JPH05117455A - Resin composition - Google Patents

Abstract

PURPOSE:To improve the adhesion of the surface of a molded article to a coating material, an adhesive, a printing ink, etc., by compounding a specific olefin resin, a copolymer resin having nonconjugated diene units, and an aminated and/or iminated polymer. CONSTITUTION:100 pts.wt. olefin resin having a bending modulus of 1,000-30,000kg/cm<2> and a melt flow rate (MFR) of 0.01-200g/10min, 0.1-900 pts.wt. copolymer resin prepd. by the block and/or random copolymn. of at least one compd. selected from the group consisting of 2-12C alpha-olefins with 0.1-30wt.% at least one compd. selected from the group consisting of nonconjugated dienes of the formula (wherein R<1> to R<5> are each H or 1-8C alkyl; and n is 1-10) and having a bending modulus of 500-30,000kg/cm<2> and an MFR of 0.1-1,000g/10min, and 0.01-400 pts.wt. aminated and/or iminated polymer having an MFR of 0.1-1,000g/10min and a content of amino and/or imino groups of 0.1-50wt.% are compounded.

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 a surface of a resin molded product, vapor cleaning using a halogen-based organic solvent is used to clean and remove dirt, machine oil, etc. adhering to the surface of the molded product before coating. 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, the inventors have found that the above problems can be solved by using a specific resin composition. Has been completed.

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

[0010]

[Chemical 5]

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

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

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

These polymers have a flexural modulus of 1,000 to 30,000 measured according to JIS-K7203.
kg / cm ² , preferably 2,000 to 20,000 k
g / cm ² , particularly preferably 3,000 to 15,000
It is preferably kg / cm ² . Further, the melt flow rate (MFR) of the polymer is not particularly limited, but the value measured according to ASTM-D1238 is usually 0.01 to 200 g / 10 minutes, preferably 0.1 to 1
Optimally, it is within the range of 00 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, cubic regular 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 independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n represents an integer of 1 to 10. ) 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 are 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1, 1,4-dienes such as 4-hexadiene, 5-methyl-1,4-heptadiene; 1,5-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-
1,5-Dienes such as 1,5-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-octadiene, 7-ethyl-1,6-octadiene, 1,6-nonadiene, 7-methyl-1,6-nonadiene, 4-methyl-1,6- 1, such as nonadien
6-dienes; 1,7-nonadiene, 8-methyl-1,
1,7-dienes such as 7-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. 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 non-conjugated dienes of the present invention has a flexural modulus of 500 to 30,000 kg / cm ² , preferably 1, according to JIS K-7203.
000 to 20,000 kg / cm ² , particularly preferably,
It is 1,500 to 15,000 kg / cm ² . 500
If it is less than 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 means 4-methyl-1,4-hexadiene and 5-
It represents a mixture of methyl-1,4-hexadiene, the mixing ratio of which is in the range of 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 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): amino group and / or imino group
A polymer having an amino group and / or an imino group used in the present invention means, from a structural point of view, an amino group and / or an imino group is irregular in a branched or linear molecular chain or It is regularly pendant, or a side chain having an amino group and / or an imino group is grafted,
It refers to all those having a structure in which an imino group is included in the molecular chain.

The polymer can be produced by a known method. For example, a method of grafting an unsaturated compound containing an amino group and / or an imino group onto a polymer, a method of converting a polar group containing a nitrogen molecule in the polymer into an amino group or an imino group by hydrogenation, hydrolysis, etc. And a method of introducing an amino group and / or an imino group into the double bond, and a method of copolymerizing an unsaturated compound containing an amino group and / or an imino group with a polymerizable monomer.

Among the polymers produced by these methods, the olefin resin as the component (a), the copolymer resin containing the non-conjugated dienes as the component (b), or the component (d) described later. A graft polymer of an unsaturated compound containing an amino group and / or an imino group onto an elastomer; a hydrogenated product of a polymer having a cyano group; a hydrolyzed product of a polymer containing an N-alkenylamide compound; Group and / or imino group introduced, and α
-A copolymer of an olefin and an unsaturated compound containing an amino group and / or an imino group is preferable. These will be described in detail below.

Graft polymer of unsaturated compound containing amino group and / or imino group: The graft polymer is, from a structural point of view, a branched or linear molecular chain, irregular or regular, Amino groups and / or balls refer to all those having a structure in which an imino group-containing unsaturated compound is graft-polymerized. Specifically, the content of the unsaturated compound containing an amino group and / or imino group is 0.1 to 50% by weight, preferably 0.5 to 45% by weight, particularly preferably 1 to 40% by weight.
And the melt flow rate (MFR) measured according to ASTM-D1238 is 0.1-10.
00g / 10 minutes, preferably 0.5-700g / 10
Min, particularly preferably 1 to 500 g / 10 min, and includes liquid, semi-solid and solid polymers at room temperature.

This amino group- and / or imino group-containing unsaturated compound graft polymer is a copolymer resin containing, as a trunk polymer, an olefin resin as the component (a) and a non-conjugated diene as the component (b). And a component (d), which will be described later, and an amino group- and / or imino group-containing unsaturated compound as a graft component as raw materials can be produced by a known method such as a kneading graft method or a solution graft method. it can.

In the case of the production by the kneading and grafting method, a mixture of the above-mentioned trunk polymer component, an unsaturated compound containing an amino group and / or an inomi group and, if necessary, a reaction initiator such as an organic peroxide is heated at 80 to 250 ° C. It is produced by melt-kneading in an extruder set to a temperature. In the case of the production by the solution grafting method, for example, in a xylene solvent, a copolymer containing a non-conjugated diene, an unsaturated compound containing an amino group and / or an imino group, and, if necessary, a reaction start of an organic peroxide or the like. It is produced by dissolving the agent and reacting it in an autoclave set to a temperature of 80 to 150 ° C.

The amino- and / or imino-group-containing unsaturated compound of the graft component used here is allylamine, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 3-aminopropyl methacrylate, 3-aminopropyl acrylate, N-methylallylamine, N-ethylallylamine, 2 (N-methylamino) ethyl methacrylate, 2- (N-methylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (N-ethylamino) Mention may be made of ethyl acrylate, 3- (N-methylamino) propyl methacrylate, 3- (N-methylamino) propyl acrylate, 3- (N-ethylamino) propyl methacrylate, 3- (N-ethylamino) propyl acrylate and the like. In That.

Of these, allylamine, N-methylallylamine, N-ethylallylamine, 2-aminoethyl methacrylate, 2-aminoethyl acrylate and the like are preferable, and 2-aminoethyl methacrylate and 2-
Aminoethyl acrylate and the like are particularly preferable.

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

In addition to the above-mentioned unsaturated compound component containing an amino group and / or imino group, an unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate or methyl methacrylate is used as a second graft copolymerization monomer; Vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; 2
Vinyl pyridine such as vinyl pyridine and 4-vinyl pyridine; vinyl ether such as methyl vinyl ether and 2-chloroethyl vinyl ether; vinyl halide such as vinyl chloride and vinyl bromide; vinyl ester such as vinyl acetate; acrylamide and the like. It is also possible to use it as a binary or multi-component graft copolymer.
These graft copolymers can be used either individually or as a mixture of two or more species.

Hydrogenated product of a polymer having a cyano group: A polymer having a cyano group means that the cyano group is irregularly or regularly pendant in a branched or linear molecular chain from a structural viewpoint. , Having a structure in which a side chain having a cyano group is grafted. Specifically, it has at least one cyano group in the molecule and has a molecular weight of 200 to 100,000, preferably 800 to 5
10,000 is particularly preferably 1,000 to 30,000, and is a polymer that is liquid, semi-solid, or solid at room temperature.

Specific examples of the polymer having a cyano group include, for example, (i) a polymer obtained by polymerizing a monomer such as ethylene or a conjugated diene with a compound having a cyano group on both sides of an azo group as an initiator, (ii) Examples thereof include copolymers of cyano group-containing unsaturated compounds and other polymerizable monomers, and graft polymers onto other trunk polymers. The polymer having these cyano groups is not limited in its production method,
Various known methods can be adopted. For example, a radical polymerization method, a solution polymerization method, an emulsion polymerization method, a solution graft polymerization method, a kneading graft polymerization method and the like can be mentioned. A description of these polymers is given below.

(I) Polymer polymerized with a compound having cyano groups on both sides of the azo group as an initiator:
For example, it can be produced by radical polymerization using 1,3-dienes as a raw material and a compound having cyano groups on both sides of an azo group as an initiator. Specifically, for example, the method described in JP-A No. 1-318017 can be mentioned. As a raw material monomer for these polymers, ethylene or at least one conjugated diene monomer is used. As the conjugated diene monomer, 1,3-butadiene, 1,3-pentadiene, isoprene, chloroprene, 2,3-dimethyl-
Examples thereof include 1,3-butadiene and 1-phenyl-1,3-butadiene. Among these, ethylene, 1,3-butadiene, 1,3-pentadiene, and isoprene are preferable, and 1,3-butadiene is particularly preferable.

As the initiator, 2,2'-azobis- (2-amidinopropane) dihydrochloride, azobisisobutyronitrile (AIBN), 1,1'-azobis (cyclohexane-1-carbonitrile) , 2,2'-azobis (2,4-dimethylvaleronitrile), and 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like can be mentioned. Among these, azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile) and the like are preferable.

As the monomer copolymerizable with the conjugated diene monomer, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate; vinyl aromatics such as styrene, α-methylstyrene and vinyltoluene. Compounds; nitrile compounds such as acrylonitrile and methacrylonitrile; vinyl pyridines such as 2-vinylpyridine and 4-vinylpyridine; vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; Examples thereof include vinyl esters such as vinyl acetate; acrylamide and the like, and they can also be used as binary or multi-component copolymers.

(Ii) Copolymer of unsaturated compound containing cyano group and other polymerizable monomer or graft polymer onto other trunk polymer: Specific examples of the copolymer and the graft polymer include ethylene-acrylonitrile. Copolymer, acrylonitrile-butadiene copolymer, acrylonitrile-styrene copolymer, acrylic rubber-graft-acrylonitrile-styrene copolymer, and acrylonitrile-
Examples thereof include butadiene / styrene copolymers.

When the copolymer is produced by the high pressure radical method, for example, ethylene, a cyano group-containing unsaturated compound and a radical initiator are kept at a pressure of 1,000 to 3,000 atm and a temperature of 90 to 300 ° C. In the reaction zone, the ratio of ethylene to the cyano group-containing unsaturated compound was 1: 0.00.
It is continuously fed so that it becomes 01 to 1: 0.1, an ethylene copolymer is obtained under the condition that the conversion rate becomes 3 to 20%, and the copolymer is continuously taken out from the reaction zone. Manufactured by

As the cyano group-containing unsaturated compound used here, acrylonitrile, methacrylonitrile,
Examples thereof include crotonnitrile and the like, and acrylonitrile is preferable. When the polymer is a copolymer with another polymerizable monomer, the copolymerizable monomer is preferably an α-olefin having 2 to 12 carbon atoms.

Specifically, ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-octene,
3-methyl-1-butene, 3-methyl-1-pentene,
4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-
1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-cyclohexyl-1-butene, Vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2,2]
1] -heptane and the like. Among these, preferred examples are ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene and the like, and particularly preferred examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

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

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

The hydrogenated product of a polymer having a cyano group used in the present invention is a product obtained by converting the cyano group into an amino group by hydrogenating the polymer having a cyano group. As a method of hydrogenation, a usual method,
A method using a homogeneous or heterogeneous hydrogenation catalyst can be adopted.

Among these catalysts used in these ordinary hydrogenations, octacarbonyl cobalt (Co ₂ (CO) ₈ ) is a homogeneous catalyst, and Raney cobalt, Raney nickel, palladium carbon (Pd) are heterogeneous catalysts. / C), platinum acid (PtO ₂ ), rhodium / alumina (Rh / Al ₂ O ₃ ) and the like are preferably used, and Raney cobalt and Raney nickel are particularly preferably used. The hydrogenation reaction conditions are from room temperature to 2
It is carried out at 50 ° C. under a hydrogen pressure of atmospheric pressure to 200 kg / cm ² .

Regarding the degree of hydrogenation, the cyano group contained in the polymer may be wholly or partially hydrogenated to an amino group, but at least one amino group does not exist per molecule. must not. By this hydrogenation operation, the portion other than the cyano group may or may not be hydrogenated, but the double bond portion of the diene polymer is preferably hydrogenated.

Among these hydrogenated polymers having a cyano group, a conjugated diene monomer was polymerized by using a compound having a cyano group on both sides of an azo group as a radical polymerization initiator, and a diene polymer having a cyano group was hydrogenated. Hydrogenated products of diene polymers having a cyano group polymerized from 1,3-butadiene as a raw material are particularly preferred. These polymers can be used alone or in combination of two or more.

Hydrolyzate of N-alkenylamide-containing polymer: N-alkenylamide-containing polymer means N-alkenylamides homopolymerized or copolymerized with another polymerizable monomer, and other trunk polymer. Refers to those graft-polymerized to

Specifically, the content of the N-alkenylamide compound is 0.01 to 100% by weight, preferably 0.0.
5 to 70% by weight, particularly preferably 0.1 to 40% by weight
And the melt flow rate (MFR) measured according to ASTM-D1238 is 0.01 to 1,0.
00 g / 10 minutes, preferably 0.05 to 700 g / 10
Min, particularly preferably 0.1 to 500 g / 10 min, and includes liquid, semi-solid and solid polymers at room temperature.

The N-alkenylamide-containing polymer can be produced by a known method. For example, a high-pressure radical polymerization method, a solution polymerization method, an emulsion polymerization method, a solution graft polymerization method, and a kneading graft polymerization method can be mentioned.

In the case of production by the high pressure radical polymerization method, for example, N-vinylacetamide, ethylene and a radical polymerization initiator are placed in a reaction zone kept at a pressure of 1,000 to 3,000 atm and a temperature of 90 to 300 ° C. It is produced by continuously supplying the copolymer, converting it to a copolymer under the condition that the conversion is 3 to 20%, and continuously taking out the copolymer from the reaction zone.

Examples of the N-alkenylamide compound used in the polymer include N-vinylacetamide and N-
Allylacetamide, N-vinylpropionamide,
Examples thereof include N-allylpropionic acid amide, and of these, N-vinylacetamide and N-allylacetamide are preferable. When the polymer is a copolymer with another polymerizable monomer, the copolymerizable monomer is preferably an α-olefin having 2 to 12 carbon atoms.

Specifically, ethylene, propylene, 1-
Butene, 1-pentene, 1-hexene, 1-octene,
3-methyl-1-butene, 3-methyl-1-pentene,
4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl-
1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-cyclohexyl-1-butene, Vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2,2]
1] -heptane and the like. Among these, preferred examples are ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene and the like, and particularly preferred examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

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

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

Examples of the hydrolysis method of the N-alkenylamide-containing polymer include a method of adding a catalyst such as an alkali or an acid, and an alcohol. The degree of hydrolysis of the N-alkenylamide-containing polymer is 100 to
1%, preferably 100 to 10%, particularly preferably 1
0 to 30%, even if it is completely hydrolyzed,
It may be partially hydrolyzed. As the hydrolyzate of the N-alkenylamide-containing polymer, a hydrolyzate of a copolymer of an N-alkenylamide compound and an α-olefin is preferable, and a hydrolyzate of a copolymer of N-vinylacetamide and ethylene is Particularly preferred.

Polymer in which an amino group is introduced into a double bond in the polymer: The polymer in which an amino group is introduced into a double bond in the polymer used in the present invention means, for example, a polymer having a double bond and a known chemical structure. The amino group was introduced by applying a specific method.

Specifically, the polymer has at least one amino group in the molecule and has a melt flow rate (MFR) of 0.0 according to ASTM-D1238.
1 to 1,000 g / 10 minutes, preferably 0.05 to 70
0 g / 10 minutes, particularly preferably 0.1-500 g / 10
Minute, including liquid, semi-solid, and solid polymers at room temperature.

The method of introducing an amino group into the double bond is not limited, and various known methods can be adopted. For example, in the double bond contained in the polymer, B--H
An amino group can be introduced by causing a hydroboration reagent having a bond to act and then acting an aminating agent such as ammonia.

As the polymer having a double bond as a raw material of these polymers, a copolymer resin containing the non-conjugated dienes of the above-mentioned component (b), a diene polymer obtained by polymerizing conjugated dienes, and known cumin Examples thereof include polyolefins polymerized by using a ski catalyst, and elastomers having a double bond as the component (d), which will be described later.

Of these, preferred is ethylene.
Non-conjugated diene copolymer resin, propylene / non-conjugated diene copolymer resin, ethylene / propylene / non-conjugated diene copolymer resin, polypropylene resin polymerized using a known Kaminsky catalyst, ethylene / propylene / Non-conjugated diene copolymer rubber (EPDM), and styrene
It is a conjugated diene block copolymer or the like. Particularly preferred are ethylene / non-conjugated diene copolymer resins, propylene / ethylene / non-conjugated diene copolymer resins, and polypropylene resins polymerized using a Kaminsky catalyst.

As a method of introducing an amino group into the double bond, a hydroboration reaction is carried out, and then an amination reaction is carried out. In this case, the hydroboration reagent is not particularly limited and may be a generally known one, but preferably a diborane / THF solution, sodium borohydride / boron trifluoride ethyl etherate, 9- Borabicyclo [3,3,1] nonene and the like. Examples of the aminating agent include ammonia, chloroamine, hydroxylamine-0-sulfonic acid, 0-mesitylenesulfonylhydroxylamine and the like.

These polymers can be used either individually or as a mixture of two or more species.

Copolymer of α-olefin with an unsaturated compound containing an amino group and / or an imino group: From the structural point of view, the copolymer means that an unsaturated compound is present in a branched or linear carbon chain. It refers to all ordinarily or regularly having a structure in which an amino group- and / or imino group-containing unsaturated compound is copolymerized with an α-olefin.

Specifically, the content of the unsaturated compound containing an amino group and / or imino group is 0.1 to 50% by weight, preferably 0.5 to 45% by weight, particularly preferably 1 to 40% by weight. The melt flow rate (MFR) measured according to ASTM-D1238 is 0.1-1.
000 g / 10 minutes, preferably 0.5-700 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 / amino group and / or imino group-containing unsaturated compound copolymer is a known method using α-olefin and an amino group and / or imino group-containing unsaturated compound as raw materials. For example, high pressure radical polymerization method,
It can be manufactured by a slurry polymerization method or the like.

In the case of production by the high pressure radical polymerization method, ethylene, an amino group- and / or imino group-containing unsaturated compound and a radical initiator are added, for example, at a pressure of 1,000 to 3,
In a reaction zone kept at 000 atm and a temperature of 90 to 300 ° C., the ratio of ethylene to an amino group- and / or imino group-containing unsaturated compound should be 1: 0.0001 to 1: 0.1. It is produced by continuously supplying the ethylene copolymer under the conditions such that the conversion rate is 3 to 20%, and continuously taking out the copolymer from the reaction zone.

In the case of production by the slurry polymerization method, propylene and an amino group- and / or imino group-containing unsaturated compound obtained by protecting an amino group and / or imino group with an organoaluminum compound or a trialkylsilane compound are known. It is produced by polymerizing at room temperature to 20 atm and temperature of 30 to 150 ° C. in a heptane solvent using the Ziegler catalyst, and hydrolyzing the resulting polymer to remove the protective group.

Examples of the unsaturated compound containing an amino group and / or an imino group used here include allylamine, 2-aminoethyl methacrylate, 2-aminoethyl acrylate, 3-aminopropyl methacrylate, 3-aminopropyl acrylate and N-methyl. Allylamine, N-
Ethylallylamine, 2- (N-methylamino) ethyl methacrylate, 2- (N-methylamino) ethyl acrylate, 2- (N-ethylamino) ethyl methacrylate, 2- (N-ethylamino) ethyl acrylate,
3- (N-methylamino) propyl methacrylate, 3
-(N-methylamino) propyl acrylate, 3-
(N-ethylamino) propyl methacrylate, 3-
(N-ethylamino) propyl acrylate etc. can be mentioned.

Of these, allylamine, N-methylallylamine, N-ethylallylamine, 2-aminoethyl methacrylate, 2-aminoethyl acrylate and the like are preferable, and 2-aminoethyl methacrylate and 2-aminoethyl methacrylate.
Aminoethyl acrylate and the like are particularly preferable.

The α-olefin as the other copolymerization component includes ethylene, propylene, 1-butene, 1-
Pentene, 1-hexene, 1-octene, 3-methyl-
1-butene, 3-methyl-1-pentene, 4-methyl-
1-pentene, 3,3-dimethyl-1-butene, 4,4
-Dimethyl-1-pentene, 3-methyl-1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1
-Hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclopentane, vinylcyclohexane, 2-vinylbicyclo [2,2] , 1] -Heptane,
And so on. Among these, preferred examples are ethylene, propylene, 1-butene, 3-methyl-
1-butene, 4-methyl-1-pentene, styrene and the like, and among them, particularly preferable examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

In addition to the above α-olefin and the unsaturated compound containing an amino group and / or an imino group, an unsaturated carboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate or methyl methacrylate may be used as a third copolymerization monomer. Acid ester; vinyl aromatic compounds such as styrene, α-methylstyrene, 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 halides such as vinyl chloride and vinyl bromide; vinyl acetate. Examples thereof include vinyl esters; acrylamide and the like, and can be used as a ternary or multi-component copolymer. These copolymers can be used either individually or as a mixture of two or more species.

Among these polymers having amino groups and / or imino groups, graft polymers of unsaturated compounds containing amino groups and / or imino groups and hydrogenated products of polymers having cyano groups are preferable, and particularly non-conjugated. A graft polymer of an unsaturated compound containing an amino group and / or an imino group onto a copolymer resin containing a diene and a hydrogenated product of a diene polymer having a cyano group are preferable.

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

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

General formula: (AB) _{n + 1} ; A- (BA) _n ; B- (AB)
_{n + 1} , or A '-[(BA) _n ] _m (In the above formula, A is a polymer block composed of a styrene compound, and A'is bound to m (BA) _n blocks. The chemical species, B is a conjugated diene polymer block, n is an integer of 1 to 20, m is an integer of 2 or more, and the proportion of the A block and A ′ in the whole molecule is 1 to 50% by weight. ) The number average molecular weight of these copolymers is from 10,000 to
1,000,000, preferably 50,000-25
It is 10,000.

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

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

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

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

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

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

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

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

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

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

Component (a), component (b), component (c),
In the case of a resin composition containing the component (d) and 100 parts by weight of the olefin resin of the component (a), the copolymer resin containing the non-conjugated diene of the component (b) is 0.1.
To 900 parts by weight, preferably 0.5 to 600 parts by weight, particularly preferably 1 to 300 parts by weight, the polymer having an amino group and / or imino group of the component (c) is 0.01 to 7 parts by weight.
50 parts by weight, preferably 0.05 to 350 parts by weight, particularly preferably 0.1 to 180 parts by weight, and the component (d) elastomer is 1 to 900 parts by weight, preferably 5 to 3 parts by weight.
00 parts by weight, particularly preferably 10 to 200 parts by weight.

Component (a), component (b), component (c),
In the case of the resin composition containing the component (e) and 100 parts by weight of the olefin resin of the component (a), the copolymer resin containing the non-conjugated diene of the component (b) is 0.1.
To 900 parts by weight, preferably 0.5 to 600 parts by weight, particularly preferably 1 to 300 parts by weight, the polymer having an amino group and / or imino group of the component (c) is 0.01 to 5 parts by weight.
00 parts by weight, preferably 0.05 to 350 parts by weight, particularly preferably 0.1 to 180 parts by weight, and the component (e) filler is 0.1 to 300 parts by weight, preferably 0.5.
˜250 parts by weight, particularly preferably 1 to 200 parts by weight.

Component (a), component (b), component (c),
In the case of the resin composition containing the component (d) and the component (e): The copolymer resin containing the non-conjugated diene of the component (b) is added to 100 parts by weight of the olefin resin of the component (a). 0.1 to 900 parts by weight, preferably 0.5 to 600
Parts by weight, particularly preferably 1 to 300 parts by weight, component (c)
The polymer having an amino group and / or an imino group of
0.01-900 parts by weight, preferably 0.05-450
Parts by weight, particularly preferably 0.1 to 240 parts by weight, the elastomer of component (d) is 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight, and component (e). The filler is 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 dienes as the component (b) is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks, etc. may be poor, or the adhesion strength may be weak. Is not preferable. On the other hand, if the amount exceeds the above range, the amount of the expensive copolymer resin added is large, so that not only the cost of the resin composition increases, but also an effect proportional to the amount of the copolymer resin added is obtained. is not.

When the compounding amount of the polymer having an amino group and / or an imino group as the component (c) is less than the above, the adhesive strength becomes extremely weak depending on the applied coating material, adhesive agent, printing ink and the like. Is not preferable. On the other hand, if the amount exceeds the above range, the amount of the expensive polymer added is large, so that not only the cost of the resin composition increases, but also the effect proportional to the added amount of the polymer cannot be obtained. In addition, the polymer is delaminated, so that the adhesion of paints, adhesives, printing inks, etc. is reduced, which is not preferable.

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

(3) Blending The resin composition of the present invention is 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 perform painting, adhesion and printing without treatment, and is characterized in that good paint adhesion, adhesion and printability 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 and the like can be obtained, but also good paint adhesion and the like can be obtained for a wider range of paint types and the like. Hereinafter, in order to more specifically describe the characteristics of the resin composition of the present invention,
As an application example, a molded product made of the resin composition, and its surface treatment and coating method will be described in detail.

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

The cleaning method using these cleaning solutions is the surface treatment method referred to herein, and includes 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 is generally aimed at a degreasing treatment for cleaning 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 treatment, 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 devices 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, only the surface treatment with these hot gases is performed, and a wider range can be obtained without performing primer coating or surface modification such as plasma treatment. It is very surprising that stronger paint adhesion can be obtained in paint types and the like.

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

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

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

[0111]

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> Heat Treatment : The coated test piece was directly coated without any treatment . Alkaline treatment : The test piece was immersed in warm water at 60 ° C. for 30 seconds, and then, an alkaline detergent (CL551 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used.
The 5% aqueous solution of 3) was immersed in a tank heated to 60 ° C for 120 seconds, and then again immersed in warm water of 60 ° C for 30 seconds.
The surface of the test piece was rinsed with tap water for 30 seconds and then with pure water for 30 seconds. Water was removed from the surface of the test piece by air blow, and the test piece was dried in an oven at 80 ° C. for 10 minutes.

Acid treatment : The test piece was immersed in warm water at 60 ° C. for 30 seconds, and then an acidic detergent (ISW3 manufactured by DUBOIS) was used.
The 5% aqueous solution of 2) was immersed in a bath heated to 60 ° C. for 120 seconds, and then again immersed in warm water of 60 ° C. for 30 seconds.
The surface of the test piece was rinsed with tap water for 30 seconds and then with pure water for 30 seconds. Moisture on the surface of the test piece was removed by air blow, and the test piece was dried in an oven at 80 ° C for 10 minutes. Hot 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 of the coating materials was prepared and spray-coated with an air spray gun so that the coating film thickness was 100 μm. Then, the one-component organic solvent-based urethane coating was baked and dried at 120 ° C. for 60 minutes and the two-component organic solvent-based urethane coating at 80 ° C. for 60 minutes.

<Evaluation of Paint Adhesion> Base line test : Using a single-edged razor, 11 vertical and horizontal parallel lines perpendicular to the surface of the test piece are drawn at 2 mm intervals to make 100 base lines. Cellophane adhesive tape (JIS
Z1522) was sufficiently pressure-bonded and kept at about 30 ° with the coating surface, and was peeled off at once in front, and the state of the portion surrounded by the substrate eyes was observed, and the number of substrate eyes which were not peeled off was recorded.

Examples 1 to 33 and Comparative Examples 1 to 9 (1) Production of Resin Molded Body Each component shown in the following Table 1 and Table 2 was blended and melt-kneaded at 200 ° C. by a twin-screw extruder. Into pellets.
A flat plate and a three-point bending elastic modulus measuring test piece were injection-molded using the pellet. The compounding ingredients in Tables 1 and 2 are as follows.

<Olefin Resin: (a) Component> Block PP (1) : Ethylene Content of 4% by Weight, JIS
-The flexural modulus measured according to K7203 is 14,0
A propylene / ethylene block copolymer having a MFR of 60 kg / 10 min, which is 00 kg / cm ² and is measured according to ASTM-D1238.

Block PP (2) : ethylene content is 13
% By weight, flexural modulus measured according to JIS-K7203 is 6,000 kg / cm ² , and ASTM-D12
A propylene / ethylene block copolymer having an MFR of 30 g / 10 min measured according to 38.

Random PP : Ethylene content 3.4% by weight, flexural modulus measured according to JIS-K7203 10,500 kg / cm ² , and ASTM-D123.
A propylene / ethylene block copolymer having an MFR measured according to 8 of 15 g / 10 min.

[0121]Single PP: According to JIS-K7203
Flexural modulus measured is 13,000 kg / cm ²,And
MFR measured in accordance with ASTM-D1238 is 25
g / 10 minutes polypropylene.HDPE : Bending measured according to ASTM-D747
Elastic modulus is 10,500 kg / cm ², And JIS-K6
MFR measured according to 760 is 20 g / 10 min.
Low-pressure polypropylene (high-density polyethylene).

<Copolymer resin containing non-conjugated dienes:
Component (b)> Copolymer (1) 7-methyl-1,6-octadiene content 7.3% by weight,
Bending elastic modulus 6,250 kg / cm ² , and MFR 3.
5 g / 10 min 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 of 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 MFR 2.8 g / 10 min propylene / 7-methyl-1,6-octadiene random copolymer.

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 propylene with MFR of 1.5 g / 10 min.
(Ethylene-4-methyl-1,4-hexadiene-5-
Methyl-1,4-hexadiene) block copolymer.

<Polymer Having Amino Group and / or Imino Group: Component (c)> AMAEPM 2- Aminoethyl Methacrylate Graft Propylene Ethylene 7-Methyl-Produced as Follows
1,6-octadiene copolymer resin. (Manufacturing method) propylene / ethylene / 7-methyl-1,6
-Octadiene random copolymer (copolymer (3): component (b)) 5 kg was dry-blended with 500 g of 2-aminoethyl methacrylate and 10.8 g of t-butylcumyl peroxide at a temperature of 200 ° C and a rotation speed. Melt kneading was performed in a twin-screw extruder set to 250 rpm and 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-aminoethyl methacrylate of the obtained graft body is 2.1% by weight, and the MFR is 2.5 g.
/ 10 minutes.

ADPH A diene polymer hydrogenated product having a cyano group produced as described below. (Production method) 1,3-into an autoclave with a capacity of 500 ml
100 g of butadiene, 90 g of isopropyl alcohol,
Then, 14 g of azoisobutyronitrile was added, and polymerization was carried out at 100 ° C. for 6 hours in an argon atmosphere. After the reaction was completed, unreacted monomers were removed, and the resulting diene polymer having a cyano group was dried. 50 g of the obtained diene polymer, 50 g of dioxane and 5 g of Raney cobalt
Was charged into an autoclave with a capacity of 200 ml, and the inside of the system was replaced with argon gas, and then hydrogen gas of 50 kg / cm ²
At 100 ° C. while supplying hydrogen gas so that
A time reaction was performed. After completion of the reaction, hydrogen was removed, and the catalyst was removed by filtration, and the produced hydrogenated product was precipitated in methanol and separated by filtration. The obtained diene polymer hydrogenated product had an iodine value of 0.4 (g / 100 g), an amino group concentration of 0.46 meq / g, an amino group number of 2.8, and a number average molecular weight of 6,100.

[0128] APEH ethylene polymer hydrogenation product having a Jiano group was prepared as follows. (Production method) In high-pressure polymerization of ethylene, azobisisobutyronitrile was used as an initiator, and the initiator concentration was 7,000.
Polymerization was carried out under the conditions of 0 ppm, a temperature of 190 ° C. and a pressure of 2,000 atm to obtain polyethylene having a cyano group. The number average molecular weight of the polyethylene was 6,000. 50 g of the obtained cyano group-containing polyethylene, 5 dioxane
After charging 0 g and Raney cobalt 5 g into an autoclave having a capacity of 200 ml and replacing the inside of the system with argon gas,
While supplying hydrogen gas so that the pressure was kept at 50 kg / cm ² , the reaction was carried out at 100 ° C. for 10 hours. After completion of the reaction, hydrogen was removed, and the catalyst was removed by filtration, and the produced hydrogenated product was precipitated in methanol and separated by filtration. The polymer obtained had an amino group concentration of 0.2 meq / g, an amino group number of 1.2, and a number average molecular weight of 6,000.

<Elastomer component: (d) component> EPM (1) : Mooney viscosity ML _{1 + 4} (100 ° C.) is 7
Ethylene / propylene / copolymer rubber having a specific gravity of 0.86. EPM (2) : Mooney viscosity ML _{1 + 4} (100 ° C) is 2
4, ethylene / propylene / copolymer rubber having a specific gravity of 0.86. EPDM : Mooney viscosity ML _{1 + 4} (100 ° C) is 47,
Ethylene / propylene / ethylidene norbornene copolymer rubber having a specific gravity of 0.86. SEBS : number average molecular weight 70,000, specific gravity 0.9
1. A hydrogenated product of styrene / butadiene block copolymer rubber which is 1.

<Filler component: (e) component> Talc : talc having a specific surface area of 39,000 cm ² / g and an average particle size of 1.8 to 2.2 μm. Potassium titanate whiskers : average diameter of 0.2-0.
Potassium titanate whiskers [K ₂ O · 6TiO ₂ ] having an average aspect ratio of 5 or more and 20 μm. Mica : Mica having an average flake diameter of 90 μm. Calcium carbonate : Specific surface area of 33,000 to 39.00
Calcium carbonate having 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 surface treatment, and the coating material was applied using an air gun. After the completion of baking and drying, the substrate was left at room temperature for 48 hours to carry out a substrate test. The flexural modulus of the obtained resin composition is shown in Tables 1 and 2, and the results of paint adhesion of the molded product are shown in Table 3.
And shown in Table 4.

[0132]

[Table 1]

[0133]

[Table 2]

[0134]

[Table 3]

[0135]

[Table 4]

[0136]

[Table 5]

[0137]

[Table 6]

[0138]

[Table 7]

[0139]

[Table 8]

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

[0141]

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. In addition, the surface of the molded body formed from the resin composition can be made stronger 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 good paint adhesion but also good paint adhesion to a wider range of paint types. Therefore, overturning the conventional wisdom that it is impossible to directly coat an olefin resin, a molded article formed from the composition of the present invention is subjected to a surface modification treatment such as primer coating or plasma treatment. Even if a paint is applied without applying it in advance, it shows good paint adhesion and is industrially very useful.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08L 51/06 LLE 7142-4J 53/00 LLY 7142-4J 101/00 LSZ 7167-4J

Claims (4)

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