JPS6348893B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition with excellent pressure bonding processability. More specifically, the present invention relates to a resin composition suitable for use in ski top sheets, which has excellent adhesion to a core material during crimping, dimensional accuracy of the composite material crimped to the core material, and excellent surface appearance. Rubber-reinforced styrene resins, represented by ABS resin, AES resin, and AAS resin, have a good balance of impact resistance, rigidity, and heat resistance, are easy to mold, and have secondary processing properties such as plating and painting properties. AES resin and AAS resin have excellent weather resistance and are therefore used in vehicles, electrical equipment, and miscellaneous goods, and are also expected to be used in leisure products such as skis and snowboards. In the case of skis, the top sheet of rubber-reinforced styrene resin is bonded to 70% by using an adhesive such as epoxy.
FRP reinforced with plywood wood board, aluminum board, glass fiber, carbon fiber, etc. in ~90℃ heat press
It is crimped to the core material of sheets, etc. The adhesion during this pressure bonding process, the dimensional accuracy of the ski product, and the appearance of the top sheet surface are important factors in the product value. Furthermore, the rigidity of the material has a large effect on dimensional accuracy and surface appearance, and if the current rubber-reinforced styrene resin has high rigidity, it has poor adhesion, which can cause the top sheet and core material to separate during use. . On the other hand, if emphasis is placed on adhesion, the dimensional accuracy of the ski product will be poor, and the unevenness of the core material will be reflected on the surface of the top sheet, resulting in poor appearance. Therefore, it has been desired to develop a material that satisfies all of adhesion, dimensional accuracy, and surface appearance. As a result of intensive research in view of the above problems, the inventors of the present application have found that by blending a glycidyl methacrylate copolymer (B) into a rubber-reinforced styrene resin (A), rigidity can be improved without impairing the basic physical properties. The present inventors have discovered that it is possible to obtain a resin composition suitable for use in ski top sheets, which has high adhesiveness to the core material, excellent dimensional accuracy and surface appearance, and has arrived at the present invention. That is, the present invention provides a rubber-reinforced styrenic resin (A) having an ethylene/propylene rubber or acrylic rubber content of 10 to 35% by weight, an aromatic vinyl monomer, a vinyl cyanide monomer, etc. and a copolymer (B) consisting of 95 to 30% by weight of one or more acrylic acid ester monomers and 5 to 70% by weight of glycidyl methacrylate.
The object of the present invention is to provide a resin composition having excellent adhesion to a core material, dimensional accuracy, and surface appearance. Rubber-reinforced styrenic resin used in the present invention
(A) is an ethylene-propylene rubber or an acrylic rubber, each of which is selected from at least two groups of aromatic vinyl monomers, vinyl cyanide monomers, and acrylic ester monomers. A graft copolymer obtained by graft polymerization of the above monomers, or this graft copolymer and at least an aromatic vinyl monomer, a vinyl cyanide monomer, or an acrylic acid ester monomer. Examples include a mixture with a copolymer obtained by polymerizing one or more monomers selected from each of the two groups. Ethylene, which makes up rubber-reinforced styrene resin
The propylene rubber includes a binary copolymer (EPR) consisting of ethylene and propylene, a ternary copolymer (EPDM) consisting of ethylene, propylene and a non-conjugated diene, etc., and one or more types thereof are used. Examples of the non-conjugated diene in the terpolymer (EPDM) include dicyclopentadiene, ethylidene norbornene, 1.4-hexadiene, 1.4-cycloheptadiene, and 1.5-cyclooctadiene. The molar ratio of ethylene to propylene in the binary copolymer (EPR) and terpolymer (EPDM) is preferably in the range of 5:1 to 1:3. Further, in the terpolymer (EPDM), it is preferable that the proportion of non-conjugated diene is in the range of 2 to 50 in terms of iodine value. Moreover, acrylic rubber is a copolymer of polyacrylic acid alkyl ester and acrylic acid alkyl ester as a main component with other vinyl monomers (including crosslinkable monomers). Examples include polybutyl acrylate, butyl acrylate-acrylonitrile copolymer, butyl acrylate-methyl methacrylate copolymer, and the like. Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, monochlorostyrene, etc.; examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, etc.; Examples of the acrylic ester monomer include ethyl acrylate, methyl methacrylate, and the like. One type or two or more types of each can be used. Polymers obtained by grafting aromatic vinyl monomers and vinyl cyanide monomers onto ethylene/propylene rubber or acrylic rubber, and co-products of aromatic vinyl monomers and vinyl cyanide monomers. Polymer resins generally called AES resins or AAS resins are preferred in terms of physical properties and cost. The content of the ethylene-propylene rubber or acrylic rubber constituting the rubber-reinforced styrene resin (A) is 10 to 35% by weight. The glycidyl methacrylate copolymer (B) used in the present invention is one or more monomers selected from aromatic vinyl monomers, vinyl cyanide monomers, and acrylic acid ester monomers. 95～
30% by weight and glycidyl methacrylate 5~
It is a copolymer consisting of 70% by weight, preferably a copolymer consisting of 90 to 50% by weight of monomer and 10 to 50% by weight of glycidyl methacrylate. Examples of aromatic vinyl monomers include styrene, α
- Examples of vinyl cyanide monomers include acrylonitrile, methacrylonitrile, etc.; examples of acrylic acid ester monomers include ethyl acrylate, methacryl Examples include acid methyl, and one type or two or more types of each can be used. There is no particular restriction on the amount of glycidyl methacrylate copolymer (B) blended into the rubber-reinforced styrene resin (A). Based on the mechanical strength of the final resin composition, it should be 0.01 to 40 parts by weight per 100 parts by weight of the polymer (A). part is preferred.
If it is less than 0.01 part by weight, the adhesiveness of the final resin composition tends to be poor, and if it exceeds 40 parts by weight, processability tends to be poor. More preferably, it is 0.1 to 10 parts by weight. There are no particular restrictions on the method for producing the rubber-reinforced styrene resin and the glycidyl methacrylate copolymer, and they can be produced by known methods. The rubber-reinforced styrene resin (A) and the glycidyl methacrylate copolymer (B) can be mixed by a commonly used method. Agents, colorants, fillers, plasticizers, etc. can be added. The present invention will be explained below with reference to Examples.
The present invention is not limited to these in any way. The numerical values in the formulation column in Table 1 represent parts by weight. Further, other resins that can be mixed with the resin composition of the present invention, such as polycarbonate, PVC, and polysulfone, can also be mixed. Examples and Comparative Examples Separately produced acrylonitrile 30 was added to a polymer obtained by graft polymerizing 50 parts by weight of ethylene-propylene-ethylidene norbornene (EPDM) with 35 parts by weight of styrene and 15 parts by weight of acrylonitrile.
By mixing a copolymer of 70 parts by weight of styrene and 70 parts by weight of styrene, a copolymer with different olefin rubber contents as shown in Table 1 was prepared.
Two types of AES resin were created. Also, separately
An AES resin having a rubber content of 15% by weight was prepared by graft polymerization of 15 parts by weight of EPDM, 60 parts by weight of styrene, and 25 parts by weight of acrylonitrile. A separately produced copolymer of 3 parts by weight of acrylonitrile and 70 parts by weight of styrene was mixed with a polymer obtained by graft polymerizing 40 parts by weight of polybutyl acrylate with 40 parts by weight of styrene and 20 parts by weight of acrylonitrile. Two types of AAS resins with different acrylic rubber contents were created. On the other hand, a copolymer was prepared by copolymerizing glycidyl methacrylate, styrene, methyl methacrylate, and acrylonitrile in the proportions shown in Table 1. A sample was prepared by kneading a composition having the formulation shown in Table 1 at a temperature of 190 to 200° C. for 5 minutes using a Banbury mixer. Test pieces for measuring basic physical properties were molded using a 5-ounce injection molding machine at a molding temperature of 220°C. Further, a 1 mm thick flat plate for adhesion measurement was compression molded at a temperature of 190°C using a hot press. “Adhesiveness Measuring Method” Araldite #136 manufactured by Ciba Geigy was used as an adhesive, and the above flat plate for measuring adhesiveness and an aluminum flat plate were pressed together using a hot press. (The heat press temperature is
(80°C, pressure: 10 kg/cm ² , 10 minutes of crimping) Judgment was made based on the degree of peeling of the resin sheet when a cut was made with a cutter on the resin sheet side of the crimped product and the resin sheet was bent from there. ◎: Good ×: Bad “Basic physical property measurement method” Izot impact strength and flexural modulus are
Measurements were made in accordance with ASTM standards, and fluidity was determined using the Koka formula.

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Claims (1)

[Scope of Claims] 1. A rubber-reinforced styrenic resin (A) containing 10 to 35% by weight of ethylene/propylene or acrylic rubber, an aromatic vinyl monomer, and a cyanide vinyl monomer. and a copolymer (B) comprising 95 to 30% by weight of one or more acrylic acid ester monomers and 5 to 70% by weight of glycidyl methacrylate. Composition. 2. The resin composition according to claim 1, wherein the copolymer (B) is blended in an amount of 0.01 to 40 parts by weight per 100 parts by weight of the rubber-reinforced styrenic resin (A).