JPH0912614A - Actinic-radiation-curing composition and cured product thereof - Google Patents

Abstract

PURPOSE: To obtain an actinic-radiation-curing composition free from any amine compound by mixing an ethylenically unsaturated compound with a photopolymerization initiator prepared by introducing a specified sulfonium salt group into a tioxanthone compound. CONSTITUTION: An ethylenically unsaturated compound (A) is mixed with a photopolymerization initiator comprising a sulfonium salt (B) of formula I [wherein R1 to R5 are each H, OH, a 1-15C aliphatic group, a halogen, a group of formula II or the like; (n) is 1-4; (Z) is a group of the formula: MQ1 or MQp-1 (OH) (wherein M is P, B, As or the like; Q is a halogen; and (p) is 4-6); X is a group of formula II (wherein R6 to R15 are each H, a halogen, an alkoxyl, a 1-20C aliphatic group, phenyl, thiophenoxy or the like)] to obtain an actinic-radiation-curing composition. This composition is freed from any amine compound, is therefore lowly odorous and has excellent curability. The component A is exemplified by a hydroxyalkyl (meth)acrylate or (meth) acrylamide. The component B is obtained by condensing a thioxanthone compound with a diphenyl sulfoxide compound.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to polymerization by irradiation with an energy ray containing an ethylenically unsaturated group-containing compound (A) and a photopolymerization initiator (B) consisting of a sulfonium salt having a specific structure. It relates to a possible energy ray-curable composition and a cured product thereof.

[0002]

2. Description of the Related Art Photoradical polymerizable compositions have been extensively studied and put to practical use in the fields of printing inks, paints, coatings, liquid resist inks, etc., in order to save energy and save space. . Many of these photoradical polymerizable compositions are composed of an ethylenically unsaturated group-containing compound, a photoradical polymerization initiator, and an amine compound as a photoradical polymerization accelerator. In printing inks and the like, thioxanthone compounds are often used as photoradical polymerization initiators because they use a large amount of color pigments.This thioxanthone compound is a hydrogen abstraction type photoradical polymerization initiator, and is an accelerator. Is used together with the amine compound.

[0003]

When a thioxanthone compound is used as the photoradical polymerization initiator, it is necessary to use an amine compound as the accelerator. Many amine compounds have a strong odor, which is a problem when producing or using printing ink.

[0004]

Means for Solving the Problems As a result of intensive research to solve the above-mentioned problems, the present inventors have found that a promoter is obtained by using a photopolymerization initiator obtained by introducing a specific sulfonium base into a thioxanthone compound. The present invention succeeded in providing an energy ray-curable composition having good curability and less odor by irradiating with energy rays (for example, ultraviolet rays, electron rays, X-rays, etc.) without using an amine compound as a component. . That is, the present invention provides an ethylenically unsaturated group-containing compound (A) and the following formula (1)

[0005]

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In the formula, X is a group represented by the formula (2)

[0007]

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(In the formula, R _{6 to} R ₁₅ are each a hydrogen atom,
In the structure of halogen atom, nitro group, alkoxy group, C _{1 to} C ₂₀ , hydroxyl group, ether group, ester group, (meth)
It is a group selected from any of an acryloyl group, an epoxy group, or an aliphatic group which may have an allyl group, a phenyl group, a phenoxy group, and a thiophenoxy group. ) R _{1 to} R ₅ are each a group selected from a hydrogen atom, a hydroxyl group, a C ₁ -C ₁₅ aliphatic group, a halogen atom, a nitro group, an alkoxy group, a phenyl group, and a group represented by the formula (2). And n is 1 to 4 and Z is the formula (3) or the formula (4).

MQ _P (3) MQ _P-1 (OH) (4)

(In the formula, M is a phosphorus atom, a boron atom, an arsenic atom or an antimony atom, Q is a halogen atom, and P is an integer of 4 to 6). } The photocurable initiator (B) which consists of the sulfonium salt shown by these is contained, The energy ray curable composition characterized by the above-mentioned, and its hardened | cured material.

Examples of the ethylenically unsaturated group-containing compound (A) used in the present invention include 2-hydroxyethyl (meth) acrylate and 2-hydroxybutyl (meth).
Hydroxyalkyl (meth) acrylates such as acrylates; glycol mono- or di (meth) acrylates such as ethylene glycol, methoxytetraethylene glycol, polyethylene glycol, propylene glycol; N, N-dimethyl (meth) acrylamide, N-methylol (Meth) acrylamides such as (meth) acrylamide; aminoalkyl (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate; hexanediol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol , Polyhydric alcohols such as tris-hydroxyethyl isocyanurate, and polyhydric alcohols of these ethylene oxide or propylene oxide adducts (meth). ) Acrylates; phenoxy (meth) acrylate, bisphenol A di (meth) acrylate, and (meth) acrylates such as ethylene oxide or propylene oxide adducts of these phenols; glycerin diglycidyl ether, trimethylolpropane triglycidyl Ethers, (meth) acrylates of glycidyl ethers such as triglycidyl isocyanurate; and reactive monomers such as melamine (meth) acrylate,

Epoxy resin (for example, phenol novolac epoxy resin, cresol novolac resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenol methane type epoxy resin, polybutanediene modified epoxy resin, alicyclic epoxy resin,
(Brominated phenol novolac epoxy resin, brominated bisphenol A type epoxy resin, amino group-containing epoxy resin, etc.) and epoxy (meth) acrylate which is a reaction product of (meth) acrylic acid, and polybasic acid anhydride to the above epoxy (meth) acrylate. (For example, maleic anhydride, succinic anhydride, phthalic anhydride, tetrahydrophthalic anhydride,
Hexahydrophthalic anhydride and the like) reacted carboxylic acid-modified epoxy (meth) acrylate, polyol component (for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, 3- Methyl-1,5-
Pentanediol, polyethylene glycol, polypropylene glycol, 1,4-dimethylolbenzene, trimethylolpropane, pentaerythritol, etc.) and acid components (eg, maleic acid, succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydro) (Meth) acrylic acid ester of polyester polyol which is a reaction product of dibasic acid such as phthalic acid or dibasic acid anhydride, or polyol (eg, ethylene glycol, neopentyl glycol, polytetramethylene glycol, polyester polyol) , Polycaprolactone polyol, etc.) and organic polyisocyanate (eg, tolylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, etc.) and hydroxyl group-containing (meth) acryl Doo (e.g., 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate) is a reaction product of a urethane (meth)
Examples thereof include reactive oligomers such as acrylate.

The photopolymerization initiator (B) composed of the sulfonium salt represented by the general formula (1) used in the present invention is, for example, the general formula (5).

[0014]

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(Wherein R _{1 to} R ₅ are groups selected from a hydrogen atom, a hydroxyl group, a C _{1 to} C ₁₅ aliphatic group, a halogen atom, a nitro group, an alkoxy group, an ester group and a phenyl group, respectively. A method in which a thioxanthone compound represented by the formula (1) and a substituted or unsubstituted diphenyl sulfoxide compound are used in a known reaction for forming a sulfonium salt (hereinafter referred to as 1)), 2) a corresponding substituted or unsubstituted sulfonium salt is previously prepared. It can be synthesized by any method of synthesizing and then converting and introducing a substituent (hereinafter referred to as 2) method. First, the method 1) will be described in detail. A thioxanthone compound represented by the formula (5) (specific examples include 2,4-diethylthioxanthone, 2,4
-Dipropyltoxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone, 2-hydroxy-3,4-dimethylthioxanthone, 1-methoxythioxanthone, 2-methoxythioxanthone. , 3-methoxythioxanthone, 4-methoxythioxanthone, 1-methyl-4-hydroxythioxanthone, 1-methyl-4-chlorothioxanthone,
1,2-dimethyl-4-chlorothioxanthone, 1,3
-Dimethyl-4-chlorothioxanthone, 2,3,4-
Trimethylthioxanthone, 3-nitrothioxanthone, 3-ethoxythioxanthone, 1,3,4-trimethyl-2-oxycarbonylmethylthioxanthone, 2
-Oxycarbonylmethyl-4-methylthioxanthone, 2-phenylthioxanthone, 1-carbonyloxymethylthioxanthone, 1-carbonyloxyethyl-3-nitrothioxanthone, 1-carbonyloxyethyl-3-ethoxythioxanthone and the like can be mentioned. ) And a substituted or unsubstituted diphenyl sulfoxide compound (eg, diphenyl sulfoxide, 4,4′-difluorodiphenyl sulfoxide, 2,2′-difluorodiphenyl sulfoxide, 3,3′-difluorodiphenyl sulfoxide, 4,2′-difluorodiphenyl sulfoxide) , 4,4'-dibromodiphenyl sulfoxide, 4,4'-dichlorodiphenyl sulfoxide,
2,2 ', 4,4-tetrachlorodiphenyl sulfoxide, 4,4'-dimethyldiphenyl sulfoxide, 4,
4'-diethyldiphenylsulfoxide, 4,4'-dimethoxydiphenylsulfoxide, 4,4'-diethyldiphenylsulfoxide, 4-methylthiodiphenylsulfoxide, 4-phenylthiodiphenylsulfoxide and the like are known methods, for example, dehydrating agents (for example, Phosphorus pentoxide,
Condensation reaction is performed at room temperature to 100 ° C. in concentrated sulfuric acid, acetic anhydride, etc., and then these reaction solutions are subjected to the reaction of formula (3) or (4) (for example, NaSbF ₆ , NaPF ₆ , NaAs).
F ₆ , NaBF ₄ , NaSbF ₅ OH, KSbF ₆ , K
The sulfonium salt can be obtained by dropping it into an aqueous solution of PF ₆ , KAsF ₆ , KSbF ₆ OH, etc.).

The method 2) will be described in detail. A sulfonium salt synthesized by the method 1), for example, the formula (6)

[0017]

[Chemical 6]

[0018] (wherein, R _{1-R 5} is the same as R _{1-R 5} in formula (5), A is represented by a halogen atom, Z is the formula (3) or (4) Known method, such as a compound represented by the formula (1), for example, in the presence of a basic compound (eg, sodium hydroxide, potassium hydroxide, potassium carbonate, etc.) in a large excess of mono- or polyalcohols (eg, methanol, Ethanol, carbitol, ethylene glycol, polyethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,4-butanediol, glycidol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, allyl alcohol, etc. ) Room temperature to 15
By reacting at 0 ° C. in the presence of an organic solvent such as dimethyl sulfoxide, if necessary, the halide part of the halide compound can be converted into

[0019]

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[0020]

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[0021]

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[0022]

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It is possible to obtain a sulfonium salt converted into a substituent such as. As typical examples of the compound represented by the general formula (1), the compounds shown in Tables 1 and 2 below can be given, but the compounds are not limited to these.

[0024]

[Table 1]

[0025]

[Table 2] The curable composition of the present invention is usually 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight of the above formula ( The photopolymerization initiator (B) represented by 1) is used as an essential component, but an appropriate ratio is various, such as the type of ethylenically unsaturated group-containing compound and energy rays, irradiation dose, desired curing time, and coating thickness. It is determined by considering the factors. The curable composition of the present invention can be prepared by a method such as mixing, dissolving or kneading.

The curable composition of the present invention can be cured to a dry-to-touch state or a solvent-insoluble state after 0.1 seconds to several minutes by irradiating energy rays such as ultraviolet rays. The composition of the present invention may further contain a pigment,
Dyes, fillers, antistatic agents, flame retardants, defoamers, flow regulators, light stabilizers, or cationic polymerization of aromatic epoxy resins, alicyclic epoxy resins, aliphatic epoxy resins, various vinyl ethers, etc. It is possible to mix and use the compound. The composition of the present invention can be used for metal, wood, rubber, plastic, glass, ceramics, paper products and the like. Further, specific applications of the present invention include paints, coating agents, inks, resists, liquid resist adhesives, molding materials, casting materials, putties, glass fiber impregnating agents, and sealing agents.

[0027]

The present invention will be described below in more detail with reference to examples. Parts in Examples are parts by weight.

(Synthesis Example of Sulfonium Salt Represented by Formula (1)) Synthesis Example 1 2,4-Diethylthioxanthone 38.4 parts, 4,4 '
-23.8 parts of difluorodiphenyl sulfoxide, 100 parts of acetic anhydride and 398 parts of methanesulfonic acid were charged,
The reaction was carried out for about 8 hours with stirring at 25 ° C., then
This reaction mixture was gradually added dropwise to 619.9 parts of an aqueous solution of NaSbF ₆ (37.1 parts of NaSbF ₆ dissolved in 582.8 parts of water), and the precipitated yellow solid was filtered and filtered with water and ethylene ether. Washed. 93.0 parts of a yellow solid was obtained. The melting point of the product is 81.1-87.
The elemental analysis values at 9 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 48.10 48.02 Hydrogen 3.25 3.20 Sulfur 8.89 8.84 Antimony 16.71 16.78 Fluorine 20.99 20.95 This production Structural formula based on the method

[0029]

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A sulfonium salt of was obtained.

Synthesis Example 2 6.1 parts of 1-chloro-4-propoxythioxanthone, 46.1 parts of 4,4'-dimethyldiphenyl sulfoxide, 200 parts of acetic anhydride, and 796 parts of methanesulfonic acid were charged, and at 25 ° C. After reacting for about 8 hours, the reaction mixture is then mixed with an aqueous solution of NaSbF ₆ 86
2.8 parts (51.7 parts of NaSbF ₆ dissolved in 810.6 parts of water) was added dropwise little by little, and the precipitated yellow solid was filtered and washed with water and ethyl ether. 135.6 parts of a yellow solid was obtained. The melting point of the product is 10
The elemental analysis values at 5.2 to 111.0 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 47.84 47.80 Hydrogen 3.52 3.48 Sulfur 8.57 8.51 Antimony 16.20 16.15 Fluorine 15.15 15.12 Chlorine 4 .72 4.70 Based on this manufacturing method,

[0032]

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A sulfonium salt of was obtained. Synthesis Example 3.2 2-Isopropylthioxanthone 50.8
Parts, diphenyl sulfoxide 40.4 parts, acetic anhydride 20
0 parts and 796 parts of methanesulfonic acid were charged and reacted at 25 ° C. for about 8 hours, and then the reaction mixture was added to 560 parts of an aqueous solution of NaPF ₆ (33.6 parts of NaPF ₆ dissolved in 526.4 parts of water). It was added dropwise little by little, and the precipitated yellow solid was filtered and washed with water and ethyl ether. 105.1 parts of a yellow solid was obtained. The melting point of the product is 79.
The elemental analysis values at 1 to 85.7 ° C. were as follows. Element Measured value (wt%) Calculated value (wt%) Carbon 57.49 57.53 Hydrogen 3.99 3.96 Sulfur 10.95 10.97 Phosphorus 5.28 5.30 Fluorine 19.52 19.50 This production Structural formula based on the method

[0034]

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A sulfonium salt of was obtained.

Synthesis Example 4. 40 parts of the compound obtained in Synthesis Example 1,
4.0 parts of sodium hydroxide and 200 parts of ethylene glycol were charged and reacted at room temperature for 24 hours, then poured into water and the precipitated yellow solid was filtered and dried to obtain a solid product at room temperature. The structural formula of the product is shown below, and the result of elemental analysis almost coincided with the calculated value.

[0037]

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Element Measured value (wt%) Calculated value (wt%) Carbon 48.31 48.26 Hydrogen 4.10 4.05 Sulfur 8.07 8.05 Antimony 15.30 15.29 Fluorine 14.33 14. 31 Examples 1 to 4 and Comparative Examples 1 and 2 The energy ray-curable compositions were blended according to the blending composition (numerical values are parts by weight) shown in Table 3 and mixed and dissolved. Apply this on paper to a thickness of 3μ and apply a high pressure mercury lamp (80
It was cured by irradiating with ultraviolet light from a road separation of 8 cm (w / cm ² ). The conditioned compositions were tested for touch dryness, cured coating gloss, and odor. Table 3 shows the results.

Touch-free property: The amount of irradiation (mJ / cm ² ) until touch-free was measured. Gloss: The surface of the cured coating film was visually evaluated after irradiation with the irradiation amount (mJ / cm ² ) until the film was dried to the touch. ○ ・ ・ ・ ・ Gloss is good △ ・ ・ ・ ・ Slightly cloudy × ・ ・ ・ ・ No gloss Odor: Irradiation dose (mJ / c) until the coated surface is dry to the touch
After irradiating m ² ), the odor of the surface of the cured coating film was observed. ○ ・ ・ ・ ・ No odor △ ・ ・ ・ ・ Slight odor × ・ ・ ・ ・ Odor

[0040]

Table 3 Examples Comparative Examples 1 2 3 4 1 2 Photopolymerization Initiator 3 Obtained in Synthesis Example 1 Photopolymerization Initiator 3 Obtained in Synthesis Example 2 Photopolymerization Initiator 3 Obtained in Synthesis Example 3 Photoinitiator 3 obtained in Example 4 KAYARAD R-114 * 1 20 20 20 20 20 20 Trimethylolpropane triacrylate 10 10 10 10 10 10 KAYARAD 551 * 2 50 50 50 50 50 50 Polyethylene glycol diacrylate 20 20 20 20 20 20 2,4-Diethylthioxanthone 33 N, N-Dimethylaminobenzoic acid Isoamyl ester 1-Touch dryness (mJ / cm ² ) 70 70 100 70 107 ^{* 3} Gloss ○ ○ ○ ○ ○ ── Odor ○ ○ ○ ○ △ ──

Note) * 1 KAYARAD R-11
4: Diacrylate of diglycidyl ether of bisphenol A manufactured by Nippon Kayaku Co., Ltd. * 2 KAYARAD R-551: Nippon Kayaku Co., Ltd.
Diacrylate of bisphenol A adduct of ethylene oxide on average 4 mol. As is clear from the results in Table 3, the energy ray-curable lung composition of the present invention has excellent curability without using an amine compound in combination, the cured coating film has good gloss, and the cured coating film has no odor. small.

[0042]

The energy ray-curable composition of the present invention comprises:
It has excellent curability, the gloss of the cured coating film is good, and the odor of the cured coating film is small, giving a cured product with excellent physical properties.

Claims (2)

[Claims] 1. An ethylenically unsaturated group-containing compound (A) and the following formula (1): (In the formula, X is a group represented by the formula (2) {Wherein R ₆ -R ₁₅ are a hydrogen atom, a halogen atom,
Aliphatic group, phenyl group and phenoxy group which may have a hydroxyl group, an ether group, an ester group, a (meth) acryloyl group, an epoxy group or an allyl group in the structure of nitro group, alkoxy group and C ₁ -C ₂₀ A thiophenoxy group. ) R _{1 to} R ₅ are each selected from a hydrogen atom, a hydroxyl group, a C ₁ -C ₁₅ aliphatic group, a halogen atom, a nitro group, an alkoxy group, an ester group, a phenyl group and a group represented by the formula (2). And n is 1 to 4, Z is the formula (3) or the formula (4) MQ _P (3) MQ _P-1 (OH) (4) (wherein M is a phosphorus atom, a boron atom, It is an arsenic atom or an antimony atom, Q is a halogen atom, and P is an integer of 4 to 6.). } The energy ray curable composition characterized by containing the photoinitiator (B) which consists of a sulfonium salt shown by these. 2. A cured product of the composition according to claim 1.