JPH0131527B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a novel unsaturated copolymer resin consisting of α-olefin and 1,4-dienes, or a composition in which other thermoplastic polymers are optionally added thereto. , relates to a method for producing a modified copolymer with excellent adhesive properties and modifying properties, which is obtained by graft polymerizing an unsaturated organic acid or its derivative. In addition to being inexpensive, α-olefin homopolymers and their copolymers have excellent mechanical strength, gloss, transparency, and
It is widely used because of its moldability, packaging properties, chemical resistance, etc. However, since the α-olefin polymer has a non-polar molecular structure, it has poor affinity with other substances, and it is not easy to use it as it is as an adhesive or a laminated material. In order to improve this property, conventionally, instead of the α-olefin polymer, modified polymers were prepared by graft-modifying it with an unsaturated organic acid or its derivative, and copolymerization of α-olefin and an unsaturated organic acid or its derivative was used. A combination of α-olefin polymers, an acid-treated α-olefin polymer, and an α-olefin polymer blended with a rubber component or an inorganic filler are used, and each has achieved its purpose to some extent. However, the way in which various products are used these days is quite severe, and therefore products that can withstand harsh conditions such as repeated cold and hot atmospheres, repeated impacts, and conditions where residual stress is present are now required. Therefore, there is a need for something that has greater affinity for other substances than conventional ones. The present invention was made based on these demands, and involves graft-modifying a specific unsaturated copolymer resin having unsaturated bonds in its molecular structure with a certain amount of an unsaturated organic acid or its derivative. It has been found that by treatment, a modified copolymer having extremely good affinity with other substances can be obtained. In a method of modifying a polymer resin and an unsaturated organic acid or its anhydride under graft polymerization conditions, the resin is at least one type of α-olefin having 2 to 12 carbon atoms and a compound represented by the formula (). 1,4-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. However, R ² and R ³
are never both hydrogen atoms. ) obtained by copolymerizing at least one of
Block and/or random with a 4-diene content of 0.5 to 20 mol%, an elastic modulus of 500 to 10,000 Kg/cm ² according to JIS-K7203, a melt index of 0.01 to 200 g/10 minutes, and a crystallinity of 20% or more by X-ray diffraction. A modified copolymer characterized in that an unsaturated copolymer resin is used, and 0.01 to 50 parts by weight of an unsaturated organic acid or its anhydride is blended and reacted with respect to 100 parts by weight of the copolymer resin. This is a method for producing a combined resin. The modified copolymer resin of the present invention can be produced in the presence of a radical generator or other promoter, but preferably in the absence of the radical generator or other accelerator. Graft modification of α-olefin polymers usually requires the combined use of an organic peroxide-based radical generator, typical examples of which are benzoyl peroxide and dicumyl peroxide. etc. (for example, in ethylene polymers), or conversely, the molecular weight of the modified product decreases so much that it can no longer maintain the physical properties of the base α-olefin polymer resin (for example, in propylene polymers). ) and other problems arose. The modified copolymer resin obtained by the present invention is characterized in that there is no such large variation in molecular weight even when the grafting rate is high. That is, the copolymer resin obtained by the present invention retains the physical characteristics of the base unsaturated copolymer resin even if the unsaturated organic acid or its derivative has a high grafting rate. It is used for various purposes that take advantage of its characteristics. For example, it can be used as an adhesive layer for coating steel pipes, synthetic paper, and dyeable fibers. Alternatively, the modified copolymer resin obtained in the present invention may be added with a metal compound, preferably an oxide, halide, carboxylate, phenoxide, β of a group A or B metal of the periodic table (for example, magnesium, zinc, etc.). - Diketonate, acetylacetonate, etc., and preferably water, an organic acid, a mercaptan, an active hydrogen compound such as an amine, etc. can be blended and heat treated to be used as a metal salt crosslinked product. In addition, the modified copolymer resin obtained by the present invention has extremely good affinity with other substances, so in addition to being used as an adhesive, it can also be used as a laminated material in the form of a film, sheet, or laminate in a molten state. Can be used. In addition, this modified copolymer resin has unsaturated bonds in its molecular structure, so it can be easily modified by crosslinking or adding various groups and compounds, so it has various functional properties. It is expected to be used as a resin. Next, each component used in the present invention will be explained. First, the unsaturated copolymer resin used in the present invention contains at least one type of α-olefin having 2 to 12 carbon atoms,
1,4-dienes represented by formula () (Here, R ¹ is an alkyl group having 8 or less carbon atoms, R ²
and R ³ each represents a hydrogen atom or an alkyl group having 8 or less carbon atoms. As the above α-olefin having 2 to 12 carbon atoms,
Ethylene, propylene, butene-1, pentene-
1, hexene-1, octene-1,3-methyl-
Butene-1,3-methyl-pentene-1,4-methyl-pentene-1,3,3-dimethyl-butene-1,4,4-dimethyl-pentene-1,3-methylhexene-1,4-methyl -Hexene-1,
4,4-dimethyl-hexene-1,5-methyl-
Hexene-1, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-
Examples include cyclohexylbutene-1, vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, and 2-vinylbicyclo[2,2,1]-heptane. Among these, preferred examples are ethylene, propylene, butene-1,
Examples include 3-methyl-butene-1, 4-methyl-pentene-1, and styrene, among which particularly preferred examples are ethylene, propylene, and 4-methyl-pentene-1. Two or more of these α-olefins may be used. In addition, 1,4- represented by the general formula ()
Examples of dienes include 1,4-hexadiene,
1,4-heptadiene, 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-
Examples include heptadiene, 5-methyl-1,4-heptadiene, 4-ethyl-1,4-octadiene, 5-methyl-1,4-octadiene, and 4-n-propyl-1,4-decadiene. Among these, 1,4-hexadiene, 4-
Methyl-1,4-hexadiene, 5-methyl-
1,4-hexadiene is preferred, especially 4-methyl-1,4-hexadiene and 5-methyl-
1,4-hexadiene is preferred. One of these,
Two or more types of 4-dienes may be used, and an example of a suitable combination thereof is a combination of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene (weight ratio 95:5 to 5:95). These α-olefins and 1,4-dienes can be copolymerized using a Ziegler-Natsuta catalyst for α-olefin polymerization using the same method and equipment as those used for producing α-olefin polymers. Saturated copolymer resins can be produced. Examples of such manufacturing methods include Japanese Patent Application No. 54-73808;
Same 54-106494, Same 54-112597, Same 54-131231, Same
55-59069 specifications, etc. can be mentioned. The α-olefin may be present in the unsaturated copolymer resin either randomly or in blocks. Preferred examples of unsaturated copolymer resins from the molecular structural standpoint are as follows. (1) A random copolymer of one or more α-olefins and one or more 1,4-dienes. (2) 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 of the random copolymerization block). (3) 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 quantity ratio, at least one is block a
A block copolymer consisting of different blocks. 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 those in the form AABABAAAB~ that make up the entire composition, there are also homopolymerized blocks of monomer A like this and monomer A
and a random copolymer block of monomer B are chemically bonded, and also contains a homopolymer of monomer A, a random copolymer of monomer A and monomer B, etc. as a mixture. also means Similarly, "polymerization block a and polymerization block b"
``A block copolymer consisting of a block copolymer consisting of a polymer block a and a polymer block b that are chemically bonded together'' is a block copolymer consisting of a polymer block a and a polymer block b that are chemically bonded. It also refers to a polymer that contains a copolymer that is bonded together, and also contains a mixture such as 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. It also has the same meaning as a so-called "block copolymer." Among the unsaturated copolymer resins produced in this way, those suitable for the present invention have a 1,4-diene content of 0.5 to 20 mol%, and have a JIS
-The elastic modulus according to K-7203 is 500 to 10000Kg/
cm ² resinous. When the content of 1,4-dienes is less than 0.5 mol%, the content of unsaturated groups in the unsaturated copolymer resin is small;
The grafting rate may not improve or the molecular weight may decrease significantly during the grafting reaction (especially in the case of unsaturated copolymer resins whose main α-olefin components are propylene or 4-methyl-1-pentene),
The disadvantage is that the grafting reaction does not substantially proceed unless a radical generator is used in conjunction with the grafting reaction.On the other hand, if it exceeds 20 mol%, the copolymerization rate is slow when producing an unsaturated copolymer resin. In the case of slurry polymerization, there is a large amount of solvent-soluble by-product polymer, which increases the viscosity of the polymerization system, resulting in poor productivity, and the resulting unsaturated copolymer becomes sticky or does not maintain its resin shape. There are drawbacks. The degree of crystallinity of unsaturated copolymer resins suitable for the present invention can be determined by X-ray diffraction method (for example, for propylene polymer resins, see G. Natta et al., Rend. Accad. Naz.
Lincei. 22 (8), 11 (1957); and regarding ethylene polymer resins, SLAggarwal et al., J. Polymer Sci.
18, 17 (1955) is 20% or more, especially 60% or more in the case of unsaturated copolymer resins whose main α-olefin component is ethylene, and 60% or more when propylene is the main α-olefin component. - In the case of an unsaturated copolymer resin as an olefin component, 30% or more is particularly desirable. Furthermore, the melt index is 0.01 to 200g/10 minutes,
Particularly preferred is 0.05 to 100 g/10 min. Specific preferred examples of these unsaturated copolymer resins include propylene and 4-methyl-1,4
- Random copolymer with hexadiene; Random copolymer with propylene and 5-methyl-1,4-hexadiene; Propylene and 4-methyl-1,4
- Random copolymer of hexadiene and 5-methyl-1,4-hexadiene; Random copolymer of propylene, ethylene, and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; Propylene A block copolymer consisting of a homopolymerization block of propylene and a random copolymerization block of propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; a homopolymerization block of propylene and a random copolymerization block of ethylene and 4- A block copolymer consisting of methyl-1,4-hexadiene and a random copolymer block with 5-methyl-1,4-hexadiene; a homopolymer block of ethylene, propylene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene; -A block copolymer consisting of a random copolymer block with methyl-1,4-hexadiene; a random copolymer block with propylene and ethylene, and a random copolymer block with propylene, 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,
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 Random copolymer blocks with -1,4-hexadiene and 5-methyl-1,4-hexadiene and random copolymer blocks with propylene, ethylene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene Random copolymer blocks of propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, propylene, ethylene and 4-methyl-1,4- Random copolymer blocks with hexadiene and 5-methyl-1,4-hexadiene, and ethylene and 4-
A block copolymer consisting of a random copolymer block of methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; ethylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene.
A block copolymer consisting of a random copolymer block with methyl-1,4-hexadiene and a random copolymer block with propylene, ethylene, 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene Random copolymer of ethylene and 1,4-hexadiene; Random copolymer of ethylene and 4-methyl-1,4-hexadiene; Ethylene and 5-methyl-1,
Random copolymer with 4-hexadiene; ethylene and 4-methyl-1,4-hexadiene and 5
-Random copolymer with methyl-1,4-hexadiene; ethylene and propylene and 4-methyl-1,4-hexadiene and 5-methyl-
Random copolymers with 1,4-hexadiene; random copolymers with ethylene and butene and with 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; ethylene with 1-hexene and 4- Random copolymers of methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; ethylene and 4-methyl-1-pentene and 4-methyl-1,4-hexadiene and 5-methyl-1, Random copolymer with 4-hexadiene; block copolymer consisting of a homopolymerized block of ethylene and a random copolymerized block of ethylene and 1,4-hexadiene;
Ethylene homopolymer block, ethylene and 4-
A block copolymer consisting of a random copolymerization block of methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; 1-butene and 4-methyl-1,4-hexadiene and 5-methyl-1 Random copolymer with ,4-hexadiene; 3-methyl-1-butene and 4-methyl-1,
Random copolymer with 4-hexadiene and 5-methyl-1,4-hexadiene; 4-methyl-
Examples include random copolymers of 1-pentene, 4-methyl-1,4-hexadiene, and 5-methyl-1,4-hexadiene. Among these, particularly preferred examples include propylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene from the viewpoint of ease of production of copolymers for obtaining α-olefin. A random copolymer of propylene; a block copolymer consisting of a homopolymer block of propylene and a random copolymer block of ethylene and 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene; Random copolymers with 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene are preferably used. In place of these unsaturated copolymer resins, if necessary, other thermoplastic polymers; phenolic,
Various stabilizers such as sulfur-based, phosphorus-based, and amine-based stabilizers (antioxidants, heat stabilizers, ultraviolet absorbers, antistatic agents, etc.); silica, mica, talc, calcium carbonate, carbon black, glass fiber, glass microscopic Spheres, carbon fibers, gypsum, clay, inorganic fillers such as aluminum hydroxide, magnesium hydroxide, titanium oxide, etc.; colorants or pigments; flame retardants; surfactants; blowing agents, etc. that do not significantly impair the effects of the present invention. The content of 1,4-dienes in the composition may be
It needs to be 0.5-20 mol%. Examples of particularly other thermoplastic polymers include ethylene, propylene, butene-1, pentene-1,4
- Single or mutual copolymer resins of α-olefins such as methyl-1-pentene; Modified products of these olefin polymers (chlorination, sulfonation, styrenation, oxidation, etc.); Other than α-olefins and α-olefins Copolymer resins with comonomers (unsaturated organic acids or derivatives thereof, vinyl esters, unsaturated organic silane compounds, etc.) or modified products thereof (including saponified products of ethylene-vinyl acetate);
Polyethylene; acrylonitrile-butadiene-
Styrene resin (ABS); polyamide; polyester; polycarbonate; resin components such as polyvinyl chloride or styrene-butadiene-styrene block copolymer, ethylene-propylene rubber (including EPDM); ethylene-1-butene rubber ( rubber components such as polyene and copolymerized terpolymer rubber); natural rubber; polybutadiene rubber; polyisoprene rubber; styrene-butadiene rubber (SBR); butyl rubber; Polymers as components are preferred. Next, the unsaturated organic acids or derivatives thereof used in the present invention include, for example, acrylic acid, methacrylic acid,
Maleic acid, itaconic acid, citraconic acid, fumaric acid, hymic acid, crotonic acid, mesaconic acid,
Sorbic acid or esters, anhydrides, metal salts, amides, imides, etc. of these acids, and among these, acrylic acid, methacrylic acid, and maleic anhydride are preferred, and in particular, graft modification without using a radical generator, so-called " In the case of "ene" addition, maleic acid, maleic anhydride, maleic acid imide and other maleic acid derivatives are preferred. Two or more types of these can also be used in combination. The modified copolymer of the present invention is produced by blending 0.01 to 50 parts by weight of the unsaturated organic acid or its derivative with 100 parts by weight of the unsaturated copolymer resin, in the presence or absence of a radical generator. This is done by subjecting it to the graft polymerization conditions described below. The preferred amount of the unsaturated organic acid or its derivative is 0.01 parts by weight per 100 parts by weight of the unsaturated copolymer resin.
~30 parts by weight, especially 0.1 to 20 parts by weight, but if this amount is less than 0.01 parts by weight, the content of unsaturated organic acids or derivatives thereof in the resulting modified copolymer will be low, resulting in poor modification of adhesive properties etc. On the other hand, if the amount exceeds 50 parts by weight, a large amount of unreacted unsaturated organic acid or its derivative will remain in the modified copolymer, and the effect of the present invention will not be fully exhibited as it is. Not only is a complicated process required to separate and remove the residue, but the excess residue itself is wasted. Furthermore, as a result of the homopolymer of an unsaturated organic acid or its derivative mixed with the modified copolymer, a problem arises in that the physical properties (characteristics) of the unsaturated copolymer resin used in the present invention are impaired. , undesirable. The modified copolymer obtained in the present invention is preferably produced in the absence of a radical generator in order to prevent fluctuations in flowability before and after graft modification and aging of the produced modified copolymer. When using a radical generator, 0.001 to 30 parts by weight, preferably 0.01 to 20 parts by weight, particularly preferably 0.1 to 10 parts by weight of the radical generator per 100 parts by weight of the unsaturated copolymer resin.
It is appropriately selected from the range of parts by weight in consideration of the amount of the unsaturated organic acid or its derivative used. As the radical generator, organic peroxides such as organic hydroperoxides, dialkyl peroxides, diacyl peroxides, peracid esters, and ketone peroxides are preferably used, and among them, di-t-butyl is a specific preferred example. peroxide,
Mention may be made of benzoyl peroxide and dicumyl peroxide. Specific examples of methods for subjecting the graft polymerization conditions include, for example, a method in which both of the above components are melt-kneaded at 100 to 300°C in a kneading machine such as an extruder, roll, or Brabender Plastograph; Examples include a method in which an unsaturated copolymer resin is impregnated with an unsaturated organic acid or a derivative thereof, and then heated and reacted. After these graft polymerization reactions, if there are any unreacted residues, vacuum drying, blow drying, solvent washing,
It is also possible to add a process such as steam cleaning. The modified copolymer resin of the present invention can be used as is, but it may also be used in combination with other thermoplastic polymers, various stabilizers, inorganic fillers, colorants or pigments,
It is of course possible to use the mixture with flame retardants, surfactants, etc., and especially when other thermoplastic polymers are added, the content of unsaturated organic acids or their derivatives in the resulting composition can be reduced. The amount should be at least 10 ^-4 % by weight, preferably at least 10 ^-2 % by weight. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Propylene and methylhexadiene (4-methyl-1,4-hexadiene and 5-methyl-1,4-
copolymer resin (mixture with hexadiene in a molar ratio of 8:2) (methylhexadiene content 8.4 mol%,
Boiling n-heptane extraction residue 93.0%, crystallinity by X-ray diffraction method 46%, melt flow rate (MFR) measured according to JIS-K-6758 1.7g/10
Three-point bending elastic modulus 8970Kg/cm ² measured in accordance with JIS-K-7203, yield stress 307Kg/cm ² measured in accordance with JIS-K-7113, stress at break 410Kg/cm 2
cm ² , elongation at break 700%) and a predetermined amount of maleic anhydride and optionally benzoyl peroxide were mixed at 190°C using a kneader under a nitrogen stream.
After kneading for a minute, the product was taken out from the kneader and heat-treated at 250° C. for 30 minutes under a nitrogen stream. The obtained product was dissolved in hot xylene and reprecipitated with a large excess of acetone to obtain a maleic anhydride-modified copolymer powder. Table 1 shows the maleic anhydride grafting rate, melt flow rate, and adhesive strength with aluminum of this modified copolymer in comparison with that of the unmodified copolymer. The maleic anhydride grafting rate was calculated from the absorbance at 1785 cm ^-1 and 1710 cm ^-1 of the infrared absorption spectrum after extracting the modified copolymer powder with boiling acetone for 16 hours. The melt flow rate was measured in accordance with JIS-K-6758. The adhesive strength of aluminum was measured as follows. First, the modified copolymer was press-formed into a 0.1 mm thick sheet, and this sheet was layered with an aluminum plate 2 mm thick, 25 mm wide, and 100 mm long and an aluminum foil 0.2 mm thick, 25 mm wide, and 100 mm long. The sheet was inserted between the sheets, and the sheet was set to a full 25 mm in the width direction and 40 mm from the end in the length direction, and pressed at 200° C. and 40 kg/cm ² for 6 minutes to bond three layers. Next, fold the non-adhesive part of the aluminum foil layer (width is 25 mm and length is 60 mm) 180 degrees from the end of the adhesive part, and then fold the folded end of the aluminum foil and the non-adhesive part of the aluminum plate. Ends (both ends are the farthest part in the 180° direction)
were clamped together, and the load required for peeling was measured using an autograph at a tensile rate of 50 mm/min at 25°C and 140°C. Comparative Example In the examples, polypropylene (manufactured by Mitsubishi Yuka Co., Ltd., Mitsubishi Noblen TA8; MFR0.9) was used instead of the copolymer of propylene and methylhexadiene.
Using 15 parts by weight of maleic anhydride, modification treatment and evaluation were carried out in the same manner as in the examples for the case where benzoyl peroxide was not added and when it was added (3 parts by weight). The results are shown in Table 1. Application example Maleic anhydride grafting rate produced in the example
100 parts by weight of a 10.2% by weight modified copolymer and 1.5 parts by weight of dicumyl peroxide were mixed in a ribbon blender, melt-kneaded at 210°C using an extruder, and then heated at 220°C for 5 minutes to obtain a modified polymer. A crosslinked product was obtained. The gel fraction was measured by boiling xylene extraction and was found to be 69%. Example 2 Ethylene, 1-butene and methyl-1,4-
Copolymerized resin with hexadiene (1-butene content
2.7 mol%, diene content 3.4 mol%, JIS-K-
Three-point bending modulus 2100Kg/ measured in accordance with 7203
cm ² , MFR6.5 measured in accordance with JIS-K-6760
g/10 min, crystallinity 32% by X-ray diffraction method) 100
30 parts by weight of maleic anhydride and 0.3 parts by weight of dicumyl peroxide were reacted in 2600 parts by weight of xylene at 135° C. for 6 hours. After the reaction, a modified copolymer was obtained by precipitating with a large excess of acetone. The maleic anhydride grafting rate of this modified copolymer was 5.9% by weight, the MFR was 1.4g/10min, and
Adhesion strength with aluminum at 25℃ is 31Kg/
It was 25mm. [Table] [Table]

Claims (1)

[Scope of Claims] 1. A method in which a polymer resin and an unsaturated organic acid or its anhydride are subjected to graft polymerization conditions to modify the resin, wherein the resin is at least one type of α-olefin having 2 to 12 carbon atoms. and 1,4-dienes represented by 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. However, R ² and R ³
are never both hydrogen atoms. ) obtained by copolymerizing at least one of
Block and/or random with a 4-diene content of 0.5 to 20 mol%, an elastic modulus of 500 to 10,000 Kg/cm ² according to JIS-K7203, a melt index of 0.01 to 200 g/10 minutes, and a crystallinity of 20% or more by X-ray diffraction. A modified copolymer characterized in that an unsaturated copolymer resin is used, and 0.01 to 50 parts by weight of an unsaturated organic acid or its anhydride is blended and reacted with respect to 100 parts by weight of the copolymer resin. Method for producing combined resin.