JP2003026715A - Ultraviolet-curing molding material, weatherproof ultraviolet-curing molding material, methods for curing them and articles produced from them - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ultraviolet-curing molding material and a weatherproof ultraviolet-curing molding material which can give moldings excellent in yellowing resistance, water resistance, heat resistance, mechanical properties, etc. SOLUTION: The molding material comprises (A) a photopolymerizable oligomer, (B) a photopolymerizable monomer, (Ca) a first component photopolymerization initiator having an absorption wavelength of 220-360 nm and a molar absorptivity of at least 50, and (Cb) a second photopolymerization initiator having an absorption wavelength of 340-500 nm and a molar absorptivity of at least 100 in such amounts that 0.1-900 pts.wt monomer (B), 0.01-30 pts.wt. photoinitiator (Ca), and 0.001-10 pts.wt. photoinitiator (Cb) are present per 100 pts.wt. oligomer (A). The weatherproof molding material comprises the above components and 0.05-30 pts.wt. (in total) additives including (D) a light stabilizer, (E) an ultraviolet absorber, (F) an antioxidant, and (G) an antistatic agent.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a push button switch used in a mobile communication device such as a mobile phone, a home telephone, an electronic notebook, a switch mounted on a car, a remote controller, a calculator, or a data input device of a personal computer. The present invention relates to a resin composition used for a member, an article used as a figurine, etc., a method for curing the resin composition, and a molded product made from the resin composition.

[0002]

2. Description of the Related Art In a data input device (push button switch member) for a mobile communication device such as a mobile phone, a base body on which a plurality of movable parts are displaceable in a conventional bearing part is made of a rubber composition such as silicone rubber. It is known that a resin key top member is fixed on the movable part of the base body, and a movable contact or the like is provided on the back surface of the movable part that can contact the fixed contact of the circuit board. Generally, the key top member is formed by injection molding or the like using a thermoplastic resin such as ABS, polyester, polycarbonate, or acrylic. And
Before the key top member is fixed to the base body, a display portion of characters, symbols or figures is formed by printing or the like on the top surface or the like, and surface treatment such as painting is performed if necessary.

[0003]

However, a molded article obtained by using the above-mentioned conventional injection molding has a heat resistance,
Although it is very excellent in electrical insulation and the like, there are problems in water resistance, yellowing resistance, ultraviolet resistance, electrification, adhesion to a thermoplastic resin sheet and the like. In addition, although injection molding is suitable for low-volume, high-volume production, the dimensional stability and thickness accuracy are poor, the cost of molds and equipment is high, and it is not suitable for high-mix low-volume production. Combined with the need to respond quickly to changes in the design of buttons used in mobile phones, etc., UV curable molding material was used to cast into a mold made of a thermoplastic resin sheet Attempts have also been made to solve the above-mentioned problems by irradiating and curing the composition to obtain a molded product.

However, conventional UV-curable molding materials still have problems in yellowing resistance, UV resistance, water resistance, heat resistance, mechanical properties, adhesion, miniaturization, etc. Depending on the use of, it was not always satisfactory. INDUSTRIAL APPLICABILITY The present invention is based on the manufacturing method by the ultraviolet irradiation resin curing method, and is equal to or more than the molded product obtained by using the conventional injection molding and the conventional ultraviolet curable molding material. Molded products with excellent productivity, dimensional accuracy, yellowing resistance, water resistance, heat resistance, mechanical properties, etc., as well as UV resistance, water resistance, heat resistance, mechanical properties, adhesion, It is an object of the present invention to provide a molded product excellent in miniaturization and precision. In particular, in the case where the molded product is a push button switch member as shown in FIG. 1, an ultraviolet curable molding material or a weather resistance imparting ultraviolet curable molding material, which is the filler 1 in the key top, and a push button switch member This is to realize firm fixation with the thermoplastic resin sheet forming the outer shell 2.

[0005]

Means for Solving the Problems The present inventors have found that the above-mentioned problems based on the injection molding method are caused by using a newly developed UV-curable molding material or weathering-imparting UV-curable molding material. It is found that this can be improved by casting it in a molding die made of a thermoplastic resin sheet and irradiating it with ultraviolet rays to cure it, and at the same time solve the problems of conventional ultraviolet curable molding materials. The present invention has been completed by finding out a compounding composition, a curing method and the like. The ultraviolet-curable molding material of the present invention comprises a photopolymerizable oligomer (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C) as a first component.
a) and a second component photopolymerization initiator (Cb), and the first component photopolymerization initiator (Ca) has an absorption wavelength of 22.
0 to 360 nm, the molar absorption coefficient is 50 or more, and the photopolymerization initiator (Cb) as the second component has an absorption wavelength of 340.
To 500 nm, a molar absorption coefficient of 100 or more, 0.1 to 900 parts by weight of the photopolymerizable monomer (B) per 100 parts by weight of the photopolymerizable oligomer (A), and photopolymerization of the first component. 0.01 to 30 parts by weight of the initiator (Ca),
The photopolymerization initiator (Cb) of the second component is 0.001-1.
0 parts by weight is blended and the viscosity of the liquid is 50 to 3000.
The thixotropy (TI) value is 0.5 to 2 at 0 mPa · S (23 ° C.). Further, the weather resistance imparted ultraviolet-curable molding material of the present invention comprises a photopolymerizable oligomer (A), a photopolymerizable monomer (B), and a photopolymerization initiator (C) as a first component.
a), a second component of a photopolymerization initiator (Cb), a light stabilizer (D), an ultraviolet absorber (E), an antioxidant (F) and an antistatic agent (G). The photopolymerization initiator (Ca) has an absorption wavelength of 220 to 360 nm and a molar absorption coefficient of 50 or more, and the second component photopolymerization initiator (Cb) has an absorption wavelength of 340 to 500 nm and a molar absorption coefficient of 100 or more and the maximum absorption wavelength of the ultraviolet absorber is 350 nm or less, and the photopolymerizable oligomer (A) 10
The amount of the photopolymerizable monomer (B) is 0.
1 to 900 parts by weight, the photopolymerization initiator (C
0.01 to 30 parts by weight of a) and 0.001 to 10 parts by weight of the second component photopolymerization initiator (Cb) are mixed, and the light stabilizer (D), the ultraviolet absorber (E), The total amount of the antioxidant (F) and the antistatic agent (G) is 0.1% by weight based on 100 parts by weight of the photopolymerizable oligomer (A).
05 to 30 parts by weight is mixed, and the viscosity of the liquid is 50 to
The thixotropy (TI) value is 0.5 to 3 at 100,000 mPa · S (23 ° C.).

In the ultraviolet curable molding material and the weather resistance imparting ultraviolet curable molding material, the photopolymerizable oligomer (A) is an epoxy (meth) acrylate (A1) having a molecular weight of 400 to 20,000, and a molecular weight. 400-20
000 urethane (meth) acrylate (A2), polyester (meth) acrylate (A3) having a molecular weight of 400 to 20000, and polybutadiene (meth) acrylate (A4) having a molecular weight of 400 to 20000, Polymerizable monomer (B)
Is a monofunctional monomer (B1), a bifunctional monomer (B
2), at least one selected from the polyfunctional monomer (B3) (however, the polyfunctional monomer indicates a trifunctional or higher functional monomer), and the photopolymerization initiator (Ca) as the first component is , Benzophenone-based photopolymerization initiator (Ca
1), at least one selected from acetophenone photopolymerization initiator (Ca2), thioxanthone photopolymerization initiator (Ca3), benzoin photopolymerization initiator (Ca4), and special group photopolymerization initiator (Ca5). That there is
Is preferred. Furthermore, in the weather resistance imparting ultraviolet-curable molding material, the light stabilizer (D) is at least one selected from hindered amine light stabilizers, and the ultraviolet absorber (E) is , Benzophenone type ultraviolet absorber (E1), salicylate type ultraviolet absorber (E2), cyanoacrylate type ultraviolet absorber (E
3), at least one selected from nickel complex salt type ultraviolet absorber (E4), benzotriazole type ultraviolet absorber (E5) and benzoate type ultraviolet absorber (E6), and the antioxidant (F) is At least one selected from a phenol-based antioxidant (F1), a phosphite-based antioxidant (F2), a thioether-based antioxidant (F3), and a phenol-phosphite-based antioxidant (F4); Antistatic agent (G) is cationic antistatic agent (G1), anionic antistatic agent (G2), nonionic antistatic agent (G3), alkylamine derivative antistatic agent (G4), fatty acid ester antistatic agent Agent (G
5), at least one selected from the terminal unsaturated antistatic agents (G6).

Further, the method for curing the ultraviolet-curable molding material and the weathering-imparting ultraviolet-curable molding material of the present invention is as follows: It is to cast an ultraviolet-curable molding material and irradiate it with ultraviolet rays to cure it. When curing by irradiating with ultraviolet rays, it is preferable to cut and cure the short wavelength of 300 nm or less, which is the absorption wavelength of the photopolymerization initiator (Ca) of the first component, by using an ultraviolet cut filter. Molded articles from the ultraviolet-curable molding material of the present invention have a glass transition temperature (Tg) of -20 after curing.
It has the characteristics of a bending strength of 10 to 300 N / mm ² , a bending elastic modulus of 90 to 7,000 N / mm ² , and a Shore D hardness of 50 to 95. Molded articles from the weathering-imparting UV-curable molding material of the present invention have a glass transition temperature (Tg) of −30 to 110 ° C. and a bending strength of 10 to 290.
N / mm ^2, flexural modulus 90~5000N / mm ^2, having a hardness of 40 to 80 Shore D characteristics. The molded article of the present invention is particularly effective when used as a push button switch member.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The constitution of the present invention will be described in detail below. [Photopolymerizable Oligomer (A)] The photopolymerizable oligomer (A) used in the present invention is an epoxy (meth) acrylate (A1) having a molecular weight of 400 to 20,000 and a molecular weight of 400.
~ 20,000 urethane (meth) acrylate (A
2), polyester (meth) acrylate (A3) having a molecular weight of 400 to 20,000, molecular weight of 400 to 20,000
At least one kind is selected from the polybutadiene (meth) acrylate (A4).

[Photopolymerizable oligomer (A): Epoxy (meth) acrylate (A1)] The molecular weight of the photopolymerizable oligomer (A) used in the present invention is 400 to 20,000.
The epoxy (meth) acrylate (A1) is an epoxy (meth) acrylate obtained by reacting a bisphenol type epoxy resin with (meth) acrylic acid or hydroxybis (meth) acrylate. Also, a bisphenol epoxy resin / polybutadiene-acrylic copolymerization type epoxy (meth) acrylate, which is obtained by previously reacting a bisphenol epoxy resin with a polybutadiene-acrylonitrile resin to form an oligomer, can be used. Furthermore, glycol epoxy (meth) acrylate obtained by modifying polyglycol diglycidyl ether can also be used.

Epoxy (meth) acrylates are further classified according to the type of bisphenol type epoxy resin involved in the reaction. Bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, bromine addition type flame retardant epoxy resin. , Bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, bromine obtained by the reaction of dimer acid modified epoxy resin, hydrogenated bisphenol A type epoxy resin, etc. The addition-type flame-retardant epoxy (meth) acrylate, dimer acid-modified epoxy (meth) acrylate, hydrogenated bisphenol A type epoxy (meth) acrylate, and the like.

Examples of the bisphenol A type epoxy resin as a resin which reacts with each other to form an epoxy (meth) acrylate include, for example, Epicoat 828 (Epicote is a trade name of Yuka Shell Epoxy Co., Ltd .; hereinafter the same) and Epicoat. Examples of the bisphenol F type epoxy resin 1001, Epicoat 1004, Epicoat 1010, etc. are, for example, Epicoat 807, Epicoat 4004P, Epicoat 4007P, and Epicoat 40.
Examples of the phenol novolac type epoxy resin such as 10P include, for example, Epicoat 152 and Epicoat 15
4, the Epicoat 630 and the Epicoat 604 and the like are the same bromine addition type flame-retardant epoxy resin, for example, the Epicoat 5046B80, the Epicoat 5048B70 and the Epicoat 5203, and the dimer acid-modified epoxy resin is, for example, Epotote YD-171. (Epototo is a trade name manufactured by Tohto Kasei Co., Ltd., the same applies below),
Examples of the hydrogenated bisphenol A type epoxy resin such as Epotote YD-721 include Epotote ST.
-3000, Epotote ST-5080, Epotote S
Examples include T-5100 and Epotote ST-4000.

By reacting these, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) acrylate, phenol novolac type epoxy (meth) acrylate, brominated flame retardant epoxy (meth) acrylate and dimer, respectively. It becomes an acid-modified epoxy (meth) acrylate and hydrogenated bisphenol A type epoxy (meth) acrylate. Examples of the bisphenol A type epoxy (meth) acrylate obtained by the reaction include, for example, Lipoxy SP-1507 (lipoxy is a trade name manufactured by Showa Highpolymer Co., Ltd .; the same applies hereinafter),
Lipoxy SP-1509, Lipoxy SP-1519-
1, lipoxy SP-1563, lipoxy VR-77, lipoxy VR-60, lipoxy VR-90, epoxy ester 3002M (epoxy ester is a trade name of Kyoeisha Chemical Co., Ltd .; the same applies hereinafter), epoxy ester 30
0M, epoxy ester 3000A and the like.

Examples of the bisphenol F type epoxy (meth) acrylate include lipoxy SP-1506. Examples of the phenol novolac type epoxy (meth) acrylate include Dicklight U.
E-5210 (Dick Light is a trade name of Dainippon Ink and Chemicals, Inc .; the same applies hereinafter), Dick Light UE-
8710, Lipoxy SP-4010, Lipoxy SP-4
060 etc. are mentioned. Examples of the bromine-added flame-retardant epoxy (meth) acrylate include Dicklight U.
E-7016 and Dick Light UE-7051-80
BH etc. are mentioned.

Examples of the dimer acid-modified epoxy (meth) acrylate include Denacol DA-172 (Denacol is a trade name of Nagase Chemitex Co., Ltd .; the same applies hereinafter) and the like. Examples of the hydrogenated bisphenol A type epoxy (meth) acrylate include lipoxy SP-9000. Examples of the bisphenol type epoxy resin for obtaining the bisphenol type epoxy resin / polybutadiene-acrylic copolymerization type epoxy (meth) acrylate include EPON Resin.
58006 (trade name of Shell Petrochemical Co., Ltd.), Epicron TSR-960 (Epiclon is a trade name of Dainippon Ink and Chemicals, Inc., the same applies hereinafter), Epicron TSR
-601 etc. are mentioned.

Examples of the bisphenol type epoxy resin / polybutadiene-acrylic copolymerization type epoxy (meth) acrylate obtained by the reaction include Dicklight UE-2083 and the like. Examples of the polyglycol diglycidyl ether include epotote PG
-202, Epotote PG-207 and the like. Examples of the glycol epoxy (meth) acrylate obtained by modifying polyglycol diglycidyl ether include epoxy ester 40ME and epoxy ester 70.
PA, epoxy ester 200PA, epoxy ester 80MF, epoxy ester 1600A, epoxy ester 200EA, epoxy ester 400EA, Denacol DM-851, Denacol DA-811, Denacol DA-721, Denacol DA-911 and the like.

[Photopolymerizable oligomer (A): urethane (meth) acrylate (A2)] The molecular weight of the photopolymerizable oligomer (A) used in the present invention is 400 to 20,000.
The urethane (meth) acrylate (A2) is a reaction between an organic polyisocyanate and a hydroxy (meth) acrylate compound, a reaction between an organic polyisocyanate and an acrylate compound, or a polyol, an organic polyisocyanate and a hydroxy (meth) acrylate. Obtained by reaction with a compound. Further, polyester-based urethane (meth) acrylate, polyether-based urethane (meth) acrylate, polycarbonate-based urethane (meth) acrylate, aliphatic urethane (meth) acrylate, and alicyclic urethane (meth) acrylate may also be used. Examples of the polyol include polyether polyols such as polypropylene glycol and polytetramethylene glycol, polyester polyols obtained by reacting polyhydric alcohol (described later) with polybasic acid (described later), polyhydric alcohol (described below) and polybasic Acid (described later)
And a caprolactone polyol obtained by the reaction of ε-caprolactone or a polyhydric alcohol (described later) and ε-caprolactone, and a polycarbonate polyol (for example, a reaction of 1,6-hexanediol with diphenyl carbonate). The polycarbonate polyol etc. which are mentioned are mentioned.

The polyols may be used alone or in admixture of two or more. When each is used alone, it is a urethane (meth) acrylate having a polyester structure, a polyether structure, a polycarbonate structure, an aliphatic structure or an alicyclic structure based on the structure contained in each. Examples of the polyhydric alcohol include neopentyl glycol, ethylene glycol, diethylene glycol, propylene glycol, 1,6-hexanediol, trimethylolpropane, pentaerythritol, tricyclodecane dimethylol, bis (hydroxymethyl) cyclohexane and the like. . Examples of the polybasic acid include succinic acid, phthalic acid, hexahydrophthalic anhydride, terephthalic acid, adipic acid, azelaic acid, tetrahydrophthalic anhydride and the like.

Examples of the organic polyisocyanate include isophorone diisocyanate, hexamethylene diisocyanate, tolylene diisocyanate, xylene isocyanate, diphenylmethane-4,4'-diisocyanate and dicyclopentanyl diisocyanate. Examples of urethane (meth) acrylates obtained by the reaction of organic polyisocyanate and hydroxy (meth) acrylate include ART RESIN UN-3300HA (ART RESIN is manufactured by Negami Kogyo Co., Ltd.).
The product name of the product. The same shall apply hereinafter), ART RESIN UN-3320
HB, Art Resin-3320HB, Art Resin UN
-3320HC, ART RESIN UN-3320HS, SHIKO UV-7550 (SHIKOH is a trade name of Nippon Synthetic Chemical Industry Co., Ltd., the same applies hereinafter) and the like.

Urethane (meth) obtained by reacting an organic polyisocyanate with an acrylic ester compound
As the acrylate, for example, Kyoeisha Chemical Co., Ltd. product name: AH-600, AT-600, UA-306H,
AI-600, UA-101T, UA-101I, UA
Examples include -306T and UA-306I. Examples of hydroxy-based urethane (meth) acrylates obtained from a polyol, an organic polyisocyanate, and a hydroxy (meth) acrylate compound include Artresin UN-5200, Artresin UN-2111A, and Artresin UN330. Examples of the polyester-based urethane (meth) acrylate include Art Resin UN-1225 and Art Resin UN-250.
0, Art Resin UN-1200TP, Art Resin U
N-1200TPK, Art Resin UN-6060P,
Art Resin UN-6060PTM, Aronix M-
1100 (Aronix is a trade name manufactured by Toagosei Co., Ltd.)
The same applies hereinafter), Aronix M-1200, Aronix M-1210, Aronix M-1310, Aronix M-1600, KAYARAD UX-3204 (K
AYARAD is a trade name of Nippon Kayaku Co., Ltd. The same shall apply hereinafter), KAYARAD UX-4101 and the like.

Examples of polyether urethane (meth) acrylates include, for example, ART Resin UN-1101.
T, Art Resin UN-1102, KAYARAD U
X-2301, KAYARAD UX-6101, KA
YARAD UX-7101, KAYARAD UX-
8101, purple light UV-3300B, purple light XP-10 and the like. Examples of the polycarbonate urethane (meth) acrylate include, for example, ART RESIN UN-100.
0PEP, Art Resin UN-9000PEP, Art Resin UN-9200A, Art Resin UN-9000
H etc. are mentioned. Examples of the aliphatic urethane (meth) acrylate include Chemlink 9500 (Chemlink is a trade name of Sartomer Co., Ltd .; the same applies hereinafter), Chemlink 9501, Chemlink 9502, Chemlink 95.
03, Chemlink 9504, Chemlink 9505 and the like. Examples of the alicyclic urethane (meth) acrylate include ART RESIN UN-380G, ART RESIN UN-500, ART RESIN UN-9832 and the like.

[Photopolymerizable oligomer (A): Polyester (meth) acrylate (A3)] The molecular weight of the photopolymerizable oligomer (A) used in the present invention is 400 to 2000.
The polyester (meth) acrylate (A3) of 0 is a polyester (meth) acrylate obtained by a condensation reaction of a polyester polyol and (meth) acrylic acid. Here, the polyester polyol is a substance obtained by a reaction between the polyhydric alcohol and the polybasic acid. Specific examples include a resin composed of phthalic anhydride / propylene glycol / acrylic acid, a resin composed of adipic acid / 1,6-hexanediol / acrylic acid, and a resin composed of trimellitic acid / diethylene glycol / acrylic acid. To be

The polyester (meth) acrylate (A3) suitable for the present invention is listed as a trade name, for example,
Aronix M-6100, Aronix M-620
0, Aronix M-6250, Aronix M-63
00, Aronix M-6400X, Aronix M-
6410X, Aronix M-6500, Aronix M-7100, Aronix M-8030, Aronix M-8060, Aronix M-8100, viscoat 700 (viscoat is a trade name of Osaka Organic Chemical Industry Co., Ltd., the same applies below), viscoat 3700 etc. are mentioned.

[Photopolymerizable oligomer (A): polybutadiene (meth) acrylate (A4)] The molecular weight of the photopolymerizable oligomer (A) used in the present invention is 400 to 200.
00 polybutadiene (meth) acrylate (A4)
Is a resin obtained by first adding diisocyanate to a terminal hydroxyl group and acrylating with hydroxy (meth) acrylate in order to acrylate a liquid polybutadiene having a reactive hydroxyl group at the terminal. Also,
A resin obtained by hydrogenating this resin may be used. For example, 1,4-butadienediol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 2,2'butylethylpropane (meth) acrylate, hydrogenated 1,6-hexanediol (meth) acrylate, etc. Is mentioned.

The polyester (meth) acrylate (A4) suitable for the present invention is listed as a trade name, for example,
Queen Beam 101 (product name of Nippon Zeon Co., Ltd.),
B-700, B-1000, B-2000, B-300
0, MN-1000-80 and MAC-1000-80
(These are product names of Nisseki Mitsubishi Petrochemical Co., Ltd.), Nisso PB TE-2000, Nisso PB TEAI-10
00, Nisso PBTEA-3000 (above, trade name by Nippon Soda Co., Ltd.), poly bdACR-LC (trade name by Idemitsu Atchem Co., Ltd.) and the like. Regarding the method of using the photopolymerizable oligomer (A), one kind or two or more kinds may be used at an arbitrary mixing ratio.

[Photopolymerizable Monomer (B)] The photopolymerizable monomer (B) used in the present invention is a monofunctional monomer (B).
1) Bifunctional monomer (B2) and polyfunctional monomer (B
At least one kind is selected from 3) (however, the polyfunctional monomer means a monomer having three or more functional groups). [Photopolymerizable Monomer (B): Monofunctional Monomer (B1)]
As the monofunctional monomer (B1) of the photopolymerizable monomer (B) used in the present invention, for example, styrene, butyl acrylate, butyl ethoxy acrylate, butyl ethyl methacrylate, cyclohexyl acrylate,
Cyclohexyl methacrylate, dicyclopentanyl acrylate, dicyclopentanyl methacrylate,
Dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl methacrylate, 2-ethylhexyl methacrylate, glycidyl methacrylate, heptadecafluorodecyl acrylate, heptadecafluorodecyl meta Acrylate,
Examples thereof include 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, ularyl methacrylate, methoxydiethylene glycol methacrylate, methoxydipropylene glycol acrylate, nonylphenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate and phenoxyhydroxypropyl acrylate.

Monofunctional monomer (B1) compatible with the present invention
Examples of butyl ethoxy acrylate include light ester BO-A (light ester is a trade name of Kyoeisha Chemical Co., Ltd .; the same applies hereinafter), and butyl ethyl methacrylate includes, for example, light ester BO. , As cyclohexyl acrylate,
For example, as biscoat 155, cyclohexyl methacrylate, for example, light ester CH, and as dicyclopentanyl acrylate, for example, FANCLyl FA-513A (FANCLILL is a trade name of Hitachi Chemical Co., Ltd.), dicyclo Examples of the pentanyl methacrylate include funkryl FA-513M, examples of the dicyclopentenyl acrylate include funkryl FA-511A, and examples of the dicyclopentenyloxyethyl acrylate include funkryl FA-.
As 512A, N, N-diethylaminoethyl methacrylate, for example, light ester DE, and as N, N-dimethylaminoethyl methacrylate, for example,
Light ester DM, 2-ethylhexyl methacrylate, for example, light ester EH, glycidyl methacrylate, for example, light ester G, heptadecafluorodecyl acrylate, for example, biscoat 17F, heptadecafluorodecyl methacrylate, , For example, Viscoat 17FM,
Examples of 2-hydroxyethyl methacrylate include light ester HO, and examples of 2-hydroxypropyl methacrylate include light ester HD.
P, uraryl methacrylate, for example, light ester L, methoxydiethylene glycol methacrylate, for example, light ester MC, methoxydipropylene glycol acrylate, for example, light ester DPM-A, 2-hydroxyethyl acrylate, For example, light ester HO
A, Aronix M-111, Aronix M-11
Examples of 3, phenoxyhydroxypropyl acrylate include Aronix M-5700 and the like.

[Photopolymerizable Monomer (B): Bifunctional Monomer (B2)] Examples of the bifunctional monomer (B2) of the photopolymerizable monomer (B) used in the present invention include:
1,6-hexanediol acrylate, ethylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 2-methacryloyloxyethyl acid phosphate, glycerin dimethacrylate, ethylene oxide adduct dimethacrylate of bisphenol A, dimethyloltricyclodecane dimethacrylate Acrylate, triethylene glycol diacrylate, 1,6-hexanediol diacrylate, ethylene oxide adduct of bisphenol A diacrylate, propylene oxide adduct of bisphenol A diacrylate, 2
-Hydroxy-3-acryloyloxypropyl methacrylate and the like can be mentioned.

Bifunctional monomer (B2) compatible with the present invention
Examples of 1,6-hexanediol methacrylate include light ester 1,6
As HX and ethylene glycol dimethacrylate,
For example, light ester EG, 1,4-butanediol dimethacrylate, for example, light ester 1,4BG, 2-methacryloyloxyethyl acid phosphate, for example, light ester P-1
Examples of M, light ester P-2M and glycerin dimethacrylate include light ester G-101P,
Examples of the dimethacrylate of ethylene oxide adduct of bisphenol A include, for example, light ester BP-2E.
As M and dimethylol tricyclodecane diacrylate, for example, light acrylate DCP-A (light acrylate is a trade name of Kyoeisha Chemical Co., Ltd .; the same applies hereinafter), and as triethylene glycol diacrylate, for example, light acrylate 3EG -A, 1,6-
Examples of the hexanediol diacrylate include light acrylate 1,6HX-A and diacrylate of an ethylene oxide adduct of bisphenol A.
Examples of light acrylate BP-4EA and diacrylate of propylene oxide adduct of bisphenol A include, for example, light acrylate BP-4PA,
Examples of 2-hydroxy-3-acryloyloxypropyl methacrylate include light ester G-201.
P etc. are mentioned.

[Photopolymerizable Monomer (B): Polyfunctional Monomer (B3)] Examples of the polyfunctional monomer (B3) of the photopolymerizable monomer (B) used in the present invention include:
Trimethylolpropane trimethacrylate, ethylene oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, ditrimethylolpropane tetraacrylate, tris (methacryloxyethyl) isocyanurate, tris (acryloxy) Examples thereof include ethyl) isocyanurate, caprolactone-modified tris (acryloxyethyl) isocyanurate, dipentaerythritol penta- and hexaacrylate, ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate and the like.

Polyfunctional monomer (B3) compatible with the present invention
Examples of trimethylolpropane trimethacrylate include, for example, Light Ester TM
P, Aronix M-309, ethylene oxide-modified trimethylolpropane triacrylate, for example, light acrylate TMP-6EO-3A, pentaerythritol triacrylate, for example,
Examples of light acrylate PE-3A and pentaerythritol tetraacrylate include light acrylate PE-4A and dipentaerythritol hexaacrylate such as light acrylate DPM-.
6A, ditrimethylolpropane tetraacrylate, for example, light acrylate DTMP-4A,
Examples of tris (methacryloxyethyl) isocyanurate include funkryl FA-731M, and examples of tris (acryloxyethyl) isocyanurate include funkryl FA-731A and caprolactone-modified trisacryloxyethyl) isocyanurate. For example, as Aronix M-325, dipentaerythritol penta- and hexaacrylate, for example, Aronix M-400, ditrimethylolpropane tetraacrylate, for example, Aronix M-408, pentaerythritol tetraacrylate, for example, Aronix. M-450 etc. are mentioned. Regarding the method of using the photopolymerizable monomer (B), 1
One kind or two or more kinds may be used in an arbitrary mixing ratio.

The compounding amount of the photopolymerizable monomer (B) used in the ultraviolet-curable molding material and the weather resistance imparting ultraviolet-curable molding material of the present invention is such that the photopolymerizable oligomer (A) is 100.
The amount is 0.1 to 900 parts by weight, more preferably 1 to 400 parts by weight, and further preferably 5 to 200 parts by weight with respect to parts by weight. When the blending amount of the photopolymerizable monomer (B) is more than 900 parts by weight based on 100 parts by weight of the photopolymerizable oligomer (A), the curing rate is poor and the curing is poor, and the glass transition temperature (Tg) is typical. It causes deterioration of heat resistance, water resistance and mechanical properties.

Further, curing shrinkage and the like increase, and residual strain and the like increase. As a result, when it is used in a state where the adhesion to the thermoplastic resin sheet is extremely lowered, it may absorb moisture in the air and the cured product may be peeled off from the thermoplastic resin sheet, resulting in a defect as a molded product. Also,
If the amount is less than 0.1 parts by weight, the viscosity of the UV-curable molding material and the weather resistance-imparting UV-curable molding material becomes high, and therefore it cannot be cast into a fine mold structure composed of a thermoplastic resin sheet. In some cases, the curing rate, flexibility, and leveling property with respect to the thermoplastic resin sheet are deteriorated, and it may not be possible to obtain a molded product having the original properties of the cured product.

[First Component Photopolymerization Initiator (Ca)] The first component photopolymerization initiator (Ca) used in the ultraviolet curable molding material and weather resistance imparting ultraviolet curable molding material of the present invention.
Is added to improve the surface curability. The photopolymerization initiator (Ca) of the first component that can be used in the present invention is preferably a compound having an absorption wavelength of 220 to 360 nm, a molar absorption coefficient of 50 or more, and a molecular weight of 100 to 400. Is more preferably 230 to 350 nm, the molar absorption coefficient is 70 or more, and the molecular weight is 120 to 300. More preferably, the absorption wavelength is 235
˜340 nm, a molar absorption coefficient of 90 or more, and a molecular weight of 130 to 250.

The amount of the first component, the photopolymerization initiator (Ca), used in the present invention is such that the photopolymerizable oligomer (A) is 100.
0.01 to 30 parts by weight, more preferably 0.01 to 25 parts by weight, still more preferably 0.1 to 20 parts by weight.
Parts by weight. When the compounding amount of the photopolymerization initiator (Ca) as the first component exceeds 30 parts by weight, the storage stability as an ultraviolet curable molding material may be deteriorated, and gelation or curing may occur during storage. . In addition, the curing rate becomes extremely fast, and the photopolymerizable oligomer (A), the photopolymerizable monomer (B) and the photopolymerization initiator (Ca) as the first component are out of balance with each other, resulting in heat resistance, In some cases, defects such as deterioration in water resistance and mechanical properties and yellow discoloration may occur, resulting in defects in molded articles requiring transparency.

When the amount of the photopolymerization initiator (Ca) as the first component is less than 0.01 part by weight, the curing rate becomes extremely slow, and the photopolymerizable oligomer (A) and the photopolymerizable Monomer (B) and first component photopolymerization initiator (Ca)
The balance of the rate of cross-linking is destroyed, resulting in poor curing. For this reason, heat resistance, water resistance, mechanical properties, etc. are extremely reduced,
In addition, the yellowing resistance is also poor, and defects may occur with respect to molded articles that require transparency. In order to solve these problems, even if the irradiation time of ultraviolet rays is shortened or lengthened, the cured product may not be able to obtain the original characteristics, and a defect may occur as a product.
The first component photopolymerization initiator (Ca) that can be used in the present invention is a benzophenone-based photopolymerization initiator (Ca).
1), at least one selected from acetophenone photopolymerization initiator (Ca2), thioxanthone photopolymerization initiator (Ca3), benzoin photopolymerization initiator (Ca4), and special group photopolymerization initiator (Ca5).

[First component photopolymerization initiator (Ca): benzophenone type photopolymerization initiator (Ca1)] The benzophenone type photopolymerization initiator of the first component photopolymerization initiator (Ca) used in the present invention. Examples of (Ca1) include benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate,
4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4 '
-Methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 2,4,6-trimethylbenzophenone, 2,2-dimethoxy-1,2
-Diphenylethan-1-one and the like.

When the benzophenone photopolymerization initiator (Ca1) suitable for the present invention is mentioned as a trade name, benzophenone is, for example, Kayacure-BP100 (Kayacure is a trade name manufactured by Nippon Kayaku Co., Ltd .; the same applies hereinafter). Examples of benzoylbenzoic acid include Sanyo OBA (Sanyo is a trade name of Nippon Paper Industries Co., Ltd .; the same applies hereinafter), and examples of methyl benzoylbenzoate include Sanyo OB.
Examples of M, 4-phenylbenzophenone include Triganol 12 (trigganol is a trade name manufactured by Akzo Co., Ltd .; the same applies hereinafter), and examples of 3,3′-dimethyl-4-methoxybenzophenone include Kayacure-MBP,
Examples of [4- (methylphenylthio) phenyl] phenylmethanone include Kayacure-BMS, 2,4.
Examples of 6-trimethylbenzophenone include Ezacure-TZT (Ezacure is a trade name manufactured by Nippon Siber Hegner Co., Ltd., the same applies hereinafter), 2,2-dimethoxy-
Examples of 1,2-diphenylethan-1-one include, for example, Irgacure 651 (Irgacure is a trade name manufactured by Ciba Specialty Chemicals Co., Ltd .; the same applies hereinafter),
Etc.

[First component photopolymerization initiator (Ca): acetophenone photopolymerization initiator (Ca2)] The acetophenone photopolymerization initiator of the first component photopolymerization initiator (Ca) used in the present invention. As (Ca2), 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one,
1- (4-isopropylphenyl) -2-hydroxy-
2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2 −
Hydroxy-2-propyl) ketone and the like can be mentioned.

When the acetophenone photopolymerization initiator (Ca2) suitable for the present invention is listed as a trade name, 2-hydroxy-2-methyl-1-phenylpropan-1-one is, for example, Darocur 1173 (Darocur is ,
Product name of Ciba Specialty Chemicals Co., Ltd. The same shall apply hereinafter), as 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, for example, Darocur 1116, and as 1-hydroxycyclohexylphenyl ketone, for example, Irgacure 1
As 84, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, for example, trade name: Darocur 953, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2 Examples of -propyl) ketone include Darocur 2959) and the like.

[First component photopolymerization initiator (Ca): thioxanthone type photopolymerization initiator (Ca3)] The thioxanthone type photopolymerization initiator of the first component photopolymerization initiator (Ca) used in the present invention. Examples of (Ca3) include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone,
2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like can be mentioned. When the thioxanthone photopolymerization initiator (Ca3) suitable for the present invention is mentioned as a trade name, examples of thioxanthone include Nisso Cure-TX (Nisso Cure is a trade name manufactured by Nippon Soda Co., Ltd., the same below), 2- Examples of methylthioxanthone include Nissocure-MTX, and examples of 2,4-dimethylthioxanthone include Kayacure-RT.
X, 2,4-dichlorothioxanthone, for example, Kayacure-CTX, 2,4-diethylthioxanthone, for example, Kayacure-DETX), 2,
Examples of 4-diisopropylthioxanthone include:
Kayacure-DITX) and the like.

[First component photopolymerization initiator (Ca): benzoin photopolymerization initiator (Ca4)] The benzoin photopolymerization initiator of the first component photopolymerization initiator (Ca) used in the present invention. Examples of (Ca4) include benzoin, benzoin methyl ether, benzoin ethyl ether, and benzyl methyl ketal. When the benzoin-based photopolymerization initiator (Ca4) compatible with the present invention is mentioned as a trade name, benzoin is, for example, Nisso Cure-B.
Examples of O and benzoin methyl ether include Nissocure-MBO, examples of benzoin ethyl ether include Nissocure-EBO, and examples of benzylmethyl ketal include Irgacure 65.

[First component photopolymerization initiator (Ca): Special group photopolymerization initiator (Ca5)] Special group photopolymerization of the first component photopolymerization initiator (Ca) used in the present invention. As the initiator (Ca5), 1-phenyl-1,
2-propanedione-2 (o-ethoxycarbonyl) oxime and the like can be mentioned, and examples of trade names include Cuantacure-PDO (Ward Brenkinsop Co., Ltd.).
Manufactured) and the like. First component photopolymerization initiator (Ca)
Regarding the method of using, one kind or two or more kinds may be used at an arbitrary mixing ratio.

[Second Component Photopolymerization Initiator (Cb)] The second component photopolymerization initiator (Cb) used in the present invention is added in order to enhance the deep-part curability (3 mm or more). Second component photopolymerization initiator (Cb) that can be used in the present invention
Has an absorption wavelength of 340 to 500 nm and a molar absorption coefficient of 1
It is a compound having a molecular weight of 250 or more and 650 or more and a molecular weight of 250 to 650. More preferably, the absorption wavelength is 350 to 490n.
m, a molar absorption coefficient of 200 or more, and a molecular weight of 30
0 to 600 compounds, more preferably 36 absorption wavelengths
0 to 480 nm, a molar absorption coefficient of 400 or more, and
It is a compound having a molecular weight of 320 to 550.

The amount of the second component, the photopolymerization initiator (Cb), used in the ultraviolet-curable molding material of the present invention is 0.001-1 with respect to 100 parts by weight of the photopolymerizable oligomer (A).
The amount is 0 parts by weight, more preferably 0.001 to 8 parts by weight, still more preferably 0.001 to 5 parts by weight. When the blending amount of the photopolymerization initiator (Cb) as the second component exceeds 10 parts by weight, the cured product turns yellow and cannot be used for a molded article requiring transparency. Further, when the compounding amount is less than 0.001 part by weight, the deep-part curability (3 mm or more) may not be improved and may not be cured, which may cause a defect as a molded product.

The second component photopolymerization initiator (Cb) that can be used in the present invention is a benzophenone photopolymerization initiator (Cb1) or an acetophenone photopolymerization initiator (Cb).
2), at least one selected from benzoin photopolymerization initiator (Cb3) and special group photopolymerization initiator (Cb4). [Second component photopolymerization initiator (Cb): benzophenone-based photopolymerization initiator (Cb1)] The benzophenone-based photopolymerization initiator (Cb1) of the second component photopolymerization initiator (Cb) used in the present invention. Examples include 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone (trade name: Sancure BTTB, Sancure is a trade name of NOF Corporation, the same applies hereinafter) and the like. Can be mentioned.

[Second component photopolymerization initiator (Cb): acetophenone photopolymerization initiator (Cb2)] The acetophenone photopolymerization initiator of the second component photopolymerization initiator (Cb) used in the present invention. Examples of (Cb2) include A: bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide, B: 2-
Hydroxy-2-methyl-1-phenyl-propane-1
-One, C: 1-hydroxy-cyclohexyl-phenyl-ketone and the like. As a trade name, for example, Irgacure 1700 (a mixture of A and B above.
Mixing ratio by weight is A / B = 1: 3), Irgacure 14
9 (mixture of A and B above. Mixing ratio by weight is A / B =
1:19), Irgacure 1800 (mixture of the above A and C. The mixing ratio is A / C = 1: 3 by weight ratio), and Darocur (the above B).

[Second component photopolymerization initiator (Cb): benzoin photopolymerization initiator (Cb3)] The benzoin photopolymerization initiator of the second component photopolymerization initiator (Cb) used in the present invention. Examples of (Cb3) include 2-benzyl-
2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (trade name: Irgacure 369) and the like can be mentioned. [Second component photopolymerization initiator (Cb): Special group photopolymerization initiator (Cb4)] The special group photopolymerization initiator (Cb) of the second component photopolymerization initiator (Cb) used in the present invention ( Examples of Cb4) include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (trade name: Irgacure 819) and bis (η ⁵ -2,4).
-Cyclopentadiene-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyltitanium (trade name: Irgacure 784), η ⁵ —
Cyclopentadienyl-η ⁶ -cumenyl-iron (1
+)-Hexafluorophosphite (1-) (trade name: Irgacure 261), 4 ', 4 "-diethylisophthalphenone (trade name: Suncure IP) and the like. The second component photopolymerization initiator ( Regarding the method of using Cb), one kind or two or more kinds may be used at an arbitrary mixing ratio.

[Light Stabilizer (D)] The light stabilizer (D) that can be used in the present invention is at least one selected from hindered amine light stabilizers. Is bis (2,2,6,6-tetramethyl-4-pyridyl) sebacate (trade name: Sanol LS-770, Sanol is a trade name of Sankyo Co., Ltd.).
The same shall apply hereinafter), bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate (trade name: Sanol LS
-765), 1- [2- {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy} ethyl] -4- {3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionyloxy} -2,2
6,6-Tetramethylpiperidine (trade name: Sanol L
S-2626), 8-benzyl-7,7,9,9-tetramethyl-3-octyl-1,2,3-triazaspiro [4,5] undecane-2-4-dione (trade name: Sanol LS- 1114), 4-benzoyloxy-2,
2,6,6-Tetramethylpiperidine (trade name: Sanol LS-744), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarbochelate ( Product name: ADEKA STAB LA-5
7. ADEKA STAB is a product name of Asahi Denka Kogyo Co., Ltd. The same shall apply hereinafter), a condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol (trade name: ADEKA STAB LA-62), Condensation product of 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol (trade name:
ADEKA STAB LA-67), 1,2,3,4-butanetetracarboxylic acid and 1,2,2,6,6-pentamethyl-
Condensation product of 4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) diethanol (trade name: ADEKA STAB LA-68), 2,2,6,6-tetramethyl-4-piperidyl-methacrylate (trade name:
ADEKA STAB LA-87), Tetrakis (1, 2, 2,
6,6, -pentamethyl-4-piperidyl) 1,2,
3,4-Butane tetracarboxylate (trade name: ADEKA STAB LA-52), tetrakis (2, 2, 6, 6,
-Tetramethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate (trade name: ADEKA STAB L
A-57), bis (2,2,6,6-tetramethyl-
4-piperidyl sebacate (trade name: ADEKA STAB L
A-77), 1,2,2,6,6-pentamethyl-4-
Piperidyl methacrylate (trade name: ADEKA STAB LA
-82), 2,2,6,6-pentamethyl-4-piperidyl methacrylate (trade name: ADEKA STAB LA-8
7), dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate of succinate (trade name: TINUVIN 622, TINUVIN is Ciba Specialty Chemicals Co., Ltd. Trade name, the same applies hereinafter), decanedioic acid bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-pepyridinyl) ester-1,1-dimethylethylhydroperoxide and octane Reaction product (trade name: Tinuvin 1
23), bis (1,2,2,6,6-pentamethyl-4)
-Piperidinyl) -sebacate 1- (methyl) -8-
(1,2,2,6,6-pentamethyl-4-piperidinyl) -sebacate (trade name: Tinuvin 292), bis (1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3, 5-bis 1,1-dimeityl] -4-hydroxyphenyl] methyl] butyl malonate (trade name: Tinuvin 114) and the like can be mentioned.

[Ultraviolet Absorber (E)] The ultraviolet absorber (E) that can be used in the present invention has a maximum absorption wavelength of 3
Benzophenone UV absorber (E1), salicylate UV absorber (E2), cyanoacrylate UV absorber (E3), nickel complex salt UV absorber (E4), benzotriazole UV absorber (E5) and a benzoate-based ultraviolet absorber (E
At least one selected from 6). Examples of the benzophenone-based ultraviolet absorber (E1) include 2,4-
Dihydroxybenzophenone (Product name: SEESORB
100 and SEESORB are trade names manufactured by Cipro Kasei Co., Ltd. The same shall apply hereinafter), 2-hydroxy-4-octyloxybenzophenone (trade name: SEESORB102), 4
-Dodecyloxy-2-hydroxybenzophenone (trade name: SEESORB103), 4-benzyloxy-
2-hydroxybenzophenone (trade name: SEESOR
B105) and the like. Examples of the salicylate-based ultraviolet absorber (E2) include phenyl salicylate (trade name: SEESORB201), 4-t-butylphenyl salicylate (trade name: SEESORB202), and the like. Cyanoacrylate UV absorber (E
As 3), for example, ethyl-2-cyano-3,3-diphenyl salicylate (trade name: SEESORB50
1) 2'-ethylhexyl-2-cyano-3,3-diphenyl salicylate (trade name: SEESORB50
2) etc. are mentioned. Nickel complex salt type ultraviolet absorber (E
As 4), [2,2′-thiobis (4-tertiary octylphenolite)]-n-butylamine nickel (II)
(Product name: SEESORB612NH), Nickel dibutyl cythiocobamate (Product name: Antigen NB
C and Antigen are trade names of Sumitomo Chemical Co., Ltd. The same shall apply hereinafter) and the like. Examples of the benzotriazole-based ultraviolet absorber (E5) include 2- (2′-hydroxy-).
5'methylphenyl) benzotriazole (trade name: ADEKA STAB LA-32), 2, (2'-hydroxy-3)
′ -T-Butyl-5′-methylphenyl) -5-chlorobenzotriazole (trade name: ADEKA STAB LA-3
6), 2-hydroxy-4-n-octoxybenzophenone (trade name: ADEKA STAB 1413), 2- (3,5
-Di-t-phenyl-2-hydroxyphenyl) -2H
-Benzotriazole (SEESORB704) and the like. Examples of the benzoate-based ultraviolet absorber (E6) include 2 ', 4'-tetra-butylphenyl-3,5-di-tetra-butyl-4-hydroxybenzoate (trade name: SEESORB712).

[Antioxidant (F)] The antioxidant (F) that can be used in the present invention includes a phenolic antioxidant (F1), a phosphite antioxidant (F2), and a thioether antioxidant. It is at least one selected from (F3) and phenol phosphite antioxidants (F4). As the phenolic antioxidant (F1), for example, 1,3,5-trimethyl-2,4,6-tris (3,5-tert-butyl-4-hydroxybenzyl) benzene (trade name: ADEKA STAB AO- 20), n-octadecyl-3- (4'-hydroxy-3 ', 5'-di-
t-Butylphenyl) propionate (trade name: ADEKA STAB AO-50), tetrakis [methylene (3,3-
Di-t-butyl-4-hydroxyhydrocinnamate)] methane (trade name: ADEKA STAB AO-60), triethylene glycol bis [3- (3-t-butyl-4)
-Hydroxy-5-methylphenyl) propinate]
(Brand name: ADEKA STAB AO-70), 3,9-bis {2- [3- (3-t-butyl-4-hydroxy-5-
Methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane (trade name: ADEKA STAB AO-8
0) and the like. Phosphite antioxidant (F
2) as 2,2-methylenebis (4,6-di-t-
Butylphenyl) octylphosphite (trade name: Adeka Stab HP-10), cyclic neopentanetetraylbis (nonylphenylphosphite) (trade name: Adekastab PEP-4C), cyclic neopentanetetraylbis (2,6-di) -Tertiary butyl-4-methylphenyl phosphite) (trade name: ADEKA STAB PEP-36), distearyl pentaerythritol diphosphite (trade name: ADEKA STAB PEP-8), cyclic neopentatetraylbis (2,4) -Di-tert-butyl phenyl phosphite) (trade name: ADEKA STAB PEP-24G), cyclic neopentanetetraylbis (2,6-di-tert-butyl-
4-Methylphenylphosphite) (trade name: ADEKA STAB PEP-36), 1,1,3-tris (2-methyl-4-di-tridecylphosphite-5-tert-butylphenyl) butane (trade name: ADEKA STAB 522A), tris (2,4-di-tert-butylphenyl) phosphite (trade name: ADEKA STAB 2112), diphenyl isodecyl phosphite (trade name: ADEKA STAB 135)
A), diphenyl isooctyl phosphite (trade name: ADEKA STAB C), tris (mixed mono- and di-nonylphenyl) phosphite (trade name: ADEKA STAB 3)
29K), tris (nonylphenyl) phosphite (trade name: ADEKA STAB 1178), triphenyl phosphite (trade name: ADEKA STAB TPP), triisodecyl phosphite (trade name: ADEKA STAB 3010), and the like. Thioether antioxidants as (F3), for example, bis [2-methyl-4-{3-n-alkyl (C ₁₂ or, C ₁₄₎ thio-propynyloxy} -5-tert-butylphenyl] Surufiddo (trade name : ADEKA STAB AO-23), pentaerythritol-tetrakis-
(Β-Uralyl-thioprochionate) (Brand name: ADEKA STAB AO-412S), ditridecyl-3,3′-
Thiodipropionate (Product name: ADEKA STAB AO-5
03A), diuralyl thiodipropionate (trade name: Knock Rack 400, Knock Rack is a product name of Ouchi Shinko Chemical Industry Co., Ltd .; the same applies hereinafter), 2-mercaptobenzimidazole (trade name: Knock Rack MB), Examples thereof include 2-mercaptomethylbenzimidazole (trade name: Nocklac MMB) and zinc salt of 2-mercaptobenzimidazole (tradename: Nocklac MBZ). Examples of the phenol phosphite-based antioxidant (F4) include, for example, 4,4′-butylidene-bis (3-methyl-6-t).
-Butylphenyl-di-tridecyl) phosphite (trade name: ADEKA STAB 260), 1,1,3-tris (2-methyl-4-dichilydecylphosphite-5-t
-Butylphenyl) butane (trade name: ADEKA STAB 52
2A), 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite (trade name: ADEKA STAB HP-10) and the like.

[Antistatic Agent (G)] The antistatic agent (G) which can be used in the present invention includes a cationic antistatic agent (G1), an anionic antistatic agent (G2) and a nonionic antistatic agent ( G3), an alkylamine derivative-based antistatic agent (G4), a fatty acid ester-based antistatic agent (G5), and an unsaturated terminal antistatic agent (G6). As the cationic antistatic agent (G1), for example, trade name: New Elegan A (New Elegan is a trade name manufactured by NOF CORPORATION), trade name: New Elegan AI, trade name: New Elegan B ,
Product Name: New Elegan C, Product Name: Elegan CM-1
300 (Elegan is a trade name of Nippon Oil & Fats Co., Ltd .; the same applies hereafter), brand name: Elegan CM-2200, brand name: Elegan N-3140, brand name: Elegan 377R, brand name: Dennol 321-ML (Dennol) Is a product name of Maruishi Yuka Kogyo Co., Ltd .; the same applies to the following: Chemistad 2009 (Chemistad is a product name of Sanyo Kasei Co., Ltd .; the same applies below), Trade Name: MIYOCOL PX # 5C Is the product name of Miyoshi Yushi Co., Ltd.
Product name: Electrostriper QN (electrostriper is a product name manufactured by Kao Corporation, the same applies hereinafter) and the like. The chemical structural formula of the anionic antistatic agent (G2) is unknown, but for example, trade name: Elegan A-2
000SG, trade name: Elegan A-2000SP, trade name: Chemistat 3033, trade name: F-Call 214
(F-Coll is a trade name manufactured by Matsumoto Yushi-Seiyaku Co., Ltd .; the same applies hereafter), TB-160 (TB is a trade name manufactured by Matsumoto Yushi-Seiyaku Co., Ltd., the same applies below), trade name: Denon 1886 (Denon is Maruhishi) Yuka Kogyo Co., Ltd. product name. The same applies hereinafter, product name: Rheostat P-200 (Rheostat is a product name of Lion Corp., the same applies below), product name: Electrostripper-PC, product name: Electrostripper -PC
-2, trade name: Electrostriper-PC-3 and the like. The chemical structural formula of the nonionic antistatic agent (G3) is unknown, but for example, trade name: Elegan S-
100, trade name: Elegan SS-100, trade name: Elegan N-1100, trade name: Elegan N-3000, trade name: Elegan 255, trade name: Denon 335, trade name: Denon 336, trade name: Denon 331, Product name: Denon 331-L, Product name: Denon 331-P, Product name:
Chemistat 1100, trade name: Chemistat 250
0, product name: MIYOCOL 320, product name: MIYOCOL 3
57, product name: MIYOCOL 368, product name: MIYOCOL 368E, product name: Register 141, product name: Anstex SA-300 (Anstex is a product name manufactured by Toho Chemical Industry Co., Ltd., the same applies hereinafter), product name : Anstex SA-300B, trade name: Anstex N-6
1, product name: Anstec MG-100, product name: Anstex PS-109, product name: Antex SP-
20, trade name: TB-109, trade name: TB-123,
Trade name: Rheostat P-100, Trade name: Limacale S-71-D (Limacale is a trade name of Riken Vitamin Co., Ltd .; the same applies below), Trade name: Limacale DS-100,
Product name: Limacer SE-3700, Product name: Limacer SE-3701, Product name: Limacer SE-301,
Trade name: Limacale SE-364 and the like. Although the chemical structural formula of the alkylamine derivative-based antistatic agent (G4) is unknown, for example, trade name: TB-128,
Bremmer PE-200 (Bremmer is a trade name of NOF CORPORATION. The same applies hereinafter) and the like. The chemical structural formula of the fatty acid ester antistatic agent (G5) is unknown, but for example, trade name: Rheostat GS-90,
Product name: Rheostat DGS (B), product name: Rheostat SS-60 and the like. As the terminal unsaturated antistatic agent (G6), polyethylene glycol monomethacrylate (trade name: Blemma-PE-90, trade name: Blemma-PE-200, trade name: Blemma-PE-35)
0), poly (ethylene glycol-propylene glycol) monomethacrylate (trade name: Bremmer-50PE)
P-300), polyethylene glycol-polypropylene glycol monomethacrylate (trade name: blemmer)
70PEP-350), methoxy polyethylene glycol monomethacrylate (trade name: Bremmer-PME-1)
00, trade name: Blemma-PME-200, trade name: Blemma-PME-400, trade name: Blemma-PME-
1000, trade name: Blemma-PME-4000), methoxy polyethylene glycol monoacrylate (trade name: Blemma-AME-400) and the like.

Generally, it is said that the deep-curing property of the ultraviolet-curable molding material is about 1 mm, and the deep-layer (3
It is said that it cannot be cured up to (mm or more). The reason for this is that only the short-wavelength photopolymerization initiator (Ca) is irradiated with ultraviolet rays, and the photopolymerization oligomer (A), the photopolymerization monomer (B), and the photopolymerization initiator (C) form crosslinks. At times, all radicals generated by the short wavelength photopolymerization initiator (Ca) are absorbed in the surface layer portion, and the deep layer (3 m
radicals cannot be generated up to m or more). For this reason,
Only the surface layer portion on the side irradiated with ultraviolet rays is cured, resulting in poor curing in the deep portion. In the ultraviolet curable molding material and the weather resistance imparting ultraviolet curable molding material of the present invention, this problem is solved by using a photopolymerization initiator having a long wavelength. That is, by using the photopolymerization initiator (Cb) having a long wavelength, the photopolymerizable oligomer (A), the photopolymerizable monomer (B), the photopolymerization initiator (Ca) as the first component, and the light as the second component When the polymerization initiator (Cb) is crosslinked, not all generated radicals are absorbed, so that by generating radicals to the deep layer (3 mm or more), curing proceeds to the deep layer (3 mm or more). However, in order to improve the curability of the deep layer (3 mm or more), when the amount of the photopolymerization initiator (Cb) exceeds 10 parts by weight, the cured product of the cured product has weather resistance, water resistance, solvent resistance, The charging property, mechanical property, heat cycle property, crack resistance, etc. are extremely lowered. Also, 0.00
If the amount is less than 1 part by weight, the curability of the deep layer (3 mm or more) may not be improved and the composition may not be cured, which is not preferable because a defect may occur as a molded product.

[Operation] When a sheet or film made of polycarbonate, polyurethane, ABS, polybutylene terephthalate, acrylic or the like is used indoors or outdoors for a long time, these sheets or film are exposed to ultraviolet rays. On the other hand, when radicals are generated by absorbing ultraviolet rays, yellowing occurs with the passage of time, and further deterioration of the sheet and film causes cracking,
It may damage the shape of the product. Further, a sublimation-based printing sheet or a pigment-based printing sheet obtained by printing a sublimation-based ink or a pigment-based ink on these sheets or films is
A cured product obtained by adhering an ultraviolet curable adhesive, a thermosetting adhesive or the like between the layer sheet or film and the second layer printed sheet or film is used indoors or outdoors as described above. Then, the first-layer sheet and film, the second-layer sublimation printing sheet, the pigment-based printing sheet, the UV-curable adhesive, the thermosetting adhesive, and the like absorb UV rays, and the second-layer sheet and film If the printing surface is yellowed, bleeding or discolored and is severe, the printing surface may not be visible. Further, these cured products are charged with static electricity and attract dust, water and the like around the cured products, which is a cause of remarkably reducing the aesthetics, water resistance and crack resistance (crack resistance) of the cured product.
The weather resistance imparting type ultraviolet-curable molding material of the present invention has these problems, and the light stabilizer (D), the ultraviolet absorber (E),
By blending an antioxidant (F) and an antistatic agent (G), yellow, bleeding, crack resistance (crack resistance), mechanical properties, chargeability, etc. of cured products and sublimation printing sheets, pigment printing By significantly reducing the fading of the sheet,
Solved this problem.

The ultraviolet absorber (E) which can be used in the weather-resistant ultraviolet-curable molding material of the present invention is characterized by using a compound having an ultraviolet absorption wavelength of 340 nm or less. When the ultraviolet absorber (E) having an ultraviolet absorption wavelength of 341 nm or more is used, it overlaps with the absorption wavelength of the photopolymerization initiator (Cb) used in the weather resistance imparting ultraviolet-curable molding material of the present invention, and the photopolymerization initiator ( Inhibits the cleavage of Cb),
It lowers the reaction, and in severe cases, it becomes an uncured product,
Not preferable.

[Light Stabilizer, UV Absorber, Antioxidant and Antistatic Agent] The light stabilizer (D), UV absorber (E), and antioxidant used in the weather resistance imparted UV-curable molding material of the present invention. The total amount of the agents (F) and the antistatic agent (G) is 0.05 to 30 parts by weight based on 100 parts by weight of the photopolymerizable oligomer (A). . If the light stabilizer (D) exceeds 10 parts by weight, the viscosity and TI value of the compounded composition may become extremely high and casting may not be possible, and if it is less than 0.01 part by weight, the compounding may occur. Even when the composition is cast and cured by irradiation with ultraviolet rays, the light stabilizer (D) does not function, and the cured product easily discolors or discolors, which is not preferable. When the amount of the ultraviolet absorber (E) exceeds 10 parts by weight, the ultraviolet absorber (E) absorbs the ultraviolet rays even if the compounded composition is cast and irradiated with the ultraviolet rays, resulting in poor curing. On the other hand, if it is less than 0.01 part by weight, the ultraviolet absorber (E) does not function, and the cured product easily discolors or discolors, which is not preferable. Antioxidant (F)
If it exceeds 15 parts by weight, the viscosity and TI value of the blended composition will be too high to allow casting. On the other hand, if the amount is less than 0.01 parts by weight, the function of the antioxidant (F) does not work well,
The cured product easily discolors or discolors, which is not preferable.
When the amount of the antistatic agent (G) exceeds 15 parts by weight, the surface resistivity of the obtained cured product is significantly lower than 10 ¹⁰ Ω / □ (1
0 ⁸ Ω / □) or, the glass transition temperature of the cured product, flexural strength,
Flexural modulus, water absorption, etc. will decrease. Also, 0.
If the amount is less than 01 parts by weight, the antistatic agent (G) does not function, the surface resistivity of the cured product is 10 ¹⁴ Ω / □ or more, and static electricity is apt to be generated, which is not preferable.

[Ultraviolet Absorption Filter] The absorption wavelength of the photopolymerization initiator (Ca) as the first component used in the present invention is 30.
If a short wavelength of 0 nm or less is cut using an ultraviolet absorption filter and is not irradiated, the cured product may turn yellow, and a molded product requiring transparency may be defective. A combination of a cold mirror system and a cold filter system is known for selectively using only those having a desired wavelength. The cold mirror is a reflector in which a metal film is multilayer-deposited on Pyrex (registered trademark) glass and reflects only ultraviolet rays and transmits infrared rays and visible rays. The cold filter specially processes quartz glass to reflect visible rays and infrared rays and to transmit only ultraviolet rays. As those used in these, specifically, cold filter (wide type) CF-W (trade name, manufactured by Kawai Optical Co., Ltd.), cold filter (standard type) CF-S (same as above), cold filter ( Heat ray absorbing glass) CF-B (same as above),
The product name of Kenko Co., Ltd. is UV-22, UV-30,
HA-30, HA-50, HY-1, V-30, U-3
30, U-340 and the like.

Further, in the present invention, if necessary, components such as a polymer, a photopolymerization initiation aid, an organic solvent and various additives can be used. As the high-molecular polymer, for example, polyester-based, polycarbonate-based, polyacrylic-based, polyurethane-based, polyvinyl-based resins and the like can be used. Examples of the organic solvent include toluene, xylene, benzene, methyl ethyl ketone, isopropanol, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monodiethyl ether, methyl alcohol and ethyl alcohol.

[Photopolymerization Initiation Aid] In the ultraviolet-curable molding material and the weathering-providing ultraviolet-curable molding material of the present invention, in order to promote deep-curing property (3 mm or more), aliphatic amine or A photopolymerization initiation aid such as aromatic amines can be used in combination. By using together with the photopolymerization initiator (Cb) as the second component in order to increase the deep-part curability (3 mm or more), an ultraviolet-curable molding material having an excellent deep-part curability (3 mm or more) can be obtained. . For example, triethanolamine, triethylenetetramine, methyldiethanolamine, triisopropanolamine, benzophenone, 4,4′-dimethylaminobenzophenone, 4,4′-diethylaminobenzophenone, 2-dimethylaminoethylbenzoic acid, 4-dimethylaminobenzoic acid. Ethyl, isoamyl 4-dimethylaminobenzoate,
2-dimethylhexyl 4-dimethylaminobenzoate 4,
4'-bis (diethylamino) benzophenone, 4-dimethylaminoacetophenone and the like can be mentioned.

The amount of the photopolymerization initiation auxiliary compounded is 0.001 to 40 parts by weight, preferably 0.01 to 30 parts by weight, and more preferably 0.01 to 100 parts by weight of the photopolymerizable oligomer (A). -25 parts by weight. The photopolymerization initiation aid used in the ultraviolet-curable molding material and the weathering-imparting ultraviolet-curable molding material of the present invention is more than 40 parts by weight, and when it is irradiated with ultraviolet rays, when it is irradiated with ultraviolet rays, In some cases, only the surface is cured to cause curing failure, or the cured product is extremely discolored in yellow, which causes a defect in a molded product requiring transparency. Further, the storage stability of the ultraviolet curable molding material and the weather resistance imparted ultraviolet curable molding material may be lowered.

If the amount is less than 0.001 part by weight, the deep-hardening property (3 mm or more) may be deteriorated and the curing may be defective. In order to solve this phenomenon, when the irradiation time of ultraviolet rays is lengthened, the cured product deteriorates, a part of the crosslink density of the cured product is sheared, and the heat resistance, water resistance and water resistance represented by the glass transition temperature (Tg) Mechanical properties and the like may be extremely deteriorated, and defects may occur as a molded product. As various additives, a silane coupling agent, a thermal polymerization inhibitor, a leveling agent, a surface lubricant, a defoaming agent, a thixotropic agent,
Examples include anti-settling agents, pigment dispersants, fillers, flame retardants, pigments and dyes.

[Silane Coupling Agent] Examples of the silane coupling agent include alkyl type, amine type, (meth) acrylate type, isocyanate type, epoxy type and thiol type. [Thermal Polymerization Inhibitor] Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, benzoquinone, 4-benzoquinone, 2,6-t-butyl-4-cresol, anthraquinone and the like. [Leveling Agent] As the leveling agent, an acrylic copolymer, an acrylic / vinyl ether copolymer, a vinyl copolymer, a vinyl polymer silicone, a silicone,
Examples thereof include silicone hydrophobic silica and silicone-based acrylic polymers. [Surface Lubricant] Examples of the surface lubricant include mineral oil activators, silicone / mineral oil mixtures, and silicone polyglycol hydrophobic silica. [Antifoaming Agent] As the antifoaming agent, a silicone nonionic activator, an aliphatic polycarboxylic acid / silicone mixture, an aliphatic amide ester, a modified acrylic copolymer, a polycarboxylic acid salt type polymeric activator, polysiloxane Examples include system copolymers. [Thixotropic property-imparting agent] As the thixotropic property-imparting agent, urethane modified polyether, urethane polymer, acrylic modified polyether, hydrogenated vegetable oil, long chain fatty acid ester polymer, high molecular fatty acid amide Etc. [Anti-Settling Agent] As the anti-settling agent, an aliphatic amide wax, an amide / polyethylene composite material, a polyethylene oxide wax, a sulfate ester anion activator,
Examples thereof include nitrogen-containing compounds. [Pigment dispersant] As the pigment dispersant, a vinyl polymer petroleum naphtha solution, an aliphatic polyvalent carboxylic acid, an amine salt of a polyester, a long-chain amine salt of a polycarboxylic acid, an amide amine of a high molecular weight polyester acid, a polyether is used. Examples thereof include amine salts of phosphoric acid esters and polyether phosphoric acid esters.

[Filler] As the filler, crystalline silica (trade name: Cruslatite VXX manufactured by Tatsumori Co., Ltd., Cruslatite AA, etc.), fused silica (trade name: F-40 manufactured by Denki Kagaku Kogyo KK), F-300, RS-90, etc.), ultrafine silica (trade name: Aerosil 200, Aerosil R-972, etc., manufactured by Nippon Aerosil Co., Ltd.), calcium carbonate (trade name: μ-Powder, manufactured by Bihoku Powder Co., Ltd.) 3S, Nitto Koka Kogyo Co., Ltd. product name: NS # 100, SS # 30
Etc.), precipitated barium sulfate (trade name: # 100, # 300, SS-55, BF-1, BM manufactured by Sakai Chemical Industry Co., Ltd.)
H, B-1, etc.), titanium oxide (as rutile type, manufactured by Sakai Chemical Industry Co., Ltd., product name: SR-1, R-32, R-42,
As anatase type such as R650, trade name: A-110, A-150, ST-G, SA-1 manufactured by Sakai Chemical Industry Co., Ltd.
Etc.), talc (Matsumura Sangyo Co., Ltd. product name: High Filler # 10, # 12, # 5000PJ, etc.), aluminum hydroxide (Showa Denko KK product name: Hydilite H-1)
0, H-21, H-32, etc.), mica (Yamaguchi Mica Industrial Co., Ltd. product name: A-11, AB-32, B-70, Y)
-1500), magnesium oxide (Kyowa Chemical Industry Co., Ltd. product name: Magsarat 30, 150, F, etc.),
Whiskers (Shikoku Chemicals Co., Ltd. product name: Arpolex Y, YS2A, YS4, etc., Otsuka Chemical Co., Ltd. product name: Tismo-D, -D101, -L, etc.), hollow glass beads (Toshiba Baro Martini) Product name: GB7
31A, EGB731B, etc.), polyethylene cotton fiber (Mitsui Chemicals, Inc. product name: FD380, FDS
S-2), glass fiber (trade name: CS411, BC273, 20MN2-20, manufactured by Asahi Fiber Glass Co., Ltd.)
Etc.), glass powder (trade name: P235, etc., manufactured by Asahi Fiber Glass Co., Ltd.) and the like.

[Flame Retardant] Examples of the flame retardant include the following. Phosphate ester compound. For example, triphenyl phosphate (trade name: TP manufactured by Daihachi Chemical Industry Co., Ltd.)
P), tricresyl phosphate (same brand name: TC
P), trixylenyl phosphate (same brand name: TX
P) etc. Halogen phosphate compound. For example, tris (chloroethyl) phosphate (trade name: CL
P), tris (chloropropyl) phosphate (trade name: TMCCP), tris (dichloropyropyr) phosphate (trade name: CRP), tris (tribromoneopentyl) phosphate (trade name: CR-900)
etc.

[Pigment] Examples of pigments include the following. Condensed azo compound. For example, trade name: Yellow 8GN, Yellow 3G, Yellow GR, Scarlet RN, Scarlet RS, Scarlet RT, Red G, Red BR manufactured by Nagase & Co. Ciba Specialty Chemicals Co., Ltd.
N, Red BT, etc. Isoindolinone compound. For example,
Product name: Yellow 2RLP, Yellow 2RLTS, Yellow 3RT, etc. Benzimidazolone compounds. For example,
Same product name: Orange GP, Orange GL, etc. Dioxazine compound. For example, the same product name: Violet B, Violet GT, etc.

[Dye] The following can be exemplified as the dye. Chromium complex compound. For example, Ciba Specialty Chemicals Co., Ltd. product names: Yellow 2GLN, Orange RG, Brown 2GL, Brown 6RL, Red 3G
L, pink 5BLG, violet red RP, etc. Cobalt complex compound. For example, the product names: yellow 2RLN, yellow 3R, orange G, red G. Phthalocyan compound. For example, the same product name: Blue GN, Blue GL, etc. These components are used, for example, when it is necessary to adjust the viscosity of the resin or improve the properties of the cured product.

[Viscosity and Thixotropic (TI) Value of UV-Curable Molding Material] The viscosity of the UV-curable molding material of the present invention is 50 to 300 at room temperature (23 ° C.).
It is important that the pressure is 00 mPa · S. The thixotropy (TI) value is 0.5-2. Viscosity at room temperature (23
If the temperature exceeds 30000 mPa · S at ℃), it may not be possible to cast even the precise details of the molding die, or air may be entrained during the casting operation. On the other hand, when it is less than 50 mPa · S, there arises a problem that the monomer component dissolves the thermoplastic resin sheet itself forming the molding die.
When the TI value of the ultraviolet-curable molding material of the present invention exceeds 2, it is not possible to cast the precise molding details, or
Entrapment of air may occur during casting. Also, T
When the I value is less than 0.5, the photopolymerizable oligomer (A), the photopolymerizable monomer (B), the photopolymerization initiator (Ca) as the first component and the photopolymerization as the second component of the compounded composition Initiator (C
b) causes layer separation. Even if the compounded composition in such a state is cast and irradiated with ultraviolet rays, a curing failure occurs and the desired molded article cannot be obtained. By using a UV curable molding material having a TI value of 0.5 to 2, it is possible to cast into a molding die such as a key top having a more complicated shape, and even the fine corners of the key top or the like can be UV cured. Allows molding material to enter.

[Viscosity and thixotropy (TI) value of weather resistance imparted UV-curable molding material] The viscosity of the weather resistance imparted UV-curable molding material at room temperature (23
It is important that it is 50 to 100,000 mPa · S at (° C.). The thixotropy (TI) value is 0.5-3. Viscosity is 100,000 mPa · S at room temperature (23 ° C)
If it is higher than the above, it may not be possible to cast even the details of the precise molding die, or air may be trapped during the casting operation. On the other hand, when it is less than 50 mPa · S, there arises a problem that the monomer component dissolves the thermoplastic resin sheet. The T of the UV-curable molding material with weather resistance of the present invention
If the I value exceeds 3, it may not be possible to cast even the precise details of the molding die, or air may be trapped during the casting operation. When the TI value is less than 0.5, the photopolymerizable oligomer (A), the photopolymerizable monomer (B), the first component photopolymerization initiator (Ca), and the second component The photopolymerization initiator (Cb), the stabilizer (D), the ultraviolet absorber (E), the antioxidant (F) and the antistatic agent (G) cause layer separation. Even if the compounded composition in such a state is cast and irradiated with ultraviolet rays, a curing failure occurs and the desired molded article cannot be obtained.

In the compounding composition of the ultraviolet-curable molding material or the weathering-imparting ultraviolet-curable molding material of the present invention, each of the above components may be used at room temperature to 80 ° C. with or without using an organic solvent. Instead, it can be obtained by mixing and dissolving.
The ultraviolet-curable molding material or the weathering-imparting ultraviolet-curable molding material of the present invention can be cured by casting it in a molding die made of a thermoplastic resin sheet and then irradiating it with ultraviolet rays by a conventional method. The curing of the ultraviolet-curable molding material or the weathering-imparting ultraviolet-curable molding material of the present invention by irradiation with light rays such as ultraviolet rays is specifically a low-pressure, high-pressure and ultra-high-pressure mercury lamp, a metal hydrolamp, an electrodeless lamp , Xenon lamp, xenon and mercury mixed lamp,
It is performed using a photochemical reaction lamp or the like.

In the present invention, the thermoplastic resin sheet that can be used in the molding die includes acrylic film, polypropylene film, polyester film, polystyrene film, polycarbonate film, nylon film, polyurethane film, polyethylene terephthalate film, polybutylene terephthalate film, styrene. -Acrylonitrile copolymer (reinforced) film, acrylonitrile-butadiene-styrene copolymer (reinforced) film, polyetherimide film, polyoxybenzylene film, polymethylpentene film, polyether sulfone film, polyetherimide film , Polyarylate film, polyether ether ketone film, polyamide imide film and the like.

The ultraviolet-curable molding material of the present invention or the UV-curable ultraviolet-curable molding material of the present invention is cast into a molding die made of a thermoplastic resin sheet and irradiated with ultraviolet rays to be cured to give a molded article. can get. As irradiation conditions of ultraviolet rays, an irradiation distance (cm), an illuminance (mW / cm ² ) and an integrated light amount (mJ / cm ² ) are 5 to 25 cm and 5 respectively.
0-300 mW / cm ² and 800-3500 mJ / c
m ² , preferably 10 to 20 cm, 70 to 260 mW
/ Cm ² and 1000 to 3000 mJ / cm ² , more preferably 12 to 18 cm, 80 to 220 mW / cm ² and 1200 to 2500 mJ / cm ² . Irradiation distance,
If the illuminance and the integrated light amount are outside of the above numerical ranges, the cured product may turn yellow, and crosslinking may proceed too much to make the cured product brittle, which requires transparency. It is not preferable because the product cannot be obtained. Further, if the irradiation distance, the illuminance, and the integrated light amount are smaller than the above numerical ranges, the deep-part curability (3 mm or more) becomes insufficient and curing failure may occur, which is not preferable.

[Cured Product Properties of UV-Curable Molding Material]
Various properties of a cured product obtained by irradiating the ultraviolet-curable molding material of the present invention with ultraviolet rays to cure the material will be described. [Glass Transition Temperature (Tg)] Glass Transition Temperature (Tg)
Is -20 to 120 ° C. Bending strength is 10 to 300
N / mm ^2, flexural modulus 90~7000N / mm ^2, a Shore D hardness is required to be 50 to 95. The specific gravity is preferably 0.7 to 2. When the Tg of the cured product of the ultraviolet curable molding material of the present invention is higher than 120 ° C., the cured product has a high crosslink density and becomes hard and brittle.

When the glass transition temperature (Tg) is lower than -20 ° C, the crosslink density of the cured product becomes extremely low,
A soft cured product is obtained. In such a case, the molded body easily absorbs moisture in the air, and if the absorbed moisture is present in the cured product, the interface between the molded body of the ultraviolet curable molding material and the thermoplastic resin sheet peels off. It may end up. Further, the Shore D hardness, the bending strength and the bending elastic modulus are outside the above numerical ranges and show small values, which is not preferable as a product. When the filler of silica, mica, precipitated barium sulfate, talc, calcium carbonate, etc. is blended with the ultraviolet curable molding material of the present invention and the specific gravity is higher than 2, the final product weight becomes heavy, and However, since the transparency is lowered, the appearance as a product is not preferable. Also, in order to make the specific gravity lighter than 0.7, hollow glass beads,
When a lot of polyethylene cotton fibers are mixed,
The molded product is brittle and its transparency is lowered, which is not preferable as a product. When a heat cycle test (−40 ° C./1 hour + 85 ° C./1 hour: 100 cycles) is performed on a molded article out of the above numerical range, the cured product may peel off from the thermoplastic resin sheet, which is not preferable.

[Cured Product Properties of UV-Resistant Molding Material Containing Weather Resistance] The properties of the cured product obtained by irradiating the weather-resistant UV-curable molding material of the present invention with ultraviolet rays to cure the material will be described. [Glass Transition Temperature (Tg)] Glass Transition Temperature (Tg)
Is −30 to 110 ° C. Bending strength is 10-290
N / mm ^2, flexural modulus 90~5000N / mm ^2, it is necessary that the Shore D hardness of 40 to 80. The specific gravity is preferably 0.7 to 2.3. Glass transition temperature (T
When g) is higher than 110 ° C., the cross-linking density of the cured product becomes high and the product becomes hard and brittle. If the glass transition temperature (Tg) is lower than -30 ° C, the crosslinked density of the cured product will be low, and a soft cured product will be obtained. In such a case, the molded body easily absorbs moisture in the air,
If the absorbed moisture is present in the molded product, the interface between the molded product of the weather resistance imparting ultraviolet-curable molding material and the thermoplastic resin sheet may be separated. Further, the Shore D hardness, the bending strength and the bending elastic modulus are outside the above numerical ranges and show small values, which is not preferable as a final product. When a large amount of silica, precipitated parium sulfate, talc, calcium carbonate, or other filler is added to the weathering-resistant ultraviolet-curable molding material of the present invention and the specific gravity is higher than 2.3, the final product weight becomes heavy. In addition, since the transparency is lowered, the appearance as a product is not preferable. Further, if a large amount of hollow beads, polyethylene cotton fibers, etc. are blended in order to make the specific gravity lighter than 0.7, the molded product becomes brittle and its transparency deteriorates, causing a problem as a product. A heat cycle test (-40 ° C / 1 hour +8
5 ℃ / 1 hour: 100 cycles) and environmental test (60 ℃)
/ 95% RH / 240 hours), the molded product may peel off from the thermoplastic resin sheet, which is not preferable.

[0074]

EXAMPLES The present invention will be described in more detail below with reference to examples. [Examples 1 to 6 and Comparative Examples 1 to 5] Of the components shown in Table 1 below, a photopolymerizable oligomer (A) having a molecular weight of 400 to 20,000 and a photopolymerizable monomer (B) were placed in a stainless steel container (volume: 1 liter) was weighed and put into each well, and while being heated to 60 ° C. using a heating heater, while being stirred with a glass rod, uniformly dissolved in 1 hour. After that, the mixture is cooled to room temperature, a required amount of the photopolymerization initiator (C) and the like is weighed, added into the stainless steel container described above, further stirred for 5 minutes, and the ultraviolet rays of Examples 1 to 6 and Comparative Examples 1 to 5 are added. A curable molding material was prepared.

As the thermoplastic resin sheet, a polycarbonate sheet (trade name: Panlite Sheet PC-2151 manufactured by Teijin Kasei Co., Ltd., thickness: 200 μm) was used. 12 molds with a predesigned key top shape
Preheated to 0 ℃, Panlite Sheet PC-215
1 is sandwiched between the molding dies and the pressure is 196.1 MPa.
(2 ton / cm ² ) was added and pressure was applied for 30 seconds, and the molding die was taken out and cooled to room temperature to prepare a thermoplastic resin sheet molding die. The UV curable molding material prepared above was cast into this thermoplastic resin sheet, and U
V-1000-1HD type (The lamp is a high pressure mercury lamp: 80
Using an ultraviolet irradiation device of W / cm, 1 lamp), ultraviolet rays were irradiated for 30 seconds to cure. Then, the surface condition of the obtained molded product and the properties of the cured product were examined. The results are shown in Table 1.

The constituent components of the ultraviolet-curable molding material shown in Table 1 used in the present invention will be described. [Photopolymerizable Oligomer (A)] {Epoxy Oligomer (A1)} (1) Epoxy Ester 3002M: Kyoeisha Chemical Co., Ltd. trade name, bisphenol A type epoxy acrylate,
Molecular weight: 630, viscosity: 50,000 mPa · S (however, 2
(2) Epoxy ester 200PA: Kyoeisha Chemical Co., Ltd. trade name, epoxy ester acrylate, molecular weight: 89
0, viscosity: 800 mPa · S (however, 23 ° C.) urethane oligomer (A2) (3) Aronix M-1600: trade name of Toagosei Co., Ltd., polyester urethane acrylate, molecular weight: 1
300, viscosity: 30000 mPa · S (however, 23 ° C)

(4) ART Resin UN-9000H: trade name of Negami Kogyo Co., Ltd., polycarbonate urethane acrylate, molecular weight: 3000, viscosity: 1500000 m
Pa · S (however, 23 ° C.) {Polyester-based oligomer (A3)} (5) Aronix M-8100: trade name manufactured by Toagosei Co., Ltd., polyester-based acrylate, molecular weight: 600,
Viscosity: 15000 mPa · S (however, 23 ° C.) (6) Art Resin UN-1255: Negami Kogyo Co., Ltd. trade name, polyester acrylate, molecular weight: 100
00, viscosity: 30000 mPa · S (however, 23 ° C.) {Butadiene-based oligomer (A4)} (7) Nisso PB TEAI-1000: Nippon Soda
Brand name, 1,2-polybutadiene resin modified with terminal methacrylate, molecular weight: 3000, viscosity: 10000
mPa ・ S (however, 23 ℃)

[Photopolymerizable monomer (B)] {Bifunctional monomer (B2)} (1) Light ester 1,6HX: Kyoeisha Chemical Co., Ltd. trade name, 1,6-hexanediol dimethacrylate,
Viscosity: 200 mPa · S (however, 23 ° C.) (2) Light acrylate DCP-A: Kyoeisha Chemical Co., Ltd. trade name, dimethylol-tricyclodecane diacrylate, viscosity: 170 mPa · S (however 23 ° C.) {many Functional monomer (B3)} (3) Light ester TMP: Kyoeisha Chemical Co., Ltd. trade name, trimethylolpropane trimethacrylate, viscosity: 250 mPa · S (however, 23 ° C.)

[Photopolymerization Initiator (Ca)] (1) Irgacure 184: trade name, manufactured by Ciba Specialty Chemicals Co., Ltd., 1-hydroxy-cyclohexyl-phenyl-ketone (2) Darocure 1173: Ciba Specialty Chemicals Co., Ltd. ) Product name, 2-hydroxy-2-methyl-1
-Phenyl-1-one [photopolymerization initiator (Cb)] (1) Irgacure 369: trade name, 2-benzyl-2-dimethylamino-1- (4-monofolinophenyl, manufactured by Ciba Specialty Chemicals Co., Ltd. ) -Butanone-1

The measurement and evaluation of the physical properties of the ultraviolet curable molding material of the present invention before and after curing are as follows. The measurement environment was evaluated after leaving the test sample for 24 hours or more in a constant temperature and humidity room at room temperature: 23 ° C. and absolute humidity: 50% RH. The properties before curing were evaluated by viscosity and thixotropy value (TI value). (1) Viscosity: JIS K-6838, unit: mPa.
S, rotation speed: 20 rpm. (50-30000 mPa ・
S was accepted. ) (2) TI value: JIS K-6838, unit: 1/10
rpm. (0.5 to 2 was passed.)

The heat resistance of the cured product depends on the glass transition temperature (T
The evaluation was performed in consideration of the result of g) and the heat cycle test. (3) Glass transition temperature: ASTM D696, but thermomechanical method, temperature rising rate: 5 ° C / min, unit: ° C. (Tg =-
20-120 degreeC was set as the pass. ) (4) Heat cycle test: -40 ° C / 1 hour + 85 ° C
/ 1 hour However, 100 cycles. (After 100 cycles,
It was visually judged that the key top was in close contact with the thermoplastic resin sheet. ) Mechanical properties include flexural strength, flexural modulus, tensile rupture strength,
The tensile elastic modulus, the tensile elongation at break, the hardness, and the pencil hardness were evaluated.

(5) Bending strength: JIS K-7171,
Unit: N / mm ² , test speed: 2 mm / min. (10-3
00 N / mm ² was regarded as acceptable. ) (6) Flexural modulus: JIS K-7171, unit: N /
mm ² , test speed: 2 mm / min. (90-7000N /
mm ² was accepted. ) (7) Tensile breaking strength: JIS K-7162, 1BA
Type dumbbell used, unit: N / mm ² , test speed: 10 m
m / min. (10 to 150 N / mm ² was accepted.) (8) Tensile elastic modulus: JIS K-7162, 1BA type dumbbell used, unit: N / mm ² , test speed: 10 mm
/ Min. (90 to 5000 N / mm ² was accepted.)

(9) Tensile elongation at break: JIS K-71
62, 1BA type dumbbell used, unit:%, test speed: 1
0 mm / min. (3 to 200% was accepted.) (10) Hardness: JIS K-7215, unit: Shore D. (50-95 was passed.) (11) Pencil hardness: JIS K-5400. (B-4H
Was accepted. ) Water resistance was evaluated by water absorption and environmental tests. (12) Water absorption rate: JIS K-7209, 23 ° C / 24
Weight increase rate after time immersion, unit:% by weight. (0.05 ~
3% by weight was accepted. ) (13) Environmental test: 60 ° C / 95% RH, (however, 24
After 0 hours, it was visually determined that the key top and the thermoplastic resin sheet were in close contact with each other and were not peeled off. )

The transparency and yellowing resistance of the cured product were measured by total light transmittance and easy fading (color difference). (14) Total light transmittance: JIS K-7361, unit:
%. (70 to 100% was accepted.) (15) Easy fading (color difference): JIS Z-8722,
Field of view: 2 °, light source: C, but ΔE display by CIELAB method. (About 240 hours after sunshine carbon weather meter, the range of ΔΕ of 8 or less was judged as the range that does not easily fade.
Carbon weatherometer is based on JIS A-1415)

[0085]

[Table 1]

From Table 1, Comparative Example 1 lacks the photopolymerizable monomer, and the viscosity before curing is 10,000 (mPa · S), which is within the preferable condition range, but the photopolymerization initiators (Ca) and (C
Since b) is too small, it does not cure even after irradiation with ultraviolet rays, and Comparative Example 2 has a high viscosity before curing and a high TI value, making it difficult to cast into a molding die. Polymerization initiator (C
Since a) and (Cb) are abundant, curing to a deep portion is insufficient and curing failure occurs, and they cannot be used as key tops. Comparative Examples 4 and 5 are key tops, but after curing In Comparative Example 4, the glass transition temperature, the heat cycle test, the bending elastic modulus, the tensile breaking strength, the tensile elastic modulus, the pencil hardness, the environmental test, the total light transmittance, and the easy discoloration (color difference) are all included in Comparative Example 4. Fail the item, and
Comparative Example 5 has a glass transition temperature, a heat cycle test, a bending strength, a tensile strength, a tensile elastic modulus, and a tensile elongation at break.
It does not pass in each of the three items of hardness, pencil hardness, total light transmittance, and easy fading (color difference), and as a result, it is understood that they are not desirable as key tops.

The UV-curable molding material of the present invention has a viscosity of 50 to 30 at room temperature (23 ° C.) as a characteristic before curing.
000mPa ・ S, thixotropy (TI) value is 0.5
Since it is ~ 2, it is possible to cast into a mold having a fine structure. Further, in the characteristics after curing by ultraviolet irradiation, the glass transition temperature is −20 to 120 ° C. and the bending strength is 10 to 3
00 N / mm ² , flexural modulus of 90-7000 N / mm ²
Also, since the Shore D hardness is 50 to 95, the ultraviolet curable molding material does not peel off from the thermoplastic resin sheet after the heat cycle test and the environmental test. Furthermore, since the water absorption rate is low, the total light transmittance is high, and the easy fading (color difference: ΔE) is small, the water resistance and the yellowing resistance are excellent. As a result, when a key top for a mobile phone or the like is produced using the ultraviolet-curable molding material of the present invention and the key top is used for a long time, the strength and transparency as the key top can be maintained for a long time. The ultraviolet-curable molding material of the invention is extremely excellent.

[Examples 7 to 11 and Comparative Examples 6 to 14] Tables 2 (Examples 7 to 11) and 3 (Comparative Examples 6 to 14) below.
Among the components shown in 1., a photopolymerizable oligomer (A) having a molecular weight of 400 to 20000, a photopolymerizable monomer (B), a light stabilizer (D), an ultraviolet absorber (E), an antioxidant (F)
And the antistatic agent (G) was weighed and put into a stainless steel container (capacity 1 liter), and while heating to 100 ° C. with a heater, stirring with a glass rod took 1 hour. It was made to dissolve uniformly. Further, measure the required amount of the photopolymerization initiator (C), etc., and set the temperature of the heater to 140
The temperature was raised to 0 ° C., and the mixture was further charged into the stainless steel container described above and stirred for 10 minutes to prepare the weather-resistant ultraviolet-curable molding materials of Examples 7 to 11 and Comparative Examples 6 to 14.

As the thermoplastic resin sheet, a polycarbonate sheet (trade name: Panlite Sheet PC-2151, manufactured by Teijin Chemicals Ltd., thickness: 200 μm) was used. 12 molds with a predesigned key top shape
Preheated to 0 ℃, Panlite Sheet PC-215
1 is sandwiched between the molding dies and the pressure is 196.1 MPa.
(2 ton / cm ² ) was added and pressure was applied for 30 seconds, and the molding die was taken out and cooled to room temperature to prepare a thermoplastic resin sheet molding die. The weather resistance-imparting UV-curable molding material prepared above was cast into this thermoplastic resin sheet, and a UV-1000-1HD type (lamp: high pressure mercury lamp: 80 W / cm, 1 lamp) manufactured by Hitec Co., Ltd. was cast. Using an ultraviolet irradiation device, ultraviolet rays were irradiated for 30 seconds to cure. Then, the surface condition of the obtained molded product and the properties of the cured product were examined. The results are shown in Table 4 (Examples 7 to 11) and Table 5 (Comparative Examples 6 to 14).

The constituent components of the weather resistance imparted UV-curable molding material shown in Tables 2 and 3 used in the present invention will be described. [Photopolymerizable oligomer (A)] {Epoxy oligomer (A1)} (1) Biscoat 540: trade name of Osaka Organic Chemical Industry Co., Ltd., bisphenol A type epoxy acrylate, molecular weight: 540, viscosity: 60,000 mPa · S ( However, 23
(° C) (2) Lipoxy SP-9000: trade name manufactured by Showa Highpolymer Co., Ltd., epoxy ester acrylate, molecular weight: 460,
Viscosity: 30000 mPa · S (however, 23 ° C) {Urethane-based oligomer (A2)} (3) ART RESIN UN-9000PEP: Negami Kogyo
Brand name, polycarbonate urethane acrylate, molecular weight: 5000, viscosity: 100,000 mPa · S
(However, 23 ° C)

{Polyester-based oligomer (A3)} (4) KAYARAD UX-3204: trade name manufactured by Nippon Kayaku Co., Ltd., polyester-based acrylate, molecular weight: 13000, viscosity: 90000 mPa · S (however,
23 ° C.) {Polyether oligomer (A4)} (5) Shiko UV-3200B: Nippon Synthetic Chemical Industry Co., Ltd.
Product name, polyether acrylate, molecular weight: 10
000, viscosity: 650,000 mPa · S (however, 23
(° C) {Butadiene-based oligomer (A5)} (6) BAC-45: trade name of Osaka Organic Chemical Industry Co., Ltd.,
Acrylate-terminated polybutadiene resin, molecular weight: 4
500, viscosity: 50000 mPa · S (however, 23 ° C)

[Photopolymerizable Monomer (B)] {Monofunctional Monomer (B1)} (1) Aronix M-5700: Toagosei Co., Ltd. trade name, 2-hydroxy-3-phenoxypropyl acrylate, viscosity: 150 mPa. -S (however, 23 degreeC) {bifunctional monomer (B2)} (1) light ester 1,6HX: 1,6-hexanediol dimethacrylate, viscosity: 200 mPa * S (however 23 degreeC) {multifunctional monomer ( B3)} (2) Aronix M-309: Toagosei Co., Ltd. trade name, trimethylolpropane triacrylate, viscosity: 150 mPa · S (however, 23 ° C.)

[Photoinitiator (Ca)] (1) Irgacure 184: trade name, manufactured by Ciba Specialty Chemicals Co., 1-hydroxy-cyclohexyl-phenyl-ketone, melting point: 49 ° C., molecular weight: 204 (2) Irgacure 651: Ciba Specialty Chemicals Co., Ltd., trade name, 2,2-dimethoxy-1,2
-Diphenylethan-1-one, melting point: 67 ° C molecular weight:
256 [Photopolymerization initiator (Cb)] (1) Irgacure 819: trade name, manufactured by Ciba Specialty Chemicals Co., bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, melting point: 133 ° C, molecular weight : 419

[Hindered Amine Light Stabilizer (D)] (1) ADEKA STAB LA-52: Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1 manufactured by Asahi Denka Co., Ltd. , 2,3,4-Butane tetracarboxylate, melting point: 50 ° C or higher, molecular weight: 847 (2) ADEKA STAB LA-77: Asahi Denka Kogyo KK, trade name, bis (2,2,6,6-tetra Methyl-4-pyrrolidyl) sebacate, melting point: 84 ° C, molecular weight: 481

[Ultraviolet Absorber (E)] [Benzophenone-based Ultraviolet Absorber (E1)] (1) SEESORB 102: trade name, 2-hydroxy-4-ocryloxybenzophenone, manufactured by Cypro Kasei Co., Ltd., melting point: 49 ° C. , Molecular weight: 326 [benzotriazole ultraviolet absorber (E5)] (1) SEESORB 704: trade name, 2- (3,5-di-t-phenyl-2-hydroxyphenyl) -2H- manufactured by Cypro Kasei Co., Ltd. Benzotriazole, melting point: 83
° C, molecular weight: 352

[Antioxidant (F)] [Phenolic Antioxidant (F1)] (1) ADEKA STAB AO-70: Tradename of Asahi Denka Kogyo Co., Ltd., triethylene glycol bis [3- (3-t -Butyl-4-hydroxy-5-methylphenyl) propionate], melting point: 80 ° C, molecular weight: 587 [phenol phosphite antioxidant (F4)] (1) ADEKA STAB 260: trade name manufactured by Asahi Denka Co., Ltd. , 4,4-butylidene-bis (3-methyl-6-t-
Butylphenyl-di-tridecyl) phosphite, melting point: -20 ° C, molecular weight: 1240

[Antistatic agent (G)] [Nonionic antistatic agent (G3)] (1) Elegan S-100: trade name of NOF CORPORATION
Structural formula and molecular weight: unknown, melting point: 0 ° C or lower [alkylamine derivative-based antistatic agent (G4)] (2) Bremmer PE-200: trade name, manufactured by NOF CORPORATION, polyethylene glycol monomethacrylate, melting point: 0 ° C Below, molecular weight: 284

The measurements and evaluations of the physical properties of the UV-curable molding material of the present invention before and after curing are as follows. Measurement environment: room temperature: 23 ° C, absolute humidity: 50% R
The test sample was left in a constant temperature and humidity chamber of H for 24 hours or more and then evaluated. The properties before curing were evaluated by viscosity and thixotropy value (TI value). (1) Viscosity: JIS K-6838, unit: mPa.
S, rotor: No. 7, rotation speed: 20 rpm. Measurement temperature: 23 ° C. (50 to 100,000 mPa · S was accepted.) (2) TI value: JIS K-6838, rotor: N
o. 7, rotation ratio: 1/10 rpm. (0.5 to 3 were passed.)

The heat resistance of the cured product depends on the glass transition temperature (T
The evaluation was performed in consideration of the measurement of g) and the result of the heat cycle test. (3) Glass transition temperature: ASTM D696, but thermomechanical method, temperature rising rate: 5 ° C / min, unit: ° C. (Tg =-
30-110 degreeC was set as the pass. ) (4) Heat cycle test: -40 ° C / 1 hour + 85 ° C
/ 1 hour However, 100 cycles. (After 100 cycles,
It was visually judged that the key top was in close contact with the thermoplastic resin sheet. (5) Crack resistance: −40 ° C./1 hour + 85 ° C./1 hour (however, after 100 cycles, the surface of the cured product was visually observed, and it was determined that no cracks were found.) Cured product Mechanical properties were evaluated by flexural strength, flexural modulus and hardness.

(6) Bending strength: JIS K-7171,
Unit: N / mm ² , test speed: 2 mm / min. (10-2
90 N / mm ² was accepted. ) (7) Flexural modulus: JIS K-7171, unit: N /
mm ² , test speed: 2 mm / min. (90-5000N /
mm ² was accepted. (8) Hardness: JIS K-7215, unit: Shore D. (40 to 80 was passed.) The water resistance of the cured product was evaluated by a water absorption rate and an environmental test. (9) Water absorption rate: JIS K-7209, weight increase rate after immersion at 23 ° C / 24 hours, unit:% by weight. (0.05-3
Weight percent was accepted. ) (10) Environmental test: 60 ° C / 95% RH, (however, 24
After 0 hours, it was visually determined that the key top and the thermoplastic resin sheet were in close contact with each other and were not peeled off. )

The antistatic property of the cured product was evaluated by the surface resistivity. (11) Surface resistivity: JIS K-6911, ^{10 10} ~
10 ¹³ Ω / □ was accepted.

The transparency and weather resistance of the cured product were evaluated by total light transmittance and easy fading (color difference) measurement. (12) Total light transmittance: JIS K-7361, unit:
%. (70 to 100% was accepted.) (13) Easy fading (color difference): JIS Z-8722,
Field of view: 2 °, light source: C, but ΔΕ display by CIELAB method. (About 240 hours after sunshine carbon weather meter, the range of ΔΕ of 4 or less was judged as the range that does not easily fade.
Carbon weatherometer is based on JIS A-1415)

[0103]

[Table 2]

[0104]

[Table 3]

[0105]

[Table 4]

[0106]

[Table 5]

From Table 5, the following can be seen. Comparative Example 6
Since the compounding amount of the photopolymerizable monomer is small, the viscosity before curing is out of the preferable condition range, casting is extremely difficult, and the photopolymerization initiators (Ca) and (Cb) are extremely small. Therefore, it does not cure even after irradiation with ultraviolet rays. In Comparative Example 7, since the thixotropy (TI) value before curing is high, it is difficult to cast into a molding die, and the physical properties as a cured product cannot be measured. Comparative Example 8 is a light stabilizer (D), an ultraviolet absorber (E), an antioxidant (F) and an antistatic agent (G).
Therefore, it does not pass the heat cycle test, environmental test, surface resistivity and easy fading (color difference) (ΔE) of the cured product. Comparative Example 9 has a viscosity of 3000 (mPa · S), but has a thixotropy (TI) value of 0.4, so that the composition components are separated, curing failure occurs, and a proper molded product is not obtained. The physical properties as a cured product cannot be measured. Comparative Example 10 has a viscosity of 7500 (mPa · S),
Although the thixotropy (TI) value is within the preferable condition range of 1.2, the compounding amount of the photopolymerization initiator (Ca) is extremely large, so that curing failure occurs, and a neat molded article is not obtained.
The physical properties as a cured product cannot be measured. In Comparative Example 11, the viscosity and the thixotropy (TI) value are within the preferable condition range, but since the compounding amount of the ultraviolet absorber (E) is large, the ultraviolet absorber absorbs the ultraviolet ray even when the ultraviolet ray is irradiated. Since it is uncured, the physical properties of the cured product cannot be measured. In Comparative Example 12, the viscosity and the thixotropy (TI) value are within the preferable condition range, but the light stabilizer (D) is extremely small, and therefore, the heat cycle test of the cured product, the water absorption rate, the environmental test, and the easy fading property ( Color difference) (△ E) does not pass. Comparative Example 1
No. 3, the viscosity and thixotropy (TI) value are within the preferable condition range, and the glass transition temperature, bending strength, bending elastic modulus, and Shore D hardness of the cured product are within the preferable condition range, but the ultraviolet absorber (E ) And antioxidant (F) are small,
Heat cycle test of cured product, water absorption and color difference (△ E)
I do not pass. In Comparative Example 14, the viscosity and the thixotropy (TI) value are within the preferable condition range, and the glass transition temperature, the bending elastic modulus, the Shore D hardness, and the total light transmittance of the cured product are within the preferable condition range, but the antistatic property is obtained. Since the amount of the agent (G) was small, the surface resistivity was out of the suitable condition range, and the test was rejected. From this, Comparative Examples 6, 7, 9, 10 and 11
Cannot be molded as a key top, and Comparative Examples 8, 12, 13 and 14 are key tops, but the characteristics of the cured product are glass transition temperature, flexural strength, flexural modulus and shore. D hardness, heat cycle test, water absorption, environmental test, surface resistivity, total light transmittance and color difference (△
It does not pass either of E), and it turns out that both are not desirable as a key top as a result.

The UV-curable molding material having weather resistance of the present invention has a viscosity of 50 to 100000 mPa · S at room temperature (23 ° C.) and a thixotropy (T) as properties before curing.
I) Since the value is 0.5 to 3, it is possible to cast into a mold having a fine structure. Further, in the properties after curing by ultraviolet irradiation, the glass transition temperature is −30 to 110 ° C., the bending strength is 10 to 290 N / mm ² , and the bending elastic modulus is 90 to 5.
Since the 000 N / mm ² and the Shore D hardness are 40 to 80, the ultraviolet curable molding material does not peel off from the thermoplastic resin sheet after the heat cycle test and the environmental test. When used outdoors, the color difference ΔΕ is small, so the color and design are vivid, the water absorption is low, the total light transmittance is high, and the water resistance, yellowing resistance, crack resistance, and antistatic properties are high. Is excellent. As a result, when a key top for a mobile phone or the like is produced using the weathering-imparting ultraviolet-curable molding material of the present invention, and when this is used for a long time, strength, transparency, color and design as the key top Since the properties can be maintained for a long period of time, the weather resistance imparted ultraviolet-curable molding material of the present invention is extremely excellent.

[0109]

EFFECTS OF THE INVENTION According to the present invention, the productivity and dimensions are equal to or higher than those of the molded product obtained by using the conventional injection molding and the molded product obtained by curing the conventional ultraviolet-curable molding material. It is possible to provide a molded product that maintains accuracy and is excellent in yellowing resistance, water resistance, heat resistance, mechanical properties, etc. Moreover, when the molded product is a push button switch member, it is a filler in the key top. Strong adhesion between the ultraviolet-curable molding material and the thermoplastic resin sheet forming the outer shell of the push button switch member can be realized. In addition, since the easy fading (color difference) ΔΕ value is small, it is difficult to discolor and has excellent antistatic properties, so the product is less prone to dust and dirt, and the color and design are vivid and the water absorption is low. , High total light transmittance, and
We can provide molded products with excellent water resistance, yellowing resistance, and crack resistance, and use adhesives of the same or different substances such as thermoplastic resin sheets, thermosetting resin sheets, plastics and metals. If there is, it can be firmly fixed for a long time.

[Brief description of drawings]

FIG. 1 is a view for explaining a push button switch member which is an example of a molded product.

[Explanation of symbols]

1: Filling material inside the key top 2: Outer shell of push button switch member

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takao Shimizu             406-1 Yoshino-cho, Saitama City, Saitama Prefecture               Shin-Etsu Polymer Co., Ltd. Tokyo factory F term (reference) 4F071 AA22 AA33 AA39 AE05 AE06A                       AE16 AF17Y AF20Y AF25Y                       AF45Y AH12                 4J011 AC04 DA02 FB01 GA05 GB08                       PA27 PA30 PA33 PA43 PA45                       PA46 PB24 PB26 PC02 QA03                       QA09 QA12 QA13 QA17 QA23                       QA24 QA27 QA34 QA39 QB04                       QB12 QB19 QB24 QC03 SA04                       SA22 SA23 SA29 SA32 SA34                       SA64 SA65 SA86 UA01 VA04                       WA07                 4J027 AA03 AB10 AB16 AB17 AB18                       AB23 AB24 AB26 AE02 AE03                       AE06 AG03 AG04 AG23 AG24                       AG27 AG33 AJ01 BA05 BA07                       BA08 BA09 BA10 BA12 BA13                       BA19 BA20 BA26 BA29 CA25                       CA26 CA27 CA29 CB10 CC05                       CD01

Claims (17)

[Claims] 1. A photopolymerizable oligomer (A), a photopolymerizable monomer (B), a photopolymerization initiator (Ca) as a first component and a photopolymerization initiator (Cb) as a second component. The component photopolymerization initiator (Ca) has an absorption wavelength of 220 to 360.
nm, the molar absorption coefficient is 50 or more, and the photopolymerization initiator (Cb) as the second component has an absorption wavelength of 340 to 500 n.
m, the molar absorption coefficient is 100 or more, 0.1 to 900 parts by weight of the photopolymerizable monomer (B) per 100 parts by weight of the photopolymerizable oligomer (A), and photopolymerization initiation of the first component 0.01 to 30 parts by weight of the agent (Ca) and 0.001 to 10 parts by weight of the photopolymerization initiator (Cb) as the second component are mixed, and the viscosity of the liquid is 50 to 30,000 mPa.
S (23 ° C), thixotropy (TI) value of 0.5 ~
2. The ultraviolet-curable molding material, which is 2. 2. The photopolymerizable oligomer (A) comprises an epoxy (meth) acrylate (A1) having a molecular weight of 400 to 20000, a urethane (meth) acrylate (A2) having a molecular weight of 400 to 20000, and a molecular weight of 400 to 20000.
The ultraviolet curable molding material according to claim 1, which is at least one selected from the polyester (meth) acrylate (A3) and the polybutadiene (meth) acrylate (A4) having a molecular weight of 400 to 20,000. 3. The photopolymerizable monomer (B) is at least one selected from a monofunctional monomer (B1), a bifunctional monomer (B2) and a polyfunctional monomer (B3). The ultraviolet-curable molding material as described in 1. 4. The photopolymerization initiator (Ca) as the first component.
, Benzophenone photopolymerization initiator (Ca1), acetophenone photopolymerization initiator (Ca2), thioxanthone photopolymerization initiator (Ca3), benzoin photopolymerization initiator (Ca4), special group photopolymerization initiator ( The ultraviolet curable molding material according to any one of claims 1 to 3, which is at least one selected from Ca5). 5. A photopolymerizable oligomer (A), a photopolymerizable monomer (B), a first component photopolymerization initiator (Ca), a second component photopolymerization initiator (Cb), and a light stabilizer (D). ), Ultraviolet absorber (E), antioxidant (F) and antistatic agent (G)
The first component photopolymerization initiator (Ca) has an absorption wavelength of 220 to 360 nm and a molar absorption coefficient of 50 or more, and the second component photopolymerization initiator (Cb) has an absorption wavelength of 340 to 500 nm, the molar absorption coefficient is 100 or more, the maximum absorption wavelength of the ultraviolet absorber is 350 nm or less, and the photopolymerizable monomer (B) is 0. 1 to 900 parts by weight, the first component of the photopolymerization initiator (Ca) is 0.01 to
30 parts by weight, 0.001 to 10 parts by weight of the second component photopolymerization initiator (Cb) is blended, and the light stabilizer (D), the ultraviolet absorber (E), and the antioxidant (F). The total amount of the antistatic agent (G) is 0.05 based on 100 parts by weight of the photopolymerizable oligomer (A).
-30 parts by weight are mixed, and the viscosity of the liquid is 50-10.
At 0000 mPa · S (23 ° C), thixotropy (T
I) A UV-curable molding material having a weather resistance value of 0.5 to 3. 6. The photopolymerizable oligomer (A) comprises an epoxy (meth) acrylate (A1) having a molecular weight of 400 to 20000, a urethane (meth) acrylate (A2) having a molecular weight of 400 to 20000, and a molecular weight of 400 to 20000.
6. The weather-resistant ultraviolet-curable molding material according to claim 5, which is at least one selected from the polyester (meth) acrylate (A3) and the polybutadiene (meth) acrylate (A4) having a molecular weight of 400 to 20,000. 7. The photopolymerizable monomer (B) is at least one selected from a monofunctional monomer (B1), a bifunctional monomer (B2) and a polyfunctional monomer (B3). The weather-resistant imparted ultraviolet-curable molding material as described in 1. 8. A photopolymerization initiator (Ca) as the first component.
, Benzophenone photopolymerization initiator (Ca1), acetophenone photopolymerization initiator (Ca2), thioxanthone photopolymerization initiator (Ca3), benzoin photopolymerization initiator (Ca4), special group photopolymerization initiator ( It is at least 1 type selected from Ca5), The weather resistance imparting ultraviolet-curable molding material in any one of Claims 5-7. 9. The weather-resistant ultraviolet-curable molding material according to claim 5, wherein the light stabilizer (D) is at least one selected from hindered amine light stabilizers. 10. The ultraviolet absorber (E) is a benzophenone type ultraviolet absorber (E1), a salicylate type ultraviolet absorber (E2), a cyanoacrylate type ultraviolet absorber (E3), a nickel complex salt type ultraviolet absorber (E4). ), A benzotriazole type ultraviolet absorber (E5) and a benzoate type ultraviolet absorber (E6), at least one selected from the group consisting of: 11. The antioxidant (F) is a phenol-based antioxidant (F1) or a phosphite-based antioxidant (F).
At least one selected from 2), a thioether antioxidant (F3) and a phenol phosphite antioxidant (F4). . 12. The antistatic agent (G) is a cationic antistatic agent (G1), an anionic antistatic agent (G2),
At least one selected from nonionic antistatic agents (G3), alkylamine derivative antistatic agents (G4), fatty acid ester antistatic agents (G5) and terminal unsaturated antistatic agents (G6). The weather-resistant imparted ultraviolet-curable molding material according to any one of 5 to 11. 13. A UV-curable molding material or a weathering-provided UV-curable molding material according to claim 1, which is cast into a molding die made of a thermoplastic resin sheet and irradiated with UV rays. A method for curing an ultraviolet-curable molding material or a weather resistance-imparting ultraviolet-curable molding material, characterized in that the curing is carried out. 14. The absorption wavelength of the first component, a photopolymerization initiator (Ca), is 300 n using an ultraviolet cut filter.
The method for curing an ultraviolet curable molding material or a weather resistance imparting ultraviolet curable molding material according to claim 13, wherein a short wavelength of m or less is cut and cured. 15. A glass transition temperature (Tg) after curing of the ultraviolet curable molding material is −20 to 120 ° C., a bending strength is 10 to 300 N / mm ² , and a bending elastic modulus is 90 to 7000.
N / mm < ² > and Shore D hardness are 50-95, The molded article obtained by hardening | curing the ultraviolet curable molding material in any one of Claims 1-4. 16. A glass transition temperature (Tg) after curing of a weather resistance imparted ultraviolet-curable molding material is −30 to 110 ° C.,
Flexural strength 10-290 N / mm ² , flexural modulus 90
A molded article obtained by curing the weather-resistant ultraviolet-curable molding material according to any one of claims 5 to 12, which has a hardness of 5,000 N / mm ² and a Shore D hardness of 40-80. 17. The molded product according to claim 15, which is a push button switch member.