JP3468311B2 - Polymerizable resin compositions and articles having their cured films - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photopolymerizable resin composition. More specifically, it is cured by irradiation of ultraviolet rays or electron beams, and the cured resin film has excellent adhesion to a wide range of adherends, and has excellent hardness, weather resistance, and solvent resistance, and is thermoformed. The present invention relates to a photopolymerizable resin composition for a surface coating suitable for a composition and an article having a cured film thereof. 2. Description of the Related Art A molded product made of a synthetic resin such as a polycarbonate resin is provided with a coating film for surface protection. This coating film is conventionally formed after molding, but it is difficult to obtain a uniform coating film,
In recent years, attention has been paid to a method of forming a coating film on a plastic plate such as polycarbonate and then thermoforming to obtain a desired shape (post-processing method). As a coating agent for producing a plastic film or a plastic plate having a cured film capable of being subjected to such thermoforming, a two-pack type is often used. In particular, acrylic polyol / isocyanate-based coating agents are often used for the purpose of improving the weather resistance of plastics. However, this coating agent is of a two-pack type and has a disadvantage that it takes a long time to cure. As a method of eliminating these drawbacks, a so-called one-pack type, fast-curing type radiation-curable coating agent has been proposed, but UV-curable paints and coating agents are more weather-resistant than conventional ones. And its use was limited to a specific field indoors. For the purpose of improving such disadvantages, it has been proposed to use additives for improving weather resistance, such as light stabilizers and / or light absorbers (JP-A-56-12).
2840, JP-A-56-141309). [0003] However, the resin compositions of these inventions are poor in moldability when subjected to thermoforming after coating and curing on a substrate, and cracks are generated. However, there were problems such as poor weather resistance and poor weather resistance, and it was not practical as a surface coating resin composition for thermoforming. [0004] In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that storage stability is good and adhesion to various substrates, weather resistance, and chemical resistance. It succeeded in providing a polymerizable resin composition suitable for a post-processable coating agent having excellent properties, hardness and abrasion resistance. That is, the present invention provides (1) a compound obtained by reacting a compound having one or more isocyanate groups in one molecule with a hydroxyl group-containing compound having two or more ethylenically unsaturated double bonds in one molecule. Photopolymerization comprising (A), compound (B) having one or more unsaturated double bonds in one molecule other than compound (A), light stabilizer (C) and / or ultraviolet absorber (D) (2) a photopolymerizable resin composition in which a photopolymerization initiator (E) is further added to the composition (1); (3) a compound (A) comprising a polyvalent isocyanate compound; A compound obtained by reacting a hydroxyl-containing compound having five or more ethylenically unsaturated double bonds in one molecule, wherein the compound (B) has a vinyl ether group and a (meth) acryloyl group Is a mixture of (1) and the photopolymerizable resin composition (2), (4)
The present invention relates to an article having a cured film of the resin composition according to the above (1) to (3), and (5) an article according to (4), wherein the article is a plastic film or a plastic plate which can be thermoformed. The compound (A) used in the present invention comprises a compound (a) having one or more isocyanate groups in one molecule and a hydroxyl group-containing compound having two or more ethylenically unsaturated double bonds in one molecule ( b) is reacted with As the compound having one or more isocyanate groups in one molecule of (a), 2-isocyanate ethyl methacrylate, 2,6-tolylene diisocyanate, 2,4-tolylene diisocyanate, diphenylmethane-4,4 ' Diisocyanate, dicyclohexylmethane-4,4 ′ diisocyanate, hexamethylene diisocyanate, tetramethylene diisocyanate,
Trimethylene xylylene diisocyanate, tetramethyl xylylene diisocyanate, phenylene diisocyanate, lysine isocyanate, xylylene diisocyanate, naphthylene diisocyanate, trimer ring compounds such as isophorone diisocyanate, or water and alcohols such as trimethylolpropane And the like. Examples of the hydroxyl-containing compound (b) having two or more ethylenically unsaturated double bonds in one molecule of the raw material for obtaining the compound (A) include trimethylolpropanedi (meth) acrylate, glyceroldiacrylate. (Meth) acrylate, pentaerythritol tri (meth) acrylate, ditrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and the like. The compound (a) having one or more isocyanate groups in one molecule and the hydroxyl-containing compound (b) having two or more ethylenically unsaturated double bonds in one molecule
Is usually reacted in a solvent, for example, 50 to 500 ppm
The reaction may be carried out at 80 to 100 ° C. for about 10 hours in the presence of a polymerization inhibitor such as hydroquinone monomethyl ether at a moderate concentration. The use ratio of the compound (a) to the compound (b) is preferably such that the isocyanate group of (b) is about 0.5 to 1.1 times the total hydroxyl groups of (a). The solvent used is not particularly limited, but non-reactive solvents such as toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and ethyl acetate and tetrahydrofurfuryl acrylate, 1,6-hexanediol acrylate,
Reactive solvents such as trimethylolpropane triacrylate and dipentaerythritol hexaacrylate. A catalyst may not be used, but 50
0 ppm or less of dibutyltin dilaurate may be used. Compound (A) obtained by the above method
Can be used singly or as a mixture of two or more at an arbitrary ratio. The use ratio of the compound (A) in the photopolymerizable resin composition of the present invention is 10 to 90% by weight, preferably 20 to 85% by weight. The compound (B) having one or more ethylenically unsaturated double bonds in one molecule used in the present invention includes, for example, a monofunctional monomer, a polyfunctional (meth)
Acrylates, acrylate-based or vinyl ether-based oligomers are exemplified. Examples of the monofunctional monomer include 2-ethylhexyl (meth) acrylate, ethyl carbitol (meth) acrylate, lauryl (meth) acrylate, phenoxyethyl (meth) acrylate, nonylphenoxyethyl (meth) acrylate, -Hydroxy-3phenoxypropyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, Nn-butyl-O- (meth)
Acryloyloxyethyl carbamate, acryloyl morpholine, trifluoroethyl (meth) acrylate,
Examples include halogen-containing monofunctional (meth) acrylates such as tribromobenzyl (meth) acrylate and perfluorooctylethyl acrylate, and silicon-containing (meth) acrylates such as (meth) acryloxypropyltris (methoxy) silane. Examples of polyfunctional (meth) acrylates include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate,
Alkylene glycol di (meth) acrylates such as propylene glycol di (meth) acrylate and neopentyl glycol di (meth) diacrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, polyethylene glycol di ( Polyoxyalkylene glycol di (meth) acrylates such as meth) acrylate and polypropylene glycol di (meth) acrylate; diacrylates of alkylene oxide adducts of bisphenol A or hydrogenated bisphenol A; ethylene glycol diglycidyl ether di (meth) Acrylates, epoxy diacrylates such as propylene glycol diglycidyl ether di (meth) acrylate, and trimethylolpropane tri (meth) acryl Over DOO, dipentaerythritol pentaacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol hexaacrylate, and the like. Examples of the acrylate oligomer include polyurethane (meth) acrylate, epoxy acrylate, polyester (meth) acrylate, and polyether (meth) acrylate. Examples of the vinyl ether oligomer include N-vinyl pyrrolidone, N-vinyl caprolactam, triethylene glycol divinyl ether, 1,4-cyclohexane dimethanol divinyl ether, bisphenol A diethyl vinyl ether, hydroquinone diethyl vinyl ether, and trimethylolpropane trivinyl ether. And the like. The compound (B) having one or more unsaturated ethylenic double bonds in one molecule can be used singly or as a mixture of two or more kinds in an optional ratio, if necessary. The usage ratio of the compound (B) in the photopolymerizable resin composition of the present invention is 5 to 60% by weight, preferably 10 to 50% by weight.
It is. In the present invention, one or both of the light stabilizer (C) and the ultraviolet absorber (D) are used. The light stabilizer (C) used in the present invention includes dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of dimethyl succinate and poly [@ 6- (1 1,1,3,3-tetramethylbutyl) imino 1,3,5-triazine-2,4 diyl {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene} (2,2,6,6-tetramethyl) 4-piperidyl) imino}], 2- (3,5-di-tert-butyl-4-hydroxybenzyl)
Bis (1,2,2,6,6-
Pentamethyl-4-piperidyl), N, N'-bis (3
-Aminopropyl) ethylenediamine-2,4bis [N
-Butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino] -6-chloro-1,3,5-triazine condensate, bis (2,2,6,6-tetramethyl-4-piperidyl) cedate, bis (1 2,2,
6,6-pentamethyl-4-piperidyl) sedate,
4-benzoyloxy-2,2,6,6-tetramethylpiperidine, poly [(6-morpholino S-triazine-2,4 diyl) [(2,2,6,6-tetramethyl-4-piperidylimino] -hexamethylene-(( 2,
2,6,6-tetramethyl-4-piperidyl) imino)]], N-2,2,6,6-tetramethyl-4-piperidyl-2- (2,2,6,6-tetramethyl-4-piperidylamino) -2-methylpropioamide, 2 -(3,5-di-tert-butyl-4-hydroxybenzyl)
Bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-n-butylmalonate and the like. From the viewpoint of preventing whitening and cracking of the coating film,
0.1 parts by weight based on 100 parts by weight of the photopolymerizable resin composition of the present invention.
It is about 01 to 8 parts by weight, preferably about 1 to 5 parts by weight. The ultraviolet absorber (D) used in the present invention
Are 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- [2-hydroxy-3,
5-bis (α, α-dimethylbenzyl) phenyl] -2
H-benzotriazole, 2- (3,5-di-tert-butyl-2-hydroxyphenyl) benzotriazole,
-(3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybendiphenone, 2-hydroxy-4-dodecyloxy Benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2 dihydroxy-4,4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzophenoneethyl-2-cyano 3,
3-diphenyl acrylate and the like. From the viewpoint of curability and abrasion resistance of the coating film, the amount used is 0.05 to 20 parts by weight based on 100 parts by weight of the photopolymerizable resin composition of the present invention.
Parts by weight, preferably about 1 to 10 parts by weight. Specific examples of the optional photopolymerization initiator (E) used in the present invention include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, acetophenone, 2,2 dimethoxy-2-phenyl. Acetophenones such as acetophenone, 2,2 diethoxy-2-phenylacetophenone, 2-methylanthraquinone,
-Ethyl anthraquinone, anthraquinones such as 1-chloroanthraquinone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone, ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenone, hydroxybenzophenone, etc. Benzophenones or xanthones, 1-hydroxycyclohexyl phenyl ketone (Irgacure 1 manufactured by Ciba-Geigy, Inc.)
84) 1- (4-isopropylphenyl) -2-hydroxy-2-methyl-propan-1-one (Darocur 1116, manufactured by Merck Ltd.), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Merck Ltd.) Radical polymerization initiator such as a reaction product of a photopolymerization initiator having a hydroxyl group such as Darocur 1173) and an isocyanate compound having a (meth) acryloyl group or a reaction product of a halide having a (meth) acryloyl group. Is mentioned. Suitable radical photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone (Irgacure 184, manufactured by Ciba-Geigy), 2
-Hydroxy-2-methyl-1-phenylpropane-1
-On (Darocure 1173, manufactured by Merck), 2,
4,6-trimethylbenzoyldiphenylphosphine oxide (Lucillin TPO, manufactured by BASF) and the like. Further, a complex of a metal fluoroborate and boron trifluoride, a metal salt of bis (perfluoroalkylsulfonyl) methane, an aryldiazonium compound, an aromatic onium salt of a group VIa element, and an aromatic onium salt of a group Va element salts, dicarbonyl chelate of the IIIa over Va "group element, thiopyrylium salts, MF ₆ anion (M is, P, a _S and S
b) selected from the group consisting of Group VIa element, triarylsulfonium complex salt, aromatic iodonium complex salt and aromatic sulfonium complex salt, polyarylsulfonium hexafluorophosphate, polyarylsulfonium hexafluoroantimony salt and the like. No. Suitable cationic photopolymerization initiators include polyarylsulfonium hexafluorophosphate and polyarylsulfonium hexafluoroantimonate (SP-170, SP-150, manufactured by Asahi Denka Co., Ltd.). When a vinyl ether compound is used as the compound (A) and / or the compound (B), it is desirable to use a cationic photopolymerization initiator alone or in combination with a radical photopolymerization initiator. The photopolymerization initiator ( E ) is used in an amount of 0.1 to 100 parts by weight of the heavy synthetic resin composition of the present invention.
5 to 10 parts by weight, particularly preferably 1 to 5 parts by weight,
If the amount is less than 0.5 part by weight, the curing speed is slow, and if it is more than 10 parts by weight, the cured product becomes brittle. The photopolymerizable resin composition of the present invention comprises a compound (A), a compound (B), an ultraviolet stabilizer (C) and / or an ultraviolet absorber (D) and an optional photopolymerization initiator (E). Is mixed by a known mixing method such as stirring. The photopolymerizable resin composition of the present invention may further comprise a polymerization inhibitor, an antioxidant, if necessary, in addition to the composition of the present invention.
Thickeners, leveling agents, flow improvers, matting agents, plasticizers, solvents, fillers, coloring agents such as pigments or dyes, and auxiliaries such as slip agents can be used in combination. Further, the polymerizable resin composition of the present invention can be used after being emulsified. When coating and curing the polymerizable resin composition of the present invention on a plastic film or a plastic plate,
After diluting the composition of the present invention with a known solvent, coating with a spray coater or a gravure coater, removing the solvent with a far-infrared ray or a hot-air drying furnace, etc., the composition can be irradiated with ultraviolet rays or an electron beam and cured. As a method of coating and printing on the base material, a known coating and printing apparatus such as a dispenser, a deep coater, a roll coater, a knife coater, screen printing and offset printing can be used in addition to a spray coater and a gravure coater. The polymerizable resin composition of the present invention can be cured by electron beam irradiation, and a composition using a photopolymerization initiator can be cured by a conventional method by ultraviolet irradiation such as a high-pressure mercury lamp, a metal halide lamp, or a xenon lamp. it can. Also, a thermal polymerization initiator such as a peroxide is used in combination with a photopolymerization initiator, and after photocuring,
Further, it can be cured by heating. Examples of the material of the plastic film or plastic plate that can be thermoformed include polycarbonate resin, polymethyl methacrylate resin, ABS resin and the like. The following are synthesis examples, examples and comparative examples.
The present invention will be described more specifically, but the present invention is not limited to only these examples. The evaluation of various properties of the composition and the cured product thereof was performed by the following methods. Viscosity: The viscosity of the composition at 25 ° C. was measured using an E-type viscometer. Adhesion: Cross-cut cellophane tape peel test for crosslinked cured film. That is, 11 lines of the coating film reaching the substrate at 1 mm intervals are inserted into the coating film at 1 mm ²
Make 100 eyes, stick a cellophane tape on it,
It peeled off suddenly, and the peeling state was measured. ○ No peeling △ Partial peeling × Full peeling moldability: After heating a 2 mm thick polycarbonate plate coated to about 10 microns in a dryer at 190 ° C for 10 minutes,
It was taken out and immediately bent against a heated metal rod having a radius of 10 cm to observe the occurrence of cracks. ○ No crack △ Partial crack ×
Overall crack abrasion resistance: Using a taper abrasion tester (CS-10F), performing 500 rotations with a load of 500 g, and HA before and after the test.
The difference in ZE (ΔH,%) was measured. ○ Less than 10 △ 10-20 × 20
Weather resistance exceeding: using a sunshine weather meter
The weather resistance test was performed for 1,000 hours and 2,000 hours, and the appearance and adhesion were tested. Appearance: ○ No cracks and whitening △ Partial cracks × Adhesion to cracks on the entire surface: ○ No peeling △ Partial peeling
× Synthetic Example 1 Synthetic Example 1 A mixture of pentaacrylate and hexaacrylate of dipentaerythritol obtained by an esterification reaction of dipentaerythritol and acrylic acid in a 1-L reaction flask (penta-form / hexa-form = 45/55 wt. %) 14
0 parts, isophorone diisocyanate (IP manufactured by Hull, IP
DI) 9.0 parts and 0.08 g of hydroquinone monomethyl ether as a polymerization inhibitor were charged all at once, and the temperature was gradually raised to 90 ° C. with stirring, and the temperature was maintained at 90 ± 2 ° C. for about 1 hour.
The reaction was continued for 0 hour to obtain 149 g of urethane acrylate. Its viscosity was 12,000 CPS at 25 ° C., and the residual amount of isocyanate group was 0.01% or less. Synthesis Example 2 A mixture of pentaacrylate and hexaacrylate of dipentaerythritol obtained by the esterification reaction of dipentaerythritol and acrylic acid in a 1-L reaction flask (penta- / hexa-form = 35/65% by weight) 14
0 parts, isophorone diisocyanate (IP manufactured by Hull, IP
DI) 6.8 parts and 0.08 g of hydroquinone monomethyl ether as a polymerization inhibitor were added all at once, and the temperature was gradually raised to 90 ° C with stirring, and kept at 90 ± 2 ° C for about 1
The reaction was continued for 0 hour to obtain 146 g of urethane acrylate. Its viscosity was 8,690 CPS at 25 ° C., and the remaining amount of isocyanate group was 0.01% or less. Synthesis Example 3 A mixture of pentaacrylate and hexaacrylate of dipentaerythritol obtained by an esterification reaction of dipentaerythritol and acrylic acid in a 1 L reaction flask (penta- / hexa-form = 35/65% by weight) 14
0 parts, 7.2 parts of hexamethylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., HDI) and 0.08 g of hydroquinone monomethyl ether as a polymerization inhibitor are charged at a time, and gradually stirred to 90 ° C. while stirring. Temperature rise, 9
The reaction was continued for about 10 hours while maintaining the temperature at 0 ± 2 ° C. to obtain 147 g of urethane acrylate. Its viscosity is 23,24 at 25 ° C.
0CPS and the residual amount of isocyanate group were 0.01% or less. Synthesis Example 4 A mixture of pentaacrylate and hexaacrylate of dipentaerythritol (pentamer /
Hexa-form = 35/65% by weight) 100 parts, polyfunctional acrylate 40 parts (manufactured by Nippon Kayaku Co., Ltd., KAYARAD®
P-1040), 6.8 parts of isophorone diisocyanate (manufactured by Hull, IPDI) and 0.08 g of hydroquinone monomethyl ether as a polymerization inhibitor were charged at one time,
While stirring, gradually raise the temperature to 90 ° C, and
And the reaction was continued for about 10 hours.
49.5 g were obtained. Its viscosity is 1860CP at 25 ° C
The residual amount of S and isocyanate groups was 0.01% or less. Reference Examples 1-4, Example 1, Comparative Examples 1-2 After uniformly mixing according to the mixing ratios shown in Table 1, the mixture was applied to a 3 mm thick polycarbonate plate to a thickness of 10 μm.
Using a 2KW (80W / CM) high pressure mercury lamp, 900
It was cured by irradiating it with ultraviolet rays of mj / cm ² . When the physical properties of the cured coating film were evaluated, the results shown in Table 1 were obtained. Table 1 (Note) * 1 KAYARAD DPHA: Nippon Kayaku Co., Ltd. Dipentaerythritol Hexa (penta) acrylate * 2 FA-731A: Hitachi Chemical Co., Ltd. Tris (acryloyloxyethyl) isocyanurate * 3 KAYARAD HDDA: Nippon Kayaku Co., Ltd. 1,6-hexanediol diacrylate * 4 THF-A: Kyoeisha Oil & Fat Co., Ltd. Tetrahydrofurfuryl acrylate * 5 KAYARAD NPGDA: Nippon Kayaku Co., Ltd. neopentyl glycol diacrylate * 6 RP-1040: Nippon Kayaku Co., Ltd. polyfunctional acrylate * 7 DVE: ISP 1,6-hexanediol divinyl ether * 8 Tinuvin PS: Ciba-Geigy UV absorber 2- (hydroxy-5-tert-butyl) Phenyl) benzotriazole * 9 Tinuvin 144: UV stabilizer (Hindered amine type) manufactured by Ciba-Geigy * 10 Irg-184: 1-Hydroxycyclohexyl phenyl ketone * 11 SP-170: Adeka Optomer SP-170 Cationic photopolymerization initiator manufactured by Asahi Denka Kogyo Co., Ltd. [Polymerization effect of the present invention] The resin composition is cured by irradiation of ultraviolet rays or electron beams, and the cured resin film has excellent adhesion to a wide range of adherends, and also has excellent weather resistance, abrasion resistance, and hardness. ,ink,
Suitable for manufacturing adhesives. In particular, by using the polymerizable resin composition of the present invention, a plastic film and a plastic plate having a cured film capable of performing thermoforming processing having excellent adhesiveness, abrasion resistance, and flexibility are manufactured. be able to. As described above, the polymerizable resin composition of the present invention may be used in the field of general coating agents, pressure-sensitive adhesives, inks, and paints, in addition to its use as a post-processing coating agent.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-2-178359 (JP, A) JP-A-1-174515 (JP, A) JP-A-5-86152 (JP, A) JP-A-59-1984 51908 (JP, A) JP-A-4-168161 (JP, A) JP-A-4-173822 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 2/00-2 / 60,290 / 06 C09D 5/00

Claims (1)

(57) Claims 1. A compound (A) obtained by reacting a polyvalent isocyanate compound with a hydroxyl group-containing compound having five or more ethylenically unsaturated double bonds in one molecule. , A mixture of a compound having a vinyl ether group and a compound having a (meth) acryloyl group (B), a light stabilizer (C) and / or
UV absorber (D) and cationic photopolymerization initiator (E)
A photopolymerizable resin composition comprising: