JPH0733810A - Photo-initiator of copolymerization and coating composition - Google Patents

Abstract

PURPOSE:To obtain a composition having less smelling trouble during printing and of printed matter and excellent hardness of cured coating and capable of being prevented from the deterioration of curability by esterifying a specific propyl ketone with poly(meth)acrylic acid. CONSTITUTION:The objective initiator is obtained by esterifying a compound of formula I [PHI is p-phenylene; (n) is 1-5] with poly(meth)acrylic acid of formula II [R1 and R2 are H or methyl; (m) is 1-10] or its halogenide derivative. The initiator composition is obtained by compounding 10-90wt.% of the initiator with 90-10wt.% of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1 or 2,4,6-trimethylbenzoyldiphenylphosphineoxide. Further, 1-10wt.% of 4,4'-bis(di- lower alkylamino)benzophenone is optionally incorporated. The coating composition is obtained by compounding a radically polymerizable double bond- containing compound with 0.1-20wt.% of the initiator composition.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION This invention relates to photoinitiators and coating compositions that cure upon exposure to ultraviolet light.

[0002]

2. Description of the Related Art In recent years, research on photocurable coating compositions, in particular, curable coating compositions by ultraviolet rays has been vigorously carried out. Among them, printing inks, overcoat varnishes, paints, adhesives, photoresists, etc. It is being put to practical use in the field. These are photoinitiators, resins (including both radically polymerizable resins and non-radically polymerizable resins), radically polymerizable monomers, pigments (not included in overcoat varnish), additives, etc. Consists of. A commonly used photoinitiator is benzophenone such as methyl o-benzoylbenzoate, Darocur 11
73, Darocur 2959, Irgacure 184, Irgacure 907 (Irgacure and Darocur are trademarks of Ciba-Geigy), and the like, Irgacure 6
Benzoin-based compounds such as 51, or thioxanthone-based compounds, EA
B (manufactured by Hodogaya Chemical Co., Ltd.), SEICOL PAA (manufactured by Seiko Chemical Co., Ltd.), Kayakyu EPA (manufactured by Nippon Kayaku Co., Ltd.) and other hydrogen donation systems are used. Since these photoinitiators do not have copolymerizability with the photocurable coating composition, they are not incorporated into the cured film and partially volatilize, causing printing, coating site or printed matter, odor of the coated matter, printed matter, etc. Causes deterioration of film physical properties such as decrease in film hardness.

For the purpose of improving these, for example, a copolymerizable photoinitiator obtained by subjecting 4 (2hydroxyethoxy) -phenyl-2hydroxy-2-propylketone (Darocur 2959 etc.) to an esterification reaction with acrylic acid chloride is known. (Japanese Patent Laid-Open No. 62-81345). Although the odor of the printed matter is considerably improved, it still has a slight odor.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a photocopolymerizable initiator composition and a photocurable coating composition for the purpose of preventing the deterioration of the odor, the cured film hardness, and the curability of the printed matter and the printed matter. It is provided.

[0005]

The present invention is based on the general formula (1)
And a compound represented by the formula: H (C ₂ H ₄ O) _n O-φ-CO-C (CH ₃ ) ₂ -OH (1) (wherein φ is a paraphenylene group, and n is an integer of 1 to 5). The poly (meth) acrylic acid represented by the general formula (2) or its acid halogenide derivative CH ₂ = CR ₁ COO- (CH ₂ CR ₂ COO) _m H (2) (in the formula, R ₁ and R ₂ Is an H or a methyl group, and m is an integer of 1 to 10), and a copolymerizable photoinitiator.

The present invention further relates to copolymerizable photoinitiators 10-9.
0% by weight and (b) 2-benzyl-2-dimethylamino-
It relates to an initiator composition consisting of 90 to 10% by weight of 1- (4morpholinophenyl) -butanone-1 or 2,4,6-trimethylbenzoyldiphenylphosphine oxide. The present invention further comprises 1 to 10% by weight of (c) 4,4'-bis (dilower alkylamino) benzophenone added to the initiator or the initiator composition. It relates to an initiator composition. Further, the present invention provides the initiator or photoinitiator composition in an amount of 0.1 to 20% by weight based on the radical-polymerizable double bond-containing compound.
The present invention relates to a coating composition formed by blending.

Specific examples of the compound of the general formula (1) of the present invention and
Then, 4- (2hydroxyethoxy) -phenyl-2
There is hydroxy-2 propyl ketone, which is Merck
Is available as Darocur 2959. General formula
Specific examples of the compound represented by (2) are as follows. CH₂= CHCOOCH₂-CH₂COOH CH₂= CHCOOCH₂-CH₂COCl CH₂= CHCOOCH₂-CH₂COBr CH₂= C (CH₃) COOCH₂-CH (CH₃) C
OOH CH₂= C (CH₃) COOCH₂-CH (CH₃) C
OCl CH₂= C (CH₃) COOCH₂-CH (CH₃) C
OBr CH₂= CHCOO (CH₂-CH₂COO)_1.4H (Aronix M5600 manufactured by Toagosei Co., Ltd.) CH₂= CHCOO (CH₂-CH₂COO)_mH CH₂= CHCOO (CH₂-CH₂COO-)-_m-1
-(-CH₂-CH ₂CO halogen atom) CH₂= C (CH₃) COO (CH₂-CH (CH₃) CO
O-)-_m-1-(-CH₂-CH (CH₃) CO halogen
atom)

The reaction method of the compound of the general formula (1) and the compound of the general formula (2) is carried out at a temperature of 80 to 120 ° C. at which the (meth) acrylic acid system does not cause gelation. Hydroquinone and methoquinone are used as polymerization inhibitors.
Further, sulfuric acid, P-toluenesulfonic acid or the like is used as an esterification catalyst. Further, cyclohexane, benzene, toluene, MIBK and the like are used as a reaction solvent if necessary. If necessary, in the case of a (meth) acrylic acid halogen system, which is carried out in a stream of air or nitrogen, it is carried out at 25 to 50 ° C. Further, it is used as an amine catalyst such as pyridine triethylamine as a dehalogenation catalyst. The reaction ratio of the compound of the general formula (1) and the compound of the general formula (2) is represented by the general formula (1)
The compound of the formula (1) is reacted with 0.1 to 1 mol of 1 OH group. Alternatively, the unreacted product may be washed with water by charging the compound of the general formula (2) in excess.

In the initiator composition of the present invention, the component (b) 2-
Benzyl 2-dimethylamino-1- (4morpholinophenyl) -butanone-1 is available as Irgacure 369 from Ciba-Geigy. Also, 2,4,6-trimethylbenzoyldiphenylphosphine oxide is BA
It is available as Lucirin TPO from SF Company. More specifically, the component (c) 4,4′-bis (dilower alkylamino) benzophenone in the initiator composition of the present invention is
4,4'-bis (dimethylamino) benzophenone,
4,4'-bis (diethylamino) benzophenone and the like are available, and these are available as EAB manufactured by Hodogaya Chemical Co., Ltd.

In the present invention, the component (b) accounts for 10 to 90% by weight, preferably 30 to 70% by weight in the initiator composition comprising the component (a). If the amount of the component (b) used is smaller than the above numerical value, the curing rate is lowered, which is not preferable, and conversely, if it is larger than the above numerical value, the effect just used cannot be recognized, which is not preferable. Also, (c)
When the components are used together in the range of 1 to 10% by weight in the initiator composition, the curability can be further improved.

The photocurable coating composition of the present invention is obtained by blending a radical diluent resin or a resin having no radical polymerizability with a reactive diluent. The radical-polymerizable resin has a weight average molecular weight of about 5,000 to 100,000 and is a resin having a viscosity of 1,000 poise or a solid at room temperature. Examples of such resins include alkyd (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, urethane-modified (meth) acrylate, and modified resins obtained by modifying these raw material resins with fatty acids, rosins, higher alcohols, and the like ( Examples thereof include (meth) acrylate. As the resin having no radical polymerizable property, a resin having a softening point of 30 ° C. or higher, preferably 70 ° C. to 120 ° C. is used. Examples of the resin having no radical polymerizability include polyester resin, epoxy ester resin, urethane resin and diallyl phthalate resin.

The reactive diluent to be added to the photocurable coating composition of the present invention can be used if it has a viscosity of 200 poise or less (25 ° C.), but it is mainly composed of 1 to 10 poise. preferable. The following reactive diluents can be used.
Alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylates of alkylene oxide adducts of alkylphenols, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, etc. Monofunctional diluent.

Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate and the like di, tri, tetra or poly. Alkylene glycol di (meth) acrylate,
Tetramethylolmethane tetra (meth) acrylate,
Trimethylolethane tri (meth) acrylate, ditrimethylolethane tritetra (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetraacrylate, glycerin tri (meth) acrylate, diglycerin tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and alkylene oxide (meth) of the polyols constituting them. Acrylate etc.

Bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate, hydrogenated bisphenol F di (meth) acrylate, hydrogenated bisphenol A alkylene oxide addition Di (meth) acrylate, hydrogenated bisphenol F alkylene oxide adduct di (meth) acrylate. Polylactonate di (meth) acrylate of alkylene glycol such as polyethylene glycol and polypropylene glycol, glycerin, diglycene,
Trimethylolpropane, ditrimethylolpropane,
Multifunctional diluents such as polylactonate (meth) acrylates such as pentaerythritol and dipentaerythritol.

The reactive diluent in the photocurable coating composition is
50 to 300 parts by weight is added to 100 parts by weight of the resin. The photoinitiator composition is added in an amount of 0.1 to 20 parts by weight based on the radically polymerizable double bond-containing compound. The use of the coating composition as a printing ink composition involves adding a pigment to a composition consisting of a resin, a reactive diluent and a photopolymerization initiator. As a method for dispersing the pigment, a triple roll, a ball mill or the like can be used. A plasticizer, a surfactant and a thermal polymerization inhibitor may be added depending on the use. Moreover, you may mix | blend the resin which does not have radical polymerizability of this invention. The resulting composition, when not mixed with a printing ink or pigment,
The overcoat varnish can be mainly coated on a paper or a metal substrate by a roll coater.

[0016]

【Example】

Production Example 1 224 Darocur 2959 was added to a four-necked flask equipped with a stirrer.
Parts, 0.4 parts of hydroquinone, and 40 parts of toluene were charged, and the temperature was raised to 80 ° C., and 4 parts of P-toluenesulfonic acid was dissolved in a stream of air / nitrogen = 1/1. Aronix M5600
Charge 173 parts dropwise. After that, the temperature was gradually raised and the acid value reached 8.5 at 115 ° C, so the solvent removal mechanism was started.

Production Example 2 224 Darocur 2959 was placed in a four-necked flask equipped with a stirrer.
Parts, hydroquinone 0.4 parts, MEK 40 parts, pyridine 84 parts were charged and dissolved with stirring, and then CH ₂ = CHCOOC
H ₂ 1 hour the reaction without added dropwise heated -CH ₂ COOCl 173 parts. After that, it is filtered and the liquid is evaporated to dryness and then 50
It is dissolved in 0 ml of ethyl acetate, washed with water three times, and then desolvated to obtain a reaction product.

EXAMPLES The present invention will be described below with reference to examples. In the examples, parts are parts by weight. Dipentaerythritol hexaacrylate 69.9% and hydroquinone 0.1% were charged to 100 ° C.
After the temperature is raised to 1, the diacrylic phthalate resin (DT15
(0, manufactured by Toto Kasei Co., Ltd.) 30 parts are gradually charged and melted, and then pumped out. A varnish having a viscosity of 2100 poise (25 ° C.) was obtained.
Using this varnish, raw materials having the following formulation were kneaded to obtain a printing ink. Base ink Carbon black 10 parts Varnish 40 parts Dipentaerythritol hexaacrylate 30 parts Pentaerythritol tetraacrylate 10 parts Initiator 10 parts

The overcoat varnish was prepared by heating and melting the raw materials of the following formulation at 50 to 80 ° C. Base clear varnish 10 parts Pentaerythritol tetraacrylate 80 parts Initiator 10 parts

The initiators used are shown below. Examples 1-
9 shows an example, and Examples 10-14 show comparative examples. Initiator m: ZLI3331 (trade name, manufactured by Merck) Initiator n: Irgacure 369 (trade name, manufactured by Ciba-Gaigy) Initiator o: Lucillin TPO (trade name, manufactured by BASF) Initiator p: EAB (trade name, Hodogaya Chemical Co., Ltd.) Name) Initiator q: Initiator of Production Example 1 Initiator r: Initiator of Production Example 2

Table 1 ────────────────────────────────── Example 1 2 3 4 5 6 7 8 9 Base Ink 90 90 90 90 90 90 90 90 Base clear 95 Initiator q 10 3 5 2.8 5 Initiator r 10 10 3 3.4 Initiator n 7 5 6.2 1.5 Initiator o 5 7 4.5 Initiator p 1.0 1.0 0.5 Odor 4.5 4.0 4.5 4.5 4.0 4.0 4.5 4.0 4.5 Hardenability (m / min) 10 10 60 25 50 30 70 70 40 Pencil hardness (H) 2H ⁺ 2H ⁺ 3H 2H ⁺ 3H 2H ⁺ 2H ⁺ 2H ⁺ 2H ⁺ ─────── ────────────────────────────

Table 2 ───────────────────────── Example 10 11 12 13 14 Base ink 90 90 90 90 Base clear 95 Initiator m 10 5 5 2.8 3.4 Initiator n 5 6.2 1.5 Initiator o 5 Initiator p 1.0 0.1 Odor 4.0 4.0 4.0 4.0 4.0 Curability 10 25 20 70 70 Pencil hardness (H) 2H ⁺ 3H 2H ⁺ 3H 3H ────── ────────────────────

The performance of the printing ink was evaluated as follows. (1) Curability: In the case of printing ink in each curable coating, the ink was 0.30 cc with RI tester (20 cm x 25 c with a simple printing machine commonly used in the printing ink industry)
m of paper is printed uniformly with 0.30 cc of ink), the overcoat varnish (Comparative Example E, Example P) is coated with a bar coater # 3, and UV irradiation (high pressure mercury lamp 1) is performed.
(20 W / cm1 light) After being dried by touch and cured, the larger the number at the conveyor speed (m / min) of the UV irradiation device, the better the curability. (2) Odor: Five printed panelists relatively judged the odor in a glass bottle in which a printed matter cured under the same conditions as the curability was finely cut, and the odor was set to (poor) 1 to 5 (good). . (3) Pencil hardness: The pencil hardness of the printed matter cured under the same conditions as the curability.

[0024]

EFFECT OF THE INVENTION The photocurable coating composition of the present invention is characterized in that it has better odor and coating hardness than conventional curable coating compositions.

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[Procedure amendment]

[Submission date] February 25, 1994

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[0005]

The present invention is based on the general formula (1)
And a compound represented by the formula: H (C ₂ H ₄ O) _n O-φ-CO-C (CH ₃ ) ₂ -OH (1) (wherein φ is a paraphenylene group, and n is an integer of 1 to 5). The poly (meth) acrylic acid represented by the general formula (2) or its acid halide derivative CH ₂ = CR ₁ COO- (CH ₂ CR ₂ HCOO) _m H (2) (in the formula, R ₁ and R ₂ Is an H or a methyl group, and m is an integer of 1 to 10), and a copolymerizable photoinitiator.

Claims (4)

[Claims] 1. A compound represented by the general formula (1) and H (C ₂ H ₄ O) _n O-φ-CO-C (CH ₃ ) ₂ -OH (1) (wherein φ is paraphenylene. Group, n represents an integer of 1 to 5.) Poly (meth) acrylic acid represented by the general formula (2) or an acid halogenide derivative thereof CH ₂ ═CR ₁ COO— (CH ₂ CR ₂ COO) _m H (2 (In the formula, R ₁ and R ₂ are H or a methyl group, and m is an integer of 1 to 10.) and a copolymerizable photoinitiator. 2. The copolymerizable photoinitiator 10 according to claim 1, which is (a).
-90% by weight and (b) 90% by weight of 2-benzyl-2-dimethylamino-1- (4morpholinophenyl) -butanone-1 or 2,4,6-trimethylbenzoyldiphenylphosphine oxide Composition. 3. The initiator composition according to claim 1, which further comprises (c) 4,4′-bis (dilower alkylamino) benzophenone in an amount of 1 to 10% by weight. 4. The photoinitiator composition according to any one of claims 1 to 3 is added to the radical-polymerizable double bond-containing compound in an amount of 0.1.
A coating composition containing about 20% by weight.