JPH0543750A - Resin composition - Google Patents

Abstract

(57) [Summary] [Purpose] Improving the adhesion of paints, adhesives, printing inks, etc. on the surface of olefin resin moldings, vapor cleaning with halogen-based organic solvents that may cause environmental damage, primer coating, and plasma. Provided is a resin composition capable of forming a molded body to which a coating material or the like can be directly applied, without performing a surface treatment such as a treatment. [Structure] An olefin resin, a copolymer resin containing non-conjugated dienes, a diene polymer containing a hydroxyl group or a hydrogenated product thereof, an organic tin compound and / or a tertiary amine compound, and optionally an elastomer and / or a filler. A resin composition containing.

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 could be solved by using a specific resin composition. The invention was completed.

That is, the present invention comprises the following component (a), component (b), component (c), and component (d) and / or component (e), and optionally component (f) and / or component A resin composition containing (g), wherein 0.1 to 900 parts by weight of the component (b) and 0.01 to 200 to 450 parts by weight of the component (c) are used with respect to 100 parts by weight of the component (a). 0.01 to 50 to 110 parts by weight of component (d) and / or 0.01 to 200 to 450 parts by weight of component (e), and optionally 1 to 900 parts by weight of component (f) and / or component (f). g) is contained in an amount of 0.1 to 300 parts by weight. 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) : Hydroxyl group-containing diene polymer or hydrogenated product thereof (d) : From organotin Component (e) : Tertiary amine compound component (f) : Elastomer component (g) : Filler

[0012]

[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): a diene polymer having a hydroxyl group
-Or its hydrogenated product Examples of the diene polymer having a hydroxyl group or its hydrogenated product used in the resin composition of the present invention include the following. Diene Polymer Having 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
10,000, which includes liquid, semi-solid or solid polymers at ambient temperature. When the content of hydroxyl groups contained in the molecule is expressed by a hydroxyl value, it is 0.5 to 650, preferably 1 to 5
00, particularly preferably 5-250 (KOH mg / g).

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

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

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

Component (d): Organotin Compound Examples of the organotin compound used in the present invention include those represented by the following formula.

[0032]

[Chemical 7]

(R ¹ , R ² , R ³ and R ⁴ in the above formula are each a saturated hydrocarbon group having 1 to 12 carbon atoms, and they may be the same or different, preferably the carbon number is It is a saturated hydrocarbon group of 3 to 12. Further, Y ¹ and Y ² are a fatty acid residue, a maleic acid derivative residue, a mercaptan residue, a mercapto acid residue, etc., which may be the same or different. Of these, a fatty acid residue or a maleic acid derivative residue is preferable, and X ¹ is an oxygen atom, a sulfur atom, a maleic acid residue, or the like, preferably an oxygen atom or a maleic acid residue. , M is 0 or an integer of 1 to 30, preferably 0 or an integer of 1 to 25, and particularly preferably 0 or an integer of 1 to 20.)

Specific examples of these organic tin compounds include:
Monobutyl / tin / trimethylmaleate / monobutyl /
Tin trioctyl malate, dibutyl tin dilaurate, dibutyl tin laurate methyl maleate, dibutyl tin dioleyl malate, dibutyl
Tin dimethyl malate, dibutyl tin malate,
Dibutyl tin methoxymethyl maleate, dibutyl
Tin dioctyl malate, dibutyl tin dioctyl thiocryate, dibutyl tin lauryl mercaptite, tribencil tin octyl malate,
Tribensyl, tin, trimethyl maleate, etc. can be mentioned. Of these, it is preferable to use a dialkyl tin compound. Each of these organotin compounds can be used alone or as a mixture of a plurality of kinds, and usually, they can be appropriately selected and used from commercially available compounds.

Component (e): Tertiary amine compound The tertiary amine compound used in the present invention includes from low molecular weight compounds having a tertiary amine structure to high molecular weight compounds. Low molecular weight compound having a tertiary amine structure The low molecular weight compound having a tertiary amine structure refers to a compound having a molecular weight of 100 to less than about 1,000. Specific examples thereof include triethylenediamine, dimethylaminopropylamine, diethylaminopropylamine, tetraguanidine and 1,8-diazabicyclo (5.
4.0) -7-undecene, N, N-bis (2-hydroxyethyl) laurylamine, and tetrakis (N
-Methyl-2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate and the like can be mentioned. These materials can be appropriately selected and used from commercially available products.

Polymer Compound Having Tertiary Amine Structure The polymer compound having a tertiary amine structure has a molecular weight of 1,000 or more, and has a molecular weight of liquid, semi-solid or solid at room temperature. Up to about 100,000 are included. Examples of the polymer compound having such a tertiary amine structure include a modified olefin polymer containing a tertiary amino group.

From the structural point of view, such a modified olefin polymer containing a tertiary amino group means that a branched or linear carbon chain contains an irregular or regular tertiary amino group. It refers to all those having a structure in which an unsaturated compound is copolymerized or a side chain having a tertiary amine structure is grafted. Specifically, the content of the tertiary amino group-containing unsaturated compound is 0.1 to 50% by weight, preferably 0.1.
5 to 45% by weight, particularly preferably 1 to 40% by weight, and the melt flow rate (MFR) measured according to JIS-K6760 is 0.1 to 1,000 g.
/ 10 minutes is preferable, and 0.5 to 7 is particularly preferable.
00g / 10 minutes.

This olefin polymer modified with a tertiary amino group is prepared by using an unsaturated compound containing a tertiary amino group.
It can be manufactured by a known method. For example, in the case of production by a high-pressure radical polymerization method, ethylene, a tertiary amino group-containing unsaturated compound and a radical polymerization initiator,
For example, pressure of 1,000 to 3,000 atm and temperature of 90 to 3
In the reaction zone kept at 00 ° C, the ratio of ethylene: tertiary amino group-containing unsaturated compound was 1: 0.0001 to 1: 1.
It is continuously supplied so that it becomes 0.1, and the conversion rate is 3 to 2
It is produced by making an ethylene copolymer at 0% and continuously taking out the copolymer from the reaction zone.

In the case of the production by the impregnation graft polymerization method, for example, a tertiary amino group-containing unsaturated compound to be reacted with pellets of an olefin polymer and a radical polymerization initiator are suspended in an aqueous solvent, It is manufactured by impregnating pellets of an olefinic polymer with a tertiary amino group-containing unsaturated compound and an initiator, and then heating the mixture to the decomposition temperature of the initiator to cause a graft reaction in the pellets for modification. In the case of production by the kneading graft method, for example, a copolymer resin containing the non-conjugated dienes is dry-blended with a tertiary amino group-containing unsaturated compound, and if necessary, an organic peroxide as a reaction initiator. It is manufactured by melt-kneading the product in an extruder set at a temperature of 80 to 250 ° C.

Such a tertiary amino group-containing unsaturated compound is represented by the following formula.

[0041]

[Chemical 8]

(R ⁵ in the above formula is hydrogen or has 1 carbon atom.
It is a saturated hydrogen group having 4 to 4, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 2 carbon atoms. R ⁶ has 2 carbon atoms
To 12 saturated hydrocarbon groups, preferably 2 to 12 carbon atoms.
6 is a saturated hydrocarbon group. R ⁷ and R ⁸ have 1 to 12 carbon atoms
Is a saturated hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 3 carbon atoms. R ⁷ and R ⁸ may be the same or different. X
² represents an oxygen atom or -NR ⁹ -, a sulfur atom, preferably an oxygen atom, -NR ⁹ - a. R ⁹ is a hydrogen atom or a saturated hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 6 carbon atoms. )

Specific examples of these tertiary amino group-containing unsaturated compounds include 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino) ethyl acrylate, 2- (dimethylamino) ethyl methacrylate, 2
-(Diethylamino) ethyl methacrylate, 2- [di (t-butyl) amino] ethyl acrylate, 2- [di (t-butyl) amino] ethyl methacrylate, 3-
(Dimethylamino) -propyl acrylamide, 3- (dimethylamino) -propyl methacrylamide, etc. can be mentioned.

Examples of the olefinic monomer component for copolymerization with the above-mentioned unsaturated compound containing a tertiary amino group include α-olefins such as ethylene, propylene and 1-butene. Of these, ethylene is particularly preferable. Further, in the case of grafting the tertiary amino group-containing unsaturated compound, the olefin polymer component as a trunk polymer is the olefin resin (component (a)), a copolymer resin containing the non-conjugated dienes. (Component (b)) and the below-mentioned olefin elastomer (component (f)-) can be mentioned, and of these, polyethylene resin, polypropylene resin and ethylene elastomer are preferably used.

Further, in the production of the modified olefin polymer containing a tertiary amino group, the monomer components which can be copolymerized with the unsaturated compound containing a tertiary amino group include methyl acrylate, ethyl acrylate and butyl. Unsaturated carboxylic acid esters such as acrylate and methyl methacrylate; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; 2-vinylpyridine, 4-vinylpyridine and the like Vinyl pyridine;
Vinyl ether such as methyl vinyl ether and 2-chloroethyl vinyl ether: vinyl chloride such as vinyl chloride and vinyl bromide: vinyl ester such as vinyl acetate: acrylamide, etc., and a ternary system, or Further, it can be used as a multi-component modified polyolefin.

These modified polyolefins may be used alone or as a mixture of plural kinds. Among the above-mentioned tertiary amine compounds, it is preferable to use a modified olefin polymer containing a tertiary amino group, which is difficult to bleed out when used.

Component (f): 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- (AB) _{n + 1} , or A ′-[(BA) _n ] _m (the above In the formula, A is a polymer block composed of a styrene compound, A ′ is a chemical species bonded to m (BA) _n blocks, B is a conjugated diene polymer block, and n is 1 to 20. , M is an integer of 2 or more, and the ratio 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 (g): Filler As the filler used in the preferred resin composition of the present invention, either an inorganic filler or an 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.

The components (a), (b), (c), (d), (e), (f) and (g) constituting the resin composition of the present invention are described above as preferred components. It goes without saying that the combination of the two is optimal.

Component (h): additional component In the resin composition of the present invention, in addition to the above components (a) to (g), 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), the component (c), and the component (d) and / or the component (e): relative to 100 parts by weight of the olefin resin of the component (a) ,
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 diene polymer having a hydroxyl group of component (c) or its hydrogenated product is
0.01 to 200 parts by weight, preferably 0.05 to 125
Parts by weight, particularly preferably 0.1 to 60 parts by weight, and the component (d) organotin compound is 0.01 to 50 parts by weight,
It is preferably 0.05 to 30 parts by weight, particularly preferably 0.
1 to 15 parts by weight, and / or the tertiary amine compound as the component (e) is 0.01 to 200 parts by weight, preferably 0.0
5 to 125 parts by weight, particularly preferably 0.1 to 60 parts by weight.

In the case of a resin composition containing the component (a), the component (b), the component (c), the component (d) and / or the component (e), and the component (f): the olefin of the component (a) Based on 100 parts by weight of resin
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 diene polymer having a hydroxyl group of component (c) or its hydrogenated product is
0.01 to 400 parts by weight, preferably 0.05 to 180
Parts by weight, particularly preferably 0.1 to 90 parts by weight, 0.01 to 100 parts by weight of the organotin compound of component (d),
It is preferably 0.05 to 40 parts by weight, particularly preferably 0.
1 to 20 parts by weight, and / or 0.01 to 400 parts by weight, and preferably 0.0 to 400 parts by weight of the tertiary amine compound as the component (e).
5-180 parts by weight, particularly preferably 0.1-90 parts by weight, and the elastomer of component (f) is 1-900 parts by weight, preferably 5-300 parts by weight, particularly preferably 1
It is 0 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 / or the component (e), and the component (g): the olefin of the component (a) Based on 100 parts by weight of resin
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 diene polymer having a hydroxyl group of component (c) or its hydrogenated product is
0.01 to 250 parts by weight, preferably 0.05 to 170
Parts by weight, particularly preferably 0.1 to 90 parts by weight, and the organotin compound of component (d) is 0.01 to 65 parts by weight, preferably 0.05 to 40 parts by weight, particularly preferably 0.1.
˜20 parts by weight, and / or the tertiary amine compound of component (e) is 0.01 to 250 parts by weight, preferably 0.05.
~ 170 parts by weight, particularly preferably 0.1 to 90 parts by weight,
And the filler of the component (g) is 0.1 to 300 parts by weight, preferably 0.5 to 250 parts by weight, particularly preferably 1 to 200 parts by weight.

Component (a), component (b), component (c), component (d) and / or component (e), component (f)
And a resin composition containing the component (g): 100 parts by weight of the olefin resin of the component (a),
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 diene polymer having a hydroxyl group of component (c) or its hydrogenated product is
0.01-450 parts by weight, preferably 0.05-230
Parts by weight, particularly preferably 0.1 to 120 parts by weight, the organotin compound of component (d) is 0.01 to 110 parts by weight,
It is preferably 0.05 to 50 parts by weight, particularly preferably 0.
1 to 25 parts by weight, and / or the tertiary amine compound as the component (e) is 0.01 to 450 parts by weight, preferably 0.0
5 to 230 parts by weight, particularly preferably 0.1 to 120 parts by weight, and the component (f) elastomer is 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 1
0 to 200 parts by weight, and the filler of the component (g),
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 diene polymer having a hydroxyl group or the hydrogenated product of the component (c) is less than the above range, the reproducibility of the paint, the adhesive and the printing ink is poor and the adhesion strength is low. It is weak and not desirable. On the other hand, if the amount exceeds the above range, the cost of the resin composition is high because the amount of the expensive diene polymer added is large, and since the diene polymer causes delamination or bleed-out, a paint or an adhesive is used. Also, the adhesion of printing ink and the like is reduced, which is not preferable.

When the compounding amount of the organotin compound as the component (d) is less than the above range, the adhesion strength may become extremely weak depending on the paint, adhesive, printing ink, etc., which is not preferable. On the other hand, when the amount exceeds the above range, the amount of the expensive compound added is large, so that not only the cost of the resin composition is increased, but also the effect proportional to the added amount of the compound cannot be obtained, and rather the deterioration of the polyolefin is caused. It is not preferable because it may promote When the content of the tertiary amine compound as the component (e) is less than the above range, the adhesion strength may be very weak, which is not preferable. On the other hand, if the amount exceeds the above range, not only the cost of the resin composition increases because the amount of the expensive compound added is large, but also the effect proportional to the amount of the compound added cannot be obtained.

By blending the elastomer component as the component (f), the rigidity and impact resistance can be adjusted. By incorporating the filler of the component (g), the coating adhesion and strength are improved, and if it is less than the above range, the effect of the improvement cannot be obtained. On the other hand, when the amount exceeds the above range, not only the moldability of the resin composition deteriorates, but also an effect proportional to the amount of the filler added cannot be obtained.

(3) Blending The resin composition of the present invention is manufactured 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, etc. adhering to the surface of the molded product inevitably in the steps from molding of the resin composition to coating. Is. However, in the molded article formed from the resin composition of the present invention, even if the surface treatment with these cleaning liquids is not performed and surface modification such as primer coating or plasma treatment is not performed, a wider range of paint types can be obtained. Strong paint adhesion is obtained.

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

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

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

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

As the paint that can be used in the painting 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, bonding and printing as described above, it is suitable 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.

[0081]

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

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

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

Acid treatment : The test piece was immersed in warm water at 60 ° C. for 30 seconds, and then acid cleaning agent (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 Adhesion of Paint> Peeling 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 47 and Comparative Examples 1 to 10 (1) Production of Resin Molded Body Each component shown in Tables 1 and 2 below was blended and melt-kneaded at 200 ° C. by a twin-screw extruder. Into pellets.
A flat plate and a three-point bending elastic modulus measuring test piece were injection-molded using the pellet. The compounding ingredients in Tables 1 and 2 are as follows.

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

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

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

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

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

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

<Diene Polymer Having Hydroxyl Group or Hydrogenated Product Thereof: Component (c)> 100 g of 1,3-butadiene, 70 g of isopropyl alcohol and 60 g of isopropyl alcohol were placed in an autoclave having a synthesis capacity of 500 ml of diene polymer having a hydroxyl group.
% Hydrogen peroxide solution 10g was added, and it was 90 in an argon atmosphere.
Polymerization was carried out at ℃ for 5 hours. After the reaction was completed, unreacted monomers were removed and the produced diene polymer was dried. The obtained polymer has a molecular weight of about 2,900 and a hydroxyl value of about 8
It was 8 (KOHmg / g).

Synthesis of the hydrogenated product 50 g of the diene polymer obtained as described above, 50 g of cyclohexane and 5 g of a 5 wt% carbon-supported ruthenium catalyst were placed in an autoclave of 200 ml capacity and the atmosphere was replaced with argon gas. Hydrogen gas 50kg / c
It was sent until it reached m ² . This was heated to 100 ° C., and a reaction was performed for 10 hours while supplying hydrogen gas so that the total pressure was maintained at 50 kg / cm ² . After completion of the reaction, hydrogen was removed, the catalyst was removed by filtration, and the produced hydrogenated product was precipitated in methanol, filtered and dried to obtain the desired product. The iodine value of the obtained diene polymer hydrogenated product was 1.5 (g / g
100 g) and the hydroxyl value was 87.8 (KOHmg / g).

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

<Organotin Compound: (d) Component> DBTDL : Dibutyltin dilaurate DOTDL : Dioctyltin dilaurate

<Tertiary Amine Compound: Component (e)> EDMA (1) : Obtained by High Pressure Radical Polymerization Method,
2- (Dimethylamino) ethylmethacrylate content 30% by weight, M measured according to JIS-K6760
An ethylene-2- (dimethylamino) ethyl methacrylate copolymer having an FR of 2 g / 10 min.

EDMA (2) : A graft copolymer obtained by grafting 2- (dimethylamino) ethyl methacrylate and styrene onto polyethylene, which is the backbone polymer obtained by the synthesis of EDMA (2) by the following impregnation graft polymerization method. 2- (dimethylamino) ethyl methacrylate content 15% by weight, styrene content 25% by weight, J
MFR measured according to IS-K6760 is 2 g / 1
A graft copolymer showing a physical property value of 0 minutes.

(EDMA by impregnation graft polymerization method
(Synthesis of (2)) In an autoclave with a capacity of 10 liters,
MFR measured according to JIS-K6760 is 100.
g / 10 min linear low density polyethylene pellets 108
0 g, 2- (dimethylamino) ethyl methacrylate 2
70 g, styrene 450 g, benzoyl peroxide 6.5 g, calcium phosphate [Ca ₃ (P
21 g of O ₄ ) ₂ ] was added to and suspended in 4 liters of water.
Then, the temperature of the suspension was kept at 50 ° C. for 3 hours to impregnate the polyethylene pellets with these 2- (dimethylamino) ethyl methacrylate, styrene and benzoyl peroxide.

Then, the reaction was carried out for 8 hours while gradually raising the temperature to 94 ° C. After the reaction was completed, the pellets obtained were washed with water, and the water was removed by a centrifugal separator.
Vacuum drying was performed at 12 ° C. for 12 hours. 2 of the obtained polymer
The content of-(dimethylamino) ethyl methacrylate is 15% by weight, the content of styrene is 25% by weight, and the MFR is 2
It was g / 10 minutes.

DMAPEM: Propylene / ethylene / 7-methyl-1,6-octadiene random copolymer resin of the trunk polymer obtained by the synthesis of DMAPEM by the following kneading and grafting method and 2- (dimethylamino) ethyl Graft polymer grafted with methacrylate 2
-(Dimethylamino) ethyl methacrylate content is
Graft polymer with 5.2% by weight and MFR measured according to JIS-K6760 of 2.2 g / 10 min.

(Synthesis of DMAPEM by kneading and grafting method) Propylene / ethylene / 7-methyl-1,6-octadiene random copolymer (the above-mentioned copolymer (3):
Component (b) 5 kg, 2- (dimethylamino) ethyl methacrylate 500 g, and t-butyl cumyl peroxide 7.2 g were dry blended, and the temperature was 200
° C, rotation speed 250 rpm. Melt kneading was carried out in a twin-screw extruder set to a discharge rate of 10 kg / h. The obtained product was dissolved in xylene, precipitated in methanol, filtered and dried to obtain the desired product. The content of 2- (dimethylamino) ethyl methacrylate in the obtained graft body was 5.2% by weight, and the MFR was 2.2 g / 10 minutes.

Low molecular weight compound (1) : A light stabilizer "Mark LA62" manufactured by Adeka Argus Co., Ltd., which is a compound having a structure represented by the following formula.

[0108]

[Chemical 9]

(Wherein R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ are the following formulas:

[0110]

[Chemical 10]

Or —C ₁₃ H ₂₇ , wherein at least one of R ¹⁰ , R ¹¹ , R ¹² and R ¹³ is N
-Methyl-2,2,6,6-tetramethyl-4-piperidyl group, the rest being a saturated hydrocarbon group having 13 carbon atoms. )

<Elastomer component: (f) 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: (g) 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.

[0115]

[Table 1]

[0116]

[Table 2]

[0117]

[Table 3]

[0118]

[Table 4]

[0119]

[Table 5]

[0120]

[Table 6]

[0121]

[Table 7]

[0122]

[Table 8]

According to the coating adhesion data shown in the above table, the copolymer resin containing the non-conjugated dienes (component (b))
The composition containing neither the diene polymer having a hydroxyl group or a hydroxyl group-containing diene polymer or a hydrogenated product thereof (component (c)), or the component (b) does not show paint adhesion at all (Comparative Examples 1 to 4 and 7). ~ 9). Further, in the composition in which the component (c) was not blended, the paint adhesion was very low (Comparative Examples 5, 6, 10). On the other hand, the resin composition of the present invention shows good paint adhesion when the one-component urethane-based paint is used and the test piece surface is untreated. Although it is shown, it can be seen that the one that was further surface-treated with an alkaline cleaning solution and then coated exhibited stronger paint adhesion (see Table 3).

[0124]

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 exhibits good paint adhesion and is extremely useful industrially.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location C08L 25/10 LDS 9166-4J 53/00 LLY 7142-4J (72) Inventor Shiro Goto Yokkaichi, Mie Prefecture 1 Toho-cho, Yokohama-shi Mitsubishi Petrochemical Co., Ltd. Yokkaichi Research Institute

Claims (4)

[Claims] 1. The following component (a), component (b), component (c), and component (d) and / or component (e) are contained, and the component (b) is added to 100 parts by weight of the component (a). ) To 0.
1-900 parts by weight, 0.01-200 parts by weight of component (c), 0.01-50 parts by weight of component (d) and / or 0.01-200 parts by weight of component (e). object. 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) : hydroxyl group-containing diene polymer or hydrogenated product thereof (d) : organotin compound component (e) : tertiary amine compound 2. A component (a), a component (b), a component (c), a component (d) and / or a component (e), and a component (f) described below, which are added to 100 parts by weight of the component (a). In contrast, 0.1 to 900 parts by weight of the component (b) and 0.01 of the component (c) are used.
To 400 parts by weight, 0.01 to 100 parts by weight of component (d) and / or 1 to 400 parts by weight of component (e), and 1 to 900 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 ^{(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) : diene polymer having a hydroxyl group or its hydrogenated product component (d) : organotin compound component (e) : tertiary amine compound component (f) : elastomer 3. A component (a), a component (b), a component (c), a component (d) and / or a component (e), and a component (g) described below are contained in 100 parts by weight of the component (a). In contrast, 0.1 to 900 parts by weight of the component (b) and 0.01 of the component (c) are used.
To 250 parts by weight, 0.01 to 65 parts by weight of component (d) and / or 0.01 to 250 parts by weight of component (e), and 0.1 to 300 parts by weight of component (g). object. 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) : hydroxyl group-containing diene polymer or hydrogenated product thereof (d) : organotin compound component (e) : tertiary amine compound component (g) : filler 4. A component (a), a component (b), a component (c), a component (d) and / or a component (e), a component (f), and a component (g), the component (a): ) With respect to 100 parts by weight, the component (b) is 0.1 to 900 parts by weight, the component (c) is 0.01 to 450 parts by weight, and the component (d) is 0.0.
1-110 parts by weight and / or component (e) 0.01-4
A resin composition containing 50 parts by weight, 0.1 to 900 parts by weight of the component (f), and 0.1 to 300 parts by weight of the component (g). 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) : Diene polymer having a hydroxyl group or its hydrogenated component (d) : Organotin compound component (e) : Tertiary amine compound component (f) : Elastomer component (g) : Filler