JP2003039609A - Resin laminate and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin laminate excellent from an aspect of the hardness of a surface layer. SOLUTION: The resin laminate is constituted by curing a resin composition on the surface of a thermoplastic resin molded object. The resin composition comprises 30-60 pts.wt. of an unsaturated monomer (A) comprising 20-90 wt.% of a monofunctional unsaturated monomer based on methyl methacrylate and 10-80 wt.% of a polyfunctional unsaturated monomer having at least two radical polymerizable double bond, 40-70 pts.wt. of a polymer (B) comprising an unsaturated monomer based on methyl methacrylate, and a radical polymerization initiator (C) added in an amount of 0.1-5 pts.wt. with respect to 100 pts.wt. of the sum total of the components (A) and (B).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin laminate having a methacrylic resin layer formed on the surface of a thermoplastic resin molding and a method for producing the resin laminate.

[0002]

2. Description of the Related Art A resin laminate having a surface layer made of a methacrylic resin has a surface layer excellent in transparency and heat resistance.
Conventionally, it has been proposed to use this laminate for sanitary products such as bathtubs and washbasins. For example, JP-A-7
No. 250772 discloses a bath or wash surface in which a thermoplastic resin sheet is laminated on a cast acrylic sheet by melt-extruding and crimping a thermoplastic resin such as ABS resin on a heat-softened cast acrylic sheet. Obtaining a dexterous sheet is described. Further, in Japanese Patent Laid-Open No. 11-147259, a thermoplastic resin sheet such as a (meth) acrylic resin sheet is molded into the shape of the inner surface of a bath, and a thermoplastic resin such as ABS resin is melted on the outer surface thereof. It is described that a bath made of a thermoplastic resin is obtained by wearing the bath.

[0003]

However, in the above-mentioned conventional resin laminate having the methacrylic resin surface layer,
The hardness of the surface layer is not always sufficient, and there is a problem that the surface is easily scratched. The purpose of the present invention is to
An object of the present invention is to provide a resin laminate having excellent surface layer hardness.

[0004]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that a curable material having a specific composition is used to form a methacrylic resin layer on the surface of a thermoplastic resin molded article. The inventors have found that the above objects can be achieved and completed the present invention.

That is, the present invention provides the following components (A) to
The present invention provides a resin laminate obtained by curing a resin composition containing (C) on the surface of a thermoplastic resin molded body. (A) 20 to 90% by weight of a monofunctional unsaturated monomer mainly composed of methyl methacrylate, and 10 to 80% by weight of a polyfunctional unsaturated monomer having at least two radically polymerizable double bonds in one molecule. % Unsaturated monomer: 30
˜60 parts by weight, (B) methyl methacrylate-based polymer of unsaturated monomer: 40 to 70 parts by weight, (C) radical polymerization initiator: a total of 10 components (A) and (B)
0.1 to 5 parts by weight with respect to 0 parts by weight.

The present invention also provides the above components (A) to (C).
After mixing and aging, the solid resin composition obtained is cured on the surface of the thermoplastic resin molded body to provide a method for producing a resin laminate.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The resin laminate of the present invention comprises, as a curable material for forming a methacrylic resin layer, 20 to 90% by weight of a monofunctional unsaturated monomer mainly composed of (A) methyl methacrylate.
And 10 to 80% by weight of a polyfunctional unsaturated monomer having at least two radically polymerizable double bonds in one molecule, an unsaturated monomer mainly composed of (B) methyl methacrylate Obtained by using a resin composition containing each component of a monomer polymer and (C) a radical polymerization initiator and curing the resin composition on at least a part of the surface of the thermoplastic resin molding. It is a thing.

As the thermoplastic resin molded product, a product obtained by molding a thermoplastic resin by a method such as extrusion molding, injection molding, press molding, or vacuum molding can be used. Examples of the thermoplastic resin include acrylonitrile. -Styrene copolymer resin (AS resin), acrylonitrile-butadiene-styrene copolymer resin (ABS resin), polycarbonate resin, polyvinyl chloride resin, etc. are mentioned, and if necessary, a mixture of two or more kinds thereof or a polymer alloy. Can also be used. If necessary, the thermoplastic resin may be mixed with a filler such as talc or glass fiber, and various additives such as an antioxidant and an ultraviolet ray inhibitor.

The monofunctional unsaturated monomer mainly composed of methyl methacrylate, which constitutes the unsaturated monomer which is the component (A) of the resin composition, is one containing 50% by weight or more of methyl methacrylate, It may be substantially methyl methacrylate alone or a mixture of 50% by weight or more of methyl methacrylate and 50% by weight or less of a monofunctional unsaturated monomer copolymerizable therewith. In the monofunctional unsaturated monomer, methyl methacrylate is preferably 70
It is at least wt%, more preferably at least 90 wt%.

Examples of monofunctional unsaturated monomers copolymerizable with methyl methacrylate include methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. , Lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl ( (Meth) acrylates such as (meth) acrylates; unsaturated acids such as acrylic acid and methacrylic acid; styrene-based monomers such as styrene and α-methylstyrene; acrylonitrile, methyl ester Acrylonitrile, maleic anhydride, phenyl maleimide, cyclohexyl maleimide, vinyl acetate and the like, of which optionally 2
It is also possible to use more than one species.

The polyfunctional unsaturated monomer having at least two radically polymerizable double bonds in the molecule, which constitutes the unsaturated monomer as the component (A), is, for example, allyl (meth). ) Acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, 1,3-butylene glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate,
Divinylbenzene, diallyl phthalate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, tetramethylolmethane tetra (meth) acrylate and the like can be mentioned, and two or more of them may be used if necessary. it can.

Regarding the amount ratio of the monofunctional unsaturated monomer and the polyfunctional unsaturated monomer in the unsaturated monomer of the component (A), the former is 20 to 90% by weight and the latter is 10 to 80% by weight. weight%
Is. When the amount of monofunctional unsaturated monomer is too large and the amount of polyfunctional unsaturated monomer is too small, the surface hardness of the laminate is insufficient. If the monofunctional unsaturated monomer is too small and the polyfunctional unsaturated monomer is too large, the impact strength and mechanical strength of the laminate are insufficient.

The unsaturated monomer polymer mainly composed of methyl methacrylate as the component (B) of the resin composition is a polymer of an unsaturated monomer containing 50% by weight or more of methyl methacrylate, and is substantially May be a homopolymer of methyl methacrylate, or 50% by weight of methyl methacrylate.
It may be a copolymer of the above and 50% by weight or less of an unsaturated monomer copolymerizable therewith. Examples of the unsaturated monomers are
These are the same as those exemplified above as the monofunctional unsaturated monomer copolymerizable with methyl methacrylate and those exemplified as the polyfunctional unsaturated monomer.

Regarding the amount ratio of the unsaturated monomer of the component (A) and the polymer of the component (B), the former is 30 to 60.
By weight, the latter is 40 to 70 parts by weight. When the amount of the unsaturated monomer is too large and the amount of the polymer is too small, the resin composition has high fluidity and adhesiveness, the handleability is not sufficient, and the shrinkage of the resin composition at the time of curing is large, and Surface smoothness is not sufficient. Further, if the unsaturated monomer content is too small and the polymer content is too large, the fluidity at the time of curing the resin composition will be insufficient.

Examples of the above-mentioned polymer include resin particles, for example,
Unsaturated monomer mainly composed of methylmethacrylate, obtained by polymerizing by emulsion polymerization, suspension polymerization, dispersion polymerization, or the like, or obtained by crushing a resin obtained by another method. Those obtained are preferably used. In this case, the particle size of the resin particles is preferably 1 μm or more from the viewpoint of handleability when preparing the resin composition, and 10 from the viewpoint of surface smoothness of the laminate.
It is preferably 0 μm or less.

It is preferable that the resin particles include partially crosslinked resin particles from the viewpoint of handleability of the resin composition. In this case, in the resin particles, the resin which is not crosslinked with the crosslinked resin particles is preferable. Regarding the amount ratio with particles, the former is 20 to 100% by weight and the latter is 0 to 80% by weight.
Is. The crosslinked resin particles can be prepared by polymerizing using an unsaturated monomer mainly containing methyl methacrylate as a raw material, containing a polyfunctional unsaturated monomer as described above. The amount of the polyfunctional monomer is usually 0.05 to 10% by weight based on the total unsaturated monomer. In addition, the resin particles may contain an antioxidant, an ultraviolet absorber, a chain transfer agent, a release agent, a dye, a pigment, an inorganic filler, etc., if necessary.

Examples of the radical polymerization initiator of the component (C) of the resin composition include 1,1'-azobis (cyclohexane-1-carbonitrile) and 2,2'-azobis (2,4,4-trimethyl). Pentane), 2,2'-azobis (2-methylpropane), 2-cyano-2-propyrazoformamide, dimethyl 2,2'-azobis (2-
Hydroxypropionate), 2,2'-azobis (2
-Methylbutyronitrile), 2,2'-azobisisobutyronitrile, 2,2'-azobis [2- (2-imidazolin-2-yl) propane], dimethyl 2,2'-azobis (2- Azo compounds such as methyl propionate); dialkyl peroxide initiators such as dicumyl peroxide, t-butyl cumyl peroxide, di-t-butyl peroxide; dibenzoyl peroxide, dilauroyl peroxide Diacyl peroxide-based initiators such as t-butylperoxy-3,
3,5-Trimethylhexanoate, t-butylperoxylaurate, t-butylperoxyisobutyrate, t-butylperoxyacetate, di-t-butylperoxyhexahydroterephthalate, di-t-butylper Oxyazelate, t-butylperoxy-2-
Peroxyester initiators such as ethylhexanoate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, t-amylperoxy-2-ethylhexanoate; t-butyl Percarbonate initiators such as peroxyallyl carbonate, t-butyl peroxyisopropyl carbonate; 1,1
-Di-t-butylperoxycyclohexane, 1,1-
Di-t-butylperoxy-3,3,5-trimethylcyclohexane, 1,1-di-t-hexylperoxy-
Examples include peroxyketal-based initiators such as 3,3,5-trimethylcyclohexane, and two or more of these may be used if necessary.

The amount of the radical polymerization initiator as the component (C) used is 0.1 parts by weight or more based on 100 parts by weight of the components (A) and (B) in view of the rate of polymerization reaction. And from the viewpoint of the stability of the polymerization reaction, it is 5 parts by weight or less.

If necessary, the above components (A) to (C) are combined with a release agent, an ultraviolet absorber, a dye, a pigment, a polymerization inhibitor,
The resin composition can be prepared by mixing with a chain transfer agent, an antioxidant, a flame retardant, a reinforcing agent, and the like. At this time, a partial polymer syrup obtained by previously partially polymerizing an unsaturated monomer mainly containing methyl methacrylate can be used as the mixed raw material.

In the preparation of the resin composition, the aging treatment is carried out during or after the above-mentioned respective components are mixed to obtain a solid resin composition such as clay or powder, in view of handleability. Is preferred. In order to obtain a solid resin composition as described above, as the polymer of the above component (B),
Usually, a mixture of the above-mentioned partially crosslinked resin particles or non-crosslinked resin particles thereof is used. In this case, the aging usually impregnates the crosslinked resin particles with the unsaturated monomer of the component (A), and dissolves the non-crosslinked resin particles in the unsaturated monomer.

The above-mentioned mixing and aging treatment is carried out, for example, by mixing the above-mentioned components in a stirring tank or the like to form a slurry,
It may be carried out by aging it in a bag made of an appropriate material or in a container such as a cell composed of at least two flat plates and a sealing material. Alternatively, each of the above components may be a twin-screw extruder or a universal mixer. It may be carried out by mixing and aging using a kneader such as a kneader or a Banbury mixer. The temperature of the aging treatment is usually 20 ° C. or higher from the viewpoint of shortening the aging time, and 100 ° C. or lower from the viewpoint of suppressing the curing reaction during aging.

The resin composition thus obtained is brought into contact with the surface of the above-mentioned thermoplastic resin molding, the unsaturated monomer in the resin composition is polymerized, and the resin composition is cured to obtain the resin composition. The resin laminate of the invention can be manufactured. The curing temperature is usually 80 ° C. or higher from the viewpoint of shortening the curing time, and 200 ° C. or lower from the viewpoint of suppressing decomposition and coloring of the laminate. The pressure during curing is usually 2 MPa or more, preferably 5 MPa or more. The time required for curing depends on the composition of the resin composition and other conditions, but is usually 1
It is 0 minutes or less.

The resin laminate is preferably manufactured by a method such as compression molding, injection molding or transfer molding. In the production of a resin laminate by these molding methods, usually, a thermoplastic resin molding is charged, and the resin composition is put into a mold preheated to a predetermined temperature, and pressure and heat are applied. It is done by

As for the structure of the mold, it is preferable to provide a space for venting gas in the peripheral portion. However, when the void is too large, the charged resin composition may overflow, and when the void is too small, the gas in the cavity may not be fully exhausted. Selected from. Further, the pressure inside the mold cavity may be reduced in advance.

The resin laminate of the present invention is excellent in the hardness of the surface layer and can be suitably used as various resin products and materials thereof. Among them, in view of the fact that the resin laminate of the present invention is also excellent in hot water resistance, it can be particularly suitably used for sanitary applications such as sanitary articles such as bathtubs and washbasins and material sheets thereof. In this case, it is preferable to use ABS resin as the thermoplastic resin molded body.

[0026]

Examples (1) Preparation of Thermoplastic Resin Molded Body 320 g of heat-resistant ABS resin [Clarastic KU670-R2] manufactured by Nippon A & L Co., Ltd., two aluminum plates (thickness: 0.3 mm, 40 cm square) and gold Frame (thickness 3
mm, inside 30 cm square)
In a press machine with a ram diameter of 215 mm heated to 00 ° C., a hydraulic pressure of 3 MPa was maintained for 7 minutes, and then a hydraulic pressure of 15 MPa was maintained for 3 minutes. Then, at room temperature, the ram diameter is 215 mm
In the press machine, the hydraulic pressure was maintained at 3 MPa for 3 minutes and the frame was opened to obtain a 30 cm square ABS resin plate having a thickness of 3 mm.

(2) Preparation of resin composition Methyl methacrylate 22 was added to a 500 ml poly cup.
Parts by weight, 28 parts by weight of ethylene glycol dimethacrylate, partially crosslinked resin particles [methyl methacrylate / ethylene glycol dimethacrylate = 99.8 /
0.2 (weight ratio) copolymer, average particle size 8 μm] 50
Parts by weight, 10 parts by weight of non-crosslinked methacrylic resin particles [Sumitex Chemical Co., Ltd., Sumipex MHF], and t-amylperoxy-2-ethylhexanoate)
0.145 parts by weight was added, and the mixture was stirred and mixed to obtain a slurry resin composition. The resin composition in the form of slurry was put in a polyethylene bag, sealed, and left to stand in a hot air drying oven at 50 ° C. for 1 hour for aging. Then cool to room temperature,
The powdery resin composition was taken out from the bag.

(3) Manufacture of resin laminate 100 g of the powdery resin composition obtained in (2) is placed on the ABS resin plate obtained in (1), and the aluminum plate (thickness) It was sandwiched between two sheets (0.3 mm, 40 cm square) and kept at room temperature for 5 minutes at a hydraulic pressure of 3 MPa in a press machine with a ram diameter of 215 mm. Then, in a press machine with a ram diameter of 215 mm heated to 100 ° C., the hydraulic pressure was increased to 15 MPa over about 2 minutes, and then the hydraulic pressure was increased to 5 MPa.
Hold for minutes. Then, at room temperature, in a press with a ram diameter of 215 mm, the pressure was maintained at a hydraulic pressure of 3 MPa for 3 minutes to open the frame to obtain a resin laminate having a transparent surface layer with a thickness of about 1 mm.

The pencil hardness of the surface layer of the obtained resin laminate was measured according to JIS-K5400, and the result was 4H.
Met. Further, a test piece of 5 cm square was cut out from the obtained resin laminated body, immersed in hot water at 90 ° C. for 600 hours, and the appearance was observed. As a result, peeling or whitening of the surface layer was not observed.

[0030]

According to the present invention, a resin laminate having a methacrylic resin layer having excellent hardness is provided,
The resin laminate is suitable for various resin products and materials thereof, including sanitary applications.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4F006 AA15 AA17 AA22 AA36 AA58                       AB24 AB64 BA02 DA04                 4F100 AK01B AK25A AK25J AK74                       AL01A BA02 CA30A EJ17                       EJ42 GB08 JB16B JJ03                       JK12 JK14 JN01

Claims (2)

[Claims] 1. A resin laminate, comprising a resin composition containing the following components (A) to (C) cured on the surface of a thermoplastic resin molding. (A) 20 to 90% by weight of a monofunctional unsaturated monomer mainly composed of methyl methacrylate, and 10 to 80% by weight of a polyfunctional unsaturated monomer having at least two radically polymerizable double bonds in one molecule. % Unsaturated polymer: 30 to 60 parts by weight, (B) methyl methacrylate-based polymer of unsaturated monomer:
40 to 70 parts by weight, (C) radical polymerization initiator: 0.1 based on 100 parts by weight of the total of the components (A) and (B).
~ 5 parts by weight. 2. The components (A) to (C) according to claim 1 are mixed and aged, and then the obtained solid resin composition is cured on the surface of the thermoplastic resin molded article. A method for producing a resin laminate.