JP2849153B2 - Resin composition and printing ink composition using urethane acrylate - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a resin composition using a hindered amine compound, urethane methacrylate, which has excellent light resistance and weather resistance of a cured product, and is particularly suitable for a printing ink. Things.

(Prior art) In recent years, ultraviolet curable printing inks have been actively developed with the aim of preventing pollution by eliminating the solvent of printing inks, improving productivity by rapid curing, or improving physical properties of cured films. . Various ultraviolet curable printing inks have been proposed so far. For example, it is described in JP-A-56-93776, JP-A-56-11664, and the like. Industrially, ultraviolet curable printing inks have been used as various inks, for example, lithographic printing inks, letterpress printing inks, concave printing inks, and screen printing inks.

(Problems to be Solved by the Invention) Ultraviolet-curable printing inks are used in various fields, and are recently used for outdoor applications. When used for outdoor applications, the cured product must have excellent light resistance and weather resistance.However, conventional UV-curable printing inks require a cured product with excellent light resistance and weather resistance. At present, there are few things.

(Means for Solving the Problems) As a result of intensive studies to improve the above problems, the present inventors have found that the following characteristic printing ink resin composition can improve the above problems. The present invention has been completed. That is, the present invention provides: (1) A hindered amine compound (a) having the formula A urethane methacrylate (A) obtained by reacting the compound (b) represented by the formula (I), an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C) as an optional component. Characteristic resin composition.

(2) A printing ink resin composition comprising the resin composition according to (1).

The urethane methacrylate (A) used in the present invention is:
In the molecule, A pindamine compound (a) having the formula: Can be obtained by reacting the compound (b) represented by In the molecule, Specific examples of the hindered amine compound having And the like.

formula, The compound (b) represented by is easily obtainable from the market. For example, Showa Rhodia Co., Ltd., product name
MOI etc. The ratio of the hindered amine compound (a) and the compound (b) used in the reaction of the compound (b) is 0.5 to 1.1 with respect to one chemical equivalent of the NH group or the OH group of the hindered amine compound (a). It is preferable to use so as to have a chemical equivalent. Particularly preferably 0.95-1.
It is the amount which becomes 05 compound equivalent. This reaction can be performed by a method known to those skilled in the art. Reaction temperature is from room temperature to 100
° C, preferably 50-80 ° C. The reaction time is preferably from 3 to 50 hours, particularly preferably from 5 to 15 hours. In the present invention, an ethylenically unsaturated group-containing compound (B) other than the component (A) is used. Representative examples of the component (B) include, for example, tetrahydrofurfury (meth) acrylate, 2-hydroxytyl (meth) acrylate, carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, isobornyl (meth) acrylate, N-vinylpyrrolidone, N-vinylpyridine, acryloylmorpholine, hydrogenated dicyclopentadiene (meth) acrylate (manufactured by Hitachi Chemical Co., Ltd., FA-513A, FA-
513M), 1.6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate hydroxypivalate, tricyclodecane dimethylol di (meth) acrylate, polyethoxydi (meth) acrylate of bisphenol A, polypropoxy of bisphenol A Di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of ε-caprolactone adduct of neopentyl glycol hydroxypivalate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropanetetra (meth) Acrylate, dipentaerythritol penta and hexa (meth) acrylate, polypentaerythritol poly (meth) acrylate, epoxy (meth)
Acrylate (for example, a reaction product of epoxy resin such as bisphenol A type, bisphenol F type and phenol novolak type, or epoxy resin such as epoxidized soybean oil, epoxidized rosin, epoxidized polybutadiene and (meth) acrylic acid), polyester ( Meth) acrylates (e.g., diol components such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,5-pentanediol, 1,6-hexanediol, and succinic acid, adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydro (Meth) acrylate of polyester diol comprising dibasic acid such as phthalic acid, (meth) acrylate of lactone-modified polyester diol comprising diol component and dibasic acid and ε-caprolact or valerolactone, etc. , Polycarbonate (meth)
Acrylates (e.g., (meth) acrylates of polycarbonate diols containing 1,6-hexanediol as a diol component), polyurethane (meth) acrylates (e.g., polyol compounds, organic diisocyanates, and (meth) acrylates having hydroxyl groups Is reacted to a point substantially free of NCO groups. Typical examples of polyol compounds include ethylene glycol, propylene glycol, 1,3-butylene glycol, neopentyl glycol, and cyclohexane. Polyols such as dimethanol, tricyclodecane dimethylol, 1,4-butanediol, 1,6-hexanediol, and trimethylolpropane, polypropylene glycol, polyethylene glycol, polytetramethylene glycol, Polyether polyols such as pyrene modified polytetramethylene glycol, said polyol or polyether polyol, or a compound such as the polyol is ε- caprolactone or valerolactone was added and an alcohol component, whereas adipic acid,
Sebasic acid, azelaic acid, dodecane dicarboxylic acid, phthalic acid, tetrahydrophthalic acid, polyester polyols containing dibasic acids such as hexahydrophthalic acid or anhydride thereof as an acid component, and the polyol / polyether polyol and polyester polyol as an alcohol component And the like.

Representative organic diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, 2,2 ', 4-trimethyl Hexamethylene diisocyanate and the like can be mentioned. These preferred use ratios in the urethanization reaction between the polyol compound and the organic diisocyanate are determined based on the amount of the polyol compound.
NCO of organic diisocyanate per 1 equivalent of OH group
The ratio is such that the group has 1.1 to 2.0 chemical equivalents, particularly preferably 1.5 to 2.0 compound equivalents.
This urethanation reaction can be performed by a procedure known to those skilled in the art. The reaction temperature of this urethanization reaction is preferably from room temperature to 100 ° C, particularly preferably from 50 to 80 ° C. The reaction time is preferably from 3 to 50 hours, particularly preferably from 5 to 15 hours. Then, in the (meth) acrylated reaction, the (meth) alkyl acid ester having a hydroxyl group is added to one chemical equivalent of the NCO group of the compound having a terminal isocyanate group obtained in the urethane reaction. OH groups are 0.9 to 15 chemical equivalents, preferably
It is preferably used so as to have a chemical equivalent of 1.0 to 1.1. Representative examples of the (meth) acrylic acid ester having a hydroxyl group include β-hydroxyethyl (meth) acrylate, β-hydroxypropyl (meth) acrylate,
ε-caprolactone-β-hydroxyethyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, and the like. ) And the like.

As the above-mentioned compound (B) containing an ethylenically unsaturated group, one or two or more compounds can be mixed and used at an arbitrary ratio, if necessary. These ethylenically unsaturated group-containing compounds (B) can be easily obtained from the market.

Next, the photopolymerization initiator (C) used as an optional component in the present invention includes, for example, benzoin, benzyl, benzoin methyl ether, benzoin isopropyl ether, acetophenone, 2,2-dimethoxy-2
-Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxycyclohexylphenylketone, 2
-Methyl-1- [4- (methylthio) phenyl] -2-
Morpholino-propan-1-one, N, N-dimethylaminoacetophenone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, 2-amylanthraquinone, 2-aminoanthraquinone, 2, 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, acetophenone dimethyl ketanol, benzophenone, methylbenzophenone, 4,
4'-dichlorobenzophenone, 4,4'-bisdiethylaminobenzophenone, Michler's ketone and the like can be mentioned. These can be used alone or in combination of two or more. Further, such a photopolymerization initiator (C)
Is N, N-dimethylaminobenzoic acid ethyl ester, N, N
-Known photosensitizers such as isoamyl dimethylaminobenzoate, triethanolamine and triethylamine can be used alone or in combination with two or more.

Use of urethane methacrylate (A) in the resin composition of the present invention and the printing ink resin composition (hereinafter, both are referred to as a composition) when the ethylenically unsaturated-containing compound (B) is 100 parts by weight. The amount is preferably
It is preferably 0.01 to 20 parts by weight, particularly preferably 0.5 to 5 parts by weight. The amount of the photopolymerization initiator (C) used is (A) component +
When the total amount of the component (B) is 100 parts by weight, it is preferably 0 to 25 parts by weight, particularly preferably 2 to 20 parts by weight.

In the composition of the present invention, if necessary, a non-reactive resin (for example, diallyl phthalate resin (manufactured by Osaka Soda Co., Ltd., Daisodap)) cyclic ketone resin (manufactured by Hitachi Chemical Co., Ltd., Hilac 80, 110H), Rosin resin, rosin-modified phenol resin, acrylic resin, etc.], thereby improving the performance of the cured film.
Also, antioxidants, ultraviolet absorbers, polymerization inhibitors, plasticizers,
Coloring components such as fillers, solvents, pigments or dyes, and other auxiliaries can be used in combination.

Examples of the above plasticizer include dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, dioctyl sebacate, butyl phthalyl butyl cricolate, tricresyl phosphate, and paraffin chloride. Examples of the filler include glass fiber, powdered silica, barite, calcium carbonate, and the like. As the polymerization inhibitor, those which prevent a dark reaction and do not hinder photopolymerization are desirable. Examples of such compounds include quinones, nitroso compounds, sulfur compounds and the like. Specifically, P-benzoquinone , 2,5-di-tert-butyl-P-benzoquinone, nitrosobenzene, phenothiazine, tert-butylhydroquinone, hydroquinone monomethyl ether, hydroquinone and the like. Further, as the pigments, for example, extender pigments such as alumina white, clay, talc, barium carbonate, precipitated barium sulfate, zinc white, lead white, graphite, ultramarine, navy blue, titanium oxide, red iron oxide, carbon black And inorganic pigments such as brilliant carmine 6B, permanent red R, benzidine yellow, lake red C, and organic pigments such as phthalocyanine blue. Other auxiliaries include antifoaming agents such as silicones, leveling agents, surfactants such as polyoxyethylene glycol alkyl ether, sodium laurate, and alkylbenzylammonium chloride; anti-skinning agents such as eugenol and methyl ethyl ketoxime; UV absorbers such as 2,2'-dihydroxy-4-methoxybenzophenone, 6-methyl-2,4-di-tert
-Antioxidants such as butylphenol, organic bentonite, aluminum octoate, thickeners such as zirica gel, flame retardants such as paramfin chloride, diphenyl chloride, dodecyl mercaptan, ethyl mercapto acetate, pentarisritol tetrakis (β-methylcaptopropion) And storage stabilizers such as triphenyl phosphide and diethylhydroxylamine. The composition of the present invention can be obtained by mixing each component. The composition of the present invention thus obtained is applied or printed on a metal plate, glass, plastic plate and film, paper, stone board, wood board, or other substrate by a conventional method, and then irradiated with ultraviolet rays or electron beams by a conventional method. By doing so, a cured product can be obtained. In some cases, the composition of the present invention can be dispersed in water and cured with peroxides to obtain a fine powder cured product. When a photopolymerization initiator is used, it can be cured by irradiating ultraviolet rays. Examples of the light source that generates such ultraviolet rays include a carbon arc lamp, a mercury vapor lamp, an ultraviolet fluorescent lamp, a tungsten lamp, an incandescent lamp, a xenon lamp, and an argon glow lamp. The resin composition of the present invention has a high curing rate, and the cured product is excellent in weather resistance, light resistance, adhesion, etc., and is useful as a printing ink resin composition, but is also used as a paint or coating agent. it can.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples. Parts in Examples are parts by weight.

[Synthesis Examples 1 to 4 of Urethane Methacrylate] Example 1. Formula 157 parts of a hindered amine compound having the following formula (ARKLS DN-10, manufactured by Adeka Argus Co., Ltd.): 155 parts, methquinone 0.1 part and methyl ethyl ketone 200
The reaction was carried out at 80 ° C. for about 15 hours until the residual NCO in the reaction solution became 0.1% by weight or less, and then methyl ethyl ketone was distilled off to obtain urethane methacrylate. It was solid.

The results of measurement of nuclear magnetic resonance (NMR) of the obtained normal organism are shown below.

The above measurement was performed by a proton decoupling method using tetramethylsilane as a reference substance and deuterium chloroform as a solvent.

Example 2. Formula 481 parts of a hindered amine compound (manufactured by Sankyo Co., Ltd., Sanol LS-770), 310 parts, methquinone 0.4 part and methyl ethyl ketone 200
The reaction was carried out at 80 ° C. for about 15 hours until the residual NCO in the reaction solution became 0.1% by weight or less, and then methyl ethyl ketone was distilled off to obtain solid urethane methacrylate.

Example 3. Formula 225 parts of a hindered amine compound (MARK LA-87, manufactured by Adeka Argus Co., Ltd.) 155 parts, methoquinone 0.2 parts and methyl ethyl ketone 200
The reaction was carried out at 80 ° C. for about 15 hours until the residual NCO in the reaction solution became 0.1% by weight or less, and then methyl ethyl ketone was distilled off to obtain solid urethane methacrylate.

Example 4. Formula 790 parts of a hindered amine compound having a MARK LA-57 (manufactured by Adeka Argus Co., Ltd.) 620 parts, methoquinone 0.7 parts and methyl ethyl ketone 300
The reaction was carried out at 80 ° C. for about 15 hours until the residual NCO in the reaction solution became 0.1% by weight or less, and then methyl ethyl ketone was distilled off to obtain solid urethane methacrylate.

[Synthesis Example of Ethylenic Inactive Group-Containing Compound (B)] Synthesis Example 1.
In the reactor, a poly-ε-caprolactone-based polyol (Placcel 205, manufactured by Daicel Chemical Co., Ltd., OH value 213.7 mg KO)
H / g, number average molecular weight 525.1) 262.6 parts, also polymer-ε
-Cabrolactone, polyol (Daicel Chemical Co., Ltd.)
Manufactured by Plaxel 208, OH value 137.8 mgKOH / g, number average molecular weight 814.4) 407.2 parts, isophorone dicyanate 227.9 parts, and after raising and lowering the temperature, reacting at 80 ° C for 13 hours, then cooling the reaction solution to 60 ° C, 55.3 parts of β-hydroxy acrylate,
Methoquinone 0.50 parts, di-n-butyltin dilaurate 0.20
After heating, the mixture was reacted at 80 ° C. for about 15 hours to obtain a polyurethane acrylate.

Synthesis Example 2. Epoxidized soybean oil (made by Adeka Argus Chemical Co., Ltd.
ADK CIZER 0-130P, oxirane oxygen content (6.9%) 24
6.7 parts, 53.3 parts of acrylic acid, 1.1 parts of benzyltrimethylammonium chloride as an esterification catalyst, and 0.15 parts of methoxyphenol as a polymerization inhibitor were charged, and the reaction was continued at a reaction temperature of 90 ° C. for about 24 hours until the oxidation became 3.0 or less. . The acid value of the reaction product is 2.1 (mgKOH / g), and the viscosity is
At 16800 CPS (30 ° C.), the appearance was a brown transparent liquid resin.
Next, 300 parts of the epoxidized soybean oil acrylate and 14 parts of isophorone diisocyanate were charged to 70 parts.
The reaction was carried out at 8080 ° C. for about 15 hours to obtain a modified epoxidized soybean oil acrylate urethane.

Examples 5 to 9 and Comparative Examples 1 and 2 After blending each component according to the composition shown in Table 1, the printing ink resin composition of the present invention was prepared by kneading with three rolls. Example 5 Each ink was printed on a polycarbonate plate with a screen so that the ink film thickness became 15 μm.
For ~ 8, use a metal halide lamp (output 2K)
The photocuring was carried out by passing a 10 cm place under W 80 W / cm on a conveyor having a line speed of 10 m. or,
In Example 9, curing was performed by electron beam irradiation. The initial adhesion immediately after curing of the cured film was evaluated according to the method described below. Accelerated exposure tester (Sunshine Carbon Weatherometer: Suga Tester WE-SU)
(N-DC type), after 12 minutes of rainfall / 60 minutes per cycle, at a black panel temperature of 63 ± 3 ° C for 1000 hours, the adhesion and appearance were examined, and the evaluation of weather resistance was performed according to the method described below. Was. Table 1 shows these results.

(Adhesion)

Cross cut to cured film-Cellophane tape peel test, film cut line reaching the substrate at 1mm interval to the film,
Vertically, make 100 pieces of 1mm stitches each with 11 pieces in each side, stick cellophane tape on it, and then peel off sharply. Cellophane tape peel test was performed for
Perform three times.

◎: No peeling after 3 tests ○: No peel after 1 test, but peel from 2nd △: 1 to 50 peels after 1st test × ... Number of peels 51 to 100 after the first test [Appearance] (A) Discoloration or fogging ◎ ... No discoloration (yellowing, whitening) or fogging ○: Some discoloration or fogging △: Discoloration or fogging is considerable ×: Discoloration or fogging is conspicuous (B) Cracks and film baldness ◎ …… None ○ ……… Somewhat unknown, but a little △ ……… × …… stand out (Effect of the Invention) By using a novel urethane methacrylate, the resin composition of the present invention becomes excellent in weather resistance and light resistance of a cured film thereof, and is suitable for printing ink for outdoor use and other purposes.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ identification symbol FI C09D 175/16 C09D 175/16 // C08G 18/81 C08G 18/81 (58) Fields surveyed (Int.Cl. ⁶ , DB Name) C08G 18/00-18/87 C08F 290/06 C08F 299/06 C09D 175/00-175/16 C09D 4/00-4/06 C08F 220/00-220/70 C08F 2/46-2/50 CA (STN)

Claims (2)

(57) [Claims] (1) In the molecule: A hindered amine compound (a) having the formula: A urethane methacrylate (A) obtained by reacting the compound (b) represented by the formula (I), an ethylenically unsaturated group-containing compound (B) other than the component (A), and a photopolymerization initiator (C) as an optional component. Characteristic resin composition. 2. A printing ink composition comprising the resin composition according to claim 1.