoxy group includes, for example, 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, limonene dioxide, 4-vinylcyclohexene dioxide, phenyl Bisphenol type epoxy resins such as glycidyl ether, bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, phenol novolak type epoxy resin,
Novolak-type epoxy resins such as cresol-novolak-type epoxy resins, brominated phenol-novolak-type epoxy resins, and polyglycidyl ethers of polyhydric alcohols.

Examples of the vinyl compound (b) include styrenes such as styrene, α-methylstyrene and p-chloromethylstyrene; alkyl vinyl ethers such as n-butyl vinyl ether, isobutyl vinyl ether, cyclohexyl vinyl ether and hydroxybutyl vinyl ether; allyl Alkenyl vinyl ethers such as vinyl ether and 1-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; alkyl divinyl ethers such as butanediol divinyl ether, triethylene glycol divinyl ether and cyclohexanediol divinyl ether Vinyl ethers; aralkyl divinyl ethers such as 1,4-benzenedimethanol divinyl ether and m-phenylenebis (ethylene glycol) divinyl ether; and aryl divinyl ethers such as hydroquinone divinyl ether and resorcinol divinyl ether.

As the dicycloorthoester compound (c), 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. As the spiro orthocarbonate compound (d), for example,
5,7,11-tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,7,11-tetraoxaspiro [5,5] undecane, and 1,4,6-trioxaspiro [4,4] nonane, 1,4,6-trioxaspiro [4,5] decane, and the like, and the compound (e) having an oxetane ring include, for example, a compound represented by the following formula. .

[0009]

Embedded image

The sulfonium salt (B) used in the present invention includes, for example, a sulfonium salt having a benzophenone structure, a sulfonium salt having a thioxanthone structure, and a sulfonium salt having both structures. These may be used alone or in combination of two or more.

As the sulfonium salt having a benzophenone structure, for example, 4-diphenylsulfonio-4'-
Phenylcarbonyl-diphenylsulfide-hexafluorophosphate, 4-diphenylsulfonio-4 '
-Phenylcarbonyl-diphenylsulfide-hexafluoroantimonate, 4-diphenylsulfonio-
4'-phenylcarbonyl-diphenylsulfide-tetrakis (pentafluorophenyl) borate, 4-di (p-fluorophenyl) sulfonio-4'-ter-
Butylphenylcarbonyl-diphenylsulfide-hexafluorophosphate, 4-di (p-fluorophenyl) sulfonio-4'-ter-butylphenylcarbonyl-diphenylsulfide-hexafluoroantimonate, 4-di (p-toluyl) sulfonio-4 '-
ter-butylphenylcarbonyl-diphenylsulfide-tetrakis (pentafluorophenyl) borate, 4-di (p-toluyl) sulfonio-4'-ter
-Butylphenylcarbonyl-diphenyl sulfide-
Hexafluorophosphate, 4-di (p-toluyl)
Examples include sulfonio-4'-ter-butylphenylcarbonyl-diphenylsulfide-hexafluoroantimonate, and sulfonium salts having a benzophenone structure described in JP-A-7-61964.

Examples of the sulfonium salt having a thioxanthone structure include 7-diphenylsulfonio-2-isopropyl-thioxanthone-hexafluorophosphate and 7-diphenylsulfonio-2-isopropyl-
Thioxanthone-hexafluoroantimonate, 7-
Diphenylsulfonio-2-isopropyl-thioxanthone-tetrakis (pentafluorophenyl) borate, 7-di (p-toluyl) sulfonio-2-isopropyl-thioxanthone-hexafluorophosphate,
7-di (p-toluyl) sulfonio-2-isopropyl-thioxanthone-hexafluoroantimonate, 7
-Di (p-toluyl) sulfonio-2-isopropyl-
Thioxanthone-tetrakis (pentafluorophenyl) borate and the like, and sulfonium salts having a thioxanthone structure described in JP-A-8-165290 can be mentioned.

The sensitizer (C) used in the present invention includes, for example, 2-ethyl-9,10-dimethoxyanthracene,
9,10-dichloroanthracene, 9,10-phenylanthracene, 1-chloroanthracene, 2-methylanthracene, 9-methylanthracene, 2-ter-butylanthracene, anthracene, 1,2-benzanthracene, 1,2,3 , 4-dibenzanthracene,
1,2,5,6-dibenzanthracene, 1,2,7,
Anthracenes such as 8-dibenzanthracene and 9,10-dimethoxydimethylanthracene; perylenes such as perylene; stilbenes such as stilbene; bis (styryl) benzenes such as bis (styryl) benzene; Of these sensitizers, preferred are, for example, anthracenes and perylenes. More preferably, for example, 2
-Ethyl-9,10-dimethoxyanthracene.

(A) Constituting the Curable Composition of the Invention
The proportion of the component (C) used is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 10 parts by weight, based on 100 parts by weight of the component (A). . Component (C) is based on 100 parts by weight of component (B).
0.5 to 50 parts by weight, preferably 0.5 to 3 parts by weight.
More preferably, it is 0 parts by weight.

[0015] The composition of the present invention may also contain a pigment (D). The pigment (D) is preferably used in an amount of 0 to 120 parts by weight, more preferably 0 to 100 parts by weight, per 100 parts by weight of the total amount of the components (A) to (C). As the pigment (D), for example, a black pigment, a yellow pigment,
Orange pigment, red pigment, purple pigment, blue pigment, green pigment,
White pigments, extenders and the like can be mentioned.

Examples of the black pigment include carbon black, acetylene black, lamp black, aniline black and the like. As the yellow pigment, for example, graphite, zinc yellow, cadmium yellow, yellow iron oxide, mineral fast yellow, nickel titanium yellow, navels yellow, naphthol yellow S, Hanza yellow G, Hanza yellow 10G, benzidine yellow G, benzidine yellow GR Quinoline yellow lake, permanent yellow NCG, tartrazine lake and the like. Examples of orange pigments include red-mouthed graphite, molybdenum orange, permanent orange GTR, pyrazolone orange, vulcan orange, indaslen brilliant orange RK, benzine orange G, and indaslen brilliant orange GK.

Examples of red pigments include red iron red, red cadmium red, lead cadmium, mercury sulfide cadmium, permanent red 4R, lithol red, lake red D, brilliant carmine 6B, eosin lake, rhodamine lake B, alizarin lake, and brilliant carmine 3B.
And the like. Examples of the purple pigment include manganese purple, fast violet B, methyl violet lake, and the like. Blue pigments include, for example, navy blue, cobalt blue, alkali blue lake, Victoria blue lake, phthalocyanine blue, metal-free phthalocyanine blue, partially chlorinated phthalocyanine blue, fast sky blue, indaslen blue BC and the like. Examples of the green pigment include chrome green, chromium oxide, pigment green B, malachite green lake, and fanal yellow green G.
Examples of the white pigment include zinc white, titanium oxide, antimony white, and zinc sulfide. As extenders,
Examples include barite powder, barium carbonate, clay, silica, white carbon, talc, alumina white and the like.

The curable composition of the present invention may further contain a solvent for dilution or a resin for modification, for example, a compound having an alcoholic hydroxyl group, a phenol resin, a polyester elastomer, or the like, as long as the cationic polymerization is not impaired. Organic carboxylic acids and acid anhydrides can be used. In addition, depending on the use, dyes, fillers, antistatic agents, flame retardants, defoamers, flow regulators, ion scavengers, light stabilizers, coupling agents, and the like can be used in combination.

The curable composition of the present invention comprises (A) to (D)
It can be prepared by mixing, dissolving, dispersing, and / or kneading the components and other various additives as required. The curable composition can be cured to a touch-dry state or a solvent-insoluble state after 0.1 seconds to several minutes by irradiating energy rays such as ultraviolet rays.

The curable composition of the present invention can be generally used as a transparent or opaque liquid product or as a powdery product for metal, wood, rubber, plastic, glass, ceramic products and the like. Further, specific applications of the present invention include paints, coating agents, inks, resists, liquid resists, adhesives, molding materials, putties, glass fiber impregnating agents, fillers, and the like.

The cured product of the present invention is obtained by irradiating the above-mentioned curable composition of the present invention with an energy ray such as ultraviolet rays to cure the composition. Usually, the above-mentioned curable composition of the present invention is irradiated with energy rays after having a thickness of about 0.1 to 1 mm. Any suitable energy ray may be used as long as it has an energy that induces the decomposition of the sulfonium salt. High energy rays such as electromagnetic wave energy having a wavelength, electron beams, X-rays, and radiations can be given. The irradiation time of the energy beam is
Although depending on the strength, usually about 0.1 to 10 seconds is sufficient. However, it is preferred to spend more time on relatively thick painted objects. After energy beam irradiation.
After 1 second to a few minutes, most compositions dry to the touch by cationic polymerization, but it is sometimes preferable to use heating in combination to promote the cationic polymerization reaction.

[0022]

EXAMPLES The present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples. Examples 1 to 6 and Comparative Examples 1 to 4 The components were blended, mixed, dissolved and kneaded in accordance with the blending composition (the numerical values are parts by weight) shown in Table 1 to obtain an energy ray-curable composition. This was applied on an aluminum test panel to a thickness of 7 μm, and a metal halide lamp (160 W
/ Cm) at a speed of 5 m / min from a distance of 8 cm, heated at 150 ° C. for 60 seconds, rubbed the cured surface with absorbent cotton impregnated with acetone, and measured the number of times required to dissolve the cured film (The greater the number of times, the better the curability.)

[0023]

Table 1 Example 1 Comparative Example 1 2 3 4 5 6 6 12 3 4 (A) component * 1 50 50 50 50 50 50 50 50 50 50 (B) component (B-1) * 2 5 5 4 5 5 5 4 (B-2) * 3 15 5 15 (C) component Anthracene 0.5 0.5 0.5 Perylene 0.5 2-ethyl-9,10-dimethoxyanthracene 0.5 0.5 (D) component Rutile titanium oxide 50 50 50 50 50 50 50 50 50 50 Other components FC-430 1 1 1 1 1 1 1 1 1 1 2-isopropyl-thioxanthone 0.5 0.5 −−−−−−−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−− Rubbing test (number of times) 70 75 80 72 100 or more 100 or more 8 12 15 10

Note) * 1 Component (A): 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate * 2 (B-1): 4-di (p-toluyl) sulfonio-4'- ter-butylphenylcarbonyl-diphenylsulfide-hexafluorophosphate * 3 (B-2): 7-di (p-toluyl) sulfonio-2-isopropyl-thioxanthone-hexafluorophosphate * 4 FC-430: Sumitomo 3M Ltd. Company, dispersant.

As is clear from the results shown in Table 1, the cured film of the curable composition of the present invention requires 7 times the number of times required for dissolving the cured film by rubbing with absorbent cotton impregnated with acetone.
The number is 0 or more, and the number of times is significantly increased as compared with the comparative example. In particular, in the case where 9,10-dimethoxy-2-ethylanthracene was added, the number of rubbings was 100 or more, indicating that the curability of the curable composition of the present invention was extremely good.

[0026]

As described above, the active energy ray-curable composition of the present invention has excellent curability and gives a cured product having excellent physical properties.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C09D 163/00 C09D 163/00 C09J 163/00 C09J 163/00 G03F 7/004 503 G03F 7/004 503 7/029 7/029 7/038 503 7/038 503

Claims (6)

[Claims] 1. An activity comprising a cationic polymerizable substance (A), a cationic photopolymerization initiator (B) which is a sulfonium salt having a benzophenone structure and / or a thioxanthone structure, and a sensitizer (C). Energy ray curable composition. 2. The active energy ray-curable composition according to claim 1, wherein the sensitizer (C) is an anthracene compound. 3. The method according to claim 1, wherein the anthracene compound is 2-ethyl-9,1.
The active energy ray-curable composition according to claim 2, which is 0-dimethoxyanthracene. 4. The active energy ray-curable composition according to claim 1, wherein the sensitizer (C) is a perylene compound. 5. The active energy ray-curable composition according to claim 1, which comprises a pigment (D). 6. A cured product of the active energy ray-curable composition according to any one of claims 1 to 5.