JPH0124812B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a thermoplastic synthetic resin molded article having excellent surface properties such as paintability, printability, and adhesiveness. More specifically, at least one selected from α-olefins having 2 to 12 carbon atoms (including ethylene) and 1,4-dienes represented by the following formula (). (Here, R ¹ is an alkyl group having 8 or less carbon atoms,
R ² and R ³ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms. ) is molded from a resin containing an unsaturated copolymer obtained by copolymerizing at least one of the above, and the surface of the resulting molded product is treated with ozone to improve adhesion, paintability, printability, and antistatic properties. The present invention relates to a method for manufacturing a molded article having excellent properties such as properties. 1 Background Polyolefin resins such as polyethylene, polypropylene, poly-1-butene, and poly-4-methyl-1-pentene are easy to manufacture and have excellent moldability, feel, packaging properties, insulation, water resistance, and chemical resistance. ,
It is well known that it is used in a wide range of fields due to its excellent mechanical strength. For example, various packaging films, wire coating materials,
These polyolefin resins are used in a wide range of fields, including laminated materials with other materials, molded products such as pipes, containers, automobile parts, and plate materials.Since these polyolefin resins are saturated hydrocarbons, they have poor adhesive properties and are difficult to paint. It is markedly inferior in various surface properties that mainly require polar groups, such as surface properties and printability, and has been pointed out as a major drawback. Many attempts have been made to compensate for this drawback of polyolefin resins. For example, surface modification treatments such as solvent treatment, flame treatment, sulfuric acid-chromic acid mixture treatment, and corona discharge treatment are performed. However, with these methods, sufficient effects cannot be obtained (solvent treatment), it is difficult to set the treatment conditions, there is a risk of deformation of the product, and the modification effect may be insufficient for molded products with complex shapes. There is uniformity (flame treatment), the strong acidity causes severe corrosion of the equipment, and it is extremely difficult to treat the waste liquid (sulfuric acid-chromic acid mixture treatment), and there are restrictions on the form of the molded product. However, there are drawbacks such as poor durability of the effect (corona discharge treatment), and it is difficult to say that it is a satisfactory treatment method that can be applied to any molded product. Unsaturated rubbers such as natural rubber, polyisoprene rubber, polybutadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-nonconjugated diene copolymer rubber (EPDM), acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene- For unsaturated resins such as styrene copolymer resins that use conjugated dienes as comonomers, various modifications are known that utilize the reactivity of carbon-carbon double bonds within the molecule. For example, hydrogen peroxide and hydrochloric acid Oxidation of EPDM by
45395) and oxidation of EPDM with potassium permanganate (US Pat. No. 4152276) (but not surface modification). However, conventionally known unsaturated rubbers or unsaturated resins have the following problems: (1) When a conjugated diene is used as a monomer, there is a C=C bond in the main chain or the tertiary carbon atom in the main chain is at an allyl position. Because of this, it is inferior in thermal stability, weather resistance, ozone resistance, etc. (2) It has poor compatibility with polyolefin resins, and (i) it may be virtually impossible to blend them. (ii) Even if blending is possible, C=C does not appear uniformly on the surface of the blended product. (iii) Mechanical properties of blends with polyolefin resins cannot be maintained. (3) Particularly compatible with polyolefin resins,
Even if EPDM, whose comonomer is a non-conjugated diene, is selected and blended, a significant decrease in the rigidity of the polyolefin resin cannot be avoided. For these reasons, even if known techniques are applied to the surface treatment of blends of polyolefin resins and conventionally known unsaturated polymers, sufficient effects may not be obtained. However, for example, thermal stability, ozone resistance, weather resistance, moldability, mechanical properties, etc. were sacrificed. 2. Purpose and Problems In view of the above-mentioned current state of surface modification of polyolefin resins, the present invention was achieved as a result of intensive research into a surface treatment method that can effectively treat any molded product under mild conditions. did. That is, the present invention provides at least one type selected from α-olefins having 2 to 12 carbon atoms (including ethylene) and 1,4-dienes represented by the following formula (). (Here, R ¹ is an alkyl group having 8 or less carbon atoms,
^R2 and ^R3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms) A resin containing an unsaturated copolymer obtained by copolymerizing is molded, and the molded product obtained is This is a method for producing a surface-treated product characterized by treating the surface with ozone, and provides a polyolefin molded product with excellent surface properties such as adhesion, paintability, printability, and antistatic properties. 3 Specific explanation (1) Unsaturated copolymer The unsaturated copolymer used in the present invention (hereinafter referred to as copolymer A) is at least one type of α-olefin having 2 to 12 carbon atoms, It is a resinous material made of a copolymer with at least one specific 1,4-diene represented by the above formula (). In this case, "resin" has an initial elastic modulus of 100 to 100,000 at room temperature.
Kgf/cm ² , preferably 500 to 80,000 Kgf/cm ² , more preferably 1,000 to 50,000 Kgf/cm ² . Constituent monomer of copolymer A having 2 to 12 carbon atoms
Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 3-methyl-1-butene, 3
-Methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-
Dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, styrene, allyl Benzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexane, 2-vinylbicyclo[2,
2,1]-heptane and the like.
Among these, preferred examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1
-pentene, 4-methyl-1-pentene, 3-methyl-1-hexene, styrene, etc., in particular propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1- Pentene is preferred. One type of these α-olefins may be used, or two or more types may be used as long as the copolymer A does not become anything other than the above-mentioned resinous material. When two or more types of α-olefins are used, the α-olefins may be randomly distributed in the copolymer A or may be distributed in blocks. Examples of the 1,4-dienes represented by the above formula (), which are one of the constituent monomers of copolymer A, include 1,4-hexadiene, 1,4-heptadiene, and 4-methyl-1,4- Hexadiene, 5-
Methyl-1,4-hexadiene, 4-ethyl-
1,4-hexadiene, 4,5-dimethyl-1,
4-hexadiene, 4-methyl-1,4-heptadiene, 4-ethyl-1,4-heptadiene, 5
-Methyl-1,4-heptadiene, 4-ethyl-
Examples include 1,4-octadiene, 5-methyl-1,4-octadiene, and 4-n-propyl-1,4-decadiene. Among these, preferred 1,4-dienes are 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and particularly preferred are 4-methyl-1,4-hexadiene. These are hexadienes and 5-methyl-1,4-hexadiene. These 1,4-dienes may be used alone or in combination of two or more, and suitable examples include:
Combination of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (95:5-5:
95). Copolymer A is a Ziegler-Natsuta catalyst for α-olefin polymerization, particularly a catalyst for producing crystalline polymers of α-olefin, to combine the above α-olefin and 1,4-dienes with α-olefin polymerization. It can be produced by copolymerization using the same method and equipment as in the production of the copolymer. Examples of such manufacturing methods include, for example, JP-A-55-165907, JP-A-56-30414, JP-A-56-30413, JP-A-56
Examples include -36508 and 56-55409. As for the number of monomer species contained in copolymer A and the distribution of each monomer species, there are no particular limitations as long as copolymer A does not become anything other than a resinous material, as stated in the above definition. Examples of preferred types of copolymer A from the viewpoint of molecular structure are as follows. (a) A random copolymer of one or more α-olefins and one or more 1,4-dienes. (b) Block copolymerization consisting of one or more α-olefin polymerization blocks and a random copolymerization block of one or more α-olefins and one or more 1,4-dienes. Coalescence (the type of α-olefin in the α-olefin polymerization block may be the same as or different from that of the α-olefin in the random copolymerization block). (c) a random copolymerization block (block a) of one or more α-olefins and one or more 1,4-dienes;
- A random copolymerization block (block b) of olefin and 1,4-dienes,
This block is a block consisting of a block in which at least one of the types, numbers, and quantitative ratios of α-olefins contained in block b and the types, numbers, and quantitative ratios of 1,4-dienes are different from those in block a. Polymer. Specific preferable examples of these copolymers A include a random copolymer of ethylene and 1,4-hexadiene, a random copolymer of ethylene and 4-methyl-1,4-
Random copolymer with hexadiene, random copolymer with ethylene and 5-methyl-1,4-hexadiene, random copolymer with ethylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene Copolymer, propylene and 1,4-
Random copolymer with hexadiene, random copolymer with propylene and 4-methyl-1,4-hexadiene, propylene with 5-methyl-1,4-
Random copolymer with hexadiene, propylene with 4-methyl-1,4-hexadiene and 5-
Random copolymer of methyl-1,4-hexadiene, random copolymer of ethylene, propylene and 1,4-hexadiene, propylene, ethylene, 4-methyl-1,4-hexadiene and 5-methyl-1, Random copolymer with 4-hexadiene, 1-butene and 4-methyl-1,4-
Random copolymer with hexadiene, 1-butene and 4-methyl-1,4-hexadiene and 5-
Random copolymer with methyl-1,4-hexadiene, 3-methyl-1-butene and 4-methyl-
1,4-hexadiene and 5-methyl-1,4
- Random copolymers with hexadiene, random copolymers of 4-methyl-1-pentene with 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, ethylene homopolymer blocks and ethylene A block copolymer consisting of a random copolymerization block with 1,4-hexadiene, an ethylene homopolymerization block, and ethylene with 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene.
A block copolymer consisting of a random copolymerization block with methyl-1,4-hexadiene, a homopolymerization block of propylene, and a random copolymerization block of propylene and 4-hexadiene.
A block copolymer consisting of a random copolymer block of methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, a random copolymer block of propylene and ethylene, and a random copolymer block of propylene, ethylene, and 4-methyl-1 , 4-hexadiene and a random copolymerization block of 5-methyl-1,4-hexadiene, a homopolymerization block of propylene, and a random copolymerization block of ethylene and 1,4-hexadiene. block copolymer,
Homopolymer blocks of propylene and ethylene with 4-methyl-1,4-hexadiene and 5-
A block copolymer consisting of a random copolymerization block with methyl-1,4-hexadiene, a homopolymerization block of ethylene, and a random copolymerization block with propylene and 1,4-hexadiene.
- A block copolymer consisting of a random copolymerization block with hexadiene, a homopolymerization block of ethylene, and propylene with 4-methyl-1,4-
A block copolymer consisting of hexadiene and a random copolymerization block with 5-methyl-1,4-hexadiene, a homopolymerization block of 1-butene, 1-butene, 4-methyl-1,4-hexadiene, and 5-methyl -A block copolymer consisting of a random copolymerization block with 1,4-hexadiene, a homopolymerization block of 4-methyl-1-pentene, 4-methyl-1-pentene and 4-methyl-1,4-hexadiene, and 5-
A block copolymer consisting of a random copolymer block with methyl-1,4-hexadiene, a random copolymer block with ethylene and 1,4-hexadiene, and a random copolymer block with propylene and 1,4-hexadiene. a random copolymer block of ethylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and a random copolymer block of propylene and 4-methyl-1,4-hexadiene and 5-methyl-hexadiene. A block copolymer consisting of a random copolymerization block with 1,4-hexadiene, a random copolymerization block of propylene with 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and a random copolymerization block with propylene and ethylene. and a random copolymerization block of propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, propylene and 4-methyl-1,4-hexadiene and 5-methyl- Random copolymer blocks with 1,4-hexadiene, propylene and ethylene with 4-methyl-1,4-hexadiene and 5-
Random copolymerization block with methyl-1,4-hexadiene, and ethylene and 4-methyl-1,
4-hexadiene and 5-methyl-1,4-
A block copolymer consisting of a random copolymer block with hexadiene, ethylene and 4-methyl-
1,4-hexadiene and 5-methyl-1,
Random copolymerization block with 4-hexadiene and ethylene, propylene and 4-methyl-1,4
-hexadiene and a block copolymer consisting of a random copolymer block with 5-methyl-1,4-hexadiene. Here, the term "block copolymer" means the following copolymer. For example, "a block copolymer consisting of a homopolymerization block of monomer A and a random copolymerization block of monomer A and monomer B" refers to a block copolymer consisting of a homopolymerization block of monomer A and a random copolymerization block of monomer A and monomer B. The blocks are chemically combined to form A~A-
In addition to the monopolymerization block of monomer A and the random copolymerization block of monomer A and monomer B that form a chemical bond, in addition to the monopolymerization block of monomer A and the random copolymerization block of monomer A and monomer B, It also means a mixture containing a homopolymer of monomer A, a random copolymer of monomer A and monomer B, etc. Similarly, "polymerization block a and polymerization block b"
A "block copolymer consisting of" refers to a block copolymer in which polymer block a and polymer block B are chemically bonded together, as well as a block copolymer in which polymer block a and polymer block B are chemically bonded. It also means a mixture containing a copolymer that is bonded to a copolymer, and also contains a polymer consisting only of polymer block a or a polymer consisting only of polymer block b, and is synthesized using a Ziegler-Natsuta catalyst. , has the same meaning as the so-called "block copolymer". The amount of 1,4-dienes contained in copolymer A is
Less than 50 mol%, usually 0.1 to 30 mol%. The objects of the present invention are that copolymer A does not become anything other than the resin-like product defined above, that the productivity and manufacturing cost of copolymer A are high, and that the composition of copolymer A and the polyolefin described below is Taking into account that the 1,4-dienes content in the copolymer A is preferably 0.5 to 20 mol%, especially 1.0
~15 mol% is preferred. The molecular weight of copolymer A is not particularly limited as long as copolymer A or the composition of copolymer A and polyolefin can be molded, and the melt index is
0.001~1000g/10 minutes, preferably 0.01~
A molecular weight corresponding to 500 g/10 min, especially 0.05 to 200 g/10 min, is common. Among such copolymers A, 4-methyl-1,4-hexadiene and 5-
An unsaturated copolymer obtained by using methyl-1,4-hexadiene in combination, a block copolymer consisting of an ethylene homopolymer block and a random copolymer block of ethylene and 1,4-hexadiene, and a propylene homopolymer block. A block copolymer consisting of a polymer block and a random copolymer block of ethylene and 1,4-hexadiene is particularly preferred, and in particular, 4-methyl-
1,4-hexadiene and 5-methyl-1,4
- Unsaturated copolymers obtained in combination with hexadiene are preferred. (2) Unsaturated copolymer resin In the present invention, a resin containing the above-mentioned copolymer A is subjected to molding. The resin containing copolymer A refers to a resin-like material of copolymer A alone and a resin containing copolymer A and α having 2 to 12 carbon atoms.
- Refers to a mixture with an olefin polymer (hereinafter referred to as polymer B) obtained by polymerizing at least one selected from olefins (including ethylene),
These are also collectively called unsaturated copolymer resins. In addition to α-olefin, this polymer B contains α
- Vinyl monomers copolymerizable with olefins or their polymer resins, such as vinyl chloride or vinylidene, vinyl acetate, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylonitrile, maleic anhydride, vinyltrimethoxysilane, etc. may be contained in the form of a copolymer in an amount of 30% by weight or less. The term "copolymer form" as used herein refers to a copolymer in the form of block, random, graft, or a combination thereof. Also, “resin-like substances” and “α-olefins”
has the same meaning as described in the section of copolymer A. Preferred examples of polymer B include ethylene polymers (including low density to high density), propylene polymers, 1-butene polymers, 1-pentene polymers, 3-methyl-1- butene-based polymer,
These include 3-methyl-1-pentene polymers, 4-methyl-1-pentene polymers, 3-methyl-1-hexene polymers, and styrene polymers. Among these, particularly preferred are ethylene polymers, propylene polymers, 1-butene polymers,
It is a 4-methyl-1-pentene polymer. Copolymer A and polymer B can be mixed and used for the molding of the present invention. In this case, copolymer A
The composition ratio of copolymer A and polymer B can achieve the purpose of the present invention if side chain unsaturated groups based on 1,4-dienes contained in copolymer A exist, but the composition ratio of Considering this, generally 1 to 99% by weight of copolymer A and 99 to 1% by weight of polymer B should be mixed. Preferably 1,4 in 100g of the composition
- The content of dienes is blended in a range of 0.002 to 0.4 mol, particularly preferably 0.01 to 0.3 mol. Examples of these blended unsaturated copolymer resins include the compositions described in JP-A-57-44639. (3) Additional components In addition to copolymer A, or copolymer A and polymer B, which are essential components, the unsaturated copolymer resin of the present invention contains silica, mica, talc, calcium carbonate, carbon black, and glass. Fibers, glass globules, carbon fibers, gypsum, clay, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, and titanium oxide, pigments, thermoplastic resins other than olefin polymers such as polyamide, polyester, polycarbonate, and polyethylene terephthalate, and phenols. Of course, various stabilizers such as antioxidants, sulfur-based, phosphorus-based antioxidants, ultraviolet absorbers, antistatic agents, etc. may also be included. (4) Surface treatment The method for producing a surface-treated molded product of the present invention includes:
The method is characterized in that the surface of the unsaturated copolymer resin molded article is treated with ozone. Ozone can be easily produced by passing oxygen or an oxygen-containing gas through a known ozone generator. The raw materials for ozone include oxygen, air,
Oxygen-containing gases can be used, such as mixtures of oxygen and inert gases such as nitrogen, helium, argon, etc., but oxygen and air are preferably used. As an ozone generator, devices that utilize discharge phenomena such as corona discharge, glow discharge, arc discharge, and silent discharge are preferably used, and among them, devices that utilize silent discharge phenomena are particularly preferred. There are no particular restrictions on the method of treating the surface of an unsaturated copolymer resin molded product with ozone, including methods in which an ozone-containing gas is brought into direct contact with the surface of an unsaturated copolymer resin molded product, a method in which an ozone-containing gas is treated with water, methanol, etc. , alcohols such as ethanol, esters such as ethyl acetate and butyl acetate, ketones such as acetone, ethers such as diethyl ether and tetrahydrofuran, hydrocarbons such as hexane and heptane, dichloromethane, chloroform,
A method of immersing an unsaturated copolymer resin molded article in an ozone-containing liquid obtained by passing it through a liquid medium such as a halogenated hydrocarbon such as carbon tetrachloride, 1,2-dichloroethane, etc., the ozone-containing liquid All methods such as spraying or coating the surface of the unsaturated copolymer resin molding can be used in the present invention, but among them, the method of directly contacting the ozone-containing liquid with the surface of the unsaturated copolymer resin molding is It is preferred because it can omit steps such as washing and drying after surface treatment. The treatment temperature and treatment time are also not particularly limited as long as a treated product with good surface properties, which is the objective of the present invention, can be obtained. Usually 1 second at a temperature of -10℃ to +100℃
Processed for 2 hours. The treatment is preferably carried out at a temperature of 0°C to 50°C for 10 seconds to 1 hour, more preferably at a temperature of 10°C to 40°C for 30 seconds to 30 minutes. There is no particular limit to the ozone concentration either. From the viewpoint of shortening processing time and ozone production efficiency,
An ozone-containing gas having an ozone concentration of 0.1 to 500 g/m ³ , preferably 1 to 200 g/m ³ , more preferably 5 to 100 g/m ³ is used directly or by passing it through the liquid medium. The unsaturated copolymer resin whose surface has been subjected to ozone treatment can be directly used as is for desired purposes such as painting and printing. Further, if necessary, after the ozone treatment, the product can be treated with a ketone, an aldehyde, an active hydrogen compound, an oxidizing agent, a reducing agent, etc., and then used for a desired purpose. (5) Features of the surface treatment of the present invention First of all, because the present invention uses a special unsaturated copolymer resin or its composition, it has excellent thermal stability and weather resistance, and It is possible to provide a modified product with excellent surface properties without losing many features. Second, as mentioned above, the surface treatment method of the present invention can be carried out under mild conditions. Thirdly, the shape of the object to be processed is arbitrary. That is, it is possible to surface-treat films, sheets, and various types of molded objects without changing their shapes. Fourth, the surface treatment cost is low and the method is simple. In particular, the method of directly bringing an ozone-containing gas into contact with the unsaturated copolymer resin molded article is simple and low-cost because the washing step and drying step can be omitted. (6) Effects According to the present invention, it is possible to produce a molded article whose surface has surface properties based on polar groups, such as adhesiveness, paintability, printability, and antistatic properties. That is, for example, unsaturated copolymer resins or their compositions, unsaturated copolymer resins or their compositions and metals, paper, wood products, other polymeric compounds that can be bonded (e.g., polyvinyl chloride, polystyrene, It is possible to bond with materials such as polymethyl methacrylate, ABS resin, various rubbers, etc. In addition, various types of painting, printing, plating, etc. can be applied to improve the aesthetic appearance and weather resistance. These effects are remarkable effects not found in conventionally known polyolefin resin materials. 4 Experimental Example In this experimental example, the effect of surface treatment was evaluated by the adhesive strength of an epoxy resin adhesive described below. Measurement of adhesive strength Two surface-treated specimens with a width of 15 mm, a length of 80 mm, and a thickness of 2 mm were coated with epoxy resin (Yuka Ciel Epoxy Co., Ltd.) whose main ingredients are bisphenol A and epichlorohydrin up to 10 mm from the edge. Manufactured by E-
After applying an epoxy resin adhesive consisting of 70 parts of 828) and 30 parts of a polyamide curing agent (manufactured by Daiichi General Co., Ltd.; Versamid 140), the two coated surfaces were pasted together, fixed with clips, and then heated at 80°C. So 3
Allowed to cure for hours. Next, both ends of the bonded test piece were held between clamps of a 500 kg load cell, and a tensile test was conducted at a tensile speed of 5 mm/min. The load at which the adhesive surface was peeled off was expressed as "adhesive strength." Example 1 Copolymer resin of propylene and a mixture of 80% 4-methyl-1,4-hexadiene and 20% 5-methyl-1,4-hexadiene (hereinafter this mixture will be abbreviated as methylhexadiene) Methylhexadiene content 8.4 mol%, ASTMD1238
Melt index measured at 230℃ according to
19.0g/10 minutes, melting point (DSC peak value) 149℃, boiling n-heptane extraction residue 93.0% by weight, JIS-6758-
The tensile modulus of the press-formed sheet was 3000 Kg/cm ² ) measured at 25° C. and a tensile speed of 50 mm/min in accordance with 1968.The test piece was press-molded into a test piece having a width of 15 mm, a length of 80 mm, and a thickness of 2 mm. This test piece was placed in an atmosphere of ozone-containing air with an ozone concentration of 34 g/ ^m3 (Ozone was produced using air as a raw material using an IO-1 ozone generator manufactured by Nippon Ozone Co., Ltd.) at 25°C for 1 minute. The adhesion and adhesive strength of the epoxy resin adhesive were measured by the method described above, and the results are shown in Table 1. Example 2 Ethylene and 80% 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene
Copolymer resin (methylhexadiene content: 3.7 mol%, melt index measured at 190°C in accordance with ASTM D1238)
0.57g/10min, melting point (DSC peak value) 120℃, density
0.920g/ml, 25℃ according to JIS-6758-1968,
The tensile modulus of the press-formed sheet (1100 Kg/cm ² ) measured at a tensile speed of 50 mm/min was molded into the same test piece as in Example 1, treated with ozone in the same manner as in Example 1, and then treated with an epoxy resin adhesive. Adhesive strength was measured. The results are shown in Table 1. Example 3 Copolymer resin of ethylene and cis-1,4-hexadiene (cis-1,4-hexadiene content
2.7 mol%, melt index 1.7 g/10 minutes measured at 190°C according to ASTM D1238, melting point (DSC peak value) 122°C, density 0.926 g/ml, JIS-
Tensile modulus of press-formed sheet measured at 25℃ and 50mm/min in accordance with 6758-1968: 1950Kg/
The surface treatment and adhesive strength measurements were carried out in accordance with Example 1 except that 2 cm ² ) was used. The results are shown in Table 1. Example 4 A composition consisting of 50 parts by weight of a propylene homopolymer (Noprene TA-5, manufactured by Mitsubishi Yuka Co., Ltd.) and 50 parts by weight of the copolymer resin of propylene and methylhexadiene used in Example 1 was prepared. Example 1 was repeated using a propylene and methylhexadiene copolymer resin instead. The results are shown in Table 1. Example 5 A composition consisting of 70 parts by weight of the same propylene homopolymer used in Example 4 and 30 parts by weight of the copolymer resin of ethylene and methylhexadiene used in Example 2 was mixed with propylene. Example 1 was repeated using in place of the copolymer resin with methylhexadiene. The results are shown in Table 1. Comparative Example 1 Example 1 was prepared using the same propylene homopolymer used to prepare the composition of Example 4 in place of the propylene and methylhexadiene copolymer resin.
repeated. The results are shown in Table 1. Comparative Example 2 Example 1 was repeated using an ethylene homopolymer (Yukalon ZF-52, manufactured by Mitsubishi Yuka Co., Ltd.) instead of the copolymer resin of propylene and methylhexadiene. The results are shown in Table 1. Comparative Example 3 The adhesive strength of the same test piece as in Example 1 was measured according to Example 1 without surface treatment. The results are shown in Table 1.

【table】

[Table] The following experimental examples show examples of application of surface-treated unsaturated copolymer resin moldings according to the present invention to coating. As the paint, an epoxy resin paint (trade name: Eponics #3100 Primer) manufactured by Dainippon Toyo Co., Ltd. was used. Adhesion test of epoxy resin paint A surface-treated test piece with a width of 50 mm, a length of 100 mm, and a thickness of 2 mm was coated with a 30 mm wide applicator using 70% of the base agent.
After applying an epoxy resin paint consisting of parts by weight and 30 parts of a curing agent, it was allowed to stand at room temperature for 24 hours to cure, forming a coating film with a thickness of 70 μm. Using a razor blade, make vertical and horizontal cuts in this cured coating film at 1 mm intervals so that the cuts reach the unsaturated copolymer resin of the base material.
Make 100 pieces (cross cut, according to JIS K-5400). Next, I applied cellophane tape 18mm wide to the cross-cut area, set it at a 45° angle with the paint film, and peeled it off all at once. At this time, the number x of gobbles remaining without being peeled off was expressed as x/100, and was used as a measure of adhesion. Examples 6 to 10, Comparative Examples 4 to 5 The unsaturated copolymer resins used in Examples 1 to 5 and Comparative Examples 1 and 2 were used, and after surface treatment according to Example 1, epoxy After applying and curing the resin paint, an adhesion test was conducted. Comparative Example 6 An epoxy resin paint was applied to the unsaturated copolymer resin used in Example 1 without surface treatment and cured, and then an adhesion test was conducted. The results are shown in Table 2.

【table】

【table】

Claims (1)

[Scope of Claims] 1. At least one selected from α-olefins having 2 to 12 carbon atoms (including ethylene) and 1,4-dienes represented by the following formula () (Here, R ¹ is an alkyl group having 8 or less carbon atoms,
^R2 and ^R3 each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms) A resin containing an unsaturated copolymer obtained by copolymerizing is molded, and the molded product obtained is A method for producing a surface-treated unsaturated copolymer resin molded article, which comprises treating the surface with ozone.