JPH10182711A - Energy ray-curable composition and its cured material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition excellent in curability even in the case of containing a pigment, comprising a quinolinium salt compound and a photocationic polymerization initiator in a composition containing a cationic polymerizable substance. SOLUTION: This composition is obtained by compounding (A) a cationic polymerizable substance (bisphenol A) with (B) a quinolinium salt compound [a compound of formula I (R1 is a substituted alkyl; R2 to R5 are each H, etc.; X is SbF4 , etc.), etc.] (e.g. N-benzyl-2-methylquninolinium hexafluoroantimonate), (C) a sulfonium salt of formula II (R6 and R7 are each H, etc.; R8 and R9 are each a halogen, etc.) having a thioxanthone structure, having >=100 maximum mol absorption coefficient in a range of 360-500nm wavelength as a photocationic polymerization initiator and (D) a pigment (carbon black, etc.) as an arbitrary component in the ratio of 34.7-99.7wt.% of the component A, 0.3-15wt.% of the total of the component B and the component C, in which 100 pts.wt. of the total of the component B an the component C is composed of 1-60 pts.wt. of the component B and 40-99 pts.wt. of the component C, and 0-70wt.% of the component D.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an energy ray-curable composition and a cured product thereof, and more particularly, to a cationically polymerizable composition which is cured by light irradiation or light irradiation and heat, and a cured product thereof. In particular, the present invention relates to an energy ray-curable composition excellent in curability and a cured product thereof in a composition containing a pigment.

[0002]

2. Description of the Related Art Examples of a catalyst for curing a cationically polymerizable cured product such as an epoxy compound by light irradiation and a composition thereof are described in JP-A-50-151997 and JP-A-50-1.
No. 58680 and the like. JP-A-56-152833, JP-A-58-37003, and JP-A-63-223002 disclose catalysts for curing cationically polymerizable compounds such as epoxy compounds by heating and compositions thereof. JP, JP-A-2-1
No. 78319, Japanese Unexamined Patent Publication No. Hei 3-17119, and the like are known. Also, a catalyst for curing a cationically polymerizable compound such as an epoxy compound by light irradiation and heat and a composition thereof are described in JP-A-2-196812.

[0003]

SUMMARY OF THE INVENTION As mentioned above,
Various studies have been made on cationically polymerizable compounds such as epoxy compounds by light irradiation or light irradiation and heat, but the curability of the composition containing the pigment is insufficient, and suggestions for improvement are not sufficient. In addition, as the field of use of the photopolymerizable composition expands, it is important to provide a novel composition in order to meet market requirements.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems. As a result, in a composition containing a cationically polymerizable substance, a quinolinium salt compound and a photo-cationic polymerization initiator having a wavelength of 360 nm were used. By containing a sulfonium salt having a maximum molar extinction coefficient of 100 or more in the wavelength region of ~ 500 nm, excellent curability,
In particular, the present invention succeeded in obtaining an energy ray-curable composition excellent in curability even when a pigment was contained, and completed the present invention. That is, the present invention provides (1) a cationically polymerizable substance (A), a quinolinium salt compound (B), and a sulfonium salt having a maximum molar extinction coefficient of 100 or more in a wavelength region of 360 to 500 nm as a cationic photopolymerization initiator ( (2) The energy ray-curable composition according to (1), wherein the sulfonium salt (C) is a sulfonium salt having a thioxanquine structure; (3) (1) or (2) containing a pigment (D)
(4) A cured product of the composition according to any one of (1) to (3), (5)
An article having a cured product film of the composition according to (4).

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Preferred examples of the cationically polymerizable substance (A) in the composition of the present invention include compounds having an epoxy group, vinyl compounds, spiro orthocarbonate compounds and the like. Examples of the compound having an epoxy group include a bisphenol-type epoxy resin which is a reaction product of bisphenols such as bisphenol A and bisphenol F with epichlorohydrin, a novolak-type epoxy resin which is a reaction product of novolak resin such as phenol novolak and epichlorohydrin, and tris. Glycidyl ether compounds such as phenol methane type epoxy resin, phenyl glycidyl ether, polyglycidyl ether of polyhydric alcohols, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl) Adipate, vinylcyclohexene dioxide,
Examples thereof include alicyclic epoxy compounds such as 2- [3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy] cyclohexanemetadioxane and 1,2-epoxy-p-vinylcyclohexene.

Examples of the vinyl compound 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, hydroxybutyl vinyl ether and hydroxyethyl vinyl ether. Alkenyl vinyl ethers such as allyl 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 p-methoxyphenyl vinyl ether; alkyl polyvinyl ethers such as butanediol divinyl ether, triethylene glycol divinyl ether, cyclohexanediol divinyl ether, and trimethylolpropane trivinyl ether;
1,4-benzenedimethanol divinyl ether, m-
Aralkyl divinyl ethers such as phenylene bis (ethylene glycol) divinyl ether; aryl divinyl ethers such as hydroquinone divinyl ether and resorcinol divinyl ether; polyester polyvinyl ethers; and polyurethane vinyl ethers.

The spiro orthocarbonate compounds include, for example, 1,5,7,11-tetraoxaspiro [5,5] undecane, 3,9-dibenzyl-1,5,5
7-11-tetraoxaspiro [5,5] undecane, 1,4,6-trioxaspiro [4,4] nonane,
And spiroorthoester compounds such as -methyl-1,4,6-trioxaspiro [4,4] nonane and 1,4,6-trioxaspiro [4,5] decane.

These components (A) may be used alone or in combination of two or more. Further, among these components (A), compounds having an epoxy group are particularly preferably used.

The quinolinium salt compound of the component (B) used in the present invention includes, for example, the following general formula [1]

[0010]

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(Wherein, R ₁ represents an alkyl group or an alkenyl group substituted with an aromatic ring, and R _{2 to} R ₅ represent a hydrogen atom, an alkyl group, a halogen atom, a nitro group, an alkoxy group, a hydroxyl group, respectively) , An optionally substituted phenyl group, an optionally substituted benzyl group, an alkyloxycarbonyl group or an alkylcarbonyl group, and X represents SbF ₄ , AsF ₆ or BF ₄ ). Compounds.

Examples of the alkyl group substituted with an aromatic ring of R ₁ include benzyl, 4-methoxybenzyl, 2-nitrobenzyl, p-bromobenzyl, vinylbenzyl, α-phenethyl, and benzhydryl. Group, a C1-C5 alkyl group substituted with an aromatic ring such as a 1-naphthylmethyl group, preferably a C1-C2 alkyl group substituted with a phenyl group or a naphthyl group. Examples of the alkenyl group include Examples include a cinnamyl group and a crotyl group.

The alkyl group for R _{2 to} R ₅ includes:
For example, methyl group, ethyl group, n- propyl group, an isopropyl group, an alkyl group C1~C5 and butyl group. Examples of the halogen atom, for example F, Cl, B _r, I
And the like. Examples of the alkoxy group include a C1-C5 alkoxy group such as a methoxy group and an ethoxy group. The optionally substituted phenyl group includes, for example, a phenyl group, a p-methylphenyl group and a p-methylphenyl group. -Ethoxyphenyl group, m-chlorophenyl group, m-nitrophenyl group and the like. Examples of the benzyl group which may be substituted include, for example, a benzyl group, a p-methylbenzyl group and a p-methylbenzyl group.
P- such as ethylbenzyl group and p-methoxybenzyl group;
(C1 to C5) alkyl or p- (C1 to C5) alkoxybenzyl group, and examples of the alkyloxycarbonyl group include C1 to C5 alkyloxy such as methyloxycarbonyl, ethyloxycarbonyl, and propyloxycarbonyl. Examples of the carbonyl group include a C1-C5 alkylcarbonyl group such as a methylcarbonyl group, an ethylcarbonyl group, and a propylcarbonyl group.

Specific examples of the quinolinium salt compound of the component (B) used in the present invention include, for example, N-benzyl-2.
-Methylquinolinium hexafluoroantimonate, N
-Benzyl-3-bromoquinolinium hexafluoroantimonate, N- (4-methoxybenzyl) quinolinium hexafluoroantimonate, N- (2-nitrobenzyl) -3-bromoquinolinium hexafluoroantimonate, N- (p-bromobenzyl) -3-bromoquinolinium hexafluoroantimonate, N-vinylbenzylquinolinium hexafluoroantimonate, N-
(Α-phenethyl) quinolinium hexafluoroantimonate, N- (α-phenethyl) -3-bromoquinolinium hexafluoroantimonate, N-benzhydrylquinolinium hexafluoroantimonate, N-benzhydryl-2- Methylquinolinium hexafluoroantimonate, N-cinnamylquinolinium hexafluoroantimonate, N-cinnamyl-2-methylquinolinium hexafluoroantimonate, N-cinnamyl-3-
Bromoquinolinium hexafluoroantimonate, N-
Crotyl-2-methylquinolinium hexafluoroantimonate, N- (1-naphthylmethyl) quinolinium hexafluoroantimonate, N- (1-naphthylmethyl) -2-methylquinolinium hexafluoroantimonate, N -(1-naphthylmethyl) -3-bromoquinolinium hexafluoroantimonate, N-benzyl-2
-Methylquinolinium hexafluorophosphate, N
-(4-methoxybenzyl) quinolinium hexafluorophosphate, N-cinnamyl-2-methylquinolinium hexafluorophosphate, N- (1-naphthylmethyl) -3-bromoquinolinium hexafluorophosphate, etc. Can be mentioned. Other than these quinolinium salts, for example, compounds described in JP-A-6-271544 are exemplified.

The cationic photopolymerization initiator (C) has a wavelength of 36.
A sulfonium salt having a maximum molar extinction coefficient of 100 or more between 0 and 500 nm. As a specific example, for example,
Examples thereof include a sulfonium salt having a thioxanthone structure, a sulfonium salt having an anthraquinone structure, and a sulfonium salt having an acridone structure. The sulfonium salt having a thioxanthone structure is, for example, represented by the following general formula (2)

[0016]

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(Wherein, R ₆ and R ₇ each represent a hydrogen atom, an alkyl group, a halogen atom, a hydroxyalkyloxy group or an alkoxy group, and R ₈ and R ₉ represent a halogen atom, an alkyl group or an alkoxy group, respectively) Represents
Y represents SbF ₆ , PF ₆ or B (C ₆ F ₅ ) ₄ . )). Examples of the alkyl group include a methyl group, an ethyl group, n- propyl group, an isopropyl group, an alkyl group C1~C5 and butyl group. Examples of the halogen atom, for example F, Cl, B _r, I and the like Examples of the alkoxy group include a C1 to C5 alkoxy group such as a methoxy group and an ethoxy group. Examples of the hydroxyalkyloxy group include a C1 to C5 hydroxyalkyl group such as a hydroxymethyloxy group and a hydroxyethyl group. Oxy groups are mentioned. Table 1 shows specific examples.

[0018]

Table 1 Table 1 Compound No. R ₆ R ₇ R ₈ R ₉ Y 1-1 -CH ₃ -CH ₃ -C ₂ H ₅ -C ₂ H ₅ PF ₆ 1-2 -CH ₃ -CH ₃ -C _{2 H 5 -C 2 H 5 SbF} 6 1-3 -F -F -C 2 H 5 -C 2 H 5 SbF 6 1-4 -OC 2 H 4 OH -OC 2 H 4 OH -C 2 H 5 - _{C 2 H 5 PF 6 1-5 -CH} 3 -CH 3 -C 3 H 7 (iso) -H PF 6 1-6 -CH 3 -CH 3 -C 3 H 7 (iso) -H SbF 6 1- 7 -F -F -C ₃ H ₇ (iso) -H PF ₆ 1-8 -F -F -C ₃ H ₇ (iso) -H SbF ₆ 1-9 -OCH ₃ -OCH ₃ -C ₃ H _{7 (iso) -H SbF 6 1-10 -H} -H -C 3 H 7 (iso) -H B (C 6 F 5) 4 1-11 -CH 3 -CH 3 -Cl -H PF 6 1-12 _{-F -F -Cl -H PF 6 1-13 -F} -F -Cl -H SbF 6

As the sulfonium salt having an anthraquinone structure, for example, the following general formula (3)

[0020]

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(Wherein, R ₁₀ and R ₁₁ each represent a hydrogen atom, a halogen atom, an alkyl group, a hydroxyalkyloxy group or an alkoxy group, and X represents SbF ₆ , PF ₆ or
B (C ₆ F ₅ ) ₄ is represented. )). Examples of the alkyl group include C1 to C5 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a butyl group. Examples of the halogen atom include F, Cl, Br, and I. Examples of the alkoxy group include C1 to C5 alkoxy groups such as a methoxy group, an ethoxy group, an n-propoxy group, and an isopropoxy group. Table 2 shows specific examples.

[0022]

TABLE 2 Compound No. substitution position _{R 10 R 11 Y 2-1 1 -CH} 3 -CH 3 PF 6 2-2 1 -CH 3 -CH 3 SbF 6 2-3 1 -F -F SbF 6 _{2-4 1 -H -HB (C 6 F} 5) 4 2-5 2 -C 3 H 7 (iso) -C 3 H 7 (iso) SbF 6 Note) substitution position sulfur atom of the anthraquinone backbone Means the bonding position.

As the sulfonium salt having an acridone structure, for example, the following general formula (4)

[0024]

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(Wherein R ₁₂ , R ₁₃ and R ₁₄ each represent a halogen atom or an alkyl group, R ₁₅ represents an alkyl group,
Represents SbF ₆ or PF _6. )). Examples of the alkyl group include a methyl group, an ethyl group,
C1-C5 alkyl groups such as n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group and the like, and examples of the halogen atom include F, Cl, B
r, I and the like. Table 3 shows specific examples.

[0026]

TABLE 3 Compound _{No. R 12 R 13 R 14 R} 15 Y 3-1 -F -F -Cl - (nC 4 H 9) SbF 6 3-2 -F -F -Cl - (nC 4 H ₉ ) PF ₆

In addition to these sulfonium salts, for example, compounds described in JP-A-8-165290 are exemplified.

The component (C) used in the present invention has a maximum molar extinction coefficient of at least 100, preferably at least 1,000, particularly preferably at least 2,000 in the wavelength region of 360 to 500 nm. Wavelength 36
Absorption is not greater than 0 nm or the molar extinction coefficient is 100
In the following cases, curing does not occur or curing is slow, which is problematic.

Preferred examples of these sulfonium salts include, for example, 1-2, No. 1-6, N
o. 1-7, no. 1-8, No. 1 1-11, No. 1; 1
-12, no. And sulfonium salts having a thioxanthone structure such as 1-13.

In the present invention, the pigment (D) is used as an optional component. Specific examples of the pigment (D) include, for example, inorganic pigments such as carbon black, graphite, molybdenum, red iron oxide, titanium dioxide, rutile type titanium dioxide coated with aluminum oxide, cyanine green, cyanine blue, Hansa yellow, and benzidine. Organic pigments such as yellow, brilliant carmine 6B, lake red C, permanent red F5R and the like can be mentioned.

The proportion of each of the components (A) to (D) used in the composition of the present invention is as follows.
It is preferably from 7 to 99.7% by weight, particularly preferably 49.
7 to 99.7% by weight. The total amount of the components (B) and (C) is preferably 0.3 to 15% by weight, particularly preferably 1 to 10% by weight, in the composition of the present invention. When the total amount of the components (B) and (C) is 100 parts by weight,
The usage ratio of the component (B) to the component (C) is such that the component (B) is 1
The amount is preferably from 60 to 60 parts by weight, particularly preferably from 10 to 50 parts by weight, and the component (C) is preferably from 40 to 99 parts by weight, particularly preferably from 50 to 90 parts by weight. The component (D) is preferably from 0 to 70% by weight, particularly preferably from 10 to 70% by weight.
６０60% by weight.

The composition of the present invention contains a solvent for dilution and a resin for modification (for example, acrylic polymer, polyurethane polymer, polyester elastomer, polyvinyl chloride polymer, acrylonitrile rubber) as long as polymerization is not impaired. And the like, for example, an organic carboxylic acid or an acid anhydride can be used for the purpose of improving electrical properties, or a polyol or other flexible prepolymer can be mixed for the purpose of imparting rubber elasticity. Dyes, fillers, antistatic agents, flame retardants, defoamers, flow regulators, light stabilizers, coupling agents, organic solvents, and the like can be mixed and used.

The energy ray-curable composition of the present invention is prepared by mixing, dissolving, dispersing and kneading the components (A) to (D) and, if necessary, other components, or (A)
The components (C) and (D), and if necessary, other components,
First, after mixing, dissolving, dispersing and kneading, the component (B) can be mixed and dissolved to prepare.

The curable composition of the present invention has a thickness of preferably 1 to 100 μm, more preferably 2 to 50 μm on the substrate.
After the application, irradiation with energy rays such as ultraviolet rays can cure to a touch-dry state or a catalyst-insoluble state after 0.1 seconds to several minutes. Examples of the substrate include metal, wood, paper, rubber, plastic, glass, and ceramic products. Examples of a method for applying the curable composition of the present invention to a substrate include a printing method such as screen printing and dry offset printing, and a method using a coater such as a roll coater, a spin coater, and a bar coater. Suitable energy rays include high-pressure mercury lamps,
Low-pressure mercury lamp, xenon lamp, metal halide lamp,
200nm ~ 50 obtained from germicidal lamp, laser light, etc.
It is preferable to use energy rays having a wavelength of 0 nm. Exposure to an energy ray depends on the intensity of the energy ray, but usually about 0.1 to 10 seconds is sufficient. However, for relatively thick coatings, it is preferable to spend more time. The polymer is cured by polymerization from 0.1 seconds to several minutes after the irradiation with the energy beam, but is preferably heated at the time of irradiation with the energy beam or after the irradiation with the energy beam in order to promote the polymerization reaction.

Specific uses of the composition of the present invention include:
For example, white ink for metal cans such as food cans, various printing inks, paints, resist inks, fillers, adhesives and the like can be mentioned. Examples of the article having a cured film of the composition of the present invention include metal cans such as cans for food cans.

[0036]

【Example】

Examples 1 to 3 and Comparative Examples 1 to 3 The energy ray-curable compositions were blended according to the blending compositions (the numerical values are parts by weight) shown in Table 4 and kneaded with a three-roll mill. This was applied on an aluminum plate to a thickness of 10 μm with a bar coater, and a metal halide lamp (80 W
/ Cm ² ) at a distance of 8 cm and ultraviolet rays of 200 mJ / c.
m ² and then cured by heating at 100 ° C. for 5 minutes. The curability of the prepared composition and the gloss of the cured coating film were tested. Table 4 shows the results.

Curability After UV irradiation: The cured coating film was rubbed with absorbent cotton impregnated with methyl ethyl ketone, and the number of times the coating film remained unchanged was measured. After heating: The cured coating film was rubbed with absorbent cotton impregnated with methyl ethyl ketone, and the number of times the coating film did not change was measured. Gloss: The surface of the cured coating film was visually judged.・ ・ ・ ... Slightly good gloss. Δ: There is slight cloudiness. X: No gloss at all.

[0038]

Table 4 Example Comparative Example 12 3 12 3 (A) Component 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate 84 68 84 84 84 84 Bisphenol A diglycidyl ether 20 (B) Component N-Benzyl-2-methylquinolinium hexachloroantimonate 14 1 N-Cinnamyl-2-methylquinolinium hexachloroantimonate 11 (C) Component Compound No. 1-7 * 43 3 4 Compound No.1-12 * 5 3 (D) component Titanium dioxide (rutile type) 100 100 100 100 100 100 Other UVI-6990 * 16 Polyester resin * 2 10 6 10 10 10 10 Surfactant (L-7604) * 3 0.4 0.4 0.4 0.4 0.4 0.4 硬化 Curing After UV irradiation (rubbing Number of times) 40 30 40 0 20 5 After heating Number of rubbing) 200 200 200 200 50 200 or more or more or more or more gloss ○ ○ ○ ○ ○ ×

Note) * 1: UV-6990: Photocationic polymerization initiator manufactured by Union Carbide Co., Ltd. Propylene carbonate 50% diluted product, no absorption at a wavelength of 360 nm or more. * 2: Polyester resin: “Byron 22” manufactured by Toyobo
0 "Molecular weight 2000-3000. * 3: L-7604: manufactured by Nippon Unicar, a surfactant. * 4: Compound No. 1-7: cationic photopolymerization initiator, wavelength 38
Molar extinction coefficient at 4 nm 5000 * 5: Compound No. 1-12: Photocationic polymerization initiator, wavelength 3
Molar extinction coefficient 4580 at 87 nm

As is clear from the results shown in Table 4, the composition of the present invention is excellent in curability by ultraviolet rays, gloss and the like in a composition containing a pigment.

[0041]

The energy ray-curable composition of the present invention comprises:
By using a quinolinium salt compound (B) which is a latent thermal cation polymerization initiator and a cation polymerization initiator (C) which is a sulfonium salt having a maximum molar extinction coefficient of 100 or more in a wavelength region of 360 to 500 nm, Particularly, it is a pigment-based material having excellent curability and gloss, and provides a cured product having excellent physical properties.

Claims (5)

[Claims] 1. A cationic polymerizable substance (A), a quinolinium salt compound (B) and a photo-cationic polymerization initiator having a wavelength of 36
An energy ray-curable composition comprising a sulfonium salt (C) having a maximum molar extinction coefficient of 100 or more in a wavelength range of 0 to 500 nm. 2. The energy ray-curable composition according to claim 1, wherein the sulfonium salt (C) is a sulfonium salt having a thioxanthone structure. 3. The energy ray-curable composition according to claim 1, further comprising a pigment (D). 4. A cured product of the composition according to any one of claims 1 to 3. 5. An article having a film of a cured product of the composition according to claim 4.