JPH0141652B2 - - 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 paintability, printability, etc. 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. ) A resin containing an unsaturated copolymer obtained by copolymerizing at least one type of , relates to a method for producing a molded article with excellent antistatic properties. 1) Background Polyethylene, polypropylene, poly-1-
Polyolefin resins such as butene and poly-4-methyl-1-pentene are easy to manufacture;
It is well known that it is used in a very wide range of fields because it has excellent moldability, feel, packaging properties, insulation, water resistance, chemical resistance, mechanical strength, etc. For example, these polyolefin resins are used in a wide range of fields, including various packaging films, wire coating materials, laminated materials with other materials, and molded products such as pipes, containers, automobile parts, and plate materials. Since it is a hydrocarbon, it is significantly inferior in various surface properties that mainly require polar groups, such as adhesion, paintability, and printability, and this 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. 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). Not only is there a limit to the form of the molded product, There are drawbacks such as poor sustainability 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 non-polymerized rubber (EPDM), acrylonitrile-butadiene-styrene copolymer resin, methyl methacrylate-butadiene-styrene For unsaturated resins such as copolymer resins that use conjugated dienes as comonomers, various modifications are known that take advantage of the reactivity of carbon-carbon double bonds within the molecule. EPDM
oxidation of EPDM with potassium permanganate (US Patent No. 45395), oxidation of EPDM with potassium permanganate (US Pat.
4152276). However, conventionally known unsaturated rubbers or unsaturated resins have the following characteristics: (1) When the comonomer is a conjugated diene, there is a C=C bond in the main chain or the tertiary carbon atom in the main chain is at the allyl position. Therefore, it is inferior in thermal stability, weather resistance, ozone resistance, etc. (2) It has poor compatibility with polyolefin resins, and (a) it may be virtually impossible to blend them. (b) Even if blending is possible, C=C does not appear uniformly on the surface of the blend molded product. (c) The mechanical properties of the blend with polyolefin resin cannot be maintained. (3) Particularly compatible with polyolefin resins, and the comonomer is a non-conjugated diene.
Even if EPDM is selected and blended, a significant decrease in the rigidity of the polyolefin resin cannot be avoided. Therefore, even if known techniques are applied to the surface treatment of blends of polyolefin resins and conventionally known unsaturated polymers, not only are sufficient effects not obtained, but many of the characteristics of polyolefins, such as , thermal stability, ozone resistance, weather resistance,
The drawback was that 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 has been developed as a result of extensive research into surface treatment methods that can effectively treat any molded product under mild conditions. Reached. That is, the present invention provides at least one kind selected from α-olefins having 2 to 12 carbon atoms (including ethylene) and 1,4 olefins represented by the following formula ().
-Dienes (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). This method provides a polyolefin-based 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
- A resin-like material consisting of a copolymer of at least one olefin and at least one specific 1,4-diene represented by the above formula (). Here, the "resin-like material" has an initial elastic modulus of 100 to 100,000 Kgf/cm ² at room temperature, preferably 500 to 80,000 Kgf/cm ² , and more preferably
It means a copolymer having a weight of 1,000 to 50,000 Kgf/cm ² . Constituent monomer of copolymer A with 2 carbon atoms
Examples of ~12 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,
Examples include allylcyclopentene, allylcyclohexene, styrene, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclohexene, and 2-vinylbicyclo[2,2,1]-pentene. Among these, preferable 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-
Mention may be made of hexene, styrene, etc., with propylene, 1-butene, 3-methyl-1-butene, and 4-methyl-1-pentene being particularly 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 copolymer A or may be distributed in blocks. Examples of the 1,4-dienes represented by the above formula (), which are other constituent monomers of copolymer A, include 1,4-hexadiene,
1,4-pentadiene, 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-
1,4-octadiene, 5-methyl-1,4
-Octadiene, 4-n-propyl-1,4
- Examples include decadiene. Among these, preferable 1,4-dienes are 1,4-hexadiene and 4-methyl-1,4
-hexadiene, 5-methyl-1,4-hexadiene, and particularly preferred are 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene. These 1,4-dienes may be used alone or in combination of two or more. Preferred examples include 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene.
-Methyl-1,4-hexadiene (95:5 to 5:95) can be mentioned. 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 into an α-olefin polymer. It can be produced by copolymerization using the same method and equipment as in the production of. Examples of such manufacturing methods include, for example,
Unexamined Japanese Patent Publication No. 55-165907, No. 56-30413, No. 56-
Examples include Publications No. 30414, No. 56-36508, and No. 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. Preferred examples of copolymer A based on the 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 and quantity ratio of α-olefin in the α-olefin polymerization block may be the same as or different from those of the α-olefin in the random copolymerization block). (c) A random copolymerization block (block a) of one or more α-olefins with one or more 1,4-dienes;
- A random copolymerization block (block b) of olefin and 1,4-dienes,
This block is composed of a block in which at least one of the type, number, and quantitative ratio of α-olefins contained in block b and the type, number, and quantitative ratio of 1,4-dienes are different from block a. Polymer. Specific preferred examples of these copolymers A include random copolymers of ethylene and 1,4-hexadiene, ethylene and 4-methyl-
Random copolymer with 1,4-hexadiene,
Random copolymer of ethylene and 5-methyl-1,4-hexadiene, ethylene and 4-methyl-1,4-hexadiene and 5-methyl-
Random copolymer with 1,4-hexadiene,
Random copolymer of propylene and 1,4-hexadiene, propylene and 4-methyl-1,4-
Random copolymer with hexadiene, random copolymer with propylene and 5-methyl-1,4-hexadiene, propylene with 4-methyl-
1,4-hexadiene and 5-methyl-1,
Random copolymer of 4-hexadiene, random copolymer of ethylene, propylene and 1,4-hexadiene, propylene, ethylene and 4-methyl-1,4-hexadiene and 5
-Random copolymer with methyl-1,4-hexadiene, 1-butene and 4-methyl-1,4-
Random copolymers with hexadiene, random copolymers with 1-butene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, 3-methyl-butene and 4-methyl-1, 4-Hexadiene and 5-methyl-
Random copolymer with 1,4-hexadiene,
4-methyl-1-pentene and 4-methyl-1,
4-hexadiene and 5-methyl-1,4-
Random copolymer with hexadiene, block copolymer consisting of ethylene homopolymer block and random copolymer block of ethylene and 1,4-hexadiene, ethylene homopolymer block and ethylene and 4-methyl-1,4-hexadiene and a random copolymerization block with 5-methyl-1,4-hexadiene, a homopolymerization block of propylene, and a random copolymerization block of propylene and 4-methyl-1,4-hexadiene.
-Hexadiene and 5-methyl-1,4-
A block copolymer consisting of a random copolymer block with hexadiene, a random copolymer block with propylene and ethylene, and a block copolymer consisting of a random copolymer block with propylene and ethylene with 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene. A block copolymer consisting of a random copolymer block, a block copolymer consisting of a homopolymer block of propylene and a random copolymer block of ethylene and 1,4-hexadiene, a homopolymer block of propylene, and a block copolymer of ethylene and 4-methyl. A block copolymer consisting of a random copolymerization block of -1,4-hexadiene and 5-methyl-1,4-hexadiene, a homopolymerization block of ethylene, and a random copolymerization block of propylene and 1,4-hexadiene. A block copolymer consisting of
A block copolymer consisting of a homopolymerization block of ethylene and a random copolymerization block of propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, a homopolymerization block of 1-butene, and 1 ―
A block copolymer consisting of a random copolymerization block of butene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, a homopolymerization block of 4-methyl-1-pentene and 4-methyl -1- Penten and 4
-Methyl-1,4-hexadiene and 5-
A block copolymer consisting of a random copolymer block with methyl-1,4-hexadiene,
A block copolymer consisting of a random copolymer block of ethylene and 1,4-hexadiene and a random copolymer block of propylene and 1,4-hexadiene, ethylene and 4-methyl-1,4-hexadiene, and 5-methyl-1 ，
Block copolymer consisting of a random copolymer block with 4-hexadiene and a random copolymer block with propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, propylene and 4-methyl ―
1,4-hexadiene and 5-methyl-
Random copolymerization block with 1,4-hexadiene and propylene, ethylene and 4-methyl-1,4-hexadiene and 5-methyl-
A block copolymer consisting of a random copolymerization block with 1,4-hexadiene, a random copolymerization block of propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, propylene and ethylene and 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-
A block copolymer consisting of a random copolymerization block with 1,4-hexadiene, ethylene and 4-methyl-1,4-hexadiene, and 5
-Random copolymerization block with methyl-1,4-hexadiene and ethylene, propylene, 4-methyl-1,4-hexadiene and 5
-Methyl-1,4-hexadiene and a random copolymerization block. Here, the term "block copolymer" means the following copolymer. For example, "Monomer A
"A block copolymer consisting of a homopolymerization block of monomer A and a random copolymerization block of monomer A and monomer B" means a block copolymer consisting of a homopolymerization block of monomer A and a random copolymerization block of monomer A and monomer B that are chemically Combined with A~
In addition to the total composition consisting of something shaped like A-ABAAABABAAA, a homopolymerized block of monomer A and a random copolymerized block of monomer A and monomer B are chemically bonded. It also means a mixture containing a homopolymer of monomer A, a random copolymer of monomer A and monomer B, etc. Similarly, "a block copolymer consisting of polymer block a and polymer block b" refers to a copolymer in which polymer block a and polymer block b are chemically bonded to each other. It also includes a copolymer in which polymer block a and polymer block b are chemically bonded, and also includes a polymer consisting only of polymer block a and a polymer consisting only of polymer block b as a mixture. , has the same meaning as the so-called "block copolymer" synthesized using a Ziegler-Natsuta catalyst. The amount of 1,4-dienes contained in copolymer A is less than 50 mol%, usually from 0.1 to 30 mol%.
The purpose of the present invention is to ensure that copolymer A does not become anything other than the resin-like product defined above, to improve the productivity and manufacturing cost of copolymer A, and to form a composition of copolymer A and the polyolefin described below. Considering that copolymer A
The content of 1,4-dienes in it is preferably 0.5~
20 mol%, especially 1.0 to 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 about 0.001 to 1000 g/10 minutes, preferably
A molecular weight corresponding to 0.01 to 500 g/10 min, in particular 0.05 to 200 g/10 min, is customary. Among such copolymers A, unsaturated copolymer resins obtained by using 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene together as comonomers, and ethylene alone A block copolymer consisting of a polymer block and a random copolymer block of ethylene and 1,4-hexadiene, a block copolymer consisting of a propylene homopolymer block and a random copolymer block of ethylene and 1,4-hexadiene Coalescence is particularly preferred, and particularly preferred is an unsaturated copolymer resin obtained by using 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene in combination. (2) Unsaturated copolymer resin In the present invention, a resin containing the above-mentioned copolymer A is used for molding. A resin containing copolymer A refers to a resin containing copolymer A alone and a resin containing copolymer A and a carbon number of 2.
It refers to a mixture with an olefin-based polymer (hereinafter referred to as polymer B) obtained by polymerizing at least one selected from ~12 α-olefins (including ethylene), and these are also unsaturated copolymers. Also collectively called composite resin. In addition to α-olefin, this polymer B contains
Vinyl monomers copolymerizable with α-olefin or its polymer resin, such as vinyl chloride or vinylidene, vinyl acetate, acrylic acid, acrylic ester, methacrylic acid, methacrylic ester, acrylonitrile, maleic anhydride, vinyltrimethoxysilane etc. may be included 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. Furthermore, the terms "resin-like material" and "α-olefin" have the same meanings as those described in the section regarding copolymer A. Preferred examples of polymer B include ethylene polymers (including from low density to high density),
Propylene polymer, 1-butene polymer,
1-pentene polymer, 3-methyl-1-butene polymer, 3-methyl-1-pentene polymer, 4-methyl-1-pentene polymer, 3-methyl-1-hexene polymer , styrenic polymers, etc. Among these, particularly preferred are ethylene polymers, propylene polymers, 1-butene polymers, and 4-methyl-1-pentene polymers. Co-saturated A and polymer B can be mixed and used in the molded article of the present invention. In this case, the composition ratio of copolymer A and polymer B can achieve the purpose of the present invention if there is a side chain unsaturated group based on 1,4-dienes contained in copolymer A. However, in consideration of effects such as quality balance, generally 1 to 99% by weight of copolymer A and 99 to 1% by weight of polymer B should be mixed. Preferably, the content of 1,4-dienes in 100 g of the composition is 0.002 to 0.4 mol, particularly preferably
Blend so that the amount is in the range of 0.01 to 0.3 mol. Examples of these blended unsaturated copolymer resins include the compositions described in Japanese Patent Application No. 1983-49013. (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, titanium oxide, etc., pigments, thermoplastic resins other than olefin polymers such as polyamide, polyester, polycarbonate, polyethylene terephthalate, etc. Of course, various stabilizers such as phenol-based, sulfur-based, phosphorus-based antioxidants, ultraviolet absorbers, antistatic agents, etc. may also be included. (4) Surface treatment The method for manufacturing the surface-treated molded product of the present invention is as follows:
The method is characterized in that the surface of the unsaturated copolymer resin molded article is treated with a specific oxidizing agent. Oxidizing agent The oxidizing agent used in the present invention is at least one selected from the following group. Organic peracids such as hydrogen peroxide, peracetic acid, perbenzoic acid, peracid, pertrifluoroacetic acid, sulfuric acid, nitric acid, potassium permanganate, manganese sulfate (), manganese pyrophosphate (), manganese acetate (), Tris Manganese compounds such as (acetonylacetonate) manganese (), chromium oxide (), potassium dichromate,
Sodium dichromate, potassium chromate,
Chromium compounds such as sodium chromate, chromyl chloride, t-butyl chromate, and osmium tetroxide. Among these oxidizing agents, examples of particularly preferred oxidizing agents include hydrogen peroxide, peracetic acid, perbenzoic acid, performic acid, sulfuric acid, nitric acid, potassium permanganate, chromium oxide, and dichromic acid. Examples include potassium. These oxidizing agents may be used alone or in combination of two or more. Examples of the combination of two or more types include a combination of hydrogen peroxide and osmium tetroxide,
Examples include the combination of potassium permanganate and sulfuric acid, the combination of sulfuric acid and nitric acid, and the combination of sulfuric acid and potassium dichromate. Combined Use of Promoter or Catalyst A promoter or catalyst can also be used in combination with these oxidizing agents. Examples of these include light, acidic substances such as hydrochloric acid, hydrobromic acid, and phosphoric acid, alkaline substances such as sodium hydroxide and potassium hydroxide, quaternary ammonium salts,
Phase transfer catalysts such as quaternary phosphonium salts, crown ethers or cryptands,
Copper acetylacetonate, molybdenum oxide, vanadium oxide, titanium oxide, nickel oxide,
Examples include metal compounds such as iron sulfate and nickel chloride. In many cases, the combination of these can provide better results under milder conditions than when they are not used together, and is one of the preferred embodiments of the present invention. Surface Treatment Method Surface treatment of an unsaturated copolymer resin molded article with an oxidizing agent is generally carried out by dissolving the oxidizing agent in a solvent. This solvent is preferably one that is stable against oxidizing agents, for example,
water, acetic anhydride, benzene, carbon tetrachloride, chloroform, etc., and if the oxidizing agent is water-soluble (e.g. hydrogen peroxide,
Water is preferably used for peracetic acid, sulfuric acid, nitric acid, potassium permanganate, chromium oxide (), etc.). The concentration of the oxidizing agent is not particularly limited as long as the surface of the object to be treated is oxidized for the purpose. An appropriate concentration can be selected depending on the oxidizing power of the oxidizing agent, treatment temperature, and treatment time. For example, 0.5 to 50% aqueous solutions are used for hydrogen peroxide, organic peracids, potassium permanganate, chromium oxide (), and 5 to 98% for sulfuric acid and nitric acid. There are no restrictions on the form of surface treatment, and methods such as immersing the object to be treated in a treatment liquid or coating or spraying the treatment liquid onto the object are usually used. The treatment temperature and treatment time are arbitrary as long as the object to be treated is not deformed. Normally -20 to +100℃,
Preferably at a temperature of about 0 to 70°C, for several seconds to 1
It is sufficient to process for a period of time, preferably about 30 seconds to 30 minutes. After treatment, the material is generally thoroughly washed and dried before being used for the desired purpose. Depending on the type of oxidizing agent, poorly soluble or insoluble products derived from the oxidizing agent may adhere to the surface of the object to be treated. In such cases, the products should be solubilized and then cleaned and It is preferable to use it dry. For example, when a workpiece is treated with sulfuric acid acidic potassium permanganate, manganese dioxide may adhere to the surface of the workpiece. It becomes solubilized and can be washed and removed. (5) Principle of surface treatment of the present invention The principle of the method of manufacturing the surface treated product of the present invention is based on the organic chemical principle that hydrocarbons having carbon-carbon double bonds are significantly more easily oxidized than saturated hydrocarbons. It is based on knowledge. The types of surface functional groups created by this oxidation are, as is well known from the oxidation of low-molecular-weight olefins.
They vary and are complicated depending on the type of oxidizing agent used and the processing conditions (temperature, time, oxidizing agent concentration, presence or absence of a promoter or catalyst, etc.), and it is difficult to specify them unambiguously. According to common sense in organic chemistry, at least one kind of oxygen-containing compounds such as epoxides, glycols, alcohols, ketones, diketones, oxycarbonyls, and carboxyls are thought to be generated on the surface of the object to be treated. (6) 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, weather resistance, and ozone resistance. , it is possible to provide a modified product with excellent surface properties without losing many of the characteristics possessed by polyolefins. Second, as mentioned above, the surface treatment method of the present invention can be carried out under mild conditions and using reagents that are easy to handle. Thirdly, the shape of the object to be processed is arbitrary. That is, it is possible to surface-treat films, sheets, and various molded products without changing their shapes. Fourth, the surface treatment cost is low and the method is simple. For example, treatment with hydrogen peroxide, sulfuric acid, potassium permanganate, etc. is particularly inexpensive. (7) Effects According to the present invention, it is possible to produce a molded article having 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, other adhesive bondable polymer compounds (e.g., polyvinyl chloride, polystyrene, polyvinyl chloride, polystyrene, It is possible to bond with methyl methacrylate, rubbers, etc.). In addition, various types of painting, printing, plating, etc. can be applied to improve the aesthetic appearance and weather resistance. 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 Methylhexadiene, a copolymer of propylene and a mixture consisting of 80% 4-methyl-1,4-hexadiene and 20% 5-methyl-1,4-hexadiene (hereinafter this mixture will be abbreviated as methylhexadiene) Content 8.4 mol%, melt index 19.0 measured at 230°C according to ASTM D1238
g/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 1668.The sheet 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 immersed in a 97% sulfuric acid aqueous solution at 15° C. for 30 minutes, washed with water, air-dried, and bonded with an epoxy resin adhesive according to the method described above, and the bond strength was measured. The results are shown in Table 1. Example 2 Ethylene and 80% 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene
A copolymer with a mixture consisting of 20% (hereinafter this mixture will be abbreviated as methylhexadiene) (methylhexadiene content 3.7 mol%, melt index 0.57 measured at 190 ° C according to ASTM D1238)
g/10 minutes, melting point (DSC peak value 120℃, density 0.920
g/ml, the tensile modulus of the press-formed sheet was measured in accordance with JIS-6758-1968 at 25°C and a tensile speed of 50 mm/min (1100 Kg/cm ² ), and was molded into the same test piece as in Example 1. Potassium permanganate 3.2g, sulfuric acid (97
%) and 50 ml of water at 15℃.
After soaking for one minute in sodium bisulfite
Example 1
The adhesive strength of the epoxy resin adhesive was measured according to the following. The results are shown in Table 1. Example 3 Copolymer of ethylene and cis-1,4-hexadiene (cis-1,4-hexadiene content 2.7 mol%, melt index measured at 190°C in accordance with ASTM D1238, 1.7 g/10 min, Melting point (DSC
Peak value) 122℃, density 0.926g/ml, JIS-6758
- Tensile modulus of press-formed sheet measured at 25℃ and tensile speed 50mm/min in accordance with 1968 (1950Kg/ ^cm2 )
All surface treatments and adhesive strength measurements were carried out in accordance with Example 2, except that the same procedure was used. The results are shown in Table 1. Example 4 The same test piece used in Example 1 was immersed in a treatment solution consisting of 3.2 g of potassium permanganate, 0.1 g of tributylbenzylammonium chloride, and 50 ml of water at 15°C for 1 minute, and then immersed in 3.3 g of sodium bisulfite. g, 1 ml sulfuric acid (97%), and 100 ml water
After being immersed in a solution consisting of for 20 seconds, washed with water and dried, the adhesive strength was measured in accordance with Example 1. The results are shown in Table 1. Example 5 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 of propylene and methylhexadiene used in Example 1
parts by weight were molded into the same test piece as in Example 1, and immersed in a treatment solution consisting of 3.0 g of potassium dichromate, 0.1 g of tributylbenzylammonium chloride, and 50 ml of water at 15°C for 1 minute, and then washed with water. - After drying, the adhesive strength was measured according to Example 1. The results are shown in Table 1. Example 6 A composition consisting of 70 parts by weight of the same propylene homopolymer used in Example 5 and 30 parts by weight of the copolymer of ethylene and methylhexadiene used in Example 2 was prepared as in Example 1. Shaped into the same specimen, 3.2 g of potassium permanganate, 2 g of phosphoric acid, and water were added.
After being immersed in a treatment solution of 50 ml at 15° C. for 1 minute, it was treated with a sulfuric acid acidic sodium bisulfite aqueous solution according to Example 2, washed with water and dried, and the adhesive strength was measured according to Example 1. The results are shown in Table 1. Example 7 The same test piece as in Example 1 was immersed in a treatment solution consisting of 15 g of hydrogen peroxide, 0.1 g of vanadium pentoxide, 0.1 g of tributylbenzylammonium chloride, and 50 ml of water at 15°C for 5 minutes, then washed with water and dried. , water washing and measurement of adhesive strength according to Example 1. The results are shown in Table 1. Example 8 The same test piece as in Example 1 was treated with chromium oxide ().
5.0g of tributylbenzylammonium chloride, 0.1g of tributylbenzyl ammonium chloride, and 50ml of water at 10°C.
After immersing in water for 10 minutes, the sample was washed with water and dried, and the adhesive strength was measured according to Example 1. The results are shown in Table 1. Example 9 The same test piece as in Example 1 was immersed in a 10% acetic acid solution of peracetic acid at 35°C for 25 minutes, washed with water, and dried.
Adhesive strength was measured according to the following. The results are shown in Table 1. Example 15 The same test piece as in Example 1 was placed in a 90% nitric acid aqueous solution at 15°C.
After soaking for 30 minutes, it was washed with water and dried. The adhesive strength measured according to Example 1 was 48 Kg/15 mm x 10 mm or more (material failure). Example 16 The same test piece as in Example 1 was treated with osmium tetroxide.
0.5 g of tributylbenzyl ammonium chloride, 0.1 g of tributylbenzylammonium chloride, and 50 ml of water at 50°C.
After soaking in water for 3 minutes, it was washed with water and dried. The adhesive strength measured according to Example 1 was 34Kg/15mm x 10mm. Comparative Example 1 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. Comparative Example 2 The same propylene homopolymer used to prepare the composition in Example 5 was subjected to surface treatment and adhesive strength measurement according to the method of Example 2. The results are shown in Table 1. Comparative Example 3 Instead of a copolymer of ethylene and methylhexadiene, an ethylene homopolymer (manufactured by Mitsubishi Yuka Co., Ltd.,
Example 2 was repeated using Yucalon ZF-52). 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: Ebonix #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. In this cured coating film, use a razor blade to make vertical and horizontal cuts at 1 mm intervals so that the cuts reach the unsaturated copolymer resin of the base material.
Make 100 pieces (cross cut; compliant with 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, since no peeling occurred, the number of remaining gobbles x was expressed as x/100 and was used as a measure of adhesion. Examples 10 to 14, Comparative Example 4.5 The unsaturated copolymer resins used in Examples 1 to 3, Examples 4 and 5, and Comparative Examples 2 and 3 for comparison were used, and Following the same method, an epoxy resin paint was applied and cured after surface treatment, and then an adhesion test was conducted. The results are shown in Table 2. Comparative Example 6 An epoxy resin paint was applied to the unsaturated copolymer resin used in Example 1 without surface treatment, and an adhesion test was conducted. The results are shown in Table 2.

【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, R ²
and R ³ each represent a hydrogen atom or an alkyl group having 8 or less carbon atoms. ) is molded, and the surface of the resulting molded product is treated with at least one oxidizing agent selected from the group consisting of the following oxidizing agents: A method for producing a surface-treated unsaturated copolymer resin molded article, the method comprising: Oxidizing agent: hydrogen peroxide, organic peracid, sulfuric acid, nitric acid,
Manganese compounds, chromium compounds, osmium tetroxide.