JP3046655B2 - Resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a resin composition.
More specifically, the present invention relates to an olefin-based resin composition suitable for coating, bonding, printing, and the like on the surface.

[0002]

2. Description of the Related Art Conventionally, when coating the surface of a resin molded product, steam cleaning using a halogen-based organic solvent is performed before the coating in order to wash and remove grease and machine oil adhered to the surface of the molded product. Has been done. In addition, olefin resins do not have polar groups in their structure and have high crystallinity, so that the adhesion of paints, adhesives, printing inks, etc. is extremely poor, and paintability, adhesiveness, printability, etc. Is poor, so the surface is modified by applying a primer in advance, or by plasma treatment, etc., to improve the adhesion, and then applying paint, adhesive or printing ink. Was.

[0003]

However, such a method has conventionally had the following problems. In other words, in painting or bonding to a resin molded body,
In the steam cleaning method using a halogen-based organic solvent, the possibility that the halogen-based organic solvent diffuses into the air and destroys the ozone layer is a problem, and in order to protect the global environment, an alternative method is quickly adopted. The transition to is required.
In addition, in the primer coating method, there is a disadvantage that an expensive primer must be used, and the cost is increased due to an increase in the number of steps, and further, it is necessary to volatilize a solvent of the primer. The work environment deteriorated, and there was a risk of fire and safety issues.

[0004] On the other hand, in the plasma processing method, a high vacuum state is required, so that expensive equipment must be installed, and the cost cannot be avoided because of the batch system. Furthermore, the surface after the plasma treatment is unstable, and the adhesion of the paint, the adhesive and the printing ink is reduced when the surface comes into contact with foreign matter, so that the adhesion performance may vary and handling is very inconvenient.

[0005] Therefore, if such a step of applying the primer and performing the plasma treatment can be omitted, the steps can be simplified, the working environment can be improved, and the cost can be reduced. Many studies have been made to improve these problems. However, in the end, this purpose has not yet been sufficiently achieved, and such priming and plasma treatment cannot be omitted for olefin resin materials. Are often given.

On the other hand, when the resin molded body is directly coated or bonded without being subjected to a treatment such as primer application, a light stabilizer, an antioxidant, a lubricant, etc. added to the resin composition. It is also known that the additives may reduce the adhesion. There is a report that a copolymer resin containing a non-conjugated diene is blended with an olefin resin, and a special surface treatment is applied 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 potassium permanganate sulfate and a 3% aqueous solution of sodium hydrogen sulfite, 57-44639), a method of performing a surface treatment with an oxidizing agent (Japanese Patent Application Laid-Open No. 57-59934), and a method of performing a surface treatment with ozone (Japanese Patent Application Laid-Open No. 61-197640).

Further, a method using a specific paint or coating composition, for example, a method of coating an olefin resin molded article with a radical polymerization-curable paint (Japanese Patent Laid-Open No.
38825, JP-A-57-59933),
A method using a resin coating composition having a hydrazine group (JP-B-3-22896) and the like are known. However, these methods use special reagents,
Environmental measures against the toxicity of sulfuric acid are indispensable, the treatment method itself is complicated, the handling is very inconvenient, and the application field is very limited due to the limitation of paints and coating compositions. There was a disadvantage that it was narrow.

[0008]

[Means for Solving the Problems]

SUMMARY OF THE INVENTION The present inventors have conducted intensive studies in view of the above problems, and as a result, have found that the above problems can be solved by using a specific resin composition. The invention has been completed.

That is, the present invention comprises the following component (a), component (b), component (c) and component (d), and optionally component (e) and / or component (f). 100
0.1 to 900 parts by weight of component (b), 0.01 to 200 to 450 parts by weight of component (c), 0.01 to 300 to 650 parts by weight of component (d), component ( e) a resin composition containing 1 to 900 parts by weight of component (f) and / or 0.1 to 300 parts by weight of component (f). 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

[0010]

Embedded image

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) : Diene polymer having a hydroxyl group or its hydrogenated component (d) : Polymer component having a carboxyl group (including an acid anhydride group) (e) : Elastomer component (f) : Filler

[0012]

DETAILED DESCRIPTION OF THE INVENTION [I] Resin composition (1) Constituents The resin composition of the present invention is basically formed from the following constituents.

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
-Homopolymers of α-olefins represented by pentene, or copolymers of these α-olefins, or copolymers of the above α-olefins and organosilicon compounds, or the olefin-based resins And a graft polymer such as an organic silicon 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 , particularly preferably 3,000 to 15,000 kg / cm ² . Also, the melt flow rate (MF
R) is not particularly limited, but ASTM-D1
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.

As the olefin resin, for example,
Polyethylene resins such as so-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, linear low-density polyethylene, stereoregular polypropylene, stereoregular poly-1-butene, and stereoregular poly-3-methyl-1-
Stereoregular poly-α-olefin resins such as butene and stereoregular poly-4-methyl-1-pentene can be exemplified. Among these olefin resins, stereoregular polypropylene (hereinafter simply referred to as “propylene resin”)
Abbreviated. Is preferred.

Among these 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 preferred. These olefin-based resins can be used alone or as a mixture of plural kinds of the above-mentioned resins, and can usually be appropriately selected and used from commercially available resins.

Component (b): copolymer containing non-conjugated dienes
Copolymer resin containing non-conjugated dienes used in the body resin present invention includes at least one selected from α- olefin having 2 to 12 carbon atoms, non-conjugated represented by the following general formula (I) At least one of dienes;

[0018]

Embedded image

(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) which 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 and 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 and 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 preferred from the viewpoint of the production technology of the copolymer, and 7-methyl-1,6-octadiene is particularly preferred. Of course, these non-conjugated dienes can be used in a mixture of two or more.

The above-mentioned α-olefin having 2 to 12 carbon atoms, which is the other raw material of the copolymer resin containing non-conjugated dienes, 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 the like. Preferred examples among these are ethylene, propylene, 1-butene, 3-methyl-
Examples thereof include 1-butene, 4-methyl-1-pentene, and styrene, and particularly preferred examples are ethylene and propylene. Two or more of these α-olefins may be used.

The copolymer resin containing a non-conjugated diene used in the present invention has a non-conjugated diene content of 0.1 to 30% by weight, preferably 0.5 to 25% by weight, particularly preferably 1 to 25% by weight.
~ 20% by weight. When the content of the non-conjugated diene is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks and the like is poor, and the adhesion strength thereof is not preferable. On the other hand, if it exceeds the above range, the productivity of resin production is poor, which is not preferable. Further, the copolymer resin containing non-conjugated dienes used in the present invention has a melt flow rate (MFR) of 0.01 to 1,000 g / g.
Ten 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 a non-conjugated diene of the present invention has a flexural modulus according to JIS K-7203 of 1,000 to 30,000 kg / cm ² , preferably 1,000.
２０20,000 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 is not exhibited. Examples of the copolymer resin include the non-conjugated dienes and block copolymers of various combinations selected from the α-olefins, and random copolymers. Are as follows.
[Here, methyl-1,4-hexadiene refers to a mixture of 4-methyl-1,4-hexadiene and 5-methyl-1,4-hexadiene, and the mixing ratio is 95: 5 to
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 copolymer, and the like.

The method for producing the copolymer resin includes:
For example, Japanese Patent Publication No. 64-2127, Japanese Patent Publication No. 64-21
No. 28, JP-B 64-9326, JP-A-59
And the methods described in JP-A-155416, JP-A-62-115008, and JP-A-2-31507.

Component (c): diene polymer having a hydroxyl group
-Or hydrogenated product thereof Examples of the diene polymer having a hydroxyl group and its hydrogenated product used in the resin composition of the present invention include the following. Diene polymer having a hydroxyl group Examples of the diene polymer having a hydroxyl group 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 50,000.
10,000, including liquid, semi-solid or solid polymers at room temperature. When the content of the hydroxyl group contained in the molecule is represented by a hydroxyl value, it is 0.5 to 650, preferably 1 to 5
00, particularly preferably 5 to 250 (KOH mg / g).

The method for producing the diene polymer is not limited, and various known methods can be employed. For example, a radical polymerization method using 1,3-dienes as a raw material,
It can be produced by an anionic polymerization method. Specifically, for example, a method described in JP-A-51-71391 can be mentioned. When it is produced 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, when produced by the above-mentioned anionic polymerization, obtained by polymerizing a conjugated diene using an anionic polymerization catalyst, for example, an alkali metal or organic alkali metal compound, according to a known method,
In a living polymer having a structure in which an alkali metal is bonded to at least one place in a molecular chain, for example, a monoepoxy compound, formaldehyde, acetaldehyde, acetone,
A halogenoalkylene oxide or a polyepoxide may be reacted.

Also, conjugated diene polymers produced by known polymerization methods include osmium tetroxide (OsO ₄ ), vanadium oxide (V ₂ O ₅ ), tungstic acid (H ₂ W
When hydrogen peroxide is allowed to act in the presence of O ₄ ), selenium dioxide (SeO ₂ ), or the like, a product obtained by adding a hydroxyl group to a double bond in the main chain is obtained, which is also used in the present invention. can do. At least one kind 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.

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

Component (d): 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 carboxyl group (an acid anhydride group is added to a branched or linear molecular chain). In general) having a structure in which a pendant is irregularly or regularly pendant, or a side chain having a carboxyl group (including an acid anhydride group) is grafted.

The polymer can be produced by a well-known method. For example, a method of copolymerizing a carboxyl group (including acid anhydride group) -containing unsaturated compound with a polymerizable monomer, a method of grafting a carboxyl group (including acid anhydride group) -containing unsaturated compound to a polymer, a polar group in the polymer A method of reacting an acid anhydride or a compound having two or more functional groups and having at least one carboxyl group, a method of converting a polar group in the polymer to a carboxyl group by oxidation or hydrolysis, and the like.

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

A copolymer of an α-olefin and an unsaturated compound containing a carboxyl group (including an acid anhydride group): The copolymer is, from a structural point of view, a polymer having a branched or linear carbon chain. , Irregular or regular, having a structure in which an unsaturated compound containing a carboxyl group (including an acid anhydride group) is copolymerized with an α-olefin. 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% by weight.
5 wt%, particularly preferably 1 to 40 wt%, 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 (including acid anhydride) -containing unsaturated compound copolymer is obtained by using α-olefin and a carboxyl group (including acid anhydride group) -containing unsaturated compound as raw materials. It can be produced by a known method, for example, a high-pressure radical polymerization method, a slurry polymerization method, or the like.

In the case of production by the high-pressure radical polymerization method,
Ethylene, an unsaturated compound containing a carboxyl group (including an acid anhydride group) and a radical initiator are mixed, for example, at a pressure of 1,000 to 1,000.
In a reaction zone maintained at 3000 atm and a temperature of 90 to 300 ° C., the ratio of ethylene to a carboxyl group-containing unsaturated compound (including an acid anhydride group) is 1: 0.0001 to 1: 0.1.
To produce an ethylene copolymer under the condition that the conversion is 3 to 20%, and the copolymer is continuously taken out from the reaction zone. Further, in the case of the production method by the slurry polymerization method, propylene and a compound obtained by complexing a carboxyl group-containing unsaturated compound with an organoaluminum compound or the like are conventionally used, for example, in a heptane solvent using a known Ziegler catalyst. Pressure ~
It is produced by polymerizing at a pressure of 20 atm and a temperature of 30-150 ° C.

The unsaturated compounds containing a carboxyl group (including an acid anhydride group) used herein include acrylic acid, methacrylic acid, 3-butenoic acid, crotonic acid, pentenoic acid,
Unsaturated carboxylic acids such as heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, maleic acid, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, and acid anhydrides thereof Can be mentioned. Among these, acrylic acid,
Methacrylic acid, undecenoic acid and the like are preferred.

As the other copolymerization component α-olefin, 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 the like. Preferred examples among these are ethylene, propylene, 1-butene, 3-methyl-
Examples thereof include 1-butene, 4-methyl-1-pentene, and styrene, and particularly preferred examples are ethylene and propylene. Two or more of these α-olefins may be used.

In addition to the α-olefin and the unsaturated compound containing a carboxyl group (including an acid anhydride group), unsaturated copolymers such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate may be used as third copolymerization monomers. 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; Vinyl halides such as vinyl chloride; vinyl esters such as vinyl acetate; acrylamide; and the like, and can be used as a ternary or multi-component copolymer. And each of these copolymers, alone,
A mixture of a plurality of types can be used.

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

The unsaturated compound graft polymer containing a carboxyl group (including an acid anhydride group) is used as a backbone polymer,
Component (a), an olefin-based resin, component (b), a non-conjugated diene-containing copolymer resin, and component (e), an elastomer, and a carboxyl group (including an acid anhydride group) as a graft component The compound can be produced by a known method, for example, a mixed grafting method or a solution grafting method, using an unsaturated compound as a raw material.

For example, in the case of the production by the mixed grafting method, a mixture of the above-mentioned trunk polymer component, a carboxyl group-containing unsaturated compound (including an acid anhydride group) and, if necessary, an organic peroxide as a reaction initiator is added to a mixture of 80%. It is manufactured by melt-kneading in an extruder set at a temperature of ２５０250 ° C. In the case of production by a solution grafting method, for example, in a xylene solvent, a copolymer containing non-conjugated dienes,
Unsaturated compounds containing carboxyl groups (including acid anhydride groups),
It is manufactured by dissolving an organic peroxide as a reaction initiator and, if necessary, reacting in an autoclave set at a temperature of 80 to 150 ° C.

Examples of the unsaturated compound containing a carboxyl group (including an acid anhydride group) of the graft component used herein include:
Acrylic acid, methacrylic acid, 3-butenoic acid, crotonic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenic 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 them, acrylic acid, methacrylic acid, maleic acid and maleic anhydride are preferred.

The backbone polymer which is another component of the graft polymer includes an olefin resin as the component (a), a copolymer resin containing a non-conjugated diene as the component (b), and Elastomers of component (e) can be mentioned, and among these, preferred are ethylene-based resins, propylene-based resins, olefin-based elastomers, styrene-based elastomers, ethylene / non-conjugated diene copolymer resins, and propylene / non- Conjugated dienes copolymer resins, ethylene / propylene / non-conjugated dienes copolymer resins, and the like. Particularly preferred are propylene-based resins and ethylene-propylene copolymer rubber (EP
M), ethylene-propylene-non-conjugated diene copolymer rubber (EPDM), and hydrogenated styrene-conjugated diene block copolymer, propylene-7-methyl-1,6-
Octadiene copolymer resin, propylene / ethylene / 7
-Methyl-1,6-octadiene copolymer resin, propylene / methyl-1,4-hexadiene copolymer resin, and the like.

In addition to the unsaturated compound containing a carboxyl group (including an acid anhydride group), unsaturated carboxylic acids such as methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate may be used as a second graft copolymerization monomer. Esters; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; methyl vinyl ether and 2-chloroethyl vinyl ether Vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate; acrylamide; and the like, and can be used as a binary or multi-component graft copolymer. These graft copolymers can be used alone or in combination of two or more.

Diene polymer or diene polymer hydrogenated product having a carboxyl group (including an acid anhydride group): The diene polymer or diene polymer hydrogenated product having a carboxyl group (including an acid anhydride group) is the same as the component (c) ) Is obtained by reacting a diene polymer having a hydroxyl group or a hydrogenated product thereof with an acid anhydride or a compound having at least one difunctional or higher carboxyl group.

Specifically, the molecular weight is from 200 to 100,0
A liquid, semi-solid, or solid polymer at room temperature of 00, preferably 500 to 50,000, particularly preferably 800 to 10,000 is included. The acid anhydride or bifunctional or more compound having at least one carboxyl group contained in the polymer may be at least one in the molecule, but the content thereof is 0.001 to 5% by weight, preferably 0 to 5% by weight. .
01 to 45% by weight, particularly preferably 0.1 to 40% by weight
Range.

The polymer is obtained by using a diene polymer having a hydroxyl group of the component (c) or a hydrogenated product thereof and an acid anhydride or a compound having at least one difunctional or more functional group having at least one carboxyl group by a known method, For example, it can be produced by a solution reaction or the like. In the case of production by the solution reaction method, for example, a hydrogenated diene polymer having a hydroxyl group and an acid anhydride are dissolved in a toluene solvent, and
It is produced by reacting in a reactor set at a temperature of １２０120 ° C.

Examples of the acid anhydride or bifunctional or more compound having at least one carboxyl group include oxalic acid, malonic acid, succinic acid, maleic acid, glutaric acid, adipic acid, citraconic acid, itaconic acid. , Pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid, norbornene-5,6
Dicarboxylic acids such as dicarboxylic acids, or acid anhydrides thereof;
β-chloropropionic acid, tartaric acid, lactic acid, iminodiacetic acid, ethylenediaminetetraacetic acid, mercaptopropionic acid and the like. Among these, dicarboxylic anhydrides and the like are preferable, and maleic anhydride, succinic anhydride and the like are particularly preferable. It is.

The diene polymer having a hydroxyl group used in the polymer is the above-mentioned component (c). Of these, preferred are those having a hydroxyl group of 1,
It is a 4-butadiene polymer or a hydrogenated product thereof, and particularly preferably a hydrogenated 1,4-butadiene polymer having a hydroxyl group.

The polymer having a carboxyl group (including an acid anhydride group) used as the component (d) of the resin composition of the present invention has been described in detail above. Preferred examples of the polymer include α-olefin and carboxyl group. A copolymer with an unsaturated compound containing a group (including an acid anhydride group) and a graft polymer with 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 (e): 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. And the like. Among these, styrene-based elastomers and olefin-based elastomers, urethane-based elastomers, silicone-based elastomers, and acrylic-based elastomers are preferred, and styrene-based elastomers and olefin-based elastomers are particularly preferred. Specific examples are described below.

Styrene Elastomer The styrene elastomer is styrene, α-
An elastomeric random or block copolymer of a styrene compound such as methylstyrene and a conjugated diene such as 1,3-butadiene and isoprene, and a hydrogenated product of these copolymers. Among these styrene-based elastomers, block copolymers of a styrene-based compound and a conjugated diene are preferable, and these block copolymers are linear or radial. For example, a 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 (where A is a polymer block composed of a styrene compound, and A ′ is bonded to m (BA) _n blocks 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 ratio of the A block and A ′ to the total molecule is 1 to 50% by weight. The average molecular weight of these copolymers is 10,000-1.
00000, preferably 50,000 to 250,000
0.

Specific examples of these styrene elastomers include styrene / butadiene random copolymer, styrene / isoprene random copolymer, styrene / butadiene / styrene triblock copolymer, and styrene / isoprene / styrene triblock copolymer. Styrene-butadiene radial block copolymers with polystyrene block ends, styrene-isoprene radial block copolymers with polystyrene block ends, styrene-butadiene multi-block copolymers, styrene-isoprene multi-block copolymers, etc. Examples include styrene / conjugated diene block copolymers and products obtained by hydrogenating them. Preferred among these styrene elastomers are hydrogenated styrene / conjugated diene block copolymers.

Olefin Elastomers Examples of olefin elastomers include copolymers of α-olefins such as ethylene, propylene, 1-butene and 1-hexene, copolymers of these with non-conjugated dienes, and 1-hexene. A homopolymer of a higher α-olefin such as an elastomeric polymer,
Mooney viscosity ML _{1 + 4} measured at 100 ° C. is usually 1 to
200, preferably 5 to 150, particularly preferably 7 to 1
00 range.

Among these olefin elastomers, ethylene elastomers are particularly preferred 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),
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, and
Examples thereof include vinyl-2-norbornene, 5-methylene-2-norbornene, 5-methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene. Among these elastomer components, olefin elastomers are particularly preferably used because the surface roughness of the molded article is hardly caused.

Component (f): Filler As the filler used in the preferred resin composition of the present invention, any of inorganic and organic fillers can be used. It may be in the form of an irregular shape or an irregular shape.

Specifically, natural silica such as quartz, synthetic silica produced by a wet method or dry method; natural silicate such as kaolin, mica, talc, asbestos; synthetic silicate such as calcium silicate and aluminum silicate; 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 flour; carbon black; fibers such as glass fibers, carbon fibers, aramid fibers, and alumina fibers. Whiskers such as 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, beryl whiskers, etc. And the like.

Among these, preferred are mica, talc, magnesium hydroxide, calcium carbonate, potassium titanate whisker, magnesium sulfate whisker, aluminum borate whisker, calcium carbonate whisker, and glass fiber, 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 component may be used alone or in combination of two or more. Various fillers can be appropriately selected and used from commercially available ones.

The components (a), (b), (c), (d), (e) and (f) constituting the resin composition of the present invention are preferably combined with each other. It goes without saying that is the best.

Component (g): Additional component In the resin composition of the present invention, in addition to the above components (a) to (f), the following are shown as long as the effects of the present invention are not significantly impaired. Various additional components can be contained. Examples of the additional component include additives, specifically, plasticizers or fluidity improvers such as paraffin oil; softeners such as olefin-based liquid rubber and conjugated diene-based liquid rubber; coloring agents Antioxidants; Neutralizers; Light stabilizers; UV absorbers; Antistatic agents; Lubricants; Dispersing aids; Molecular weight regulators; Crosslinking agents; Nucleating agents; And the like.

(2) Quantitative ratio The quantitative ratio of the above components constituting the resin composition of the present invention is as follows. In the case of a resin composition containing component (a), component (b), component (c) and component (d): based on 100 parts by weight of the olefin resin of 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, particularly preferably 1 to 300 parts by weight, the hydroxyl group-containing diene polymer of the component (c) or a hydrogenated product thereof is
0.01 to 200 parts by weight, preferably 0.05 to 125 parts
Parts by weight, particularly preferably 0.1 to 60 parts by weight, and the polymer having a carboxyl group (including an acid anhydride group) of component (d) is 0.01 to 300 parts by weight, preferably 0.1 to 300 parts by weight.
The amount is from 0.05 to 175 parts by weight, particularly preferably from 0.1 to 80 parts by weight.

In the case of a resin composition containing component (a), component (b), component (c), component (d), and component (e): based on 100 parts by weight of olefin resin of component (a) hand,
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, particularly preferably 1 to 300 parts by weight, the hydroxyl group-containing diene polymer of the component (c) or a hydrogenated product thereof is
0.01 to 400 parts by weight, preferably 0.05 to 180 parts
Parts by weight, particularly preferably 0.1 to 90 parts by weight, and the polymer having a carboxyl group (including an acid anhydride group) of component (d) is 0.01 to 550 parts by weight, preferably 0.0 to 90 parts by weight.
5 to 250 parts by weight, particularly preferably 0.1 to 120 parts by weight and the elastomer of component (e) 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 1 to
0 to 200 parts by weight.

In the case of a resin composition containing component (a), component (b), component (c), component (d), and component (f): based on 100 parts by weight of olefin resin of component (a) hand,
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, particularly preferably 1 to 300 parts by weight, the hydroxyl group-containing diene polymer of the component (c) or a hydrogenated product thereof is
0.01 to 250 parts by weight, preferably 0.05 to 170 parts
Parts by weight, particularly preferably 0.1 to 90 parts by weight, and the polymer having a carboxyl group (including an acid anhydride group) of component (d) is 0.01 to 400 parts by weight, preferably 0.0 to 400 parts by weight.
5 to 240 parts by weight, particularly preferably 0.1 to 120 parts by weight, and the elastomer of component (f) is 0.1 to 30 parts by weight.
0 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 component (a), component (b), component (c), component (d), component (e) and component (f): olefin resin 100 of component (a) For parts by weight,
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, particularly preferably 1 to 300 parts by weight, the hydroxyl group-containing diene polymer of the component (c) or a hydrogenated product thereof is
0.01 to 450 parts by weight, preferably 0.05 to 230 parts
Parts by weight, particularly preferably 0.1 to 120 parts by weight, and the polymer having a carboxyl group (including an acid anhydride group) of component (d) is 0.01 to 650 parts by weight, preferably 0.0
5 to 300 parts by weight, particularly preferably 0.1 to 150 parts by weight, the elastomer of the component (e) is 1 to 900 parts by weight,
Preferably 5-300 parts by weight, particularly preferably 10-2
00 parts by weight and the filler of component (f) are 0.1 to
The amount is 300 parts by weight, preferably 0.5 to 250 parts by weight, particularly preferably 1 to 200 parts by weight.

When the copolymer resin containing the non-conjugated diene of the component (b) is less than the above range, the reproducibility of paints, adhesives, printing inks and the like is poor, or the adhesive strength is low. Is not preferred. On the other hand, if the amount exceeds the above range, the amount of the expensive copolymer resin is large, so that not only the cost as the resin composition is increased, but also an effect proportional to the amount of the copolymer resin is obtained. is not.

If the amount of the hydroxyl group-containing diene polymer or its hydrogenated component (c) is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks and the like is poor, and the adhesion strength is low. It is not desirable because it is weak. On the other hand, when the amount exceeds the above range, the amount of the expensive diene polymer to be added is large, so that not only the cost as a resin composition becomes high, but also the diene polymer is delaminated or bleeds out, so that a paint, an adhesive Also, the adhesion of the printing ink and the like decreases, which is not preferable.

When the amount of the polymer having a carboxyl group (including an acid anhydride group) of the component (d) is less than the above,
Depending on the paint, adhesive and printing ink to be applied,
The adhesion strength may be very low, which is not preferable. On the other hand, if it exceeds the above range, the amount of the expensive polymer to be added is large, so that not only the cost of the resin composition becomes high but also the effect proportional to the amount of the polymer is not obtained. In addition, since the polymer reacts with delamination or the diene polymer having a hydroxyl group of the component (c) or a hydrogenated product thereof to increase the crosslink density, the adhesion of paints, adhesives, printing inks, and the like occurs. This is not preferred because the properties are reduced.

By blending the elastomer component (e) and / or the filler of component (f), not only the rigidity and impact resistance can be adjusted, but also the blending of these components further increases the rigidity and impact resistance. Advantageously, it is possible to obtain adhesion of a strong paint, adhesive, printing ink and the like. However, when each of the component (e) and the component (f) exceeds the above range, the moldability of the resin composition deteriorates, which is not preferable.

(3) Compounding The resin composition of the present invention is produced by mixing the above-mentioned components. The order of mixing these constituent components is not particularly limited, and any method such as a method of mixing the above constituent components at the same time, a method of mixing arbitrary two components in advance, and then mixing the remaining components is adopted. Is also good.
As the mixing method, any conventionally known kneading machine such as a Brabender plastograph, a single-screw or twin-screw extruder, a high-speed 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 formed into a resin molded article by molding it by various molding methods. The molded article formed from the resin composition of the present invention is directly used, that is, without performing steam cleaning with a halogen-based organic solvent that may cause environmental destruction, and surface modification such as primer coating or plasma treatment. It is possible to apply a paint, an adhesive and a printing ink without performing a treatment, and has a feature that good paint adhesion, adhesiveness, printability, and the like are obtained.

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

[II] Molded Article A molded article is 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) and the like. It does not matter. In particular, the present invention is effective for a molded article injection-molded into a complicated shape.

[III] Surface Treatment of Molded Article The molded article formed from the resin composition of the present invention can be directly applied with a paint or the like as described above. By performing the surface treatment, strong adhesion can be obtained in a wide variety of paint types and the like. Surface treatment with a cleaning solution containing no halogen-based organic solvent A cleaning solution containing no halogen-based organic solvent refers to various types of fluorocarbons, 1,1,
1-Trichloroethane, perchlorethylene, and general cleaning liquid excluding halogenated organic solvents such as trichlene. Examples of such a cleaning liquid include a solvent-type cleaning liquid, an emulsion-type cleaning liquid, and an aqueous cleaning liquid.

Specifically, examples of the solvent type cleaning liquid include: aliphatic hydrocarbons such as kerosene and d-limonene; aromatic hydrocarbons such as toluene and xylene; methanol, ethanol, and the like.
Alcohols such as isopropyl alcohol are exemplified. 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. Examples of the aqueous cleaning liquid include an alkaline cleaning liquid in which an alkali component such as sodium hydroxide, potassium hydroxide, sodium silicate and sodium carbonate is used in combination with a surfactant, and an acidic cleaning liquid in which an acid component such as phosphoric acid is used in combination with a surfactant. And a neutral cleaning solution using a nonionic surfactant, water such as pure water or warm water. Among these washing liquids, preferably, an aqueous washing liquid and an emulsion-type washing liquid, and particularly preferably,
It is an aqueous cleaning solution.

The cleaning method using these cleaning liquids is the surface treatment method referred to here, such as immersion cleaning method, shower cleaning method,
Any cleaning method such as a power wash method, an ultrasonic immersion cleaning method, and a wiping method can be selected. Of these, immersion cleaning, shower cleaning, and power wash are preferred. The temperature of the cleaning solution can be used from room temperature to 150 ° C., but is preferably from 30 to 120 ° C., particularly preferably from 40 to 100 ° C. The processing time is in the range of 5 seconds to 60 minutes, preferably 15 seconds to 30 minutes, particularly preferably 30 seconds to 20 minutes.

The surface treatment with these cleaning liquids is generally intended to be a degreasing treatment for cleaning and removing grease and machine oil which are inevitably adhered to the surface of the molded product in the process from molding to coating of the resin composition. It is. However, in the molded article formed from the resin composition of the present invention, only surface treatment with these cleaning liquids, without performing surface modification such as primer application or plasma treatment, is possible in a wider range of paint types. Strong paint adhesion is obtained.

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

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

In the molded article formed from the resin composition of the present invention, the surface treatment with these hot gases is merely performed, and a broader range can be obtained without surface modification such as primer application or plasma treatment. It is very surprising that stronger paint adhesion can be obtained for various kinds of paints.

[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, to a molded body obtained by molding the above resin composition,
The coating is applied directly as it is or after 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 application by spraying, brushing,
Although there is application by a roller or the like, any method can be adopted.

As the paint that can be used in the coating step, use is generally made of a water-based paint such as an organic solvent-based paint and a water-soluble resin paint, a water-dispersible resin paint, and an aqueous emulsion paint that are widely used. Can be. Specifically, there can be mentioned paints in which the resin component or the cross-linking component of these paints is composed of components such as acrylic, epoxy, polyester, alkyd, urethane and melamine. 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] Example of Use The molded article formed from the resin composition of the present invention has good suitability for coating, adhesion and printing as described above, and therefore, is suitable for automobile bumpers, mudguards and 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 fixtures, and audio equipment;
It can be used as a packaging material such as synthetic paper and a laminated film; various industrial parts such as a substrate to be printed; and various daily miscellaneous goods such as a color box and a storage case.

[0086]

The present invention will be described more specifically with reference to the following Examples and Comparative Examples. The molding conditions and test method for obtaining a test sample from the resin composition manufactured in each experimental example are as follows. In these experimental examples, the characteristics of the resin composition of the present invention were shown by the coating performance of the molded article. The “parts” in the experimental examples are parts by weight.

<Molding conditions> Molding machine : Injection molding machine manufactured by Meiki Seisakusho M40A-SJ Molding temperature : 230 ° C Molded product : Flat plate (65 mm × 65 mm × 2 mm) Three-point bending modulus test piece (90 mm × 10 mm × 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 applied without any treatment . Alkali treatment : After immersing the test piece in hot water at 60 ° C. for 30 seconds, an alkaline cleaner (CL551, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
The 5% aqueous solution of 3) was immersed in a tank heated to 60 ° C. for 120 seconds, and then immersed again in 60 ° C. warm water for 30 seconds.
The test piece surface was rinsed with tap water for 30 seconds, and then with pure water for 30 seconds. The water on the surface of the test piece was blown off by air blow and 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 subjected to an acid cleaning agent (ISW3 manufactured by DUBOIS).
The 5% aqueous solution of 2) was immersed in a tank heated to 60 ° C for 120 seconds, and then immersed again in 60 ° C warm water for 30 seconds.
The test piece surface was rinsed with tap water for 30 seconds, and then with pure water for 30 seconds. The water on the surface of the test piece was blown off by air blow and dried in an oven at 80 ° C. for 10 minutes. Hot gas treatment : The molded specimen was treated at 80 ° C. for 30 minutes while flowing nitrogen in an oven.

<Coating> Coating was performed using a one-part organic solvent-based urethane coating, a two-part organic solvent-based urethane coating, and a one-part organic solvent-based acrylic coating. Coating method : Each coating material was prepared and spray-coated using an air spray gun so that the coating film thickness was 100 μm. Thereafter, the one-component organic solvent-based urethane paint has a temperature of 120 ° C. for 60 minutes, the two-component organic solvent-based urethane paint has a temperature of 80 ° C. for 60 minutes, and the one-component organic solvent-based acrylic paint has a temperature of 100 ° C. for 60 minutes. Baking and drying under the following conditions.

<Evaluation of Paint Adhesion> Peel strength : After applying a treatment to prevent the paint from adhering to the upper half of the test piece, each paint was applied to a thickness of 100 μm and baked and dried. A cellophane adhesive tape (example: Nichiban width 24 mm) is adhered to the entire surface of the test piece,
A 1cm wide cut is made in the vertical direction to reach the substrate. The side where the coating film was not adhered was peeled off by hand, attached to a tensile tester, and the load when peeled off at a rate of 50 mm / min in the 180 ° direction was recorded. In addition, when the coating film was broken, it was described as broken.

Examples 1 to 46 and Comparative Examples 1 to 19 (1) Production of Resin Molded Body The components shown in Tables 1 and 2 below were blended and melt-kneaded at 200 ° C. by a twin screw extruder. Into pellets.
Using the pellets, a flat plate and a test piece for measuring three-point bending modulus were injection-molded. The components in Tables 1 and 2 are as follows.

<Olefin resin: (a) component> Block PP (1) : ethylene content of 4% by weight, JIS-
The flexural modulus measured according to K7203 is 14,00
A propylene / ethylene block copolymer having a MFR of 0 g / cm ² and an MFR of 60 g / 10 min as measured according to ASTM-D1238.

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

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

Single PP : Flexural modulus measured according to JIS-K7203 of 13,000 kg / cm ² and AST
MFR measured according to M-D1238 is 25 g / 1
0 minute polypropylene. HDPE : The flexural modulus measured according to ASTM-D747 is 10,500 kg / cm ² and JIS-K6760.
Low-pressure polyethylene (high-density polyethylene) having an MFR of 20 g / 10 min as measured according to.

<Copolymer Resin Containing Non-Conjugated Dienes:
(b) Component> Copolymer (1) 7-methyl-1,6-octadiene content 7.3% by weight,
Flexural modulus 6,250kg / cm ² and MFR 3.5g / 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.
Propylene-4-methyl-1,4-hexadiene-5-methyl-1,4-hexadiene random copolymer at 5 g / 10 min.

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. 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 of 1.5 g / 10 min. Of propylene- (ethylene-4-methyl-1,4-hexadiene-5-methyl-
1,4-hexadiene) block copolymer.

<Hydrogen-containing diene polymer or hydrogenated product thereof: component (c)> In a 500 ml-volume autoclave of a hydroxyl-containing diene polymer, 100 g of 1,3-butadiene, 70 g of isopropyl alcohol and 60 g of isopropyl alcohol were added.
10% aqueous hydrogen peroxide, and 90 g in an argon atmosphere.
Polymerization was carried out at 5 ° C. for 5 hours. After completion of the reaction, unreacted monomers were removed, and the resulting diene polymer was dried. The resulting polymer has a molecular weight of about 2,900 and a hydroxyl value of about 8
8 (KOH mg / g).

Synthesis of the hydrogenated product 50 g of the diene polymer, 50 g of cyclohexane and 5 g of 5 wt% carbon-supported ruthenium catalyst obtained as described above were charged into an autoclave having a capacity of 200 ml, and the system was purged with argon gas. Hydrogen gas 50kg / c
It was fed until the m ^2. The temperature was raised to 100 ° C., and the reaction was carried out for 10 hours while supplying hydrogen gas so that the total pressure was maintained at 50 kg / cm ² . After the completion of the reaction, hydrogen was removed and the hydrogenated product produced after removing the catalyst by filtration was precipitated in methanol, separated by filtration and dried to obtain the desired product. The hydrogenated diene polymer obtained had an iodine value of 1.5 (g / g).
100 g) and the hydroxyl value was 87.8 (KOH mg / g).

Diene polymer : The diene polymer having a hydroxyl group obtained above. Diene polymer hydrogenated product (1) : Hydrogenated diene polymer having a hydroxyl group obtained above. Diene polymer hydrogenated product (2) : A diene polymer hydrogenated product having a hydroxyl group having an iodine value of 0.5 (g / 100 g) and a hydroxyl value of 46.9 (KOH mg / g), synthesized by the method described above.

<Polymer Having Carboxyl Group (Including Acid Anhydride Group): Component (d)> EEA (1 ): Ethylene having an acrylic acid content of 13% by weight and an MFR of 7 g / 10 minutes, produced by a high-pressure radical polymerization method. -Acrylic acid copolymer. EEA (2 ): an ethylene-acrylic acid copolymer produced by a high-pressure radical polymerization method and having an acrylic acid content of 15% by weight and an average molecular weight of 3,000. MEPR : A maleic anhydride-grafted 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 grafting method.

MPEM : maleic anhydride-grafted propylene-ethylene-7-methyl-1,6-octadiene copolymer resin produced as follows. (Production method) Propylene ethylene 7-methyl-1,6
500 g of maleic acid was dry-blended with 5 kg of an octadiene copolymer (the copolymer (3)), and a twin-screw was set at 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 in an extruder.
The obtained product was dissolved in xylene, precipitated in methanol, separated by filtration and dried to obtain the desired product. The resulting graft polymer had a maleic anhydride content of 4.1% by weight.

MDPH : a hydrogenated diene polymer having a carboxyl group produced as follows. (Manufacturing method) 100 g of the hydrogenated diene polymer (2), 300 ml of dry toluene and 12 g of maleic anhydride were added to an autoclave having a capacity of 1000 ml, and the mixture was reacted at 90 ° C for 6 hours in a nitrogen atmosphere. After completion of the reaction, the product was precipitated in methanol, separated by filtration and dried to obtain the desired product. The resulting polymer had a maleic anhydride content of 5.4% by weight.

<Elastomer Component: (e) Component> EPM (1) : Mooney viscosity ML _{1 + 4} (100 ° C.) 70,
An ethylene / propylene / copolymer rubber having a specific gravity of 0.86. EPM (2) : Mooney viscosity ML _{1 + 4} (100 ° C.) is 24,
An ethylene / propylene copolymer rubber having a specific gravity of 0.86. EPDM : Mooney viscosity ML _{1 + 4} (100 ° C.) 47,
An ethylene / propylene / ethylidene norbornene copolymer rubber having a specific gravity of 0.86. SEBS : number average molecular weight 70,000, specific gravity 0.91
Hydrogenated styrene-butadiene block copolymer rubber.

<Filler Component: (f) 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 whisker : average diameter of 0.2 to 0.5
A potassium titanate whisker [K ₂ O · 6TiO ₂ ] having a μm 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
0 cm ² / g, calcium carbonate having 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.

<Additive: Component (g)> HALS (hindered amine light stabilizer): "Sanol 770" (bis-2,2,6,6-tetramethyl-4-pipedinyl sebacate) manufactured by Sankyo Co., Ltd. . Lubricant : "Neutron" (Oleamide) manufactured by Nippon Seika

(2) Coating of Resin Molded Body The above-described surface treatment was applied to the flat plate molded by the production of the resin molded body, and the paint was applied using an air gun. After baking and drying, the film was left at room temperature for 48 hours to perform a peel strength test. Tables 1 and 2 show the flexural modulus of the obtained resin composition, and Tables 3 and 4 show the results of paint adhesion of the molded body.

[0111]

[Table 1]

[0112]

[Table 2]

[0113]

[Table 3]

[0114]

[Table 4]

[0115]

[Table 5]

[0116]

[Table 6]

[0117]

[Table 7]

[0118]

[Table 8]

According to the coating adhesion data shown in the above table, the copolymer resin containing non-conjugated dienes (component (b))
It can be seen that a composition containing neither, or one or both of a diene polymer having a hydroxyl group or a hydrogenated product thereof (component (c)) shows no or very low paint adhesion (Comparative Example) 1-9). Further, when the additive ((g)) is added without blending the polymer having a carboxyl group (component (d)), the paint adhesion is sharply reduced (see Comparative Examples 10 to 13). In contrast, the resin composition of the present invention, even if an additive is present,
It can be seen that the combination of the component (d) shows excellent paint adhesion (see Examples 42 to 45). In addition, looking at the paint adhesion when a one-pack type urethane-based paint is used, in the case of the resin composition of the present invention, those obtained by coating the surface of the test piece without treatment also show good paint adhesion. However, those that have been surface treated with an alkaline cleaning solution and then painted,
It can be seen that the paint exhibits stronger paint adhesion.

[0120]

Since the resin composition of the present invention is composed of the above-mentioned specific components, a molded article formed from the resin composition is subjected to steam cleaning with a halogen-based organic solvent which may cause environmental destruction. It is possible to apply paints, adhesives, etc. directly, and print printing inks without performing surface modification treatment such as primer coating or plasma treatment without applying paint, and good paint adhesion. , Adhesiveness, printability, etc. are obtained. Further, the surface of the molded article formed from the resin composition is further strengthened only by performing a relatively simple surface treatment such as a surface treatment with a cleaning solution containing no halogenated organic solvent or a surface treatment with a warm gas. Not only high paint adhesion and the like, but also good paint adhesion and the like can be obtained for a wider range of paint types. Further, even if additives such as light stabilizers, lubricants, and antioxidants of commonly used resins are further added to the resin composition of the present invention, the adhesion of paints, adhesives, printing inks, and the like is reduced. And good adhesion. Therefore, contrary to the conventional wisdom that it is impossible to apply directly to an olefin resin, molded articles formed from the composition of the present invention are subjected to surface modification treatment such as primer coating and plasma treatment. Even if a coating material is applied without prior application, it exhibits good paint adhesion and is industrially extremely useful.

──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. ⁷ Identification code FI C08L 101/08 C08L 101/08 (72) Inventor Shiro 1 Toho-cho, Yokkaichi-shi, Mie Pref. (56) References JP-A-5-32829 (JP, A) JP-A-5-15844 (JP, A) JP-A-4-198232 (JP, A) JP-A-4-93330 (JP, A) ( 58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 23/00 C08L 47/00 C08L 53/00 C08L 101/08 C08K 3/00 C08K 7/00

Claims (4)

(57) [Claims] 1. A composition comprising the following component (a), component (b), component (c) and component (d), wherein component (b) is 0.1 to 900 parts by weight based on 100 parts by weight of component (a). Parts, component (c) in an amount of 0.01 to 200 parts by weight, and component (d) in an amount of 0.0
A resin composition containing 1 to 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) : a diene polymer having a hydroxyl group or a hydrogenated component thereof (d) : a polymer having a carboxyl group (including an acid anhydride group) 2. Component (a), component (b), component (c), component (d) and component (e), wherein component (b) is added to 100 parts by weight of component (a). 0.1-90
A resin composition containing 0 parts by weight, 0.01 to 400 parts by weight of the component (c), 0.01 to 550 parts by weight of the component (d), and 1 to 900 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) : a diene polymer having a hydroxyl group or a hydrogenated component thereof (d) : a polymer component having a carboxyl group (including an acid anhydride group) (e) : an elastomer 3. Component (a), component (b), component (c), component (d) and component (f), wherein component (b) is added to 100 parts by weight of component (a). 0.1-90
A resin composition containing 0 parts by weight, 0.01 to 250 parts by weight of the component (c), 0.01 to 400 parts by weight of the component (d), and 0.1 to 300 parts by weight of the component (f). 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) : a diene polymer having a hydroxyl group or a hydrogenated component thereof (d) : a polymer component having a carboxyl group (including an acid anhydride group) (f) : a filler 4. It comprises the following components (a), (b), (c), (d), (e) and (f), and 100 parts by weight of component (a) (B) is set to 0.
1 to 900 parts by weight, component (c) 0.01 to 450 parts by weight, component (d) 0.01 to 650 parts by weight, component (e)
1 to 900 parts by weight and component (f) 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) : a diene polymer having a hydroxyl group or a hydrogenated component thereof (d) : a polymer component having a carboxyl group (including an acid anhydride group) (e) : an elastomer component (f) : a filler