JPH0578589A - Resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition which can give a molding which is directly coatable, bondable, printable or liable to like treatment by mixing an olefinic resin with a specified polymer in a specified mixing ratio. CONSTITUTION:The objective composition comprises 100 pts.wt. olefinic resin (e.g. propylene/ethylene block copolymer), 0.1-900 pts.wt. block and/or random copolymer resins each comprising at least one 2-12 Calpha-olefin (e.g. propylene) and at least one nonconjugated diene and 0.01-400 pts.wt. polymer containing carboxyl or acid anhydride groups (e.g. ethylene/acrylic acid copolymer).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a resin composition.
More specifically, the present invention relates to an olefin resin composition suitable for coating, adhering, printing, etc. on the surface.

[0002]

2. Description of the Related Art Conventionally, when coating the surface of a resin molded body, before coating, steam cleaning using a halogen-based organic solvent is performed in order to clean and remove dust and machine oil adhering to the surface of the molded body. Is being done. In addition, since the olefin resin does not have polar groups in its structure and has high crystallinity, the adhesion of paints, adhesives, printing inks, etc. is extremely poor, resulting in poor paintability, adhesiveness and printability. The surface is inferior, so the surface is modified by applying a primer in advance or by plasma treatment to improve the adhesion, and then paint, adhesive is applied or printing ink is printed. It was

[0003]

However, in such a method, there have been the following problems conventionally. That is, in coating and adhesion to the resin molded body,
In the vapor cleaning method using a halogen-based organic solvent, the possibility that the halogen-based organic solvent diffuses into the atmosphere and destroys the ozone layer is a problem, and an alternative method should be promptly adopted to protect the global environment. Is required to move to.
In addition, in the primer coating method, there is a drawback that the cost is high due to the fact that an expensive primer must be used and the number of steps is large, and further it is necessary to volatilize the solvent of the primer. In addition to the poor working environment, there was a risk of fire and there was a problem with safety.

On the other hand, in the plasma processing method, since a high degree of vacuum is required, an expensive apparatus must be installed, and the batch method cannot avoid an increase in cost. Further, the surface after the plasma treatment is unstable, and the adhesion of the paint, the adhesive and the printing ink is deteriorated when it comes into contact with a foreign substance, so that the adhesion performance may vary, which is very inconvenient to handle.

Therefore, if the steps of applying the primer and the plasma treatment can be omitted, the steps can be simplified, the working environment can be improved, and the cost can be reduced. Also, much research has been done to improve these problems. However, in the end, this purpose has not yet been fully achieved, and such primer coating and plasma treatment cannot be omitted in the olefin resin material, and after such treatment, painting, adhesion and printing are performed. Etc. are often applied.

It has been reported that a olefin resin is mixed with a copolymer resin containing non-conjugated dienes and subjected to a special surface treatment to improve the adhesion of paints, adhesives, printing inks and the like. For example, a method of performing a surface treatment with a halogen cationic compound (Japanese Patent Publication No. 63-64460), a method of performing a surface treatment with a saturated aqueous solution of sulfuric acid-acidic potassium permanganate and an aqueous solution of sulfuric acid-acidic sodium bisulfite of 3% (Japanese Patent Laid-open No. Sho-63-62) 57-44639), a method of performing a surface treatment with an oxidizing agent (JP-A-57-59934), a method of performing a surface treatment with ozone (JP-A-61-197640), and the like.

Further, a method of using a specific paint or coating composition, for example, a method of coating an olefin resin molded article with a radical polymerization curable paint (JP-A-57-57).
38825, JP-A-57-59933),
A method using a resin coating composition having a hydrazine group (Japanese Patent Publication No. 3-22896) is known. However, these methods require the use of special reagents,
Environmental measures against the toxicity of sulfuric acid acidity are indispensable, the treatment method itself is complicated, the handling is very inconvenient, and the coating and coating composition are limited, so its application field is very It had the drawback of being narrow.

[0008]

[Means for Solving the Problems]

(Summary of the Invention) As a result of intensive studies conducted by the present inventors in view of the above problems, it was found that the above problems can be solved by using a specific resin composition. The invention was completed.

That is, the present invention provides the following components (a), (b) and (c), and optionally (d) and / or
Alternatively, the component (e) is included, and the component (b) is 0.1 to 900 parts by weight, the component (c) is 0.01 to 400 to 900 parts by weight, and the component (d) is based on 100 parts by weight of the component (a). 1 to
It is a resin composition containing 900 parts by weight and 0.1 to 300 parts by weight of the component (e). Component (a) : olefin resin component (b) : at least one selected from α-olefins having 2 to 12 carbon atoms and at least one non-conjugated diene represented by the following general formula (I) Block and / or random copolymer resin

[0010]

[Chemical 5]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R
⁵ independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10. ) Component (c) : Polymer component (d) having a carboxyl group (including acid anhydride group ) : Elastomer component (e) : Filler

(Detailed Description of the Invention) [I] Resin Composition (1) Constituent Components The resin composition of the present invention is basically formed from the following constituent components.

Component (a): Olefin Resin The olefin resin used in the present invention includes:
Ethylene, propylene, 1-butene, 3-methyl-1-
Butene, 4-methyl-1-pentene, 1-hexene, 1
A homopolymer of α-olefin represented by pentene or the like, a copolymer of these α-olefins with each other, a copolymer of the above α-olefins with an organosilicon compound, or the olefin resin There may be mentioned a graft polymer such as an organosilicon compound.

These polymers have a flexural modulus of 1,000 to 30,000 kg measured according to JIS-K7203.
/ Cm ² , preferably 2,000 to 20,000 kg / cm ² , and particularly preferably 3,000 to 15,000 kg / cm ² . Further, the melt flow rate (MF
R) is not particularly limited, but ASTM-D1
The value measured according to 238 is usually 0.01 to 200 g /
Optimally, it is within the range of 10 minutes, preferably 0.1 to 100 g / 10 minutes.

Examples of the olefin resin include:
So-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, linear low-density polyethylene, and other polyethylene resins, stereoregular polypropylene, stereoregular poly-1-butene, stereoregular poly-3-methyl-1-
Examples include stereoregular poly-α-olefin resins such as butene and stereoregular poly-4-methyl-1-pentene. Among these olefin resins, stereoregular polypropylene (hereinafter simply referred to as "propylene resin")
Is abbreviated. ) Is preferred.

Among the propylene-based resins, a copolymer of propylene and another olefin is preferable, and a copolymer of ethylene is particularly preferable. The copolymer may be a random copolymer or a block copolymer, but a block copolymer is particularly preferable. These olefin-based resins may be used alone or as a mixture of a plurality of the above-mentioned resins, and usually, they may be appropriately selected and used from commercially available resins.

Component (b): Copolymer containing non-conjugated dienes
Body resin The copolymer resin containing non-conjugated dienes used in the present invention is at least one selected from α-olefins having 2 to 12 carbon atoms and a non-conjugated compound represented by the following general formula (I). At least one of the dienes,

[0018]

[Chemical 6]

(Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are
Each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10, respectively. ) For example, it can be produced by block and / or random copolymerization using a known method and apparatus similar to the polymerization of α-olefins using a known Ziegler catalyst or the like.

Examples of the non-conjugated dienes represented by the general formula (I) that can be used in the present invention include 1,4-hexadiene, 4-methyl-1,4-hexadiene and 5-methyl-diene.
1,4-Dienes such as 1,4-hexadiene and 5-methyl-1,4-heptadiene; 1,5-heptadiene,
5-methyl-1,5-heptadiene, 6-methyl-1,
1,5-dienes such as 5-heptadiene, 1,5-octadiene, 5-methyl-1,5-octadiene, 6-methyl-1,5-octadiene; 1,6-octadiene, 6-methyl-1, 6-octadiene, 7-methyl-
1,6 such as 1,6-octadiene, 7-ethyl-1,6-octadiene, 1,6-nonadiene, 7-methyl-1,6-nonadiene, 4-methyl-1,6-nonadiene
-Dienes; 1,7-nonadiene, 8-methyl-1,7
-1,7-dienes such as nonadiene; various non-conjugated dienes such as 1,11-dodecadiene and 1,13-tetradecadiene; and the like.

Among these, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-
Methyl-1,5-heptadiene, 6-methyl-1,5-
Octadiene, 6-methyl-1,6-octadiene, 7
-Methyl-1,6-octadiene, 7-ethyl-1,6
Branched non-conjugated dienes such as -octadiene and 8-methyl-1,7-nonadiene are preferable from the viewpoint of the production technology of the copolymer, and 7-methyl-1,6-octadiene is particularly preferable. Of course, these non-conjugated dienes can be used in a mixture of two or more kinds.

The α-olefins having 2 to 12 carbon atoms, which are the other raw material of the copolymer resin containing non-conjugated dienes, 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, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2] , 1] -heptane,
And so on. Among these, preferred examples are ethylene, propylene, 1-butene, 3-methyl-
1-butene, 4-methyl-1-pentene, styrene and the like, and among them, particularly preferable examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

The copolymer resin containing non-conjugated dienes used in the present invention has a content of non-conjugated dienes of 0.1 to 30% by weight, preferably 0.5 to 25% by weight, particularly preferably 1
.About.20% by weight. If the content of the non-conjugated dienes is less than the above range, the reproducibility of the paint, the adhesive, the printing ink and the like is poor and the adhesion strength thereof is weak, which is not preferable. On the other hand, when the amount exceeds the above range, the productivity of resin production is deteriorated, which is not preferable. Further, the melt flow rate (MFR) of the copolymer resin containing non-conjugated dienes used in the present invention is 0.01 to 1,000 g /
10 minutes, preferably 0.05 to 500 g / 10 minutes, particularly preferably 0.1 to 200 g / 10 minutes are suitable for the present invention.

Further, the copolymer resin containing the non-conjugated dienes of the present invention has a flexural modulus of 1,000 to 30,000 kg / cm ² , preferably 1,000 according to JIS K-7203.
~ 20,000 kg / cm ² , particularly preferably 1,500 ~
It is 15,000 kg / cm ² . If it is less than 1,000 kg / cm ² , the heat resistance of the resin will not be exhibited. Examples of the copolymer resin include the non-conjugated dienes, various combinations of block copolymers selected from the α-olefins, and random copolymers. Among these, preferred are the copolymer resins. Are as follows.
[Here, methyl-1,4-hexadiene represents a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and the mixing ratio thereof is 95: 5.
It is in the range of 5:95. ]

Ethylene / methyl-1,4-hexadiene random copolymer, ethylene / 7-methyl-1,6-octadiene random copolymer, propylene / methyl-
1,4-hexadiene random copolymer, propylene
7-methyl-1,6-octadiene random copolymer,
Propylene-ethylene-methyl-1,4-hexadiene random copolymer, propylene-ethylene-7-methyl-1,6-octadiene random copolymer, propylene-ethylene-methyl-1,4-hexadiene block copolymer , Propylene / ethylene / 7-methyl-1,6-
Octadiene block copolymers and the like.

The method for producing the copolymer resin is as follows:
For example, Japanese Examined Patent Publication No. 64-1272 and Japanese Patent Examined Publication No. 64-21.
28, JP-B-64-9326, JP-A-59
The methods described in JP-A-155416, JP-A-62-115008, JP-A-2-311507 and the like can be mentioned.

Component (c): carboxyl group (acid anhydride group
The polymer having a carboxyl group (including an acid anhydride group) used in the present invention is, from a structural viewpoint, a branched or linear molecular chain having a carboxyl group (an acid anhydride group). (Including) are irregularly or regularly pendant, or have a structure in which a side chain having a carboxyl group (including an acid anhydride group) is grafted.

The polymer can be produced by a known method. For example, a copolymerization method of an unsaturated compound containing a carboxyl group (including an acid anhydride group) and a polymerizable monomer, a method of grafting an unsaturated compound containing a carboxyl group (including an acid anhydride group) to a polymer, a polar group in the polymer Examples thereof include a method of reacting an acid anhydride or a compound having at least one carboxyl group with at least one bifunctional group, and a method of converting a polar group in a polymer into a carboxyl group by oxidation or hydrolysis.

Among the polymers produced by these methods, a copolymer of an α-olefin and an unsaturated compound containing a carboxyl group (including an acid anhydride group); the component (a)
Olefin resin, a copolymer resin containing a non-conjugated diene of the above component (b), or a graft polymer of a carboxyl group (containing an acid anhydride group) -containing unsaturated compound onto the elastomer of the following component (d); A diene polymer having a carboxyl group or a diene having a carboxyl group, which is obtained by reacting a diene polymer having a hydroxyl group described below or a hydrogenated product thereof with an acid anhydride or a difunctional or more functional compound having at least one carboxyl group. Polymer hydrogenates are preferred. These will be described in detail below.

Copolymer of α-olefin and unsaturated compound containing a carboxyl group (including acid anhydride group): The copolymer is a branched or linear carbon chain from a structural viewpoint. , Refers generally to those having a structure in which a carboxyl group (including an acid anhydride group) -containing unsaturated compound is copolymerized with an α-olefin irregularly or regularly. Specifically, the content of the unsaturated compound containing a carboxyl group (including an acid anhydride group) is 0.1 to 50% by weight, preferably 0.5 to 4
5% by weight, particularly preferably 1 to 40% by weight, and the melt flow rate (MFR) measured according to ASTM-D1238 is 0.1 to 1000 g / 10.
Min, preferably 0.5 to 700 g / 10 min, particularly preferably 1 to 500 g / 10 min, and includes liquid, semi-solid and solid polymers at room temperature.

This α-olefin / carboxyl group (containing acid anhydride group) -containing unsaturated compound copolymer is prepared by using α-olefin and a carboxyl group (containing acid anhydride group) -containing unsaturated compound as raw materials. It can be produced by a known method such as a high pressure radical polymerization method or a slurry polymerization method.

In the case of the production by the high pressure radical polymerization method,
Ethylene, a carboxyl group (including an acid anhydride group) -containing unsaturated compound and a radical initiator, for example, a pressure of 1000 ~
In the reaction zone kept at 3000 atm and a temperature of 90 to 300 ° C., the ratio of ethylene to a carboxyl group (including acid anhydride group) -containing unsaturated compound was 1: 0.0001 to 1: 0.1.
It is produced by continuously feeding the above-mentioned mixture to obtain an ethylene copolymer under the condition that the conversion is 3 to 20%, and continuously taking out the copolymer from the reaction zone. Further, in the case of the production method by the slurry polymerization method, propylene and those obtained by complexing a carboxyl group-containing unsaturated compound with an organic aluminum compound or the like, using a known Ziegler catalyst or the like, for example, in a heptane solvent, It is produced by polymerizing at a pressure of normal pressure to 20 atm and a temperature of 30 to 150 ° C.

Examples of the unsaturated compound containing a carboxyl group (including an acid anhydride group) used here include acrylic acid, methacrylic acid, 3-butenoic acid, crotonic acid, pentenoic acid,
Unsaturated carboxylic acids such as heptenoic acid, octenoic acid, nonenic acid, decenoic acid, undecenoic acid, maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, and their acid anhydrides, etc. Can be mentioned. Among these, acrylic acid,
Methacrylic acid and undecenoic acid are preferred.

The α-olefin as the other copolymerization component includes 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, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2] , 1] -heptane,
And so on. Among these, preferred examples are ethylene, propylene, 1-butene, 3-methyl-
1-butene, 4-methyl-1-pentene, styrene and the like, and among them, particularly preferable examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

In addition to the above-mentioned α-olefin and carboxyl group (including acid anhydride group) -containing unsaturated compound, as the third copolymerization monomer, unsaturated compounds such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate are used. Carboxylic acid ester; styrene, α-
Vinyl aromatic compounds such as methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether; vinyl chloride and odor. Examples thereof include vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate; acrylamide and the like, and they can be used as a ternary or multi-component copolymer. And these copolymers, each alone,
It is possible to use a mixture of a plurality of types.

Graft polymer of unsaturated compound containing carboxyl group (including acid anhydride group): The graft polymer is a branched or linear molecular chain from a structural viewpoint.
It refers to all those having a structure in which a carboxyl group (including an acid anhydride group) -containing unsaturated compound is graft-polymerized irregularly or regularly. Specifically, the content of the unsaturated compound containing a carboxyl group (including an acid anhydride group) is 0.1 to 0.1%.
50% by weight, preferably 0.5 to 45% by weight, particularly preferably 1 to 40% by weight, ASTM-D
Melt flow rate (MF
R) is 0.1 to 1000 g / 10 minutes, preferably 0.
5 to 700 g / 10 minutes, particularly preferably 1 to 500 g /
It is 10 minutes long and includes liquid, semi-solid and solid polymers at room temperature.

This carboxyl group (including acid anhydride group) -containing unsaturated compound graft polymer is used as a trunk polymer.
Containing the olefin resin as the component (a), the copolymer resin containing the non-conjugated dienes as the component (b), the elastomer as the component (d) described below, and a carboxyl group (including an acid anhydride group) as a graft component. Using an unsaturated compound as a raw material, it can be produced by a known method such as a kneading graft method or a solution graft method.

For example, in the case of production by the kneading and grafting method, a mixture of the above-mentioned trunk polymer component, a carboxyl group (including acid anhydride group) -containing unsaturated compound, and, if necessary, an organic peroxide as a reaction initiator, It is produced by melt-kneading in an extruder set at a temperature of ˜250 ° C. In the case of production by the solution grafting method, for example, in a xylene solvent, a copolymer containing non-conjugated dienes,
Unsaturated compound containing carboxyl group (including acid anhydride group),
And, if necessary, it is produced by dissolving an organic peroxide as a reaction initiator and reacting it in an autoclave set at a temperature of 80 to 150 ° C.

The carboxyl group (including acid anhydride group) -containing unsaturated compound of the graft component used here is
Acrylic acid, methacrylic acid, 3-butenoic acid, crotonic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenoic acid,
Decenoic acid, undecenoic acid, maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-
Examples thereof include unsaturated carboxylic acids such as 5,6-dicarboxylic acid, and acid anhydrides thereof. Among these, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like are preferable.

As the trunk polymer which is another component of the graft polymer, the olefin resin as the component (a), the copolymer resin containing the non-conjugated dienes as the component (b), and The elastomer of the component (d) can be exemplified, and among these, preferred are ethylene resins, propylene resins, olefin elastomers, styrene elastomers, ethylene / non-conjugated diene copolymer resins, propylene / non Examples thereof include conjugated diene copolymer resins and ethylene / propylene / non-conjugated diene copolymer resins. Particularly preferred are propylene resin and ethylene / propylene copolymer rubber (EP
M), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), and styrene / conjugated diene block copolymer hydrogenated product, propylene / 7-methyl-1,6-
Octadiene copolymer resin, propylene / ethylene / 7
Examples thereof include -methyl-1,6-octadiene copolymer resin and propylene-methyl-1,4-hexadiene copolymer resin.

In addition to the above-mentioned unsaturated compound component containing a carboxyl group (including an acid anhydride group), an unsaturated carboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate or methyl methacrylate is used as a second graft copolymerization monomer. Esters; vinyl aromatic compounds such as styrene, α-methylstyrene, vinyltoluene; nitrile compounds such as acrylonitrile, methacrylonitrile; vinylpyridines such as 2-vinylpyridine, 4-vinylpyridine; methyl vinyl ether, 2-chloroethyl vinyl ether, etc. Examples thereof include vinyl ethers; vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate; acrylamides and the like, and they can also be used as binary or multi-component graft copolymers. These graft copolymers can be used either individually or as a mixture of two or more species.

Diene polymer or diene polymer hydrogenated product having a carboxyl group (including acid anhydride group): The diene polymer or diene polymer hydrogenated product having a carboxyl group (including acid anhydride group) is, for example, a hydroxyl group It is obtained by reacting a diene polymer or a hydrogenated product thereof with an acid anhydride or a bifunctional or higher functional compound having at least one carboxyl group.

Specifically, the molecular weight is 200 to 100,0.
00, preferably 500 to 50,000, particularly preferably 800 to 10,000, which are liquid, semi-solid and solid polymers at room temperature. Further, the acid anhydride or the bifunctional or more functional compound having at least one carboxyl group contained in the polymer may be at least one in the molecule, and the content thereof is 0.001 to 50% by weight, preferably 0. It is in the range of 0.01 to 45% by weight, particularly preferably 0.1 to 40% by weight.

The polymer is produced by a known method, for example, a solution reaction or the like, using a diene polymer having a hydroxyl group or a hydrogenated product thereof and an acid anhydride or a compound having two or more functional groups and at least one having a carboxyl group as a raw material. can do. In the case of the production by the solution reaction method, for example, it is produced by dissolving a diene polymer hydrogenated product having a hydroxyl group and an acid anhydride in a toluene solvent and reacting them in a reactor set at a temperature of 80 to 120 ° C. It

Examples of the acid anhydride or the compound having two or more functional groups and at least one having a carboxyl group as used herein include oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, citraconic acid and itaconic acid. , Pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, norbornene-5,6
A dicarboxylic acid such as dicarboxylic acid or an acid anhydride thereof;
β-chloropropionic acid, tartaric acid, lactic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, mercaptopropionic acid and the like can be mentioned. Among these, dicarboxylic acid anhydrides and the like are preferable, and maleic anhydride and succinic anhydride are particularly preferable. Is.

Further, examples of the diene polymer having a hydroxyl group or its hydrogenated product used for producing the polymer include the following. (I) Hydroxyl group-containing diene polymer Examples of the hydroxyl group-containing diene polymer used in the present invention include polyhydroxybutadiene. Specifically, it has at least one hydroxyl group in the molecule and has a molecular weight of 200 to 100,000, preferably 500 to 50,000, and particularly preferably 800 to
10,000, which includes liquid, semi-solid or solid polymers at ambient temperature. When the content of hydroxyl groups contained in the molecule is expressed by a hydroxyl value, it is 0.5 to 650, preferably 1 to 5
00, particularly preferably 5-250 (KOH mg / g).

The method for producing the diene polymer is not limited, and various known methods can be adopted. For example, using 1,3-dienes as a raw material, a radical polymerization method,
It can be produced by an anionic polymerization method. Specifically, for example, the method described in JP-A-51-71391 can be used. In the case of producing by the above radical polymerization method, it can be easily obtained by polymerizing a diene monomer using, for example, hydrogen peroxide as a polymerization initiator. Further, in the case of producing by the anionic polymerization, according to a known method, a conjugated diene was obtained by polymerizing with an anionic polymerization catalyst, for example, an alkali metal or an organic alkali metal compound,
Living polymer having a structure in which an alkali metal is bonded to at least one position in a molecular chain, for example, a monoepoxy compound, formaldehyde, acetaldehyde, acetone,
A halogeno alkylene oxide or polyepoxide may be reacted.

Further, the conjugated diene polymer produced by a known polymerization method is osmium tetroxide (OsO ₄ ), vanadium oxide (V ₂ O ₅ ), tungstic acid (H ₂ W)
O ₄ ), selenium dioxide (SeO ₂ ) and the like are reacted with hydrogen peroxide to give a compound having a hydroxyl group added to the double bond in the main chain, which is also used in the present invention. can do. At least one type of conjugated diene monomer is used as a raw material monomer for these polymers. Examples of the conjugated diene monomer include 1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, 2,3-dimethyl-1,3-butadiene and 1-phenyl-1,3-butadiene.

(Ii) Hydrogenated Products of Diene Polymer Having Hydroxyl Group As hydrogenated products of diene polymer having hydroxyl group,
The diene polymer having the above hydroxyl group, the usual method,
For example, it can be obtained by hydrogenation by the method described in JP-A-51-71391. Regarding the degree of hydrogenation, the double bond contained in the polymer may be wholly or partially hydrogenated, but the iodine value is usually 0 to 20, particularly 0 to 5 (g / g).
100 g) is preferred. These diene polymers having a hydroxyl group and hydrogenated products thereof can be used alone or as a mixture of several kinds.

The polymer having a carboxyl group (including an acid anhydride group) used as the component (c) of the resin composition of the present invention has been described above in detail. Preferred examples of the polymer include α-olefin and carboxyl. A copolymer with an unsaturated compound containing a group (including an acid anhydride group) and a graft polymer of an unsaturated compound containing a carboxyl group (including an acid anhydride group) are particularly preferable. A copolymer with an unsaturated compound containing an anhydride group) and a graft polymer of an unsaturated compound containing a carboxyl group (including an acid anhydride group) onto an olefin elastomer.

Component (d): Elastomer The elastomer component used in the preferred resin composition of the present invention is a polymer that exhibits rubber elasticity at room temperature and is selected from natural rubber and synthetic rubber. Specific examples of the synthetic rubber include styrene elastomer, butadiene rubber, isoprene rubber, olefin elastomer, acrylonitrile-butadiene copolymer rubber, chloroprene rubber, butyl rubber, urethane elastomer, silicone elastomer, fluorine elastomer and acrylic elastomer. Etc. Among these, styrene elastomers and olefin elastomers, urethane elastomers, silicone elastomers, acrylic elastomers are preferable, and styrene elastomers and olefin elastomers are particularly preferable, and specific examples are described below.

Styrenic Elastomer Examples of the styrenic elastomer include styrene and α-
It is an elastomeric random or block copolymer of a styrene compound such as methylstyrene and a conjugated diene such as 1,3-butadiene or isoprene, and a hydrogenated product of these copolymers. Among these styrene elastomers, a block copolymer of a styrene compound and a conjugated diene is preferable, and these block copolymers are linear and radial. For example, the general formula is represented by the following formula.

General formula: (AB) _{n + 1} ; A- (BA) _n ; B- (A-
B) _{n + 1} , or A '-[(BA) _n ] _m (In the above formula, A is a polymer block made of a styrene compound, and A'is bonded to m (BA) _n blocks. Chemical species, B is a conjugated diene polymer block, n is an integer of 1 to 20, m is an integer of 2 or more, and the proportion of A block and A ′ in the whole molecule is 1 to 50% by weight. The average molecular weight of these copolymers is 10,000 to 1,
, 000,000, preferably 50,000 to 250,000
It is 0.

Specific examples of these styrene elastomers are styrene / butadiene random copolymers, styrene / isoprene random copolymers, styrene / butadiene / styrene triblock copolymers, styrene / isoprene / styrene triblock copolymers. , Polystyrene block-terminated styrene-butadiene radial block copolymer, polystyrene block-terminated styrene-isoprene radial block copolymer, styrene-butadiene multi-block copolymer, styrene-isoprene multi-block copolymer, etc. Examples thereof include styrene / conjugated diene block copolymers and products obtained by hydrogenating these. Among these styrene elastomers, hydrogenated styrene / conjugated diene block copolymers are preferable.

Olefin-based Elastomer The olefin-based elastomer is a copolymer of α-olefins such as ethylene, propylene, 1-butene and 1-hexene, a copolymer of these with a non-conjugated diene, or 1-hexene. A higher α-olefin homopolymer such as an elastomeric polymer,
The Mooney viscosity ML _{1 + 4} measured at 100 ° C is usually 1 to
200, preferably 5-150, particularly preferably 7-1
In the range of 00.

Among these olefin elastomers, ethylene elastomers are particularly preferable in terms of quality and stability. Specifically, ethylene / propylene copolymer rubber (EPM), ethylene / 1-butene copolymer rubber, ethylene / propylene / 1-butene copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber (EPDM),
There are ethylene / 1-butene / non-conjugated diene copolymer rubber, ethylene / propylene / 1-butene / non-conjugated diene copolymer rubber and the like.

Specific examples of the non-conjugated diene include dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, dicyclooctadiene, methylene norbornene, 5-ethylidene-2-norbornene, 5-
Examples thereof include vinyl-2-norbornene, 5-methylene-2-norbornene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene. Among these elastomer components, an olefin elastomer is particularly preferably used because the surface roughness of the molded body is unlikely to occur.

Component (e): Filler As the filler used in the preferred resin composition of the present invention, either an inorganic or organic filler can be used, and the shape thereof is plate-like, spherical or fiber. It may have a shape or an irregular shape.

Specifically, natural silica such as quartz, synthetic silica produced by a wet method or a dry method; natural silicates such as kaolin, mica, talc and asbestos; synthetic silicates such as calcium silicate and aluminum silicate; water. Magnesium oxide,
Metal hydroxides such as aluminum hydroxide; Metal acid compounds such as alumina and titania; Calcium carbonate; Metal powders such as aluminum and bronze; Wood powder; Carbon black; Fibers such as glass fiber, carbon fiber, aramid fiber and alumina fiber Substances: Polymer liquid crystal substances: Potassium titanate whiskers, magnesium sulfate whiskers, aluminum borate whiskers, calcium carbonate whiskers, magnesium borate whiskers, zinc oxide whiskers, silicon carbide whiskers, silicon nitride whiskers, sapphire whiskers, beryllia whiskers, etc. And the like.

Among these, preferred are mica, talc, magnesium hydroxide, calcium carbonate, potassium titanate whiskers, magnesium sulfate whiskers, aluminum borate whiskers, calcium carbonate whiskers, and glass fibers, and particularly preferred are , Talc, calcium carbonate, potassium titanate whiskers, magnesium sulfate whiskers and glass fibers. These filler components may be surface-treated with a surfactant, a coupling agent or the like. The filler components may be used alone or in combination of two or more. Various fillers can be appropriately selected from commercial sources and used.

Regarding each of the components (a), (b), (c), (d) and (e) constituting the resin composition of the present invention, a combination of the above-mentioned components is preferable. Needless to say.

Component (f): additional component In the resin composition of the present invention, in addition to the above components (a) to (e), the following components are used as long as the effects of the present invention are not significantly impaired. Additional components can be included. Examples of the additional component include additives, specifically, plasticizers such as paraffin oil or fluidity improvers; softeners such as olefin liquid rubber and conjugated diene liquid rubber; colorants. Antioxidants; Neutralizers; Light stabilizers; UV absorbers; Antistatic agents; Lubricants; Dispersing aids; Molecular weight modifiers; Crosslinking agents; Nucleating agents; Flame retardants Etc. can be mentioned.

(2) Amount Ratio The amount ratio of the above-mentioned components constituting the resin composition of the present invention is as follows. In the case of a resin composition containing the component (a), the component (b), and the component (c): the olefin resin 1 of the component (a)
The copolymer resin containing the non-conjugated diene of the component (b) is 0.1 to 900 parts by weight, preferably 0.5 to 600 parts by weight, and particularly preferably 1 to 300 parts by weight with respect to 00 parts by weight. , And a polymer having a carboxyl group (including an acid anhydride group) of the component (c), 0.01 to 400 parts by weight, preferably 0.05 to 250 parts by weight, particularly preferably 0.1.
It is 1 to 120 parts by weight.

In the case of a resin composition containing the component (a), the component (b), the component (c), and the component (d): the component (b) is added to 100 parts by weight of the olefin resin of the component (a). The copolymer resin containing non-conjugated dienes in 1) is 0.1 to 900 parts by weight, preferably 0.5 to 600 parts by weight.
Parts by weight, particularly preferably 1 to 300 parts by weight, component (c)
The polymer having a carboxyl group (including an acid anhydride group) of 0.01 to 750 parts by weight, preferably 0.05 to
350 parts by weight, particularly preferably 0.1 to 180 parts by weight,
And the component (d) elastomer is 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 parts by weight.
~ 200 parts by weight.

In the case of a resin composition containing the component (a), the component (b), the component (c), and the component (e): the component (b) is added to 100 parts by weight of the olefin resin of the component (a). The copolymer resin containing non-conjugated dienes in 1) is 0.1 to 900 parts by weight, preferably 0.5 to 600 parts by weight.
Parts by weight, particularly preferably 1 to 300 parts by weight, component (c)
The polymer having a carboxyl group (including an acid anhydride group) is 0.01 to 500 parts by weight, preferably 0.05 to 3 parts by weight.
50 parts by weight, particularly preferably 0.1 to 180 parts by weight, and the component (e) filler is 0.1 to 300 parts by weight,
Preferably 0.5 to 250 parts by weight, particularly preferably 1 to
It is 200 parts by weight.

In the case of a resin composition containing the component (a), the component (b), the component (c), the component (d), the component (e) and the component (f): the olefin resin 100 of the component (a) The copolymer resin containing the non-conjugated diene as the component (b) is 0.1 to 900 parts by weight, preferably 0.5 to 600 parts by weight, and particularly preferably 1 to 300 parts by weight.
The amount of the polymer having a carboxyl group (including an acid anhydride group) as the component (c) is 0.01 to 900 parts by weight, preferably 0.05 to 450 parts by weight, and particularly preferably 0.
1 to 240 parts by weight, the component (d) elastomer is 1 to
900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, and the component (e) filler is 0.1 to 300 parts by weight, preferably 0.5 to 25 parts by weight.
0 parts by weight, particularly preferably 1 to 200 parts by weight.

When the content of the copolymer resin containing the non-conjugated diene as the component (b) is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks, etc. may be poor, or the adhesion strength may be weak. Is not preferable. On the other hand, if the amount exceeds the above range, the amount of the expensive copolymer resin added is large, so that not only the cost of the resin composition increases, but also an effect proportional to the amount of the copolymer resin added is obtained. is not.

When the compounding amount of the polymer having a carboxyl group (including an acid anhydride group) of the component (c) is less than the above,
Depending on the paint, adhesive and printing ink to be applied,
The adhesion strength may be extremely weak, which is not preferable. On the other hand, if the amount exceeds the above range, the amount of the expensive polymer added is large, so that not only the cost of the resin composition increases, but also the effect proportional to the added amount of the polymer cannot be obtained. In addition, the polymer is delaminated, so that the adhesion of paints, adhesives, printing inks, etc. is reduced, which is not preferable.

Further, not only can the rigidity and impact resistance be adjusted by blending the elastomer component of component (d) and / or the filler of component (e), but also by blending them, It is convenient because it can obtain strong adhesive properties such as paints, adhesives and printing inks. However, if the component (d) and the component (e) each exceed the above ranges, the moldability of the resin composition is deteriorated, which is not preferable.

(3) Blending The resin composition of the present invention is produced by mixing the above-mentioned constituents. The order of mixing these respective constituents is not particularly limited, and any method such as a method of simultaneously mixing the above constituents, a method of preliminarily mixing two arbitrary components, and then a method of mixing the remaining components can be adopted. Good.
As a mixing method, any conventionally known kneader such as a Brabender plastograph, a single or twin screw extruder, a powerful screw type kneader, a Banbury mixer, a kneader and a roll can be used.

The above-mentioned resin composition of the present invention can be molded into a resin molded product by various molding methods. A molded article formed from the resin composition of the present invention is directly as it is, that is, without being subjected to vapor cleaning with a halogen-based organic solvent that may cause environmental damage, and surface modification such as primer coating and plasma treatment. It is possible to apply a paint, an adhesive and a printing ink without performing a treatment, and has a characteristic that good paint adhesion, adhesiveness, printability and the like are obtained.

Further, the surface of the molded article formed from the resin composition is only subjected to relatively simple surface treatment such as surface treatment with a cleaning liquid containing no halogen-based organic solvent or surface treatment with hot gas. As a result, not only stronger paint adhesion, etc. can be obtained, but also good paint adhesion etc. can be obtained for a wider range of paint types. In order to more specifically describe the characteristics of the resin composition of the present invention, a molded article made of the resin composition, its surface treatment, and a coating method will be described in detail as an application example.

[II] Molded Body A molded body can be produced using the resin composition of the present invention by any molding method such as injection molding, compression molding, extrusion molding (sheet molding, blow molding, film molding). It doesn't matter. In particular, it is effective in a molded body injection-molded into a complicated shape.

[III] Surface Treatment of Molded Product As described above, the molded product formed from the resin composition of the present invention can be directly coated with a paint or the like, but it is relatively simple as shown below. By applying the surface treatment, strong adhesion can be obtained in a wide variety of paints. Surface treatment with cleaning liquid that does not contain halogen-based organic solvent Cleaning liquid that does not contain halogen-based organic solvent means various fluorocarbons that are widely used as cleaning solvents at present.
1-Trichloroethane, perchlorethylene, and general cleaning liquids excluding halogen-based organic solvents such as trichlene. Examples of such cleaning liquids include solvent-based cleaning liquids, emulsion-based cleaning liquids, and water-based cleaning liquids.

Specifically, solvent-based cleaning liquids include aliphatic hydrocarbons such as kerosene and d-limonene; aromatic hydrocarbons such as toluene and xylene; methanol, ethanol,
Alcohols such as isopropyl alcohol may be mentioned. Examples of the emulsion type cleaning liquid include those obtained by emulsifying and dispersing a solvent such as kerosene, d-limonene, silicon and toluene in water with a surfactant. As the water-based cleaning liquid, an alkaline cleaning liquid in which an alkaline component such as sodium hydroxide, potassium hydroxide, sodium silicate and sodium carbonate is used in combination with a surfactant, an acidic cleaning liquid in which an acid component such as phosphoric acid is used in combination with a surfactant, etc. , A neutral cleaning solution using a nonionic surfactant, pure water, water such as warm water, and the like. Among these cleaning liquids, water-based cleaning liquids and emulsion-type cleaning liquids are preferable, and particularly preferable are
It is an aqueous cleaning solution.

The cleaning method using these cleaning solutions is the surface treatment method referred to herein, and includes the immersion cleaning method, the shower cleaning method,
It is possible to select any cleaning method such as a power wash method, an ultrasonic immersion cleaning method, and a wiping method. Among these, the immersion cleaning method, the shower cleaning method, and the power wash method are preferable. The temperature of the cleaning liquid may be from room temperature to 150 ° C, but is preferably 30 to 120 ° C, particularly preferably 40 to 100 ° C. The processing time is 5 seconds to 60 minutes, preferably 15 seconds to 30 minutes, and particularly preferably 30 seconds to 20 minutes.

The surface treatment with these cleaning liquids generally aims at a degreasing treatment for washing and removing hand marks, machine oil, etc. adhering to the surface of the molded product inevitably in the steps from molding of the resin composition to coating. Is. However, in the molded article formed from the resin composition of the present invention, even if the surface treatment with these cleaning liquids is not performed and surface modification such as primer coating or plasma treatment is not performed, a wider range of paint types can be obtained. Strong paint adhesion is obtained.

Surface Treatment with Hot Gas The surface treatment with hot gas refers to an operation of placing the molded body in a heated gas. In this process, the gas may be flowing or stationary, and the molded body may be moved into the hot gas or may be left stationary. The gas used may be a gas that does not cause environmental pollution, and examples thereof include inert gases such as nitrogen and argon, air, and carbon dioxide. Of these, air and nitrogen are preferred.

The temperature of the heated gas is 40 to 2
00 ° C, preferably 50 to 160 ° C, particularly preferably 60
It is in the range of to 140 ° C. The time (treatment time) for placing the molded body in a heated gas is 5 seconds to 120 minutes, preferably 30 seconds to 90 minutes, and particularly preferably 1 to 60 minutes. Examples of operations that can perform this operation include an oven, a dryer, a super dryer, and an electric furnace.

A molded article formed from the resin composition of the present invention can be subjected to a surface treatment with these hot gases only, and can be used in a wider range without subjecting it to primer coating or surface modification such as plasma treatment. It is very surprising that stronger paint adhesion can be obtained in various paint types.

[IV] Coating When coating a molded article formed from the resin composition of the present invention, a surface modification step such as primer coating or plasma treatment can be omitted from the conventional coating step. That is, in the molded body obtained by molding the resin composition,
The coating is applied directly as it is, or after performing a surface treatment with a cleaning liquid containing no halogen-based organic solvent or a surface treatment with a hot gas. As means for applying the paint, spray coating, brush coating,
Although there is coating with a roller or the like, any method can be adopted.

As the paint that can be used in the painting process, use of widely used organic solvent-based paints and water-based paints such as water-soluble resin paints, water-dispersible resin paints and water-based emulsion paints. You can Specific examples include paints in which the resin component or cross-linking component of these paints is an acrylic, epoxy, polyester, alkyd, urethane, or melamine-based component. Among these, preferred are acrylic paints, epoxy paints, urethane paints and melamine paints, and particularly preferred are acrylic paints, urethane paints and melamine paints.

[V] Application Example Since the molded article formed from the resin composition of the present invention has good suitability for painting, adhesion and printing as described above, it is possible to use bumpers for automobiles, mudguards, side moldings,
Automotive exterior parts such as wheel caps and spoilers;
Automotive interior parts such as instrument panels, levers, knobs and linings; electric products such as pots, vacuum cleaners, washing machines, refrigerators, lighting equipment, audio equipment; packaging films,
It can be used as a packaging material such as a synthetic paper and a laminated film; various industrial parts such as a substrate to be printed, or various sundries such as a color box and a storage case.

[0084]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples below. Molding conditions and test methods for obtaining a test sample from the resin composition produced in each experimental example are as follows. In these experimental examples, the characteristics of the resin composition of the present invention are shown by the coating performance of the molded product. In addition, "part" in an experimental example is a weight part.

<Molding conditions> Molding machine : Injection molding machine manufactured by Meiki Seisakusho M40A-SJ Molding temperature : 230 ° C Molded product : Flat plate (65 mm x 65 mm x 2 mm) Three-point bending elastic modulus test piece (90 mm x 10 mm x 4 mm) ) Flexural modulus : Measured in accordance with JIS K-7203. MFR : Measured according to ASTM D-1238.

<Surface Treatment> No Treatment : The molded test piece was directly coated without any treatment . Alkaline treatment : The test piece was immersed in warm water at 60 ° C. for 30 seconds, and then, an alkaline detergent (CL551 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used.
The 5% aqueous solution of 3) was immersed in a tank heated to 60 ° C for 120 seconds, and then again immersed in warm water of 60 ° C for 30 seconds.
The surface of the test piece was rinsed with tap water for 30 seconds and then with pure water for 30 seconds. Water was removed from the surface of the test piece by air blow, and the test piece was dried in an oven at 80 ° C. for 10 minutes.

Acid treatment : The test piece was immersed in warm water at 60 ° C. for 30 seconds, and then an acidic detergent (ISW3 manufactured by DUBOIS) was used.
The 5% aqueous solution of 2) was immersed in a bath heated to 60 ° C for 120 seconds, and then again immersed in warm water of 60 ° C for 30 seconds.
The surface of the test piece was rinsed with tap water for 30 seconds and then with pure water for 30 seconds. Moisture on the surface of the test piece was removed by air blow, and the test piece was dried in an oven at 80 ° C for 10 minutes. Heated gas treatment : The molded test piece was treated at 80 ° C. for 30 minutes while flowing nitrogen in an oven.

<Coating> Coating was performed using a one-component organic solvent-based urethane coating and a one-component organic solvent-based acrylic coating. Coating method : Each coating material was prepared and spray-coated with an air spray gun so that the coating film thickness was 100 μm. Thereafter, the one-component organic solvent-based urethane coating was baked and dried at 120 ° C. for 60 minutes and the one-component organic solvent-based acrylic coating was baked at 100 ° C. for 60 minutes.

[0089] making 100 pieces of cross-cut the <paint adhesion Evaluation> cross-cut adhesion test single-edged parallel lines aspect eleven increments perpendicular to the surface of the specimen using a razor pulling at 2mm intervals. On top of that, cellophane adhesive tape (JIS Z152
2) is sufficiently pressure-bonded, kept at about 30 degrees from the coating surface, and peeled off at once in front, observing the state of the part surrounded by the grid,
The number of crosses that did not peel off was recorded.

Examples 1 to 35 and Comparative Examples 1 to 9 (1) Production of Resin Molded Body Each component shown in Tables 1 and 2 below was blended and melt-kneaded at 200 ° C. by a twin-screw extruder. Into pellets.
A flat plate and a three-point bending elastic modulus measuring test piece were injection-molded using the pellet. The compounding ingredients in Tables 1 and 2 are as follows.

<Olefin resin: (a) component> Block PP (1) : Ethylene content 4% by weight, JIS-
Flexural modulus measured according to K7203 is 1400
A propylene / ethylene block copolymer having a MFR of 0 g / cm ² and an MFR measured according to ASTM-D1238 of 60 g / 10 min.

Block PP (2) : ethylene content 13% by weight, flexural modulus 6,000 kg / cm ² measured according to JIS-K7203, and MFR 30 g / measured according to ASTM-D1238. 10 minutes of propylene
Ethylene block copolymer.

Random PP : ethylene content 3.4% by weight, flexural modulus measured according to JIS-K7203 is 10,500 kg / cm ² , and MFR measured according to ASTM-D1238 is 15 g / 10 min. Of propylene
Ethylene random copolymer.

Single PP : Flexural modulus measured according to JIS-K7203 is 13,000 kg / cm ² , and AST
MFR measured according to M-D1238 is 25g / 1
0 minutes polypropylene.

HDPE : Flexural modulus measured according to ASTM-D747 is 10,500 kg / cm ² , and JIS
-MFR measured in accordance with K6760 is 20 g / 1.
0 minute low pressure polyethylene (high density polyethylene).

<Copolymer resin containing non-conjugated dienes:
Component (b)> Copolymer (1) 7-methyl-1,6-octadiene content 7.3% by weight,
Flexural modulus 6,250 kg / cm ² and MFR 3.5 g / 1
0 minute propylene-7-methyl-1,6-octadiene random copolymer.

Copolymer (2) 4-methyl-1,4-hexadiene content 13.6% by weight, 5-methyl-1,4-hexadiene content 3.4% by weight, flexural modulus 9,000 kg / cm ² , And MFR is 17.
5 g / 10 min propylene-4-methyl-1,4-hexadiene-5-methyl-1,4-hexadiene random copolymer.

Copolymer (3) 7-methyl-1,6-octadiene content 6.8% by weight,
Ethylene content 1.2% by weight, flexural modulus 4,700 kg / cm
² , and a propylene / ethylene / 7-methyl-1,6-octadiene random copolymer having an MFR of 2.8 g / 10 min.

Copolymer (4) 4-methyl-1,4-hexadiene content 5.3% by weight,
5-methyl-1,4-hexadiene content 1.3% by weight,
Ethylene content 16% by weight, flexural modulus 6,400 kg / cm ²
And MFR is 1.5 g / 10 min propylene. (Ethylene-4-methyl-1,4-hexadiene-5-methyl-
1,4-hexadiene) block copolymer.

<Polymer Having Carboxyl Group (Including Acid Anhydride Group): Component (c)> EAA (1 ): Ethylene Produced by High Pressure Radical Polymerization, Acrylic Acid Content 13% by Weight, MFR 7 g / 10 min -Acrylic acid copolymer. EAA (2 ): an ethylene-acrylic acid copolymer having an acrylic acid content of 15% by weight and an average molecular weight of 3,000 produced by a high-pressure radical polymerization method. MEPR : A maleic anhydride graft / ethylene / propylene copolymer rubber having a maleic anhydride content of 2% by weight and an MFR of 0.1 g / 10 minutes, produced by a kneading and grafting method.

MPEM : Maleic anhydride graft-propylene-ethylene-7-methyl-1,6-octadiene copolymer resin produced as described below. (Manufacturing method) propylene / ethylene / 7-methyl-1,6
Biaxially blending 5 kg of octadiene copolymer (the above-mentioned copolymer (3)) with 500 g of maleic acid and setting a temperature of 230 ° C., a rotation speed of 300 rpm, and a discharge rate of 10 kg / h without using a reaction initiator. The mixture was kneaded and kneaded in an extruder.
The obtained product was dissolved in xylene, precipitated in methanol, filtered and dried to obtain the desired product. The content of maleic anhydride in the obtained graft polymer was 4.1% by weight.

MDPH : A diene polymer hydrogenated product having a carboxyl group produced as described below. (Production method) 100 g of 1,3 butadiene, 70 g of isopropyl alcohol, and 5 g of 60% hydrogen peroxide were added to an autoclave having a capacity of 500 ml, and polymerization was carried out at 90 ° C. for 5 hours in an argon atmosphere. After the reaction was completed, unreacted monomers were removed, and the produced diene polymer having a hydroxyl group was dried. Obtained Polymer Diene Polymer 5
0 g, cyclohexane 50g and 5 wt% of carbon supported ruthenium catalysts 5g, after purging the system with charged argon gas autoclave capacity 200 ml, while supplying hydrogen gas so as to maintain the hydrogen gas 50 kg / cm ² 1
Reaction was carried out for 0 hours. After completion of the reaction, hydrogen was removed and the catalyst was removed by filtration, and the produced hydrogenated product was precipitated in methanol and filtered off. The obtained diene polymer hydrogenated product had an iodine value of 0.5 (g / 100 g) and a hydroxyl value of 46.9 (KOH mg / g). 1000 ml capacity
100 g of the diene polymer hydrogenated product having a hydroxyl group produced by the above-mentioned method, 300 ml of dry toluene and 12 g of maleic anhydride were added to the autoclave of 1. and reacted at 90 ° C. for 6 hours in a nitrogen atmosphere. After the reaction,
The product was precipitated in methanol and dried to obtain the desired product.
The content of maleic anhydride in the obtained polymer was 5.4% by weight.

<Elastomer component: (d) component> EPM (1) : Mooney viscosity ML _{1 + 4} (100 ° C.) is 70,
Ethylene / propylene / copolymer rubber with a specific gravity of 0.86. EPM (2) : Mooney viscosity ML _{1 + 4} (100 ° C) is 24,
Ethylene / propylene copolymer rubber with a specific gravity of 0.86. EPDM : Mooney viscosity ML _{1 + 4} (100 ° C) is 47,
Ethylene / propylene / ethylidene norbornene copolymer rubber with a specific gravity of 0.86. SEBS : number average molecular weight 70,000, specific gravity 0.91
Is a hydrogenated product of styrene / butadiene block copolymer rubber.

<Filler component: (e) component> Talc : Talc having a specific surface area of 39,000 cm ² / g and an average particle size of 1.8 to 2.2 μm. Potassium titanate whiskers : average diameter 0.2-0.5
Potassium titanate whiskers [K ₂ O · 6TiO ₂ ] having a micrometer and an average aspect ratio of 20 or more. Mica : Mica having an average flake diameter of 90 μm. Calcium carbonate : Specific surface area of 33,000 to 39.00
Calcium carbonate with 0 cm ² / g and an average particle size of 0.1 to 0.5 μm. Barium sulfate : Barium sulfate having an average particle size of 0.5 to 0.8 μm. Glass fiber : Glass fiber having an average diameter of 12 to 14 μm and a cut length of 6 mm.

(2) Coating of Resin Molded Body The flat plates molded by the above-mentioned resin molded body were each subjected to the surface treatment described above, and the coating material was applied using an air gun. After completion of baking and drying, the mixture was allowed to stand at room temperature for 48 hours to carry out a cross-cut test. The flexural modulus of the obtained resin composition is shown in Tables 1 and 2, and the results of paint adhesion of the molded product are shown in Table 3.
And shown in Table 4.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

[0111]

[Table 6]

[0112]

[Table 7]

[0113]

[Table 8]

According to the coating adhesion data shown in the above table, the copolymer resin containing the non-conjugated dienes (component (b))
It can be seen that a composition containing neither or both of a polymer having a carboxyl group (including an acid anhydride) (component (c)), or both does not show paint adhesion at all or is extremely low ( See Comparative Examples 1-9). Further, looking at the paint adhesion when a one-pack type urethane-based paint was used, in the case of the resin composition of the present invention, the one in which the surface of the test piece was coated without treatment also showed good paint adhesion. However, it can be seen that the ones which were further surface-treated with an alkaline cleaning solution and then painted exhibited stronger paint adhesion (see Examples 8 and 16).

[0115]

Since the resin composition of the present invention is composed of the above-mentioned specific components, a molded article formed from the resin composition can be vapor-cleaned with a halogen-based organic solvent which may cause environmental damage. It is possible to directly apply paints, adhesives, etc. and to print printing inks, etc. without applying a primer or applying surface modification treatment such as plasma treatment, etc. , Adhesiveness and printability are obtained. Further, the surface of the molded body formed from the resin composition is further strengthened by simply performing a relatively simple surface treatment such as a surface treatment with a cleaning liquid containing no halogen-based organic solvent or a surface treatment with hot gas. Not only is it possible to obtain good paint adhesion, but also good paint adhesion to a wider range of paint types. Therefore, overturning the conventional wisdom that it is impossible to directly coat an olefin resin, a molded article formed from the composition of the present invention is subjected to a surface modification treatment such as primer coating or plasma treatment. Even if a paint is applied without applying it in advance, it shows good paint adhesion and is industrially very useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display area C08L 23/02 LCB 7107-4J LCD 7107-4J LCG 7107-4J LCK 7107-4J LCL 7107-4J LCM 7107-4J LCN 7107-4J 23/16 LCY 7107-4J 23/26 LDA 7107-4J 33/02 LHR 7921-4J 35/00 7921-4J 45/00 LKB 7921-4J 47/00 LKJ 7142-4J 51 / 06 LLD 7142-4J LLE 7142-4J 53/00 LLV 7142-4J LLY 7142-4J

Claims (4)

[Claims] 1. A component (a), a component (b) and a component (c) below, wherein 0.1 to 900 parts by weight of the component (b) and 100 parts by weight of the component (a) are used. ) 0.01
~ 400 parts by weight of a resin composition. Component (a) : Olefin-based resin component (b) : At least one selected from α-olefins having 2 to 12 carbon atoms and at least one non-conjugated diene represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer having carboxyl group (including acid anhydride group) 2. The following component (a), component (b), component (c), and component (d) are included, and the component (b) is 0.1 to 900 relative to 100 parts by weight of the component (a). A resin composition containing parts by weight, 0.01 to 750 parts by weight of the component (c), and 1 to 900 parts by weight of the component (d). Component (a) : Olefin-based resin component (b) : At least one selected from α-olefins having 2 to 12 carbon atoms and at least one non-conjugated diene represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer component having carboxyl group (including acid anhydride group) (d) : Elastomer 3. The following component (a), component (b), component (c), and component (e) are contained, and the component (b) is 0.1 to 900 per 100 parts by weight of the component (a). A resin composition containing parts by weight, 0.01 to 500 parts by weight of the component (c), and 0.1 to 300 parts by weight of the component (d). Component (a) : Olefin-based resin component (b) : At least one selected from α-olefins having 2 to 12 carbon atoms and at least one non-conjugated diene represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer component having carboxyl group (including acid anhydride group) (e) : Filler 4. The following component (a), component (b), component (c), component (d), and component (e) are contained, and the component (b) is added to 100 parts by weight of the component (a). 0.1-90
0 parts by weight, 0.01 to 900 parts by weight of the component (c), 1 to 900 parts by weight of the component (d) and 0.1 to 100 parts of the component (e).
A resin composition containing 300 parts by weight. Component (a) : Olefin-based resin component (b) : At least one selected from α-olefins having 2 to 12 carbon atoms and at least one non-conjugated diene represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer component having carboxyl group (including acid anhydride group) (d) : Elastomer component (e) : Filler