JPS6364460B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing a rigid resin molded article with excellent paintability, printability, and adhesiveness.
More specifically, at least one selected from α-olefins having 2 to 12 carbon atoms (including ethylene),
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. ) by molding a resin containing an unsaturated copolymer obtained by copolymerizing at least one of the above, and treating the resulting molded product with a halogen cationic compound, resulting in a resin molded product with excellent printability, etc. This provides a method for obtaining 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, chemical resistance,
It is used in a wide range of fields due to its excellent mechanical strength. For example, various packaging films, wire coating materials,
It is used in laminated materials with other materials, pipes and containers, automobile parts, plate materials, etc. However, since these polyolefin resins are saturated hydrocarbons, they are markedly inferior in various surface properties that mainly require polar groups, such as adhesion, paintability, and printability, which 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 product deformation, and the modification effect may be uneven in molded products with complex shapes. It is strongly acidic and causes severe corrosion of equipment, and is highly toxic, making it extremely difficult to treat wastewater (sulfuric acid-chromic acid mixture treatment).There are restrictions on the form of molded products. Not only
There are drawbacks such as poor sustainability of effects (corona discharge treatment), and it is difficult to say that it is a safe and stable treatment method that can be applied to any molded product. On the other hand, vulcanized products of unsaturated rubber such as natural rubber, polyisoprene, and polybutadiene, or acrylonitrile-butadiene-styrene copolymer resins,
There is a method in which the surface of a resin molded product containing a conjugated diene as a comonomer, such as methyl methacrylate-butadiene-styrene copolymer resin, is treated with a treatment agent consisting of an alkyl hypohalite, active hydrogen, and a functional group-containing compound ( Tokuko Sho 55-7858, Sho 55-
12053). However, these unsaturated rubber vulcanizates or resin molded products have poor thermal stability and weather resistance because (1) there is a C=C bond in the main chain or the tertiary carbon atom in the main chain is at the allyl position. , inferior in 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) Even if a rubber that is particularly compatible with the polyolefin resin is selected and blended, a significant decrease in the rigidity of the polyolefin resin cannot be avoided. Therefore, even if the above-mentioned known invention is applied to a blend of a polyolefin resin and the polymer described in the invention, sufficient effects may not be obtained. For example, it has the drawback of sacrificing thermal stability, ozone resistance, weather resistance, moldability, mechanical properties, etc. 1. Purpose and Issues In view of the above-mentioned current state of surface modification of polyolefin resins, we have conducted extensive research into surface treatment methods that can safely and effectively treat any molded product under mild conditions. We have arrived at the present invention. That is, the present invention provides 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 of The purpose of this invention is to produce a polyolefin molded article with excellent adhesiveness, paintability, printability, antistatic properties, etc. by treating it with a halogen cationic compound. 2 Specific explanation (1) Unsaturated copolymer The unsaturated copolymer used in the present invention has 2 carbon atoms.
A resinous copolymer of at least one α-olefin of ~12 and at least one specific 1,4-diene represented by the above formula () (hereinafter referred to as "copolymer A"). It is. Resin-like means that the initial elastic modulus at room temperature is 100~
100000Kg/cm ² , preferably 500-80000Kg/
cm ² , more preferably 1000 to 50000 Kg/cm ² . A structural 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.
Preferred examples of these 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., and in particular ethylene, 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 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-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, and 5-methyl-1,4-hexadiene, and particularly preferred are 4-methyl-1,4-hexadiene. hexadiene and 5
-Methyl-1,4-hexadiene. These 1,4-dienes may be used alone or in combination of two or more, and preferred examples include 4-dienes.
-Methyl-1,4-hexadiene and 5-methyl-
Combined use of 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, Japanese Patent Applications No. 54-73808, No. 106494, No. 106495, No. 112597,
Examples include 131231. 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 (α- of α-olefin polymerization block
The type and quantity ratio of the olefin 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 and one or more 1,4-dienes, and a random copolymerization block of α-olefins and 1,4-dienes. The copolymerization block (block b), the type, number, and quantitative ratio of α-olefins contained in this block b, and the type, number, and quantity of 1,4-dienes;
and a block copolymer consisting of block a and a different block in at least one quantitative ratio. Specific preferred examples of these copolymers A include random copolymers of ethylene and 1,4-hexadiene, 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 copolymer block with 1,4-hexadiene, an ethylene homopolymer block, 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 propylene, and a random copolymerization block of propylene and 4-
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 propylene and 1,
A block copolymer consisting of a random copolymerization block with 4-hexadiene, a homopolymerization block of ethylene, and propylene and 4-methyl-1,4
-Hexadiene and a random copolymer block with 5-methyl-1,4-hexadiene, a homopolymer block of 1-butene, 1-butene and 4-methyl-1,4-hexadiene, and a 5-methyl-1,4-hexadiene block copolymer. A block copolymer consisting of a random copolymerization block with methyl-1,4-hexadiene, a homopolymerization block of 4-methyl-1-pentene, and 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 -A block copolymer consisting of a random copolymerization block with 1,4-hexadiene,
Random copolymer blocks of propylene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and propylene, ethylene, 4-methyl-1,4-hexadiene and 5-methyl-1,4- A block copolymer consisting of a random copolymerization block with hexadiene,
Random copolymer blocks 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-1,
A block copolymer consisting of a random copolymer block with 4-hexadiene, ethylene and 4-methyl-1,4-hexadiene and 5-methyl-
Random copolymerization block with 1,4-hexadiene and ethylene, propylene and 4-methyl-
1,4-hexadiene and 5-methyl-1,
Examples include block copolymers consisting of random copolymerization blocks with 4-hexadiene. Here, the term "block copolymer" means the following copolymer. For example, "a block copolymer consisting of a homopolymerized block of monomer A and a random copolymerized block of monomer A and monomer B" means a homopolymerized block of monomer A,
A random copolymer block of monomer A and monomer B is chemically combined to form A〓A-
In addition to those with a shape like ABAAABABAA that make up the entire composition, there are also homopolymerized blocks of monomer A like this and monomer A
and a random copolymerization block of monomer B,
It also includes a chemically bonded copolymer, and also includes a homopolymer of monomer A, a random copolymer of monomer A and monomer B, etc. as a mixture. 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 intention of the present invention is that the copolymer A does not become anything other than the resin-like product defined above, the productivity and manufacturing cost of the copolymer A, and the composition of the copolymer A and the polyolefin described below. 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 a mixed resin 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, in particular 0.05 to 200 g/10 min, is usual. Among such copolymers A, 4-methyl-1,4-hexadiene and 5-
An unsaturated copolymer resin obtained by using methyl-1,4-hexadiene in combination, a block copolymer consisting of a homopolymerized block of ethylene and a random copolymerized block of ethylene and 1,4-hexadiene, and a monopolymerized resin of propylene. A block copolymer consisting of a polymer block and a random copolymer block of ethylene and 1,4-hexadiene is particularly preferred, and especially 4-methyl-1, 4-methyl-1,
An unsaturated copolymer obtained by using a combination of 4-hexadiene and 5-methyl-1,4-hexadiene is preferred. (2) Resin for molding In the present invention, a resin containing the above-mentioned copolymer A is used for molding. The resin containing copolymer A refers to the above-mentioned homoresin-like material of copolymer A and copolymer A with a carbon number of 2 to 2.
It means a mixture with an olefin-based polymer resin (hereinafter referred to as polymer B) obtained by polymerizing at least one type selected from the 12 α-olefins (including ethylene), and these are also combined with unsaturated copolymer resins. Collectively called polymer resins. In addition to α-olefin, this polymer B contains α-
Vinyl monomers copolymerizable with olefins or their polymers, such as vinyl chloride or vinylidene, vinyl acetate, acrylic acid, acrylic esters, methacrylic acid, methacrylic esters, acrylonitrile, maleic anhydride, vinyltrimethoxysilane, etc. It may be contained in the form of a polymer in an amount of up to 30% by weight. The term "copolymer form" as used herein refers to a copolymer in the form of block, random, graft, or a combination thereof. Further, "α-olefin" has the same meaning as that described in the section of copolymer A, and as polymer B, the same resinous material as copolymer A is used. 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 copolymers, and 4-methyl-1-pentene polymers. Here, the term "M-based polymer" refers to not only the homopolymer of α-olefin "M" but also its homopolymer, "M" and other α-olefins, and vinyl monomers (as mentioned above). ) and mixtures thereof. However, in the case of a copolymer, α-olefin “M” must account for at least a majority. Copolymer A and polymer B can be mixed to obtain a resin used for molding in the present invention. At this time, the composition ratio of copolymer A and polymer B is such that, if there is a side chain unsaturated group based on 1,4-dienes contained in copolymer A, the object of the present invention can be achieved. 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
It is blended in a range of 0.002 to 0.4 mol, particularly preferably 0.01 to 0.3 mol. Examples of these unsaturated copolymer resin compositions include the compositions described in Japanese Patent Application No. 55-49013. (3) Additional components The unsaturated copolymer resin of the present invention or the composition thereof includes copolymer A or copolymer A, which is an essential component.
In addition to polymer B, silica, mica, talc, calcium carbonate, carbon black, glass fiber,
Glass spheres, 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, phenolic resins, It goes without saying that various stabilizers such as sulfur-based and phosphorus-based antioxidants, ultraviolet absorbers, and antistatic agents may be included. (4) Surface Treatment The molded article surface treatment method of the present invention is characterized in that the unsaturated copolymer resin is treated with a halogen cationic compound. (a) Halogen cationic compound The halogen cationic compound referred to in the present invention is:
A compound that generates a halogen cation alone or in a suitable solvent, particularly an element or compound that generates a halogen cation or hypohalous acid in the presence of the active hydrogen compound described below, is used together with the active hydrogen compound. Examples of these halogen cationic compounds include halogens such as chlorine, bromine, and iodine; hypohalous acids such as hypochlorous acid, hypobromous acid, and hypoiodic acid; sodium hypochlorite; Metal salts of hypohalous acids such as potassium chlorate, calcium hypochlorite (salt powder), sodium hypobromite, potassium hypobromite, calcium hypobromite, sodium hypoiodite, hypochlorite Hypohalous acid esters such as t-butyl acid, t-amyl hypochlorite, t-butyl hypobromite, and t-butyl hypoiodite, monochloroamine, monobromamine, monoiodoamine, N- N-haloamines such as monochloromethylamine, N-monochloroethylamine, N-monobromobutylamine, N-monochloroaniline, trichloromelamine, N-chloroacetamide, N-bromoacetamide, N-chlorourea, N-chlorosuccinimide, N-bromosuccinimide, N-chlorophthalimide, N-bromophthalimide, sodium benzenesulfochloramide (chloramine-
B), Sodium-p-toluenesulfochloramide (chloramine-T), N,N-dichlorotoluenesulfamide, trichloroisocyanuric acid, sodium dichloroisocyanurate, potassium dichloroisocyanurate, tribromoisocyanuric acid, N-chloroethyl Urethane, N-haloamide or N-haloimide such as N,N-dichloroethyl urethane, haloisocyanate such as chloroisocyanate, iodoisocyanate,
Examples include quinone-N-haloimides such as quinone-N-chloroimide and quinone-N-bromoimide. Among these, hypohalites, N-haloamides, and N-haloimides are preferred.
Specific particularly preferred examples include sodium hypochlorite, calcium hypochlorite, sodium hypobromite, N-chloroacetamide, N-chlorourea, N-chlorosuccinimide, N-bromosuccinimide, N-chloroacetamide, N-chlorourea, N-chlorosuccinimide, N-bromosuccinimide, -Chlorophthalic acid imide, N-
Examples include bromophthalic acid imide, chloramine-B, chloramine-T, trichloroisocyanuric acid, sodium dichloroisocyanurate, N,N-dichloroethyl urethane, and the like. (b) Active hydrogen compound The active hydrogen compound that may be used for the surface treatment of the present invention contains a hydroxyl group, a carboxyl group,
A compound having at least one group selected from a mercapto group, an amino group (excluding tertiary amino groups), and an acid amide group (excluding acid amides of secondary amines). Examples of these compounds include water,
Ammonia, alcohols, phenols, carboxylic acids, mercaptans, thiophenols,
Examples include primary and secondary amines, acid amides, N-monosubstituted acid amides, and the like. There is no particular restriction on the molecular weight of these compounds. Examples of alcohols include methanol, ethanol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, t-butyl alcohol, 2-ethylhexanol, ethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, propylene glycol. Monoalkyl ether, ethylene glycol monoester, diethylene glycol, polyethylene glycol, polypropylene glycol,
pentaerythritol, monoethanolamine,
diethanolamine, triethanolamine,
Examples include 1,4-butanediol, glycerin, glucose, mannose, fructose, and the like. Examples of phenols include phenol, cresol, catechol, resorcinol, hydroquinone, pyrogallol, methyl salicylate, α-naphthol, β-naphthol, o-, m-, and p-
Aminophenol, bisphenol A, o-, m
-, and p-hydroxyacetophenone. Examples of carboxylic acids include acetic acid, propionic acid, glycolic acid, acrylic acid, methacrylic acid,
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, phthalic acid,
Examples include β-hydroxypropionic acid, succinic acid monoester, succinic acid monoamide, benzoic acid, naphthalene carboxylic acid, acetylsalicylic acid, salicylic acid, ethylenediaminetetraacetic acid, β-benzoylpropionic acid, and lactic acid. Examples of mercaptans and thiophenols include methyl mercaptan, ethyl mercaptan, thioglycol, thioglycolic acid, β-mercaptoethanolamine, β-mercaptopropionate, thiophenol, α-thionaphthol, β-thionaphthol, etc. can be mentioned. Examples of primary and secondary amines include methylamine, ethylamine, diethylamine, ethylenediamine, polyethyleneimine, hexamethylenediamine, aniline, benzylamine, phenylenediamine, sulfanilic acid, α-naphthylamine, β-naphthylamine, Glycine, alanine, etc. can be mentioned. Examples of acid amides and N-monosubstituted acid amides include formamide, N-methylformamide, acetamide, N-methylacetamide, malonic acid diamide, succinic acid diamide, maleic acid diamide, fumaric acid diamide, benzoic acid amide, Examples include phthalic acid diamide, acetanilide, and N-acetyl-p-toluidine. Among these compounds, water, methanol, ethanol, ethylene glycol, ethylene glycol monoester, polyethylene glycol, pentaerythritol, monoethanolamine, diethanolamine, triethanolamine, glycerin, phenol, methyl salicylate, aminophenol, bisphenol A , acetic acid, glycolic acid, oxalic acid, malonic acid, succinic acid, adipic acid, phthalic acid, acetylsalicylic acid, salicylic acid, thioglycolic acid, ethylenediamine, polyethyleneimine, hexamethylenediamine, formamide, acetamide, malonic acid diamide, maleic acid diamide , etc. are preferably used. (c) Surface treatment method In the treatment of the present invention, an active hydrogen compound is not necessarily required, and the treatment proceeds by immersing the molded article in the liquid or solution of the halogen cationic compound and then leaving it in the air. do. However, it is desirable to use an active hydrogen compound in combination, and usually the active hydrogen in the active hydrogen compound is 0.01 to 1 mole of the halogen cationic compound.
The treatment is carried out in the presence of an active hydrogen compound in an amount corresponding to 100000 g atoms, preferably 0.1 to 10000 g atoms, more preferably 0.5 to 1000 g atoms. The use of a processing solvent is optional, but when used in conjunction with an active hydrogen compound, it may itself function as a solvent (e.g., water, methanol, ethanol, ethylene glycol, propylene glycol, ethylene glycol monoester, ethanolamine). , diethanolamine, acetic acid, thioglycol, ethylenediamine, etc.) often do not require a particular solvent. When using a treatment solvent, any solvent may be used as long as it does not inhibit surface treatment, such as carbon tetrachloride, toluene, 1,2-dichloroethane, acetone, diethyl ether, tetrahydrofuran, and ethyl acetate. In this case, the concentration of halogen cationic compounds is usually between 0.001 and 100
It is about mol/l. The surface treatment temperature and time are also not particularly limited as long as the effects of the present invention can be obtained. Usually at a temperature of -50 to +100℃, preferably -10 to +70℃ for 1 second to 200 minutes.
Preferably, a time of about 10 seconds to 100 minutes is sufficient. A catalyst or accelerator can also be used in combination with the surface treatment. In many cases, better effects can be obtained than when these are not used in combination, and their combination is one of the preferred embodiments of the present invention. Examples of these include organic or inorganic acids such as acetic acid, p-toluenesulfonic acid, hydrochloric acid, sulfuric acid, phosphoric acid, quaternary ammonium salts, quaternary phosphonium salts, crown ethers or cryptands, etc. can. When the active hydrogen compound has an acidic group such as a carboxyl group, it is preferable because it itself acts as a promoter. The surface treatment method is not particularly limited as long as the halogen cationic compound, or the halogen cationic compound and the active hydrogen compound, come into contact with the surface of the object to be treated to modify the surface. It can take various forms. For example, a method of immersing the object to be treated in a treatment liquid containing an active hydrogen compound, a halogen cationic compound, and optionally the catalyst or promoter; a method of immersing the object to be treated in a halogen cationic compound or a solution thereof; method, a method of applying the treatment liquid to the object to be treated, a method of first applying an active hydrogen compound to the object to be treated, and then applying a halogen cationic compound, a method of first applying a halogen cationic compound to the object, and then applying active hydrogen. Examples include a method of applying a compound. When a catalyst or promoter is used in combination with the latter two methods, they may be added to either the active hydrogen compound or the halogen cationic compound, or to both. After surface treatment, it is common to thoroughly wash the material with a solvent such as water, acetone, ethyl acetate, or carbon tetrachloride, and then use it for the desired purpose. (5) Principle of surface treatment of the present invention Although the details of the principle by which the surface of an unsaturated copolymer resin molded product is modified by the treatment method of the present invention are unknown, halogen cations (X) first attacks the carbon-carbon double bond on the surface of the object to be treated, producing a three-membered cyclic carbonium ion, and then the anion (Y) derived from the halogen cationic compound and/or active hydrogen compound is thought to react. is reasonable. (6) Features of the method for producing a surface-treated product of the present invention First of all, in the present invention, since a special unsaturated copolymer resin or its composition is used, thermal stability, weather resistance, and ozone resistance are improved. It is possible to provide a modified product with excellent surface properties without losing many of the characteristics of 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 a combination of water and sodium or calcium hypochlorite 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, unsaturated copolymer resins and metals, paper, wood, other bondable polymeric compounds (for example, polyvinyl chloride, polystyrene,
It is possible to bond with materials such as polymethyl methacrylate, rubber, etc.). We also offer various types of painting, printing,
It is possible to apply plating, etc., and it is possible to improve the appearance and weather resistance. 3 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%, ASTM
Melt index 19.0g/10min measured at 230℃ according to D1238, melting point (DSC peak value) 149
°C, boiling n-heptane extraction residue 93.0% by weight, JIS
-6758-1968 tensile modulus of press-formed sheet measured at 25℃ and 50mm/min tensile modulus 3000Kg
/cm ² ) was press-molded into a test piece with a width of 15 mm, a length of 80 mm, and a thickness of 2 mm. This test piece was immersed in a sodium hypochlorite aqueous solution containing 5% by volume of acetic acid and 4% by weight in terms of active chlorine at 15°C for 1 minute, washed with water and air-dried, and then applied to an epoxy resin adhesive using the method described above. Adhesion and adhesive strength were measured. The results are shown in Table 1. Example 2 The same test piece as in Example 1 was immersed in a treatment solution consisting of 1.0 g of N-bromosuccinimide, 25 ml of ethylene glycol, and 25 ml of acetone at 25°C for 10 minutes, then washed with acetone and air-dried. , the adhesive strength using an epoxy resin adhesive was measured. The results are shown in Table 1. Example 3 The same test piece as in Example 1 was treated with 1.0 g of trichloroisocyanuric acid, 15 g of salicylic acid and 50 ml of acetone.
After immersing it in a treatment solution consisting of for 10 minutes at 25℃,
After cleaning with acetone and air drying, the adhesive strength using an epoxy resin adhesive was measured. The results are shown in Table 1. Example 4 The same test piece as in Example 1 was immersed in a treatment solution consisting of 10 g of sodium dichloroisocyanurate, 0.1 g of tributyloctylammonium chloride and 50 ml of water at 15°C for 1 minute, then washed with water and air-dried.
The adhesive strength using an epoxy resin adhesive was measured. The results are shown in Table 1. Example 5 The same test piece as in Example 1 was immersed in a 10% ethyl acetate solution of N,N-dichloroethyl urethane at 25°C for 5 minutes, washed with acetone, air-dried, and bonded with an epoxy resin adhesive. The strength was measured.
The results are shown in Table 1. Example 6 The same test piece as in Example 1 was immersed in a treatment solution consisting of 1.0 g of N-promosuccinimide, 10 ml of propylene glycol, and 30 ml of acetone at 25°C for 10 minutes, then washed with acetone and air-dried to form an epoxy resin. The adhesion strength of the adhesive was measured. Table 1 shows the results.
Shown below. Example 7 The same test piece as in Example 1 was immersed in a treatment solution consisting of 5 g of N,N-dichlorourethane, 5 g of malonic acid, and 50 ml of acetone at 15°C for 5 minutes, then washed with acetone and air-dried. The adhesive strength using an epoxy resin adhesive was measured. The results are shown in Table 1. Example 8 Copolymer resin of ethylene and methylhexadiene (methylhexadiene content 3.7 mol%, ASTM
Melt index 0.57g/10min measured at 190℃ according to D1238, melting point (DSC peak value) 120
℃, density 0.920 g/ml, and tensile modulus of press-formed sheet measured at 25° C. and a tensile speed of 50 mm/min according to JIS-6758-1968, 1100 Kg/cm ² ). Then, the adhesive strength using an epoxy resin adhesive was measured. The results are shown in Table 1. Example 9 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 1950Kg measured at 25℃ and tensile speed 50mm/min in accordance with 6758-1968
The adhesive strength using an epoxy resin adhesive was measured in the same manner as in Example ¹ , except that the epoxy resin adhesive was used. The results are shown in Table 1. Example 10 A composition consisting of 50 parts by weight of a propylene homopolymer (manufactured by Mitsubishi Yuka Co., Ltd., Noblen TA-5) and 50 parts by weight of the copolymer resin of propylene and methylhexadiene used in Example 1 was prepared. The adhesive strength of the epoxy resin adhesive was measured in accordance with Example 1 except for the use of the adhesive. The results are shown in Table 1. Example 11 Low density polyethylene (manufactured by Mitsubishi Yuka Co., Ltd., Yucalon
ZF-52) 70 parts by weight and 30 parts by weight of the copolymer resin of ethylene and methylhexadiene used in Example 8. Adhesive strength was measured. The results are shown in Table 1. Comparative Example 1 Example 1 was repeated using the propylene homopolymer used in Example 10 instead of the propylene and methylhexadiene copolymer resin. The results are shown in Table 1. Comparative Example 2 Example 1 was repeated using the low-density polyethylene (Yukalon ZF-52, manufactured by Mitsubishi Yuka Co., Ltd.) used in Example 11 instead of the copolymer resin of propylene and methylhexadiene. The results are shown in Table 1. Comparative Example 3 The copolymer resin of propylene and methylhexadiene used in Example 1 was bonded with an epoxy resin adhesive 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 method for epoxy resin paint
After applying an epoxy resin paint consisting of 70 parts by weight of base agent and 30 parts of curing agent using a 30 mm applicator,
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; 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, the number x of gobbles remaining without being peeled off was expressed as x/100, and was used as a measure of adhesion. Examples 12 to 16, Comparative Examples 4 and 5 The same unsaturated copolymer resin as used in Example 1, Examples 8 to 11, and Comparative Examples 1 and 2 was used, and the treatment time was 5 minutes. Everything else is Example 1
After surface treatment using the same method as above, an epoxy resin paint was applied and cured, 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】

【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. ) A surface-treated unsaturated product characterized by molding a resin containing an unsaturated copolymer obtained by copolymerizing at least one of the following: and treating the resulting molded product with a halogen cationic compound. A method for producing copolymer resin molded articles. 2. Production of a surface-treated unsaturated copolymer resin molded article according to claim 1, characterized in that the treatment of the molded article is contact treatment with a halogen cationic compound in the presence of an active hydrogen compound. Law.