JPH0578588A - 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 copolymer resin and a specified polymer in a specified mixing ratio. CONSTITUTION:The objective composition comprises 100 pts.wt. olefinic resin (e.g. polypropylene/ethylene block copolymer), 0.1-900 pts.wt. block and/or random copolymer resins each comprising at least one 2-12 C alpha-olefin (e.g. propylene) and at least one nonconjugated diene and 0.01-400 pts.wt. hydroxylated polymer (e.g. ethylene/2-hydroxyethyl methacrylate/methyl methacrylate terpolymer).

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 a resin composition comprising the following component (a), component (b), and component (c), and optionally component (d) and / or component (e): To 100 parts by weight of (a), the component (b) was added in an amount of 0.
1 to 900 parts by weight, 0.01 to 400 to 900 parts by weight of component (c), 1 to 900 parts by weight of component (d) and / or 0.1 to 300 parts by weight of component (e). is there. 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 having hydroxyl group (d) : 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): Polymer Having Hydroxyl Group The polymer having a hydroxyl group used in the present invention is a hydroxyl group-containing unsaturated compound or a polar group capable of introducing or generating a hydroxyl group by some chemical modification after polymerization. Homopolymers such as unsaturated compounds containing groups, copolymers with other polymerizable monomers, and graft polymers onto other polymers, resulting in a structurally branched or linear structure. The hydroxyl groups are irregular or regularly pendant on the molecular chain, or the side chains having hydroxyl groups are
It refers to all types of grafted structures.

The polymer can be produced by a known method. For example, a polymerization method of a hydroxyl group-containing unsaturated compound,
Copolymerization method of a hydroxyl group-containing unsaturated compound with another polymerizable monomer, a method of grafting a hydroxyl group-containing unsaturated compound to a polymer, a diol compound, a polyol compound, an epoxy-containing compound, or a bifunctional or more functional group in a polar group in the polymer. Examples of the method include a method of reacting a compound having at least one hydroxyl group, and a method of generating a hydroxyl group by oxidizing or hydrolyzing a polar group in a polymer. Among the polymers produced by the above production method or the like, a copolymer of an α-olefin and a hydroxyl group-containing unsaturated compound, or the component (a): an olefin resin,
Component (b): a copolymer resin containing non-conjugated dienes,
And component (d) described below: a graft polymer of a hydroxyl group-containing unsaturated compound onto an elastomer, and a hydrolyzate of a vinyl ester-containing polymer are preferable.

A specific description will be given below. Copolymer of α-olefin and a hydroxyl group-containing unsaturated compound: From the structural point of view, the copolymer means that a hydroxyl group-containing unsaturated compound is irregular or regularly present in a branched or linear carbon chain. , Α-olefins and copolymers having a structure. Specifically, the content of the hydroxyl group-containing unsaturated compound is 0.1 to 50% by weight, preferably 0.5 to 45% by weight, and particularly preferably 1 to 40% by weight. Melt flow rate (MFR) measured in conformity is 0.1 to 1,0
00g / 10 minutes, preferably 0.5-700g / 10
Min, particularly preferably 1 to 500 g / 10 min, and includes liquid, semi-solid and solid polymers at room temperature.

Such a copolymer of an α-olefin and a hydroxyl group-containing unsaturated compound is produced by a known method using the α-olefin and a hydroxyl group-containing unsaturated compound as a raw material, for example, a high-pressure radical polymerization method or a slurry polymerization method. can do. In the case of production by the high-pressure radical polymerization method,
Ethylene, a hydroxyl group-containing unsaturated compound, and a radical polymerization initiator, for example, a pressure of 1,000 to 3,000 atm,
In the reaction zone kept at a temperature of 90 to 300 ° C., the ratio of ethylene: hydroxyl group-containing unsaturated compound was 1: 0.0001 to
It is continuously fed so that it becomes 1: 0.1, and the conversion rate is 3 ~.
It is produced by making an ethylene copolymer at 20% and continuously taking out the copolymer from the reaction zone. In the case of the production by the slurry polymerization method, propylene and a compound obtained by complexing a hydroxyl group-containing unsaturated compound with an organic aluminum compound or the like are used using a known Ziegler catalyst or the like, for example, in a heptane bath medium, pressure, normal pressure to 20. Atmospheric pressure, temperature 30-150 ℃
It is manufactured by polymerizing in.

Examples of such a hydroxyl group-containing unsaturated compound include 2-hydroxyethyl methacrylate and 2
-Hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate,
Methacrylates or acrylates such as diethylene glycol monomethacrylate and poly (ethylene glycol) monomethacrylate; unsaturated alcohols such as allyl alcohol, 9-decen-1-ol, 10-undecen-1-ol; 2-hydroxyethyl vinyl ether, diethyl Examples thereof include vinyl ethers such as ren glycol monovinyl ether; allyl ethers such as 2-hydroxyethyl allyl ether. Among these, methacrylate / acrylates and unsaturated alcohols are preferable, and 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 10-undecen-1-ol and the like are particularly preferable.

The α-olefin which is the other copolymerization component has a carbon number of 2 to 12, and specifically, 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, vinylcyclo Mention may be made of pentane, vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane, and the like. Among these, preferred examples are
Ethylene, propylene, 1-butene, 3-methyl-1-
Butene, 4-methyl-1-pentene, styrene and the like, and particularly preferred examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

In addition to the above α-olefin and hydroxyl group-containing unsaturated compound components, as a third copolymerization monomer component, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate: α-methyl Vinyl aromatic compounds such as styrene and vinyltoluene: Acrylonitrile, nitrile compounds such as methacrylonitrile: 2-vinylpyridine,
4-vinyl pyridine, etc. vinyl pyridine: methyl vinyl ether, 2-chloroethyl vinyl ether, etc. vinyl ether: vinyl chloride, vinyl bromide, etc. vinyl halide: vinyl acetate, etc. vinyl ester: acrylic aluminide, etc. It can also be used as a ternary or multi-component copolymer. These copolymers can be used alone or as a mixture of plural kinds.

Graft Polymer of Hydroxyl Group-Containing Unsaturated Compound From the structural point of view, the graft polymer is a branched or linear molecular chain in which a hydroxyl group-containing unsaturated compound is grafted irregularly or regularly. Refers to all those having a polymerized structure. Specifically, the content of the hydroxyl group-containing unsaturated compound is 0.1 to 50% by weight, preferably 0.5 to
45% by weight, particularly preferably 1 to 40% by weight, and the melt flow rate (MFR) measured according to ASTM-D1238 is 0.1 to 1,000 g /
10 minutes, preferably 0.5 to 700 g / 10 minutes, particularly preferably 1 to 500 g / 10 minutes, liquid at room temperature,
Includes semi-solid and solid polymers.

This hydroxyl group-containing unsaturated compound graft polymer comprises an olefin resin as component (a), a copolymer resin containing non-conjugated dienes as component (b) and a component (d) described below as a trunk polymer component. It can be produced by a well-known method, for example, a kneading graft method, a solution graft method or the like, using the above-mentioned elastomer and a hydroxyl group-containing unsaturated compound as a graft component as raw materials. For example, in the case of production by a kneading graft method, with the trunk polymer component,
It is produced by melt-kneading a hydroxyl group-containing unsaturated compound and, if necessary, an organic peroxide as a reaction initiator in an extruder set at a temperature of 80 to 250 ° C.

In the case of production by the solution grafting method,
For example, a copolymer containing non-conjugated dienes, a hydroxyl group-containing unsaturated compound, and, if necessary, an organic peroxide as a reaction initiator is dissolved in a xylene solvent at a temperature of 80 to 150.
It is produced by reacting in an autoclave set at ℃. Examples of the hydroxyl group-containing unsaturated compound of the graft component used here include 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, and 2-hydroxyethyl acrylate.
Methacrylates or acrylates such as hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 2-hydroxybutyl methacrylate, 2-hydroxybutyl acrylate, diethylene glycol monomethacrylate, and poly (ethylene glycol) monomethacrylate. Kinds; allyl alcohol, 9-decen-1-ol, 10-undecene-1
-Unsaturated alcohols such as ol; vinyl ethers such as 2-hydroxyethyl vinyl ether and diethyllen glycol monovinyl ether; and allyl ethers such as 2-hydroxyethyl allyl ether.
Among these, methacrylate / acrylates are preferable, 2-hydroxyethyl methacrylate, 2-
Hydroxyethyl acrylate and the like are particularly preferable.

As the trunk polymer component 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 Examples of the elastomer of the component (d) described below include ethylene-based resins, propylene-based resins, olefin-based elastomers,
Examples thereof include styrene elastomer, ethylene / non-conjugated diene copolymer resin, propylene / non-conjugated diene copolymer resin, ethylene / propylene / non-conjugated diene copolymer resin. Particularly preferably, propylene resin, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPD).
M), and styrene / conjugated diene block copolymer hydrogenated product, propylene / 7-methyl-1,6-octadiene copolymer resin, propylene / ethylene / 7-methyl-1,6-octadiene copolymer resin ,propylene·
Methyl-1,4-hexadiene copolymer resin etc. are mentioned.

In addition to the above-mentioned hydroxyl group-containing unsaturated compound component, as a second copolymerization graft monomer component, unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate; styrene, α-methyl Vinyl aromatic compounds such as styrene 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, Examples thereof include vinyl halides such as vinyl bromide: vinyl esters such as vinyl acetate: acrylamide and the like, and they can also be used as binary or multi-component graft copolymers. These graft polymers can be used either individually or as a mixture of plural kinds.

Hydrolyzate of Vinyl Ester-Containing Polymer The vinyl ester-containing polymer is a homopolymer of a vinyl ester, or a copolymer with another polymerizable monomer, and a graft polymer onto another trunk polymer. Etc.
Specifically, the vinyl ester compound content is 0.01
% To 100% by weight, preferably 0.05 to 70% by weight, particularly preferably 0.1 to 40% by weight.
Melt flow rate (MFR) measured according to TM-D1238 is 0.01 to 1,000 g / 10 minutes, preferably 0.05 to 700 g / 10 minutes, and particularly preferably 0.1 to 500 g / 10 minutes. It includes liquid, semi-solid and solid polymers at room temperature.

The vinyl ester-containing polymer can be produced by a known method. For example, a high pressure radical polymerization method, a solution polymerization method, an emulsion polymerization method, a solution graft polymerization method, and a kneading graft polymerization method can be mentioned. In the case of production by a high-pressure radical polymerization method, for example, a vinyl ester compound, ethylene and a radical polymerization initiator are added at a pressure of 1,000 to 3,000 and a temperature of 90 to 300.
The vinyl ester compound and ethylene were continuously fed into the reaction zone kept at 0 ° C. to prepare a copolymer under the conditions such that the conversion rate was 3 to 20%. From the reaction zone, the copolymer was obtained. Is continuously produced. Examples of vinyl ester compounds used in the polymer include vinyl formate, vinyl acetate, vinyl acrylate, vinyl crotonic acid, vinyl caprylate, vinyl laurate, vinyl chloroacetate, vinyl oleate, vinyl stearate, and the like. Of these, vinyl acetate is preferred.
When the polymer is a copolymer with another polymerizable monomer, the copolymerizable monomer has a carbon number of 2 to 1
2 α-olefins are preferred.

Specifically, 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 [2,2,2]
1] -heptane and the like. Among these, preferred examples are ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene and the like, and particularly preferred examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

When the polymer is a graft polymer, the backbone polymer thereof is an olefin resin as the component (a), a copolymer resin containing non-conjugated dienes as the component (b), and Examples of the component d) include elastomers, and among these, ethylene resins, propylene resins, olefin elastomers, styrene elastomers, ethylene / non-conjugated diene copolymer resins, propylene / non-conjugated dienes are preferable. Polymer resin,
Examples thereof include ethylene / propylene / non-conjugated diene copolymer resins. Particularly preferably, propylene resin, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPD).
M), styrene / conjugated diene block copolymer hydrogenated product, propylene / 7-methyl-1,6-octadiene copolymer resin, propylene / ethylene / 7-methyl-1,
6-octadiene copolymer resin, propylene / methyl-
1,4-hexadiene copolymer resin etc. are mentioned.

Even if the polymer is a copolymer or a graft polymer, a monomer component other than the above-mentioned monomer components, such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate, is used as a copolymerizable monomer component. Saturated carboxylic acid ester; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinyl viridines such as 2-vinyl pyridine and 4-vinyl pyridine; methyl vinyl ether;
Vinyl ether such as 2-chloroethyl vinyl ether:
Examples thereof include vinyl halides such as vinyl chloride and vinyl bromide: vinyl esters such as vinyl acetate: acrylamide and the like, and binary and multi-component copolymers and graft copolymers are also possible. These (co) polymers and graft (co) polymers may be used alone or as a mixture of a plurality of types.

The hydrolyzate of the vinyl ester-containing polymer is produced by hydrolyzing the vinyl ester-containing polymer. Examples of the hydrolysis method of the vinyl ester-containing polymer include a method of adding a catalyst such as an alkali or an acid and an alcohol. The degree of hydrolysis of the vinyl ester-containing polymer is 100 to 1%, preferably 100 to 10%, particularly preferably 100 to 3
It is 0%, and may be completely hydrolyzed or partially hydrolyzed. As the hydrolyzate of the vinyl ester-containing polymer, a hydrolyzate of a copolymer of a vinyl ester compound and an α-olefin is preferable, and a hydrolyzate of a copolymer of vinyl acetate and ethylene is particularly preferable. Among these polymers having a hydroxyl group, a copolymer of α-olefin and a hydroxyl group-containing unsaturated compound, and a graft polymer of a hydroxyl group-containing unsaturated compound are preferable, and particularly a copolymer of ethylene and a hydroxyl group-containing unsaturated compound. Further, a graft polymer of a hydroxyl group-containing unsaturated compound onto a copolymer resin containing non-conjugated dienes is preferable.

Component (d): Elastomer The elastomer component used in the preferred resin composition of the present invention is a polymer exhibiting 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 include 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 the optimum one. 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 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. The polymer having a hydroxyl group of the component (c) is 0.01
To 400 parts by weight, preferably 0.05 to 250 parts by weight,
It is particularly preferably 0.1 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 hydroxyl 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, the component (d) elastomer is 1 to 900 parts by weight, Preferably 5 to 300 parts by weight,
It is particularly preferably 10 to 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 hydroxyl group of 0.01 to 500 parts by weight, preferably 0.05 to 350 parts by weight, particularly preferably 0.1 to 180 parts by weight, the filler of the component (e),
0.1 to 300 parts by weight, preferably 0.5 to 250 parts by weight, particularly preferably 1 to 200 parts by weight.

In the case of a resin composition containing the component (a), the component (b), the component (c), the component (d), and the component (e): to 100 parts by weight of the olefin resin of the component (a) Then, the copolymer resin containing the non-conjugated dienes of the component (b) is 0.1 to 900 parts by weight, preferably 0.5.
To 600 parts by weight, particularly preferably 1 to 300 parts by weight, the hydroxyl group-containing polymer of component (c) is 0.01 to 90 parts by weight.
0 parts by weight, preferably 0.05 to 450 parts by weight, particularly preferably 0.1 to 240 parts by weight, the elastomer of component (d) is 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, and the filler of the component (e) are 0.1 to 300 parts by weight, preferably 0.5 to 250 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 hydroxyl group as the component (c) is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks, etc. is poor and the adhesion strength is weak, which is not preferable. .. On the other hand, when 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 becomes high, but also because the polymer causes delamination or bleed-out, a coating composition,
Adhesiveness of adhesives, printing inks, etc. decreases, which is not preferable.

By blending the elastomer component of the component (d) and / or the filler of the component (e), not only the rigidity and impact resistance can be adjusted, but also the blending thereof makes the composition stronger. This is convenient because it is possible to obtain the adhesion of paints, adhesives, printing inks, and the like. However, if the amount exceeds the above range, 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-type 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 liquids is the surface treatment method referred to herein, and includes immersion cleaning method, 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 and the like 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.

The molded article formed from the resin composition of the present invention can be used in a wider range without subjecting it to a surface treatment such as a hot gas, without applying a primer or surface treatment such as plasma treatment. It is very surprising that stronger paint adhesion can be obtained in various paint types.

[IV] Coating When a molded article formed from the resin composition of the present invention is coated, 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 step, 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 product formed from the resin composition of the present invention has good suitability for painting, adhesion, and printing as described above, it can be used for automobile bumpers, 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.

[0078]

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 pieces were 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 two-component organic solvent-based urethane 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. Then, the one-component organic solvent-based urethane coating was baked and dried at 120 ° C. for 60 minutes and the two-component organic solvent-based urethane coating at 80 ° C. for 60 minutes.

<Evaluation of Paint Adhesion> Peel Strength : After treatment for preventing the paint from adhering to the upper half of the test piece, each paint was applied to a coating film thickness of 100 μm, and baked and dried. Adhere the cellophane adhesive tape (example: Nichiban width 24mm) to the entire surface of the test piece,
With a width of 1 cm, make a cut up and down to reach the substrate. The side with no coating film adhered was peeled by hand, and the load was recorded when it was attached to a tensile tester and peeled at a speed of 50 mm / min in the 180 ° direction. In addition, when the coating film was ruptured, it was described as rupture.

Examples 1 to 34 and Comparative Examples 1 to 9 (1) Manufacture 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 of 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 is 13% by weight, flexural modulus measured according to JIS-K7203 is 6,000 kg / cm ² , and MFR measured according to ASTM-D1238 is 30 g / 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 : Bending elastic 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 Hydroxyl Group : Component (c)> EHM (1) Obtained by the high pressure radical polymerization method, the content of 2-hydroxyethyl methacrylate is 10% by weight, the content of methyl acrylate is 10% by weight, and the MFR is 100 g. / 10 min ethylene-2-hydroxyethyl methacrylate / methyl acrylate terpolymer. Ethylene-2-hydroxyethyl methacrylate / methyl acrylate obtained by EHM (2) high-pressure radical polymerization method, having a 2-hydroxyethyl methacrylate content of 10% by weight, a methyl acrylate content of 10% by weight, and an MFR of 13 g / 10 min. Ternary copolymer. EHM (3) An ethylene-2-hydroxyethyl methacrylate copolymer obtained by a high-pressure radical polymerization method, having a 2-hydroxyethyl methacrylate content of 10% by weight and an MFR of 7 g / 10 min.

HMEPM 2-Hydroxyethyl Methacrylate Graft-Propylene-Ethylene-7-methyl-1,6-octadiene Copolymer Resin Produced as Follows : (Production Method) Propylene
50 g of an ethylene-7-methyl-1,6-octadiene copolymer (the above copolymer (3)), 40 g of 2-hydroxyethyl methacrylate and 1000 ml of chlorobenzene were added, and the mixture was heated and stirred at 130 ° C. to dissolve. In this solution,
1.5 g of benzoyl peroxide dissolved in 200 ml of chlorobenzene was added dropwise over 2 hours, and the mixture was stirred at 130 ° C for 3 hours.
A time reaction was performed. After the reaction was completed, the product was precipitated in acetone, filtered and dried to obtain the desired product. The 2-hydroxyethyl methacrylate content of the obtained polymer is
It was 1.7% 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 above-mentioned surface treatment and coated with an air gun. After the completion of baking and drying, the peel strength test was conducted by leaving it at room temperature for 48 hours. The bending modulus of elasticity 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 Tables 3 and 4.

[0099]

[Table 1]

[0100]

[Table 2]

[0101]

[Table 3]

[0102]

[Table 4]

[0103]

[Table 5]

[0104]

[Table 6]

[0105]

[Table 7]

[0106]

[Table 8]

According to the coating adhesion data shown in the above table, the copolymer resin containing the non-conjugated dienes (component (b))
And a polymer having a hydroxyl group (component (c)),
Alternatively, the composition containing no component (b) does not exhibit paint adhesion at all (see Comparative Examples 1 to 9). Also,
The resin composition of the present invention, when looking at the paint adhesion when a one-component urethane-based paint is used, shows that the coating of the surface of the test piece without treatment also shows good paint adhesion. Further, it can be seen that the product which was surface-treated with an alkaline cleaning solution and then coated exhibited stronger paint adhesion (see Table 3).

[0108]

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 front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08L 21/00 LBK 8016-4J 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 29/06 LGY 6904-4J 29/10 LGZ 6904-4J 33/06 MLY 7921-4J 45/00 LKB 7921-4J 47/00 LKJ 7142-4J 51/04 LKX 7142-4J LKY 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 a hydroxyl group 2. A component (a) 10 comprising the following components (a), (b), (c), and (d).
0.1 to 900 parts by weight of the component (b) with respect to 0 parts by weight,
0.01 to 750 parts by weight of component (c) and 1 of component (d)
A resin composition containing 900 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 a hydroxyl 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 (e). 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 hydroxyl group (e) : Filler 4. A component (a) comprising the following component (a), component (b), component (c), component (d) and component (e):
0.1 to 900 parts by weight of component (b), 0.01 to 900 parts by weight of component (c), and component (d) per 100 parts by weight.
1 to 900 parts by weight and component (e) from 0.1 to 300
A resin composition containing 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 hydroxyl group (d) : Elastomer component (e) : Filler