JPS6049598B2 - Laminated molded product - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention has an outer coating layer made of a crosslinked curable resin having excellent surface hardness, scratch resistance, abrasion resistance, surface gloss, transparency, and weather resistance, and The present invention relates to a laminate with improved adhesion between the layer and the thermoplastic base resin layer.

More specifically, the present invention relates to a laminate molded product including an outer coating layer made of a transparent crosslinked curable resin, an intermediate adhesive layer made of a modified ethylene-propylene copolymer, and a base resin layer made of a thermoplastic resin. In general, thermoplastic resins, regardless of whether they are transparent or opaque, have lower surface hardness than metals, glass, etc., and are more susceptible to scratching and friction, so their surfaces are easily scratched, and they also have poor surface gloss and weather resistance. is also inferior.

In particular, polyolefins such as polyethylene, polypropylene, poly4-methyl-1-pentene, polystyrene, α-olefin copolymers containing different types of α-olefins as main components, polymethyl methacrylate, and polycarbonate are molded from any thermoplastic resin. The major disadvantages of these molded bodies are that they have poor surface hardness, abrasion resistance, scratch resistance, and surface gloss, and these molded bodies are used for limited applications in limited fields. It was just that. Many proposals have been made as methods for improving the above-mentioned hole spots in molded bodies made of these thermoplastic resins.

Most of these methods involve coating the surface of these molded bodies with an outer coating layer made of a crosslinked curable resin. Among these film layer forming elements, resins or resin forming components are specifically silicone monomers, silicone oligomers, or compositions of these components and various polymers (as disclosed in JP-A-54-622). , JP-A-54-62267, JP-A-54-62268, JP-A-54-62
No. 999, U. S.P. 4O9884O specification,
JP-A-52-15426, Ger. Offen.
Specification of 285l22, JP-A-54-50041, JP-A-54-864-Gin, JP-A-53-90339
No. 72077, Japanese Patent Application Laid-Open No. 1983-72077,
．． Publication No. 4627, Japanese Unexamined Patent Publication No. 138476/1983,
Japanese Patent Application Laid-open No. 51-97634, U. S. P. 397l
No. 872, Ger. Offen. 2456565
No. Specification, G. B. 2Ol86 Specification, U. S. P
．． 399899l specification, JP-A-53-47466, JP-A-52-138565, JP-A-Sho 50-
34033! Publication No. 52-82433,
Japanese Patent Application Laid-Open No. 52-128155, U. S. P. 397
187), a resin composition consisting of methylolmelamine and other curing components (Japanese Patent Application Laid-open No. 48-801)
No. 76, JP-A-51-126265, JP-A-49-36814, JP-A-51-119038
No. 51-11903 Unagi Publication, Belg. 8
No. 43l98 Specification Ger. Offen. 245656
Specification No. 5, U. S. P. 4Ol894l) and polyfunctional acrylic carboxylic acid ester monomers (Japanese Patent Publication No. 53-43553,
-43984, JP 53-102936, JP 53-104638, JP 53-25
354, etc.) are known. Even if a film layer made of these crosslinked curable resins is formed on the thermoplastic resin molded product, the adhesion between the film and the thermoplastic resin base layer is not good, so these laminate molded products do not have the film layer. The disadvantage is that it is easy to peel off. Furthermore, methods are known in which various treatments are applied to the surface of the base resin molded body in order to improve these drawbacks. For example, methods such as cleaning treatment using an organic solvent, surface treatment using corona discharge, and surface treatment using a primer have been proposed. but,
Even with these surface treatments, it was not possible to bond the base/layer made of the thermoplastic resin and the coating layer made of the crosslinked curable resin sufficiently for practical use. The inventors have determined surface hardness, scratch resistance, abrasion resistance, surface gloss,
To provide a laminate molded product having an outer coating layer made of a crosslinked and curable resin having excellent transparency and weather resistance, and having improved adhesion between the coating layer and a base resin layer made of a thermoplastic resin. As a result of studying the above, it was discovered that the above object could be achieved by applying an intermediate adhesive layer made of a modified ethylene-propylene copolymer with specific properties between the two layers to form a laminated molded product, and the present invention was achieved. .

That is, the present invention provides an outer coating layer made of A transparent crosslinked curable resin, Bα,β monounsaturated dicarboxylic acid, its anhydride, or its ester component graft copolymerized,
An intermediate adhesive layer made of a modified ethylene-propylene copolymer whose saponification value is in the range of 5.5 to 180 mg/g and whose [η] is in the range of 0.3 de/g or more, and C thermoplastic It is a laminated molded product consisting of a base resin layer made of resin.

The base resin layer C constituting the laminate molded product of the present invention is a molded product made of a thermoplastic resin, and the shape thereof may be a film, sheet, plate, or any other shape.

Specifically, the thermoplastic resin constituting the base resin layer includes polyolefins such as an α-olefin homopolymer or a copolymer containing α-olefin as a main component, polyacrylic acid ester resin, polycarbonate resin, Examples include polyester resin and polyamide resin. In these thermoplastic resin houses, the base resin layer C constituting the laminate molded product of the present invention is preferably a polyolefin, a polyacrylic acid ester resin, or a polycarbonate resin, and particularly preferably a polyolefin. Specifically, the polyolefins include ethylene, propylene, 1-butene, 1-
hexene, 4-methyl-1-pentene, 1-octene,
homopolymers of α-olefins such as 1-decene;
- A copolymer consisting of a mixture of two or more olefins, or a copolymer containing the above α-olefin as a main component, and containing lower aliphatic vinyl phonates such as vinyl acetate and vinyl propionate, methyl acrylate, metal salts of acrylic acid, and methacrylate. Examples include copolymers containing a small amount (for example, 30 mol % or less) of other components such as acrylic carboxylic acid esters such as methyl acid, metal salts of methacrylic acid, and salts of acrylic carboxylic acids.

Among these polyolefins, polyolefins having crystallinity are usually used. Specific examples of the polyacrylic carboxylic acid ester resin include homopolymers or copolymers of acrylic carboxylic acid ester monomers such as methyl acrylate, ethyl acrylate, ethyl methacrylate, and ethyl methacrylate. can.

Among these polyacrylic carboxylic acid ester resins, polymethyl methacrylate is preferably used in the thermoplastic resin base resin layer of the present invention. Specific examples of the polycarbonate resin include bisphenol A1 polycarbonate, polyacrylic glycol carbonate, and the like.

Specifically, the polyester resin includes polyethylene terephthalate, polytetramethylene terephthalate,
Examples include bisphenol A1 isophthalic acid/terephthalic acid copolycondensate and oxybenzoic acid condensate.

Specific examples of the polyamide resin include nylon 6, nylon 6,6, nylon 10, and nylon 12.

In addition to the above resins, polyacetal, polystyrene,
Examples include acrylonitrile, styrene copolymer, acrylonitrile, butadiene-styrene copolymer, polysulfone resin, polyphenylene oxide, modified polyphenylene oxide, polyphenylene sulfide resin, and polyethersulfone resin.

The intermediate adhesive layer B constituting the laminate molded product of the present invention has α, β
It is obtained by graft copolymerization of a monounsaturated dicarboxylic acid, its anhydride, or its ester component, and its saponification value is 5.5.
It is made of a modified ethylene/propylene copolymer whose [η] is in the range of 0.3 to 180 mg/g and 0.3 de/g or more.

The composition ratio of ethylene component units and propylene component units of the modified ethylene/propylene copolymer is such that the ethylene content is usually 25 to 50 mol%, preferably 25 to 45 mol%, particularly preferably 30 to 40 mol%. The range and propylene content are usually in the range from 50 to 75 mol%, preferably from 55 to 72 mol%, particularly preferably from 60 to 70 mol%. The crystallization rate of the modified ethylene/propylene copolymer as measured by X-ray diffraction is usually 20% or less, preferably in the range of 2 to 20%, particularly preferably in the range of 5 to 18%. In addition, the modified ethylene/propylene copolymer was heated at 135°C in a decalin solution.
[η] measured in is required to be 0.3 df/g or more, preferably in the range of 0.4 to 20 C1'/g, particularly preferably in the range of 0.5 to 10 d'/g. The modified ethylene. The grafting component of the propylene copolymer is α,β monounsaturated dicarboxylic acid, its anhydride, or its ester, and the preferred grafting component is α,β monounsaturated dicarboxylic acid, its anhydride, or its ester.
β-monounsaturated dicarboxylic acid or its anhydride.

Examples of the α,β-monounsaturated dicarboxylic acid or its anhydride include maleic acid, maleic anhydride, citraconic acid, citraconic anhydride, fumaric acid, and mesaconic acid. suitable. Examples of the esters of α,β monounsaturated dicarboxylic acids include mono-lower alkyl esters and di-lower alkyl esters of the α,B monounsaturated dicarboxylic acids. Here, specific examples of lower alkyl groups include methyl group, ethyl group, propyl group, isopropyl group,
Examples include butyl group. These α and β
Among the esters of monounsaturated dicarboxylic acids, monolower alkyl maleic acid esters are preferred. The modified ethylene. The grafting ratio of the grist component of the propylene copolymer needs to be in the range of 5.5 to 180 mg/g, more preferably 10 to 140 mg/g as the saponification value of the modified ethylene/propylene copolymer.
9/g, particularly preferably from 30 to 120 m9
/g range.

If the saponification value is less than 5.5 m / g, the adhesive strength between the base resin layer C and the outer coating layer A described below will be poor,
A laminated molded product with sufficient strength cannot be obtained. Furthermore, if the saponification value is greater than 180 m9/g, the [η] of the graft-modified copolymer becomes small and the cohesive force decreases.
The water resistance of the outer scarlet membrane layer A deteriorates. The thickness of the intermediate adhesive layer made of the modified ethylene/propylene copolymer is arbitrary, but is usually 15μ or less, preferably 0.001 to 1
0μ, particularly preferably in the range of 0.03 to 2μ.

As a method for laminating the intermediate adhesive layer made of the modified ethylene/propylene copolymer on the base resin layer C, an organic solvent solution or aqueous suspension of the modified ethylene/propylene copolymer is applied and then dried. For example, a method or a method of heat-pressing a thin film or sheet of the modified ethylene-propylene copolymer can be exemplified.

Before laminating the modified ethylene/propylene copolymer layer on the base resin layer C, the surface of the base resin layer is usually washed with various solvents, an alkaline aqueous solution, a surfactant, or the like, if necessary. Surface treatments such as ultrasonic cleaning, electrolytic cleaning, and blasting can be performed, and more specifically, sandblasting, acid or alkali etching, flame treatment, corona discharge treatment, arc discharge treatment, glow discharge treatment, Examples include plasma discharge treatment and chemical conversion treatment. The outer coating layer A constituting the laminate molded product of the present invention is made of a transparent crosslinked curable resin, and forms a laminate molded product with the thermoplastic resin layer C via the intermediate adhesive layer B. There is. In order to improve properties such as surface hardness, abrasion resistance, and scratch resistance of the transparent cross-linked cured resin layer that constitutes this outer coating layer, the inorganic filler described below is added to the extent that does not impair transparency. It's okay to stay. Examples of the transparent cross-linked curable resin constituting the outer coating layer include a transparent cross-linked curable resin made of a polyfunctional acrylic carboxylic acid ester component unit or a transparent cross-linked curable resin made of a silicone resin. can do. Among these transparent cross-linked curable resins, cross-linked curable resins composed of polyfunctional acrylic carboxylic acid ester component units are preferred, and among these, cross-linked curable resins composed of polyfunctional methacrylic ester component units are preferred. It is particularly preferable that there be. Further, it is particularly preferable that the outer coating layer is a transparent crosslinked curable resin formed from a polyfunctional acrylic carboxylic acid ester component unit and a finely powdered inorganic filler. Although the thickness of the outer coating layer is arbitrary, it is usually in the range of 0.1 to 30P1, preferably 0.5 to 20μ, particularly preferably 1 to 18μ. One of the transparent cross-linked curable resins constituting the outer coating layer, the transparent cross-linked curable resin composed of polyfunctional acrylic carboxylic acid ester component units, is a transparent cross-linked curable resin composed of polyfunctional acrylic carboxylic acid ester component units. It is made by polymerizing monomers or prepolymers and crosslinking and curing them.

The crosslinking-curing type polymerization reaction can be caused by radical polymerization, photopolymerization, radiation polymerization, etc. in the presence of a polymerization initiator. Here, the polyfunctional acrylic carboxylic acid ester monomer has two or more acrylic carboxylic acid ester units in one molecule,
Therefore, it is a compound having two or more acrylic unsaturated carbons or carbon bonds in one molecule, and may contain other unsaturated carbons or carbon bonds in some cases. Furthermore, the prepolymer of the polyfunctional acrylic carboxylic acid ester monomer is the prepolymerization of the polyfunctional acrylic carboxylic acid ester by thermal polymerization, radical polymerization, photopolymerization, etc.
These are polymers that have been polymerized, for example, into a dimer to 250-mer by radiation polymerization or the like, or a mixture thereof. Specifically, the acrylic carbonic acid component units constituting these polyfunctional acrylic carboxylic acid ester monomers or their prepolymers include acrylic acid,
Methacrylic acid, 2-ethyl acrylic acid, 2-propylacrylic acid, 2-isopropylacrylic acid, 2-butyl acrylic acid, 2-pentylacrylic acid, 2-hexyl acrylic acid, atropaic acid, 3-methylacrylic acid, 3-ethyl acrylic acid Examples include 3-propylacrylic acid, 3-isopropylacrylic acid, and the like. Among the polyfunctional acrylic carboxylic acid ester component units, polyfunctional acrylic ester component units and polyfunctional methacrylic ester component units are preferred. Specifically, the polyfunctional acrylic carboxylic acid ester monomer constituting the transparent crosslinked curable resin includes, for example, ethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, 1 , 3-butylene diol diacrylate, 1,6-hexane diol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, tetramethylolethane triacrylate, tetramethylolmethane tetraacrylate, isopropyl diglycidyl Ether diacrylate, 2-propanol diglycidyl ether diacrylate, glycidol diacrylate, glycerin diacrylate, glycerin triacrylate, xylylene glycol diacrylate, hydroquinone diacrylate, resorcine diacrylate, cyclohexanedimethanol diacrylate, etc. , as a methacrylic acid ester monomer,
For example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol. Dimethacrylate, tetraethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, neopentyl glycol dimethacrylate, dipropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethylolethane trimethacrylate, tetramethylolethane trimethacrylate, tetramethylolmethanetetramethacrylate, ethanediglycidyl
Examples include ether dimethacrylate, 2-propanol diglycidyl ether dimethacrylate, glycidol dimethacrylate, glycerin dimethacrylate, glycerin trimethacrylate, xylylene glycol dimethacrylate, hydroquinone dimethacrylate, resorcin dimethacrylate, and cyclohexanedimethanol dimethacrylate.

These monomers may be used alone or in combination of two or more in any proportion. The polyfunctional acrylic carboxylic acid ester monomer or its prepolymer (hereinafter referred to as polyfunctional acrylic crosslinked resin raw material).

), the method for forming the outer coating layer of the transparent cross-linked curable resin on the intermediate adhesive layer made of the above-mentioned ethylene-propylene copolymer includes an intermediate adhesive layer made of the modified ethylene-propylene copolymer On the surface of the adhesive layer, a solution composition or suspension consisting of the polyfunctional acrylic crosslinked resin raw material, a polymerization initiator, and optionally the finely powdered inorganic filler described below, and further a solvent as required. A method is employed in which a crosslinking and curing reaction is caused by applying the composition, drying it, and then heating it or irradiating it with light, ionizing radiation, or radiation. The method for preparing the solution composition or suspension composition includes mixing the above-mentioned raw materials and using a roll, Panbury mixer, ball mill, attriter, whitsupah, oaks mixer, desolver, homogenizer, colloid mill, sand mill, A uniformly dispersed or dissolved composition can be obtained by a kneading operation using a vibrating mill, mixer, stirring mixing tank, or the like. Here, as the polymerization initiator blended into the composition, radical initiators such as organic peroxides, inorganic peroxides, nitrile compounds, azo compounds, diazo compounds, sulfinic acid compounds; acetophenone compounds, benzoin Examples include photosensitizers such as type compounds; ionic initiators such as hydroxy acids, Lewis acids, and alkali metals. The blending ratio of these polymerization initiators is usually 0.001 to 2 parts by weight per 10 parts by weight of the polyfunctional acrylic crosslinked resin raw material.
part by volume, preferably in the range of 0.005 to 1 part by volume. The method for applying the composition containing the polyfunctional acrylic crosslinked resin raw material onto the intermediate adhesive layer made of the modified ethylene-propylene copolymer includes a brush coating method;
Conventionally known methods such as a spray method, a dipping method, a percoat method, a roll coater method, a spin coater method, and a gel coat method are employed. In addition, the method for drying the paint film is as follows:
Examples include a natural drying method, a forced drying method using a carrier gas, and a heating drying method using an infrared oven, a far-infrared oven, a hot air oven, and the like. In addition, the above-mentioned coating film is cured,
Examples of methods for forming the film include a method of crosslinking and curing with light, a method of crosslinking and curing with heat, a method of crosslinking and curing with electron beams, a method of crosslinking and curing with radiation, and the like. Among the exemplified methods, a method suitable for each component of the coating composition is adopted. In order to increase the thickness of the coating, it is also possible to adopt a method of repeatedly applying, drying, and heating crosslinking and curing the polyfunctional acrylic crosslinked resin raw material. Further, as the cross-linked curable resin made of silicone resin, which is one of the transparent cross-linked curable resins constituting the outer coating layer, any cross-linked curable silicone resin that has the effect of improving surface hardness may be used. can be used.

The transparent crosslinked curable silicone resin can be formed by thermal polycondensation of an organic silicon compound monomer capable of producing it. Here, specifically, the organosilicon compound monomer capable of producing a crosslinked curable silicone resin includes:
For example, organotrialkoxysilanes, tetraalkoxysilanes, organotriacyloxysilanes, vinyltrialkoxysilanes, aminoalkylalkoxysilanes, epoxyalkylalkoxysilanes, silicon-functional polysiloxanes, carbon-functional polysiloxanes, or partially hydrolyzed products thereof. Examples include one or a mixture of two or more of oligomers or oligomers. More specifically, organotrialkoxysilanes include methyltrimethoxysilane, ethyltrimethoxysilane, n
-butyltrimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, etc.; tetraalkoxysilanes include tetramethoxysilane, tetraethoxysilane, etc. , tetrapropoxysilane, tetrabutoxysilane, etc.; Examples of organotriacyloxysilane include methyltriacetoxysilane, ethyltriacetoxysilane, isopropyltriacetoxysilane, phenyltriacetoxysilane, vinyltriacetoxysilane, methyltripropionyloxysilane, ethyltriacetoxysilane, etc. Examples of vinyltrialkoxysilanes such as propionyloxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, and vinyltributoxysilane; examples of aminoalkylalkoxysilanes include aminomethyltriethoxysilane, N-β-aminoethylaminomethyltrisilane, etc. Epoxyalkylalkoxysilanes such as methoxysilane and γ-aminopropyltriethoxysilane include γ
-Glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, etc., silicon-functional polysiloxanes include 1,3-dimethoxytetramethyldisiloxane, 1,5-dimethoxyhexamethyltrisiloxane, 1, 7-dimethoxyoctamethyltetrasiloxane, 1,9-dimethoxydecamethylpentasiloxane, 1,3-diethoxytetramethyldisiloxane, 1,5-diethoxyhexamethyltrisiloxane, 1,7-diethoxyoctamethyltetrasiloxane ,
1,9-diethoxydecamethylpentasiloxane, 1,
Examples of carbon-functional polysiloxanes such as 3-dimethoxyhexaethyltrisiloxane include 1,3-bis(hydroxymethyl)-1,1'',3,3-tetramethyldisiloxane. Oligomers or partial hydrolysates of organosilicon compounds can also be used as silicone resin raw materials. From the silicone resin raw materials, the above-mentioned As a method for forming an outer coating layer of a transparent crosslinked curable resin, on the surface of the intermediate adhesive layer made of the modified ethylene-propylene copolymer, the silicone resin raw material and, if necessary, the finely powdered inorganic powder described below are applied. A composition consisting of a filler and, if necessary, a solvent.
After coating and drying, a transparent crosslinked cured film is formed by heat treatment.

Here, as a method for applying the composition containing the silicone resin raw material onto the intermediate adhesive layer made of the modified ethylene-propylene copolymer, the same method as described above can be employed. It can also be used as a method of drying the applied coating film.
A method similar to that described above can be employed. By heat-treating the laminate molded body coated with the composition containing the silicone resin raw material in this way, the coating film can be crosslinked and cured, and a crosslinked and cured outer coating can be formed. The heating temperature at that time varies depending on the type of the thermoplastic resin constituting the base resin layer of the laminate molded product and the modified ethylene-propylene copolymer constituting the intermediate adhesive layer, but is usually 40 to 150℃.
'C1 is preferably in the range of 50 to 130°C and lower than the softening temperature of the resins of both layers. If treated at temperatures above the softening temperature, either of the layers may be deformed. The time required for heat treatment is usually 3
The duration is approximately 1 hour, preferably 1 to 3 hours. In order to increase the thickness of the outer coating layer made of the silicone resin, a method may be adopted in which the silicone resin raw material is repeatedly applied and dried, and then heated. If necessary, a fine powdery inorganic filler may be blended into the outer coating layer A made of the transparent crosslinked curable resin to the extent that the transparency of the coating is maintained.

The average particle size of the fine powder inorganic filler is arbitrary as long as it is in the form of a powder, but it is usually 1 mμ to 10μ.
, preferably in the range of 1.5 mμ to 1μ. In order to maintain the transparency of the outer coating layer A, the refractive index of the finely powdered inorganic filler is usually 1.40 to 1.60,
Preferably it is in the range of 1.42 to 1.58. Specifically, such fine powder inorganic fillers include glass powder, mica, glass beads, glass flakes, diatomaceous earth, anhydrous silica, hydrated silica, silica stone, silica sand, quartz,
Examples include kaolinite, montmorillonite, sericite, talc, chlorite, pottery stone, and feldspar. In addition, the surface of these finely powdered inorganic fillers can be coated with alkyl carboxylates, silane couplers, titanium couplers,
Those surface-treated with C'2Si(CH3)2, alcohol, etc. can also be used in the same manner. Furthermore, colloidal silica, methanol silica sol, ethanol silica sol, isopropanol silica sol, etc. in which the inorganic filler is suspended in water or alcohol can also be used. Among these fine powder inorganic fillers, blending fine powder silica improves the surface hardness, scratch resistance, and abrasion resistance of the outer coating layer, and does not impair transparency and surface gloss. Particularly preferred, especially Ce2Si(
It is preferable to blend finely powdered silica or alcohol silica sol surface-treated with CH3)2. The blending ratio of these fine powder inorganic fillers is as follows:
The amount is usually 5 to 25 parts by volume, preferably 5 to 15 parts by volume per 00 parts by weight. The laminate molded product of the present invention includes, in addition to the three layers of the outer coating layer A, the intermediate adhesive layer B, and the base resin layer C, the base resin layer C
There is no problem even if a layer made of another material is laminated on the outside via the .

The laminate molded product of the present invention is used for various purposes.

Specifically, examples include lighting panels, sky domes, solar water heater panels, glass boxes, watch glasses, various lenses such as glasses, cameras, and contact lenses, optical prisms, blood bags, and coffee. Manufacturer's shower domes, coffee dispensers, water tanks, covers for lighting equipment, covers for stereo devices such as players, dials and covers for various meters, cover level sensors for car headlamps and taillamps, shatterproof films and separation plates for glass. Various types of films such as molded films, insulating films, agricultural films, optically regenerated video discs, viewing windows for various devices such as clothes dryers, electric washers, dryers, and oil tanks, windshields for motorcycles, jives, motorboats, etc. Automobile glass (windshield, rear window, opera window, triangular window, sunroof), window glass for greenhouses, houses, aquariums, etc., tableware, mirrors, various containers such as oil bottles and cosmetic bottles, relay cases,
Fuse boxes, motorcycle side covers and mudguards, fenders, curtains, screens, tablecloths, waterproof and moisture-proof films, tarpaulins, insulation films, floor tiles, floor sheets, doors, table boards, wall tiles, countertop decorative boards, Shelves, wall sheets, wallpaper, furniture, lightweight wallboards, tableware, chairs, bathtubs, toilets, refrigerated cars, wall panels,
Water supply and drainage pipes, raceways, ducts, curtain rods, rain gutters,
Insulation materials, waterproof coatings, curtains, window frames, automobile foils, various containers, automobile interior materials, vanity tables, flower boxes, particle boards, roof tiles, rain shutters, shutters, waterproof pans,
Examples include vibrators, wiring materials, gear cams, knobs, solenoid valve frames, fans, internal springs, pumpers, brakes, etc.In addition to the above, we also produce home appliances, automobile parts, vending machine parts, civil engineering and construction materials, and general industrial materials. It can also be used for office information equipment, electronic parts, packaging materials, sports equipment, medical equipment, and nuclear power related parts.Next, the present invention will be specifically explained with reference to Examples.

In addition, in the main text of the specification or the examples, evaluation was performed by the following method. (1) Saponification value Weigh accurately about 0.5 g of a sample into a flask, add 50 cc of p-xylene (150 cc of 5DMS), and heat to dissolve.

Next, 25 cc of N/2 potassium hydroxide was added, a reflux condenser was attached, and the mixture was heated to 135°C for 1 hour. Then, cool to room temperature, use phenolphthalein as an indicator, and
Perform back calibration with dihydrochloric acid standard solution. A blank test was also conducted, and the saponification value was determined using the following formula. (2) Refractive index A sufficiently dried inorganic substance is placed in a liquid with a known refractive index for 2W.
After adding t% and thoroughly dispersing, visually check the transparency.

The refractive index is set to be the same as that of the most transparent liquid. (3
) Photographs are taken using a particle size transmission electron microscope.

The diameter of particles of 3,000 to 500 pieces of bait is measured and the arithmetic mean thereof is determined.

(4) Taper wear Measurement was performed according to ASTM D-1044.

(5) Dropping sand abrasion 800 g of silicon carbide abrasive material is dropped onto the coating according to the method of JIST 8l47-1975.

Wear resistance is determined by the difference in haze level (HAZE) before and after the test. The smaller the number, the better the wear resistance. Note that the HA pressure was measured according to ASTM DlOO3. In addition, when the resin layer of the substrate was not a transparent resin, the judgment was made visually.
(6) Adhesion The test was conducted according to the cross-cut test in JIS K54OO-1979.

Judgment is indicated by how many out of 1 (1) pieces are glued together. (7) Denran E Measured according to ASTMDlOO3.

(8) GlOSS Measured according to ASTM D523.

(9) Pencil hardness Measured according to JISK565l.

(No. 11 weather resistance test piece was held in a Sunsia In Weathermeter for 4 (1) hours, and changes in the appearance of the outer coating layer were visually observed to evaluate adhesion.

(11) Water resistance After immersing the test piece in pure water at 40°C for 240 hours, changes in the appearance of the outer coating layer were visually observed to evaluate adhesion.

(12) Hot water resistance After immersing the test piece in pure water at 80°C for 240 hours, changes in the appearance of the outer coating layer were visually observed to evaluate adhesion.

(13) Heat Resistance After holding the test piece in a gear type aging device of 80'C for 24 (2) minutes, changes in the appearance of the outer coating layer were visually observed to evaluate adhesion.

(14) Heat cycle resistance The test piece was kept in an air-open environment at 80°C for 2 hours, then left at room temperature for 1 hour, and then placed in a cold room at -30°C for 2 hours.
Hold for an hour and then leave at room temperature for 1 hour.

This cycle was repeated 10 times, and changes in the appearance of the outer coating layer were visually observed and adhesion was evaluated. (15)
After immersing the test piece in petroleum benzine at 25°C for 24 hours,
The appearance was observed and the adhesion was evaluated.

Reference Example 1 As an ethylene/propylene copolymer, propylene content is 67 mol%, decalin [η] at 135°C
is 2.05 de/G. Crystallinity by X-ray diffraction is 12%
Copolymer 3k9 was added to 10' of toluene, and the system was purged with nitrogen for 1 hour.

After raising the temperature of the system to 145°C and completely dissolving the copolymer in toluene, while stirring the system, 3822 g of maleic anhydride and 175 g of di-tert-butyl peroxide were added from separate feed ports for 4 hours. After stirring was continued for 2 hours at 145°C as a post-reaction, the system was gradually cooled to room temperature.After cooling, a portion of the reaction liquid was collected and poured into a large amount of acetone. According to
A gram-like modified copolymer was precipitated.

The obtained precipitate was separated in a furnace, washed repeatedly with large amounts of acetone, and then dried at room temperature for two days and nights. The saponification value of the modified copolymer was 60 mg/g, the crystallinity was 6.5°C, and [η] was 0.7 when measured in decalin at 135°C.
It was 6C1e/g. After the completion of the graft modification reaction, the reaction solution was further diluted with toluene until the concentration of the maleic anhydride graft modified ethylene/propylene copolymer was 20 g.
A solution of /e was prepared.

Reference Example 2 In a desolver, 5 parts by weight of benzoin ethyl ether, 7 parts by weight of n-butanol, and 10 parts by weight of 1,6-hexanediol dimethacrylate were charged, and while stirring at high speed at room temperature, the average particle size was is 20n1μ, and the refractive index is 1.
45 fine powder silica manufactured by Tamoto Aerosil Co., Ltd., trade name R-
972) was gradually added and thoroughly stirred until a uniform dispersion was obtained.

After that, the attritor filled with steatite balls (
The mixture was transferred to a tank (manufactured by Mitsui Miike Seisakusho) and mixed for 2 hours by rotating an agitator at 150 r'Pm while cooling the tank with water. Thereafter, a marked weight part of n-butanol was added, and after further mixing for 1 min, the mixture was taken out from the attritor and used as a coating composition [A1].
Example 1 Polypropylene [Mitsui Petrochemical Industries K. K. An injection square plate made from Mitsui Petrochemical Polypropylene SJ3l3 (manufactured by Mitsui Petrochemical Co., Ltd., trade name: Mitsui Petrochemical Polypropylene SJ3l3) was immersed in 1,1,1-trichloroethane vapor.
After exposing for a minute, the sample prepared in Reference Example 1. The injection square plate was immersed in a water-maleic acid graft modified ethylene◆propylene copolymer solution for 20 seconds and slowly pulled up.

After drying at room temperature for 5 minutes, heating was performed at 80'C for 3 minutes. The thickness of the intermediate adhesive layer obtained here was 1.5 μm. Next, the coating composition [A1] prepared in Reference Example 2
After immersing the test piece in the water for 3 hours and slowly pulling it out,
It was dried for 5 minutes at room temperature under a nitrogen stream, and cured by irradiating it with a high-pressure mercury lamp in a nitrogen atmosphere. The mixed thickness of the resulting outer coating layer was 10 microns. Table 1 shows the physical properties of this laminate. Examples 2 to 3 Based on the method of Reference Example 1, maleic anhydride graft modified ethylene/propylene copolymer solutions with different saponification values were synthesized, and the thickness of the intermediate adhesive layer was the same as in Example 1. I made it so that

Thereafter, a laminate molded body was produced in the same manner as in Example 1.
Its physical properties are shown in Table 1. Comparative Example 1 In Reference Example 1, except that the maleic anhydride graft modified ethylene/propylene copolymer solution [8] was not used,
A laminate molded body was produced in the same manner as Matsutaku.

The physical properties are shown in Table 1. Comparative Examples 2 to 3 According to the method of Reference Example 1, maleic anhydride graft-modified ethylene-propylene copolymer solutions having different saponification values were synthesized.

A laminate molded product was produced in the same manner as in Example 1, except that the intermediate layer was treated to have the same thickness as in Example 1.
Its physical properties are shown in Table 1. Comparative Example 4 In Example 1, the maleic anhydride graft modified ethylene/propylene copolymer solution used to form the intermediate adhesive layer was replaced with a commercially available chlorinated propylene primer (
A laminate molded product was produced in the same manner as Matsutaku except that the material was changed to RB-291 (manufactured by Memoto B Chemical Co., Ltd.).

Its physical properties are shown in Table 1. Examples 4-5 100 parts by weight of triethylene glycol dimethacrylate, 2 parts by weight of benzoin methyl ether, methanol silica sol (manufactured by Nissan Chemical, 30% methanol suspension of anhydrous silica with an average particle size of about 15 mμ and a refractive index of about 1.50) ) 13 parts by volume of heel and 4 parts by volume of n-butanol were placed in a mixing container equipped with a stirring device, and stirred and mixed at 36 [Pm] for 3 minutes while cooling with water to prepare the coating composition [A2]. Prepared.

Next, an ethylene◆propylene copolymer with a propylene content of 60 mol% and decalin at 135°C
η] is 1.93df/G. ．． 240 mL of toluene was added to 75 g of a copolymer with a crystallinity of 12% as determined by X-ray diffraction, and the inside of the pressurized reactor was replaced with nitrogen for 1 hour.

The temperature of the system was heated to 145°C to completely form the copolymer. After dissolving in maleic anhydride 6.9g/30ml, toluene and di-tert-butyl peroxide 2.4g/3
Each solution of 0Tf1.1 toluene was continuously added dropwise over 4 hours. After the completion of the dropwise addition, the reaction was carried out at 145°C for 2 hours, and the saponification value was 53 m9/g, the crystallization rate was 5.5%, and the results were measured in the same manner as above. A maleic anhydride graft-modified ethylene-propylene copolymer solution (25
0 g/'-toluene) was obtained. This maleic anhydride graft modified ethylene/propylene copolymer solution was diluted with toluene to a predetermined concentration, intermediate adhesive layers of different thicknesses were prepared in the same manner as in Example 1, and coating compositions [~]
A laminate molded body was prepared using the same method as in Example 1.
These physical properties are shown in Table 2. Ij Example 6 The maleic anhydride-grafted modified ethylene-propylene copolymer solution prepared in Example 4 was diluted to 17.5 g/l with 1,1,1-trichloroethane.

A 4-methyl-1-pentene polymer (manufactured by Mitsui Petrochemical Industries K-K, trade name TPX) was immersed in this solution for 2 taps and 2 hours, slowly pulled up, and dried at room temperature for 5 minutes. The thickness of the adhesive intermediate layer obtained here was about 1 μm. Next, the TP was added to the coating composition [A1] prepared in Reference Example 2.
After dipping X for 1 @ and slowly pulling it up, Example 1
It was photocured in the same manner as above to obtain a crosslinked and cured resin outer coating layer of 5μ. Table 3 shows the physical properties of this laminate. Example 7 A polypropylene sheet with an adhesive intermediate layer attached was prepared in the same manner as in Example 1 except that SJ5lO was used instead of SJ3l3 of polypropylene.

Next, a silicone-based coating composition (X-12 manufactured by Shin-Etsu Chemical Co., Ltd.
-917) for 3 hours, and then immediately placed in an air vent at 80°C and baked for 1 hour to obtain a laminated molded product having an outer coating layer with a thickness of 8μ. The physical properties are shown in Table 3. Examples 8 to 101 Comparative Examples 5 to 6 Ethylene Propylene Copolymers of 5 types of copolymers with different propylene contents ([η] is 1.5 to 2.2 de/g
), a maleic anhydride graft-modified ethylene-propylene copolymer solution was prepared by the method of Reference Example 1.

Claims (1)

[Scope of Claims] 1 (A) an outer coating layer made of a transparent crosslinked curable resin;
(B) A graft copolymer of α,β-unsaturated dicarboxylic acid, its anhydride, or its ester component, whose saponification value is in the range of 5.5 to 180 mg/g, and whose [η] is A laminate molded product comprising an intermediate adhesive layer made of a modified ethylene/propylene copolymer having a concentration of 0.3 dl/g or more, and (C) a base resin layer made of a thermoplastic resin. 2. The laminate molded article according to claim 1, wherein the outer coating layer A is a transparent crosslinked curable resin composed of polyfunctional acrylic carboxylic acid ester component units. 3. The laminate molded product according to claim 1, wherein the outer coating layer A is a transparent cross-linked curable silicone resin. 4 Outer coating layer A has an average particle size of 0.1 mμ to 20μ
The laminate molded article according to claim 1, which contains a finely powdered inorganic filler having a refractive index of 1.40 to 1.60. 5. The laminate molded product according to claim 1, wherein the thickness of the outer coating layer A is in the range of 0.1 to 30μ. 6 The composition ratio of ethylene and propylene in the modified ethylene/propylene copolymer of intermediate adhesive layer B is such that the ethylene content is 25 to 50 mol% and the propylene content is 5
The laminate molded article according to claim 1, wherein the content is in the range of 0 to 75 mol%. 7. The laminate molded product according to claim 1, wherein the modified ethylene-propylene copolymer of the intermediate adhesive layer B has a crystallization rate of 20% or less. 8. The laminate molded product according to claim 1, wherein the modified ethylene/propylene copolymer of the intermediate adhesive layer B is a modified ethylene/propylene copolymer graft copolymerized with maleic acid or maleic anhydride component. 9. The laminate molded product according to claim 1, wherein the thickness of the intermediate adhesive layer B is in the range of 0.001 to 10μ. 10. The laminate molded product according to claim 1, wherein the base resin layer C is a polyolefin.