JPH10296924A - Laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent occurrence of a crack or the like due to temperature change in the course of long-time use by laminating a molded material of acrylic resin integrally with a base with a layer constituted of a copolymer of ethylene and an unsaturated glycidyl monomer or further of one or more kinds of other unsaturated ethylene monomers interlaid. SOLUTION: A molded material of acrylic resin is laminated integrally with a base with a layer constituted of a copolymer of ethylene and an unsaturated glycidyl monomer or further of one or more kind of other unsaturated ethylene monomers interlaid. Herein unsaturated glycidyl is a compound having one unsaturated bond copolymerizable with the unsaturated ethylene monomer in one molecule and having one or more glycidyl groups. Accordingly, the acrylic resin molded material and the base are laminated firmly. Thereby the acrylic resin molded material can be made hard to peel from the base and, moreover, occurrence of a crack or the like due to temperature change in the course of long-time use can be prevented.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a laminate.

[0002]

2. Description of the Related Art Acrylic resin moldings are excellent in transparency, surface gloss, surface hardness, weather resistance, etc., and are integrally laminated on the surface of various base materials such as metals, plastics and woods. Used.

[0003] Conventionally, as a laminate obtained by integrally laminating such an acrylic resin molded body on a substrate, for example, an acrylic resin molded body and a substrate are formed of an acrylic resin, a urethane resin, or the like.
An adhesive bonded using an epoxy-based adhesive or the like is known. However, although such a laminate is laminated with sufficient strength immediately after manufacture, when used for a long period of time, cracks and the like tend to occur due to temperature changes and the like during the period, and the appearance tends to be impaired. It is in.

[0004] As a laminate in which cracks and the like are hardly generated even by a temperature change, an acrylic resin molded body is made of ethylene-based resin.
Laminates laminated integrally with a substrate via a layer made of vinyl acetate copolymer, ethylene-vinyl chloride copolymer, etc. are known. There was a tendency to peel off.

[0005]

Accordingly, the present inventors have been keen to develop a laminate in which the acrylic resin molded article is hardly peeled off from the base material and cracks are hardly generated even by a temperature change during long-term use. As a result of the examination, the laminated body in which the acrylic resin molded body was integrally laminated to the base material via the layer made of the specific copolymer, the acrylic resin molded body hardly peeled off from the base material, and the temperature during long-term use The inventors have found that cracks are unlikely to occur even by the change, and have reached the present invention.

[0006]

That is, according to the present invention, there is provided an acrylic resin molded article comprising a copolymer of ethylene and an unsaturated glycidyl monomer, or one or more other ethylenically unsaturated monomers. It is intended to provide a laminate which is integrally laminated with a base material via a layer composed of:

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the laminate of the present invention, a copolymer comprising ethylene and an unsaturated glycidyl monomer or ethylene and an unsaturated glycidyl monomer and one or more other ethylenically unsaturated monomers is used. In the copolymer (1), unsaturated glycidyl has one unsaturated bond capable of copolymerizing with an ethylenically unsaturated monomer in one molecule, and has one glycidyl group.
Compounds having at least one compound represented by general formula (1) (Wherein R ¹ represents a hydrocarbon group having one carbon-carbon double bond), an unsaturated glycidyl ester compound represented by the general formula (2): [Wherein, R ² represents a hydrocarbon group having one carbon-carbon double bond, and X represents a general formula (3) , General formula (4) Or general formula (5) Represents a divalent residue represented by. Unsaturated glycidyl ether compound, p-glycidyl styrene and the like. Note that the divalent residue represented by the general formula (4) or (5) may have a substituent on the benzene skeleton.

The unsaturated glycidyl ester compounds include glycidyl acrylate, glycidyl methacrylate, monoglycidyl itaconate, diglycidyl itaconate, monoglycidyl butenetricarboxylate, diglycidyl butenetricarboxylate, triglycidyl butenetricarboxylate, glycidyl p-styrene carboxylate and the like,

Examples of the unsaturated glycidyl ether compound include allyl glycidyl ether, 2-methylallyl glycidyl ether, and styrene-p-glycidyl ether.

The copolymer may be a copolymer of ethylene and an unsaturated glycidyl monomer, or may be a copolymer of these and another ethylenically unsaturated monomer. Here, the other ethylenically unsaturated monomer is a compound having a carbon-carbon double bond other than ethylene and unsaturated glycidyl, such as propylene, butene-1, decene-1 and the like. Olefin compounds, vinyl ester compounds such as vinyl acetate, vinyl propionate and vinyl benzoate; alkyl acrylate compounds such as methyl acrylate, ethyl acrylate and propyl acrylate; methacrylic acid such as methyl methacrylate and ethyl methacrylate Alkyl ester compounds,
Maleic anhydride, dimethyl maleate, maleic acid ester compounds such as diethyl maleate, vinyl halide compounds such as vinyl chloride, vinyl methyl ethers, vinyl ether compounds such as vinyl ethyl ether, acrylic acid amide compounds such as acrylamide, and the like, Preferred are vinyl acetate, alkyl acrylate compounds and the like. These other ethylenically unsaturated monomer units may be used alone or in combination of two or more.

The content of the ethylene unit in the copolymer is usually from 50 to 99.5% by weight, the content of the unsaturated glycidyl monomer unit is usually from 0.05 to 95% by weight and other ethylenically unsaturated monomer units. The content is usually 0 to 50% by weight. If the unsaturated glycidyl monomer unit content is less than 0.05% by weight, the adhesive strength tends to be insufficient, and if it exceeds 95% by weight, the heat resistance tends to decrease. Preferably it is 1 to 60% by weight. When another ethylenically unsaturated monomer is used as a copolymer component, the content of the monomer unit is usually 1% by weight or more. The effect of the present invention can be obtained even when the content of other ethylenically unsaturated monomer units exceeds 50% by weight, but is usually 50% by weight or less, preferably 40% by weight or less from the viewpoint of economy. It is. Such a copolymer may further contain another monomer as a copolymer component as long as the object of the present invention is not impaired.

The copolymer may be blended with additives such as stabilizers, pigments, fillers, and foaming agents which are commonly used. Melt index of copolymer (J
It is a value measured in accordance with IS K6760.
Called I. ) Is 600 g / 10 min or less,
It is preferable in that a stronger adhesive force can be obtained. Note that MI
Is usually 0.01 g / 10 min or more.

The acrylic resin in the acrylic resin molded product is not particularly limited, and may be the same as that usually used, for example, 50 to 100% by weight of a methyl methacrylate unit and 0 to 50% by weight of another vinyl monomer unit. (Co) polymer and the like. Here, as other vinyl monomers, for example, ethyl methacrylate, propyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl methacrylate Such as methacrylate compounds, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, benzyl acrylate, 2-ethylhexyl acrylate, acrylate compounds such as 2-hydroxyethyl acrylate, Unsaturated fatty acids such as acrylic acid and methacrylic acid, styrene, α-methylstyrene, acrylonitrile, methacrylonitrile, maleic anhydride, phenylmaleimide, and cyclohexylmaleimide. It is. Also, two or more acrylic resins may be blended, and a rubber component for improving impact strength, an ultraviolet absorber for improving weather resistance, a hindered amine light stabilizer, an antioxidant, a flame retardant, a coloring agent Agents, pigments and the like.

The shape of the acrylic resin molded article is not particularly limited, and may be, for example, a film, a sheet, or a plate. The thickness of such a molded body is usually about 0.01 to 10 mm. These molded products can be easily produced by a usual method such as an extrusion molding method, an injection molding method, a press molding method and the like. Also, a picture or pattern for decoration may be printed or painted on both sides or one side thereof.

Examples of the base material include metals such as iron, stainless steel and aluminum, polyolefins such as polyethylene and polypropylene, thermoplastic resins such as acrylonitrile-butadiene-styrene (ABS) resin, polycarbonate resin and polyphenylene ether resin, and melamine resins. Plastics such as thermosetting resins such as urea resins and phenolic resins, and natural woods, laminated wood, and woods such as particle boards can be used. The surface of the metal may be plated with zinc, tin or the like.

The method for producing the laminate of the present invention is not particularly limited. For example, ethylene and an unsaturated glycidyl monomer, or one or more other ethylenically unsaturated There is a method in which a two-layer laminate in which a layer made of a copolymer with a monomer is integrally laminated is superposed on the surface of a substrate, and then heated and pressed. The heating temperature is usually about 60 to 120 ° C., and the pressure is not particularly limited, but is usually 0.5 to 50 kg / cm.
Approximately ² , pressurization time is not particularly limited, but is usually 60 to 18
It is about 0 seconds.

The two-layer laminate may be produced, for example, by a co-extruder, or may be produced by integrally laminating a film-shaped copolymer on one surface of an acrylic resin molded product. Then, after dispersing or dissolving the copolymer in a solvent, the copolymer may be applied to one surface of an acrylic resin molded article and dried.
Here, examples of the solvent include xylene, heptane, decane, chlorobenzene, toluene, and the like, and the amount of the solvent is usually about 2 to 30 times the weight of the copolymer.

When the base material is plastic, it may be manufactured by simultaneously and integrally laminating an acrylic resin molded body, a layer made of a copolymer and a base material using a co-extruder. Good.

[0019]

According to the laminate of the present invention, the acrylic resin molded body and the base material are firmly laminated, and cracks hardly occur in the acrylic resin molded body due to temperature changes during long-term use. Gutters, window frames, deck materials,
It can be used for furniture, home appliances and the like.

[0020]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

The evaluation method in each embodiment is as follows. (1) Thermal Shock Test Using a thermal shock tester (manufactured by Tabai Seisakusho), one cycle shown below was continuously executed for 30 cycles to apply a thermal shock to the laminate. 1 cycle: leave at -30 ° C for 30 minutes, then 80 ° C
And let stand at -30 ° C for 30 minutes. Thereafter, the acrylic resin molded body side surface of the laminate was visually observed, and changes in appearance (cracks, peeling of the acrylic resin laminate) were evaluated according to the following criteria. Cracking: Occurrence observed ○ Occurrence not observed × Peeling of acrylic resin molded article: Peeling observed ○ Peeling not observed ×

(2) Molding strain test After the laminate was left at room temperature for 24 hours after production, ethanol was applied to the acrylic molded body, and the occurrence of cracks was visually evaluated. Cracking: Occurrence observed ○ Occurrence not observed ×

Example 1 Acrylic resin (Sumipex HT55, manufactured by Sumitomo Chemical Co., Ltd.)
X) with a single screw extruder (screw diameter 60 mmφ) and 600
It was extruded at a resin temperature of 260 ° C. using a T-die having a width of mm to obtain an acrylic resin molded product (continuous film shape, width 30 cm, thickness 100 μm). A single screw extruder (screw diameter: 64% by weight of ethylene unit, 6% by weight of glycidyl methacrylate unit and 30% by weight of methyl acrylate unit (manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7M, MI = 9 g / 10 min)) The resin was extruded at a resin temperature of 190 ° C. using a T-die having a width of 60 mm and a width of 600 mm to obtain a copolymer film (continuous film, width 30 cm, thickness 20 μm). The acrylic resin molded product and the copolymer film were cut out to 30 cm × 30 cm, respectively, and the copolymer film was placed on a particle board (30 cm × 30 cm).
Acrylic resin molded article was placed in this order, temperature 105 ° C, pressure 3
Pressing was performed at 5 kg / cm ^{2 for} 150 seconds to obtain a laminate. Table 1 shows the evaluation results of the obtained laminate.

Example 2 An aluminum plate (30 cm) was used in place of the particle board.
X 30 cm, thickness 2 mm), and the same procedure as in Example 1 was carried out to obtain a laminate. Table 1 shows the evaluation results.

Example 3 A copolymer comprising 88% by weight of ethylene units and 12% by weight of glycidyl methacrylate units (manufactured by Sumitomo Chemical Co., Ltd., Bond First E, MI = 3 g / 10 min.) Instead of the copolymer (Bond Fast 7M) ) Was obtained in the same manner as in Example 1 except that (1) was used. Table 1 shows the evaluation results.

Example 4 An acrylic resin (manufactured by Sumitomo Chemical Co., Ltd.) was supplied from a main extruder (screw diameter: 65 mm) of a two-layer extruder (feed lock type).
SUMIPEX HT55X) was supplied at a resin temperature of 250 ° C., and 83% by weight of ethylene units and 12 units of glycidyl methacrylate units were obtained from a sub-extruder (screw diameter: 45 mm).
% By weight, a copolymer composed of 5% by weight of vinyl acetate units (manufactured by Sumitomo Chemical Co., Ltd., Bondfast 7B, MI = 7 g / 10
Min) at a resin temperature of 200 ° C. and a feed lock (temperature of 260 ° C.) and a T-type (600 mm width).
Layered laminate (film, acrylic resin molded body thickness 12
5 μm, and the thickness of the layer made of the copolymer was 25 μm).
A single screw extruder (screw diameter 65m) made of ABS resin (Clarastic SR, manufactured by Sumitomo ABS Latex Co., Ltd.)
m) and a T-die (600 mm width) using a resin temperature of 22
It was extruded into a sheet at 0 ° C., and the copolymer layer side of the two-layer laminate was supplied to the ABS resin side at a point where it entered a cooling roll at 70 ° C. to obtain a laminate. Table 1 shows the evaluation results.

Example 5 A copolymer composed of 64% by weight of ethylene units, 6% by weight of glycidyl methacrylate units and 30% by weight of methyl acrylate units (manufactured by Sumitomo Chemical Co., Ltd., Bondfast 20)
M, MI = 20 g / 10 minutes) 5 g of xylene 5 at 70 ° C.
It was dissolved in 0 ml to obtain a copolymer solution. An acrylic resin (Sumipex MH, manufactured by Sumitomo Chemical Co., Ltd.) was molded at a resin temperature of 260 ° C. using an injection molding machine to obtain an acrylic resin molded body (180 mm × 180 mm, thickness 2 mm). The solution of the copolymer obtained above was sprayed on one surface of the acrylic resin molded product by spraying, and then dried at 60 ° C. for 15 minutes to obtain a two-layer molded product. This two-layered molded body was placed on a particle board with the copolymer layer side down,
Pressing was performed at 05 ° C., a pressure of 30 kg / cm ² and a pressing time of 150 seconds to obtain a laminate. Table 1 shows the evaluation results.

Comparative Example 1 An ethylene-vinyl acetate copolymer (Evatate D3010, manufactured by Sumitomo Chemical Co., Ltd., MI = 6, 90% by weight of ethylene unit) was used in place of the copolymer (Bond First 7M) film.
A laminate was obtained in the same manner as in Example 1, except that vinyl acetate units (10% by weight) were used. Table 1 shows the evaluation results.

Comparative Example 2 An epoxy adhesive (KONISHI BOND E set L, manufactured by Konishi Co., Ltd.) was applied to the surface of the particle board, and an acrylic resin molded body obtained by the same operation as in Example 1 was placed thereon. It was pressurized at a pressure of 1 kg / cm ² and then left at room temperature for 24 hours to obtain a laminate. Table 1 shows the evaluation results.

[0030]

[Table 1]

Claims (6)

[Claims] An acrylic resin molded article is formed via a layer comprising a copolymer of ethylene and an unsaturated glycidyl monomer, or one or more other ethylenically unsaturated monomers.
A laminate that is integrally laminated with a base material. 2. The copolymer has an ethylene unit of 50 to 99.5.
2. The laminate according to claim 1, which is a copolymer consisting of 0.05% by weight of an unsaturated glycidyl monomer unit and 0% to 50% by weight of another ethylenically unsaturated monomer unit. 3. The copolymer has a melt index of 600 g.
The laminate according to claim 1, wherein the laminate is at most / 10 minutes. 4. The laminate according to claim 1, wherein the acrylic resin is a (co) polymer of 50 to 100% by weight of methyl methacrylate monomer units and 0 to 50% by weight of other vinyl monomer units. . 5. The laminate according to claim 1, wherein the substrate is a metal, plastic or wood. 6. A layer comprising a copolymer of ethylene and an unsaturated glycidyl monomer, or one or more other ethylenically unsaturated monomers, is integrally laminated on one surface of the acrylic resin molded article. A two-layer laminate obtained.