JPH0680831A - Olefinic resin composition - Google Patents

Abstract

PURPOSE:To provide the subject composition excellent in adhesiveness coatability and printability, useful for molded products, etc., comprising an olefin resin, specific copolymer resin, hydroxyl group-bearing polymer, phosphoxy acid compound and tertiary amine compound at specified proportion. CONSTITUTION:The objective composition comprising (A) 100 pts.wt. of an olefin resin such as PE, (B) 0.1-90 pts.wt. of block and/or random copolymer resin from (1) at least one kind of 2-12C alphaolefins and (2) at least one kind of nonconjugated dienes of the formula (R<1>-R<5> are each H or 1-8C alkyl; n is 1-10), (C) 0.01-400 pts.wt. of a hydroxyl group-bearing polymer such as polyhydroxybutadiene, (D) 0.01-300 pts.wt. of a phosphoxy acid compound such as diarylphosphonous acid and (E) 0-200 pts.wt. of a tertiary amine compound such as triethylamine.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an olefin 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 dirt, machine oil, etc. adhering to the surface of the molded body. Is being done. In addition, since olefin resins do not have polar groups in their structure and have high crystallinity, the adhesion of paints, adhesives, printing inks, etc. is extremely poor, resulting in poor paintability, adhesiveness, and printability. Since the surface is inferior, the surface is modified by applying a primer in advance or plasma treatment to improve the adhesiveness, 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 safety problems.

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 when it comes into contact with a foreign substance, the adhesion of the paint, the adhesive and the printing ink deteriorates, and thus 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 objective has not been fully achieved yet, 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.

On the other hand, when the resin molding is directly coated or adhered without being treated with a primer or the like, a light stabilizer, an antioxidant, a lubricant, etc. added to the resin composition. It is also known that the additive of 1) may reduce the adhesion. It has been reported that an 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 potassium sulfate permanganate and a 3% aqueous solution of sodium sulfate acid sodium bisulfite (Japanese Patent Laid-Open No. Sho 63-64). 57-44639), a method of performing surface treatment with an oxidizing agent (JP-A-57-59934), a method of performing 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 (Japanese Patent Laid-Open No. 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, handling is very inconvenient, and the coating and coating composition are limited. It had the drawback of being narrow. There is also a proposal to provide a polyolefin resin composition having excellent coating properties and paint adhesion by adding a phosphoric acid ester compound having a specific structure to a polyolefin resin (JP-A-3-265637). However, with this composition, paint adhesion cannot be obtained when surface modification treatment such as primer coating or plasma treatment is omitted (Comparative Example 11).

[0008]

[Means for Solving the Problems]

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

That is, the present invention comprises the following components (a), (b), (c), (d), optionally (e), and further (f) and / or (g). Including 100 parts by weight of the component (a), the component (b) was added to 0.
1 to 900 parts by weight, component (c) from 0.01 to 400 to 900 parts by weight, component (d) from 0.01 to 300 to 65 parts by weight
0 parts by weight, component (e) 0 to 200 to 450 parts by weight,
1 to 900 parts by weight of component (f), and / or component (g)
Is an olefin resin composition containing 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) : Polymer component having hydroxyl group (d) : Phosphorus oxyacid compound component (e) : Tertiary amine compound component (f) : Elastomer component (g) : Filler

[0012]

[Detailed Description of the Invention]

[I] Resin composition (1) Constituents The olefin resin composition of the present invention is basically formed from the constituents shown below.

Component (a): Olefin Resin The olefin resin used in the present invention is
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 organic silicon compound, or the olefin resin There may be mentioned a graft polymer such as an organic silicic 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 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 resins.

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

[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
Examples include 1,7-dienes such as nonadiene; various non-conjugated dienes such as 1,11-dodecadiene and 1,13-tetradecadiene;

Among these, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 6-
Methyl-1,5-heptadiene, 6-methyl-1,5-
Octadiene, 6-methyl-1,6-octadiene, 7
-Methyl-1,6-octadiene, 7-ethyl-1,6
Branched non-conjugated dienes such as -octadiene and 8-methyl-1,7-nonadiene are preferred from the viewpoint of copolymer production technology, and 7-methyl-1,6-octadiene is particularly preferred. Of course, these non-conjugated dienes can be used in a mixture of two or more 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 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, and particularly preferably 1
-20% by weight. If the content of non-conjugated dienes is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks, etc. is poor, or their adhesion strength 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 copolymer resin containing non-conjugated dienes used in the present invention has a melt flow rate (MFR) of 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.

Furthermore, the copolymer resin containing the non-conjugated dienes of the present invention has a flexural modulus of 500 to 30,000 kg / cm ² , preferably 1,000 to 5,000, according to JIS K-7203.
20,000 kg / cm ² , particularly preferably 1,500 to 1
It is 5,000 kg / cm ² . If it is less than 500 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,
It represents a mixture of 4-hexadiene and 5-methyl-1,4-hexadiene, and the mixing ratio thereof is 95: 5 to 5:95.
It is in the range of. ]

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.

As a method for producing the copolymer resin,
For example, Japanese Patent Publication No. 64-2127 and Japanese Patent Publication No. 64-21.
28, JP-B-64-9326, JP-A-59
The methods described in JP-A-155416, JP-A-62-115008 and JP-A-2-311507 can be mentioned.

Component (c): Polymer Having Hydroxyl Group The polymer having a hydroxyl group used in the present invention is a hydroxyl group-containing unsaturated compound or a polar group capable of introducing or generating a hydroxyl group by some chemical modification after polymerization. It is at least one (co) polymer selected from the group consisting of a homopolymer such as an unsaturated compound having a group, a copolymer with another polymerizable monomer, and a graft polymer onto another polymer. As a result, structurally, a branched or linear molecular chain has irregular or regularly pendant hydroxyl groups, or a side chain having a hydroxyl group,
It refers to the entire range from oligomers having a grafted structure to polymers.

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

A specific description will be given below. Copolymer of α-olefin and a hydroxyl group-containing unsaturated compound The copolymer means that a hydroxyl group-containing unsaturated compound is irregularly or regularly present in a branched or linear carbon chain from a structural viewpoint. , Refers to all those having a structure copolymerized with α-olefin. Specifically, the content of the hydroxyl 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, the melt flow rate is not particularly limited, but preferably the melt flow rate (MFR) measured according to ASTM-D1238 is , 0.01-
1,000 g / 10 minutes, particularly preferably 0.1-500
G / 10 min, including liquid, semi-solid, and solid oligomers to polymers at room temperature.

Such a copolymer of an α-olefin and a hydroxyl group-containing unsaturated compound can be prepared by a known method using the α-olefin and a hydroxyl group-containing unsaturated compound as a raw material, for example, a high pressure radical polymerization method or a Ziegler-Natta catalyst. It can be produced by a conventional polymerization method. In the case of production by the high-pressure radical polymerization method, ethylene, a hydroxyl group-containing unsaturated compound, and a radical polymerization initiator are added, for example, at a pressure of 1,00.
Continuously fed into the reaction zone maintained at 0 to 3,000 atm and temperature of 90 to 300 ° C so that the ratio of ethylene: hydroxyl group-containing unsaturated compound is 1: 0.0001 to 1: 0.1. And an ethylene copolymer with a conversion of 3 to 20%,
It is produced by continuously removing the copolymer from the reaction zone. In the case of production by a polymerization method using a Ziegler-Natta catalyst, for example, a product obtained by complexing a hydroxyl group-containing unsaturated compound with an organic aluminum compound or the like and propylene, using a known Ziegler catalyst or the like, for example, in the presence of heptane or In the absence, pressure, normal pressure to 20 atm, temperature 30 to
It is produced by copolymerizing at 150 ° C.

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

The α-olefin which is the other copolymerization component has a carbon number of 2 to 12, and specifically, ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1 -Octene, 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-butene, 4,4-dimethyl-1-pentene, 3-methyl -1-hexene, 4-
Methyl-1-hexene, 4,4-dimethyl-1-hexene, 5-methyl-1-hexene, allylcyclopentane, allylcyclohexane, styrene, allylbenzene, 3-cyclohexyl-1-butene, vinylcyclopropane, vinylcyclo Mention may be made of pentane, vinylcyclohexane, 2-vinylbicyclo [2,2,1] -heptane, and the like. Among these, preferred examples are
Ethylene, propylene, 1-butene, 3-methyl-1-
Butene, 4-methyl-1-pentene, styrene and the like, and particularly preferred examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

In addition to the above α-olefin and hydroxyl group-containing unsaturated compound components, unsaturated carboxylic acid esters such as methyl acrylate, ethyl acrylate, butyl acrylate, and methyl methacrylate as a third copolymerization monomer component; α-methyl Vinyl aromatic compounds such as styrene and vinyltoluene: nitrile compounds such as acrylonitrile and methacrylonitrile; 2-vinylpyridine,
Vinyl pyridine such as 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; acrylic aluminide; 1,3-butadiene , 1,3-pentadiene, conjugated dienes such as isoprene and the like, ternary system,
It can also be used as a multi-component copolymer. These copolymers can be used alone or as a mixture of plural kinds.

Graft Polymer of Hydroxyl Group-Containing Unsaturated Compound From the structural point of view, the graft polymer is a branched or linear molecular chain in which irregular or regular hydroxyl group-containing unsaturated compound is grafted. It refers to all those having a polymerized structure. Specifically, the content of the hydroxyl group-containing unsaturated compound is 0.1 to 50% by weight, preferably 0.5 to
The melt flow rate is 45% by weight, particularly preferably 1 to 40% by weight, and the melt flow rate is not particularly limited, but preferably the melt flow rate (MFR) measured according to ASTM-D1238 is 0. 01 to 1,0
00 g / 10 minutes, particularly preferably 0.1-500 g / 1
It is 0 minute and includes liquid, semi-solid and solid polymers at room temperature.

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

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

As the trunk polymer component which is another component of the graft polymer, the olefin resin as the component (a), the copolymer resin containing the non-conjugated dienes as the component (b), and Examples of the elastomer of the component (f) described below include ethylene-based resins, propylene-based resins, olefin-based elastomers,
Examples thereof include styrene elastomer, ethylene / non-conjugated diene copolymer resin, propylene / non-conjugated diene copolymer resin, ethylene / propylene / non-conjugated diene copolymer resin and the like. Further, particularly preferably, a block or random propylene-based resin, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), and styrene / conjugated diene block copolymer hydrogenated product, Examples include propylene / 7-methyl-1,6-octadiene copolymer resin, propylene / ethylene / 7-methyl-1,6-octadiene copolymer resin, propylene / methyl-1,4-hexadiene copolymer resin, and the like. To be

In addition to the above-mentioned unsaturated compound component containing a hydroxyl group, unsaturated carboxylic acid ester such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, etc. as the second copolymer graft monomer component; styrene, α-methyl Vinyl aromatic compounds such as styrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether; vinyl chloride; Vinyl halides such as vinyl bromide; vinyl esters such as vinyl acetate; acrylamide; conjugated dienes such as 1,3-butadiene, 1,3-pentadiene, isoprene, and the like.
It is also possible to use it as a multi-component graft copolymer. These graft polymers can be used either individually or as a mixture of a plurality of types.

Hydrolyzate of Vinyl Ester-Containing Polymer The vinyl ester-containing polymer includes homopolymers of vinyl esters, copolymers with other polymerizable monomers, graft polymers onto other trunk polymers, and the like. Point to. Specifically, the content of vinyl ester compound is 0.01 to 1
It is in the range of 00% by weight, preferably 0.05 to 70% by weight, particularly preferably 0.1 to 40% by weight, and the melt flow rate is not particularly limited, but preferably A
The melt flow rate (MFR) measured according to STM-D1238 is 0.01 to 1,000 g / 10 minutes,
It is particularly preferably 0.1 to 500 g / 10 minutes, and includes a polymer which is liquid, semi-solid or solid at room temperature.

The vinyl ester-containing polymer can be produced by a known method. For example, a high pressure radical polymerization method, a solution polymerization method, an emulsion polymerization method, a solution graft polymerization method, and a kneading graft polymerization method can be mentioned. In the case of production by a high-pressure radical polymerization method, for example, a vinyl ester compound, ethylene and a radical polymerization initiator are added at a pressure of 1,000 to 3,000 atm and a temperature of 90 to 3
A vinyl ester compound and ethylene were continuously fed into the reaction zone kept at 00 ° C to prepare a copolymer under the conditions such that the conversion rate was 3 to 20%. It is manufactured by continuously taking out the coalescence. Examples of vinyl ester compounds used for the polymer include vinyl formate, vinyl acetate, vinyl acrylate, vinyl crotonic acid, vinyl caprylate, vinyl laurate,
Examples thereof include vinyl chloroacetate, vinyl oleate, and vinyl stearate, and of these, vinyl acetate is preferred. 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, preferable examples are ethylene, propylene, 1-butene, 3-methyl-1-butene, 4-methyl-1-pentene, styrene and the like, and particularly preferable examples are ethylene and propylene. Two or more kinds of these α-olefins may be used.

When the polymer is a graft polymer onto another polymer, its backbone polymer is a copolymer containing the olefin resin as the component (a) and the non-conjugated dienes as the component (b). Examples thereof include resins and elastomers of the component (f) described below. Among them, ethylene-based resins, propylene-based resins, olefin-based elastomers, styrene-based elastomers, ethylene
Examples thereof include non-conjugated diene copolymer resins, propylene / non-conjugated diene copolymer resins, ethylene / propylene / non-conjugated diene copolymer resins and the like. Further, particularly preferably, a block or random propylene-based resin, ethylene / propylene copolymer rubber (EPM), ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), 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 and the like can be 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 pyridines such as 2-vinyl pyridine and 4-vinyl pyridine; methyl vinyl ether,
Vinyl ether such as 2-chloroethyl vinyl ether;
Vinyl halides such as vinyl chloride and vinyl bromide; vinyl esters such as vinyl acetate; acrylamide; conjugated dienes such as 1,3-butadiene, 1,3-pentadiene, isoprene, etc. It is also possible to use a system copolymer and a graft copolymer. These (co) polymers and graft (co) polymers may be used alone or as a mixture of plural kinds.

The example of the hydrolyzate of the vinyl ester-containing polymer is produced by hydrolyzing the above vinyl ester-containing polymer. Examples of the hydrolysis method of the vinyl ester-containing polymer include a method of adding a catalyst such as an alkali or an acid and an alcohol. The degree of hydrolysis of the vinyl ester-containing polymer is 100 to 1%,
Preferably 100 to 10%, particularly preferably 100
It is up to 30%, and it may be completely hydrolyzed or partially hydrolyzed. As the hydrolyzate of the vinyl ester-containing polymer, a hydrolyzate of a copolymer of a vinyl ester compound and α-olefin is preferable, and a hydrolyzate of a copolymer of vinyl acetate and ethylene is particularly preferable. Among these polymers having a hydroxyl group, a copolymer of α-olefin and a hydroxyl group-containing unsaturated compound, and a graft polymer of a hydroxyl group-containing unsaturated compound are preferable, and particularly a copolymer of ethylene and a hydroxyl group-containing unsaturated compound. A graft polymer of a hydroxyl group-containing unsaturated compound onto a copolymer resin containing propylene, a hydroxyl group-containing unsaturated compound, and non-conjugated dienes is preferable.

Component (d): phosphorus oxyacid compound The phosphorus oxyacid compound used in the present invention is a compound having a structure in which an oxygen atom is directly bonded to a phosphorus atom (phosphorus oxyacid structure). It refers to polymer compounds. Low molecular weight compound having phosphorus oxyacid structure The low molecular weight compound having a phosphorus oxyacid structure is a phosphorus compound represented by the following general formula and having a molecular weight of 100 to less than about 1,000.

[0046]

[Chemical 7]

[0047]

[Chemical 8]

(R ⁶ and R ⁸ in the above formula are hydrogen atoms; substituents consisting of hydrocarbons which may contain an alkyl chain, an aliphatic ring, an aromatic ring structure, etc .; R ¹⁰ C (O) S- R ¹¹
A and R ¹³ S-, etc.; R ¹² N-. R ⁷ and R ⁹ are a hydrogen atom; a substituent having an alkyl chain, a polyalkylene glycol chain, an aliphatic ring, an aromatic ring structure or the like; and R ¹⁴
C (O)-and the like. Moreover, n is an integer of 0-2.
R ⁶ and R ⁸ or (OR ⁷ ) and (OR ⁹ ) are
When a plurality of phosphorus atoms are bonded, R ⁶ and R ⁸ or R ⁷ and R ⁹ may be the same or different. Here, R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are substituents having an alkyl chain, a polyalkylene glycol chain, an aliphatic ring, an aromatic ring structure or the like. )

Of these, those represented by the above formula [Chemical formula 8] are preferable. However, R ⁸ is a hydrogen atom;
R ⁹ is a substituent such as an alkyl chain, an aliphatic ring and an aromatic ring structure, and R ⁹ is a hydrogen atom; a substituent such as an alkyl chain, a polyalkylene glycol chain, an aliphatic ring and an aromatic ring structure. And n is an integer of 0 to 2. R
^{When 8} or (OR ⁹ ) is bound to a plurality of phosphorus atoms, R ^{8 and} R ⁹ may be the same or different. Among these, particularly preferably, n = 0 in the above formula, and more specifically represented by the following formula.

[0050]

[Chemical 9]

(R ¹⁵ in the above formula is a substituent having an alkyl chain, a polyalkylene glycol chain, an aliphatic ring, an aromatic ring structure or the like. M is an integer of 1 to 3, preferably 1 or 2 When (OR ¹⁵ ) is bound to a plurality of phosphorus atoms, R ¹⁵ may be the same or different.

Typical examples of these are diaryl phosphinic acid, dialkyl phosphinic acid, aryl phosphinic acid, alkyl phosphine, diaryl phosphinic acid, dialkyl phosphinic acid, aryl phosphonic acid, alkyl phosphonic acid, phosphorous acid and phosphorus. Examples thereof include acids and compounds having an ester derivative structure thereof, and preferred examples include phosphinic acid, phosphonic acid, phosphoric acid and compounds having an ester derivative structure thereof. Particularly preferred examples include acidic phosphoric acid ester derivatives. Further, even if it is a phosphorus compound having a structure not corresponding to the above formula, it changes at any step during the production of the composition of the present invention, and becomes a phosphorus oxyacid compound having a structure corresponding to the above formula, Of course, it is included in the present invention.

Specific examples of these particularly preferable phosphoric acid ester derivatives include phosphoric acid monobutyl ester,
Phosphoric acid dibutyl ester, phosphoric acid mono (2-ethylhexyl) ester, phosphoric acid di (2-ethylhexyl) ester, phosphoric acid mono (isodecyl) ester, phosphoric acid di (isodecyl) ester, phosphoric acid mono (lauryl) ester, phosphorus Acid di (lauryl) ester, phosphoric acid mono (tridecyl) ester, phosphoric acid di (tridecyl) ester, phosphoric acid mono (nonylphenoxyethyl) ester,
Examples thereof include phosphoric acid di (nonylphenoxyethyl) ester. These phosphorus oxyacid compounds can be used either individually or as a mixture of two or more species, and are usually selected appropriately from commercially available compounds.

Polymer Compound Having Phosphoric Acid Structure As a polymer compound having a phosphorus oxy acid structure, a polymer having at least one phosphorus oxy acid structure in its molecule and having a molecular weight of 1,000 to 500,000 is used. It is contained and may be liquid, semi-solid or solid at room temperature. From a structural point of view, a polymer compound having such a phosphorus oxyacid structure is a group having a phosphorus oxyacid structure or having a phosphorus oxyacid structure in a branched or linear molecular chain or at the end of the molecular chain. Indicates a general structure having a pendant.

Specifically, the homopolymerization of the phosphorus oxyacid structure-containing polymerizable compound obtained by addition polymerization or condensation polymerization, and the copolymer and phosphorus oxyacid structure composed of the phosphorus oxyacid structure-containing polymerizable compound and another polymerizable monomer Examples thereof include a graft modified polymer having a side chain or a molecular chain terminal. Here, the phosphorus oxyacid structure-containing polymerizable compound has at least one phosphorus oxyacid structure,
In addition, it refers to all compounds having at least one unsaturated group capable of addition polymerization or functional group capable of condensation polymerization.
Further, as the other polymerizable monomer which can be copolymerized, in the case of addition polymerization, α-olefins, vinyl aromatics, unsaturated carboxylic acids, unsaturated nitriles, vinyl ethers,
In the case of condensation polymerization of vinyl esters, conjugated dienes, vinyl halides, acrylamides, etc., diol compounds, polyol compounds, dicarboxylic acid compounds, polycarboxylic acid (including acid anhydride) compounds, diamine compounds, diimines Examples thereof include compounds, lactams, lactones and formaldehyde. Further, as the trunk polymer in the case of a graft modified polymer, an olefin polymer, a styrene polymer, an acrylic polymer, a diene polymer, polyamides, polyimides, polyesters, polyurethanes, polyethers And polyketones.

Among these polymer compounds having a phosphorus oxyacid structure, copolymers or graft modified polymers using a phosphorus oxyacid structure-containing compound, phosphorus pentoxide, phosphorus oxychloride, etc. as the phosphorus oxyacid structure-containing polymerizable compound. Is preferred. Further, using an unsaturated compound containing a phosphorus oxyacid structure, phosphorus pentoxide, phosphorus oxychloride, etc., α
-A modified olefin polymer containing a phosphoroxy acid structure, such as a copolymer modified with an olefin or graft-modified onto an olefin polymer as a trunk polymer, is particularly preferable because it is difficult to bleed out when used.

Specifically, the content of the phosphorus oxyacid structure-containing compound is 0.1 to 50% by weight, preferably 0.5 to 4%.
It represents 0% by weight, particularly preferably 1 to 30% by weight, and has a number average molecular weight of 1,000 to 500,000, preferably 1,500 to 300,000, particularly preferably 2,000 to 100,000. belongs to. The phosphorus oxyacid structure-containing modified olefin polymer can be produced by a known method using a phosphorus oxyacid structure-containing unsaturated compound, phosphorus pentoxide, phosphorus oxychloride and the like. For example, in the case of production by a high-pressure radical polymerization method, ethylene, a phosphorus oxyacid structure-containing unsaturated compound and a radical polymerization initiator are kept in a reaction zone where the pressure is maintained at 1,000 to 3,000 atm and the temperature at 90 to 300 ° C. And the ratio of ethylene: phosphoric acid-containing unsaturated compound is 1: 0.0.
It is produced by continuously taking out the polymer from the reaction zone so as to be 001 to 0.1.

In the case of production by the kneading and grafting method, for example, an olefin resin, a copolymer resin or an elastomer containing the above-mentioned non-conjugated diene is dry blended with a phosphorus oxyacid structure-containing unsaturated compound, and the reaction is carried out if necessary. Using an organic peroxide as an initiator, the temperature is 80 to 250 ° C.
It is manufactured by melt-kneading in an extruder set to. In the case of production by solution reaction, for example, it is produced by causing phosphorus oxychloride to act excessively on a polymer having a hydroxyl group and partially hydrolyzing the obtained product under alkaline conditions. Such a phosphorus oxyacid structure-containing unsaturated compound is represented by the following formula.

[0059]

[Chemical 10]

R ¹⁶ in the above formula is a hydrogen atom or a saturated hydrocarbon having 1 to 4 carbon atoms, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 2 carbon atoms. X ¹ is a carbonyl group, an aromatic ring, an aliphatic ring or an alkyl chain having 1 to 12 carbon atoms, preferably a carbonyl group or an aromatic ring,
Particularly preferred is a carbonyl group. R ¹⁷ is a polyalkylene glycol composed of an oxygen atom, an alkylglycoxyl group having 1 to 12 carbon atoms, an alkoxyl chain having an oxygen atom on the X ¹ group side having 1 to 12 carbon atoms, and a glycol unit having 1 to 6 carbon atoms. Chain, sulfur atom or —NR ¹⁹ R ²⁰ —
And preferably an oxygen atom, an alkylglycoxyl group having 1 to 12 carbon atoms or an alkoxyl group having an oxygen atom on the X ¹ group side having 1 to 12 carbon atoms, and particularly preferably an oxygen atom or 1 to 12 carbon atoms. 6 is an alkylglycoxyl group. R ¹⁸ is a hydrogen atom or a substituent having an alkyl chain having 1 to 12 carbon atoms, a polyalkylene glycol chain having a glycol unit having 1 to 6 carbon atoms, an aliphatic chain, an aromatic chain structure, or the like, and preferably hydrogen. An atom or an alkyl group having 1 to 12 carbon atoms, particularly preferably a hydrogen atom. In addition, when (OR ¹⁸ ) is bound to plural phosphorus atoms, R ¹⁸ may be the same or different. R ¹⁹ is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 4 carbon atoms. R ²⁰ is an alkyl chain having 1 to 12 carbon atoms or an alkoxyl chain having 1 to 12 carbon atoms and having an oxygen atom on the phosphorus atom side, preferably an alkyl chain having 1 to 6 carbon atoms or an alkoxy chain having 1 to 6 carbon atoms It is an alkoxyl chain having an oxygen atom on the phosphorus atom side, and particularly preferably an alkoxyl chain having an oxygen atom on the phosphorus atom side having 1 to 6 carbon atoms.
n is an integer of 1 to 3, preferably 1 to 2. m is 0 or 1, preferably 1.

Specific examples of particularly preferable unsaturated compounds containing a phosphorus oxyacid structure include phosphoric acid mono (2-acryloyloxyethyl) ester, phosphoric acid di (2-acryloyloxyethyl) ester and phosphorus. Examples thereof include acid mono (2-methacryloyloxyethyl) ester and phosphoric acid di (2-methacryloyloxyethyl) ester.

Examples of the olefinic monomer component in the case of copolymerizing with the above-mentioned unsaturated compound containing a phosphorus oxyacid structure include α-olefins such as ethylene, propylene and 1-butene. Then
Ethylene is preferred. Further, as the olefin polymer component as a trunk polymer in the case of grafting the phosphorus oxyacid structure-containing unsaturated compound, an olefin resin (component (a)), a copolymer resin containing the non-conjugated dienes (component (B)) and the below-mentioned olefin elastomer component (component (f-)), and the like. Among these, a polyethylene resin, a polypropylene resin, a copolymer resin containing the non-conjugated dienes and ethylene. It is preferable to use a system elastomer.

In the production of these phosphorus oxyacid structure-containing modified olefin polymers, examples of the monomer component which can be copolymerized with the phosphorus oxyacid structure-containing unsaturated compound include methyl acrylate, ethyl acrylate, butyl acrylate and methyl methacrylate. Unsaturated carboxylic acid esters; vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether; vinyl chloride, odor Vinyl halide such as vinyl chloride; vinyl ester such as vinyl acetate; acrylamide; 1,3-butadiene, 1,3-pentadiene,
Examples thereof include conjugated dienes such as isoprene and the like, and these can also be used as a ternary type or a multi-component modified polyolefin. Further, as the polymer having a hydroxyl group that is modified by the action of phosphorus oxychloride, a polymer having the hydroxyl group (component (c)),
Examples thereof include a diene polymer having a hydroxyl group or a hydrogenated product thereof. A specific example is shown below.

I) Polymer Having Hydroxyl Group (Component (c)) ii) 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 represented 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 mentioned. When produced by the above radical polymerization method, it can be easily obtained by polymerizing a diene monomer using, for example, hydrogen peroxide as a polymerization initiator. Further, in the case of producing by the anionic polymerization, according to a known method, a conjugated diene was obtained by polymerizing using 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 the molecular chain, for example, a monoepoxy compound, formaldehyde, acetaldehyde, acetone,
A halogeno alkylene oxide or polyepoxide may be reacted.

Further, the conjugated diene polymer produced by a known polymerization method is osmium tetroxide (OsO ₄ ), vanadium oxide (V ₂ O ₅ ), tungstic acid (H ₂ W)
O ₄ ), selenium dioxide (SeO ₂ ) and the like are reacted with hydrogen peroxide to give a product having a hydroxyl group added to a 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.

Iii) 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.

Among these hydroxyl group-containing polymers, a hydroxyl group-containing diene polymer or a hydrogenated product thereof, a copolymer of an α-olefin and a hydroxyl group-containing unsaturated compound, and a graft polymer of a hydroxyl group-containing unsaturated compound are preferable. , Particularly a diene polymer having a hydroxyl group or a hydrogenated product thereof, a copolymer of ethylene and a hydroxyl group-containing unsaturated compound, and a graft polymer of a hydroxyl group-containing unsaturated compound onto a copolymer resin containing a non-conjugated diene are preferable. . These phosphorus oxyacid-modified polyolefins can be used either individually or as a mixture of plural kinds. Among the phosphorus oxyacid compounds listed above, it is preferable to use polymer compounds higher than low molecular weight 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 triethylamine, tributylamine, triethylenediamine, diethylphenylamine, dibutylphenylamine, N-ethylpiperidine,
Dimethylaminopropylamine, diethylaminopropylamine, tetraguanidine, 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. These materials can be appropriately selected and used from commercially available products.

Polymer Compound Having Tertiary Amine Structure Further, the polymer compound having a tertiary amine structure has at least one tertiary amine structure in its molecule and has a molecular weight of 1,000 or more. It contains up to about 500,000 polymers and may be liquid, semi-solid or solid at room temperature. From the structural point of view, a polymer compound having such a tertiary amine structure means that a tertiary amine structure is present in a branched or linear molecular chain or at the end of the molecular chain, It refers to all those having a structure in which a group having a primary amine structure is pendant.

Specifically, homopolymerization of a tertiary amine structure-containing polymerizable compound obtained by addition polymerization or condensation polymerization, and a copolymer of a tertiary amine structure-containing polymerizable compound and another polymerizable monomer. Alternatively, a graft-modified polymer having a tertiary amine structure at the side chain or the molecular chain terminal can be used. Here, the tertiary amine structure-containing polymerizable compound is a compound having at least one tertiary amine structure and at least one addition-polymerizable unsaturated group or condensation-polymerizable functional group. Refers to the whole. Further, as the other polymerizable monomer that can be copolymerized,
In the case of addition polymerization α-olefins, vinyl aromatics, unsaturated carboxylic acids, nitriles, vinyl ethers, vinyl esters, conjugated dienes, vinyl halides and acrylamides, in the case of condensation polymerization diol compounds, Examples thereof include polyol compounds, dicarboxylic acid compounds, polycarboxylic acid (including acid anhydride) compounds, diamine compounds, diimine compounds, lactams, lactones and formaldehyde. Further, as the trunk polymer in the case of a graft modified polymer, an olefin polymer, a styrene polymer, an acrylic polymer, a diene polymer, polyamides, polyimides, polyesters, polyurethanes, polyethers And polyketones.

Among these polymer compounds having a tertiary amine structure, a copolymer or a graft modified polymer using a polymerizable compound having a tertiary amine structure capable of addition polymerization is preferable. Furthermore, a modified olefin polymer containing a tertiary amine structure, such as a copolymer of an unsaturated compound containing a tertiary amine structure and an α-olefin or a graft modified polymer onto an olefin polymer as a trunk polymer, It is particularly preferable because it is difficult to bleed out when used.

Specifically, the content of the tertiary amino group-containing unsaturated compound is 0.1 to 50% by weight, preferably 0.5 to
45% by weight, particularly preferably 1 to 40% by weight, and the melt flow rate (MFR) measured according to JIS-K6760 is 0.1 to 1,000 g / 1.
It is preferably 0 minutes, particularly preferably 0.5 to 700.
g / 10 minutes.

This tertiary amino group-containing modified olefin polymer is prepared by using a tertiary amino group-containing unsaturated compound,
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 production by the impregnation graft polymerization method, for example, pellets of an olefinic polymer, a tertiary amino group-containing unsaturated compound and a radical polymerization initiator are suspended in an aqueous solvent to prepare a tertiary polymer. It is manufactured by impregnating pellets of an olefinic polymer with an amino group-containing unsaturated compound and an initiator, and then heating to the decomposition temperature of the initiator to cause a graft reaction in the pellets and modification. In the case of production by the kneading and grafting method, for example, an olefin polymer, an elastomer, or a copolymer resin containing the non-conjugated dienes is dry-blended with a tertiary amino group-containing unsaturated compound, if necessary. An organic peroxide is used as a reaction initiator, and the temperature is 80 to 2
It is produced by melt-kneading in an extruder set at 50 ° C.

Examples of such a tertiary amino group-containing unsaturated compound include vinylpyrimidines such as 2-vinylpyrimidine and 4-vinylpyrimidine, and those represented by the following formula.

[0077]

[Chemical 11]

R ²¹ in the above formula is a hydrogen atom or a saturated hydrocarbon having 1 to 4 carbon atoms, preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 2 carbon atoms. X ² is a carbonyl group, an aromatic ring, an aliphatic ring or an alkyl chain having 1 to 12 carbon atoms, preferably a carbonyl group or an aromatic ring,
Particularly preferred is a carbonyl group. R ²² has 1 carbon atom
To a hydrocarbon group, an alkoxyl chain having an oxygen atom on the X ² group side having 1 to 12 carbon atoms, a sulfur atom or —NR ²⁵
R ²⁶ - and is, preferably alkoxylated chain or -NR with oxygen atoms in X ² group side of 1 to 12 carbon atoms ²⁵ R ²⁶ -
And particularly preferably an alkoxyl chain having an oxygen atom on the side of the X ² group having 1 to 6 carbon atoms. R ²³ and R ²⁴ are substituents having an alkyl chain having 1 to 12 carbon atoms, a polyalkylene glycol chain having a glycol unit having 1 to 6 carbon atoms, an aliphatic chain, an aromatic chain structure, and the like, and preferably having carbon atoms. An alkyl group having 1 to 6 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms. Also, here R ²³ ,
R ²⁴ may be the same or different. R ²⁵ is
It is a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a saturated hydrocarbon group having 1 to 4 carbon atoms. R ²⁶ is
It is a hydrocarbon group having 2 to 12 carbon atoms, preferably a hydrocarbon group having 2 to 6 carbon atoms, and particularly preferably 2 to
6 is a saturated hydrocarbon group. n is 0 or 1, preferably 1, m is 0 or 1, preferably 1.

Specific examples of preferable unsaturated compounds containing a tertiary amino group include 2- (dimethylamino) ethyl acrylate, 2- (diethylamino) ethyl acrylate, 2- (dimethylamino) ethyl methacrylate and 2 (dimethylamino) ethyl methacrylate. -(Diethylamino) ethyl methacrylate, 2- [di (t-butyl) amino] ethyl acrylate, 2- [di (t-butyl) amino] ethyl methacrylate, 3- (dimethylamino) -propylacrylamide, and 3- (dimethyl) Amino) -propylmethacrylamide and the like can be mentioned.

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

Further, in producing the modified olefin polymer containing a tertiary amino group, the monomer components copolymerizable with the unsaturated compound containing a tertiary amino group are 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; vinyl ethers such as methyl vinyl ether and 2-chloroethyl vinyl ether. Examples include vinyl halides such as vinyl chloride and vinyl bromide: vinyl esters such as vinyl acetate: acrylamide and the like, and these can be used as a ternary or even a multi-component modified polyolefin. is there.

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 high molecular compound rather than a low molecular compound.

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-based elastomers, block copolymers of styrene-based compounds and conjugated dienes are preferable, and these block copolymers are linear and radial. For example, the general formula is represented by the following formula.

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

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 multiblock copolymer, styrene / isoprene multiblock 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-
Vinyl-2-norbornene, 5-methylene-2-norbornene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like can be mentioned. 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 or organic filler can be used, and the shape thereof is plate-like, spherical or fiber. It may be shaped or irregular.

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 hydroxide such as aluminum hydroxide; Metal acid compound such as alumina and titania; Calcium carbonate; Metal powder such as aluminum and bronze; Wood powder; Carbon black; Fiber such as glass fiber, carbon fiber, aramid fiber and alumina fiber Substances: polymeric 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 component may be used alone or in combination of two or more. Various fillers can be appropriately selected and used from the market.

The components (a), (b), (c), (d) and (e) and the component (f) which compose the resin composition of the present invention.
It is needless to say that the combination of the components described above as the preferable components and the component (g) are 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. Component (a), component (b), component (c), component (d)
In the case of the resin composition comprising 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, and the polymer having a hydroxyl group of component (c) is 0.01 to 400 parts by weight, preferably 0.05 to 250 parts by weight. Parts by weight, particularly preferably 0.1 to 1
20 parts by weight, and the phosphorus oxyacid compound of the component (d) is 0.
01 to 300 parts by weight, preferably 0.05 to 175 parts by weight, particularly preferably 0.1 to 80 parts by weight, and the tertiary amine compound of component (e) are 0 to 200 parts by weight, preferably 0. 05-125 parts by weight, particularly preferably 0.1.
It is 1 to 60 parts by weight.

In the case of a resin composition comprising component (a), component (b), component (c), component (d), component (e) and component (f): 100 parts by weight of olefin resin of component (a) With respect to parts, 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 polymer having a hydroxyl group of (c) is 0.0
1 to 750 parts by weight, preferably 0.05 to 350 parts by weight, particularly preferably 0.1 to 180 parts by weight, component (d)
0.01 to 550 parts by weight, preferably 0.05 to 250 parts by weight, particularly preferably 0.1 to 550 parts by weight.
1 to 120 parts by weight, the tertiary amine compound of component (e) is 0 to 400 parts by weight, preferably 0.05 to 180 parts by weight, particularly preferably 0.1 to 90 parts by weight, and component (f). The elastomer is 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight.

In the case of a resin composition comprising component (a), component (b), component (c), component (d), component (e) and component (g): 100 parts by weight of olefin resin of component (a) With respect to parts, 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 polymer having a hydroxyl group of (c) is 0.0
1 to 500 parts by weight, preferably 0.05 to 350 parts by weight, particularly preferably 0.1 to 180 parts by weight, component (d)
0.01-400 parts by weight, preferably 0.05-240 parts by weight, particularly preferably 0.1.
1 to 120 parts by weight, the tertiary amine compound as the component (e) is 0 to 250 parts by weight, preferably 0.05 to 170 parts by weight, particularly preferably 0.1 to 90 parts by weight, and the component (g). 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.

In the case of a resin composition comprising component (a), component (b), component (c), component (d), component (e), component (f) and component (g): 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 100 parts by weight of the olefin resin. 300 parts by weight, 0.01 to 900 parts by weight, preferably 0.05 to 900 parts by weight of the polymer having a hydroxyl group of component (c).
450 parts by weight, particularly preferably 0.1 to 240 parts by weight,
The phosphorus oxyacid compound as the component (d) is 0.01 to 650.
Parts by weight, preferably 0.05 to 300 parts by weight, particularly preferably 0.1 to 150 parts by weight, the tertiary amine compound of component (e) is 0 to 450 parts by weight, preferably 0.05 to
230 parts by weight, particularly preferably 0.1 to 120 parts by weight,
The elastomer of the component (f) is 1 to 900 parts by weight, preferably 5 to 300 parts by weight, particularly preferably 10 to 200 parts by weight.
The weight part and the filler of the component (g) are 0.1 to 30.
It is 0 part 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 of the component (b) is less than the above range, the reproducibility of the paint, the adhesive, the printing ink, 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 can be obtained. is not.

When the compounding amount of the polymer having a hydroxyl group as the component (c) is less than the above range, the reproducibility of the adhesion of paints, adhesives, printing inks, etc. is poor, or the adhesion strength is weak, which is not preferable. . On the other hand, when the amount exceeds the above range, the amount of the expensive polymer added is large, so that not only the cost of the resin composition is increased, but also the polymer is delaminated or bleeds out, so that the coating composition is
Adhesiveness of adhesives, printing inks, etc. decreases, which is not preferable.

When the blending amount of the phosphorus oxyacid compound as the component (d) is less than the above range, the adhesion strength may become extremely weak depending on the coating material, adhesive, printing ink, etc. to be applied, 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 increases, but also the effect proportional to the added amount of the compound cannot be obtained. In addition, the compound reacts with the polymer having a hydroxyl group of the above component (c) to accelerate gelation,
It is not preferable because the adhesion of paints, adhesives, printing inks, etc. is reduced.

When the compounding amount of the tertiary amine compound as the component (e) is less than the above range, the adhesive strength may be very weak depending on the coating material, adhesive agent, printing ink and the like to be applied, which is preferable. Absent. On the other hand, when 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. Further, the compound causes delamination, bleed-out, and the like, so that the adhesion of paints, adhesives, printing inks, and the like decreases, which is not preferable.

Further, not only the rigidity and impact resistance can be adjusted by blending the elastomer component of the component (f) and / or the filler of the component (g), but also by blending them, It is advantageous because it can obtain strong adhesion of paints, adhesives and printing inks. However, if the component (f) and the component (g) each exceed the above range, the moldability of the resin composition is deteriorated, which is not preferable.

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

The above-mentioned resin composition of the present invention can be molded into a resin molded product by various molding methods. A molded article formed from the resin composition of the present invention is directly as it is, that is, without being subjected to vapor cleaning with a halogen-based organic solvent that may cause environmental damage, and surface modification such as primer coating and plasma treatment. It is possible to apply paints, adhesives and printing inks 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 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. 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 and the like. In order to describe the characteristics of the resin composition of the present invention more specifically, a molded article made of the resin composition, its surface treatment, and a coating method will be described in detail as one application example.

[II] Molded Product A molded product 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, the features of the composition of the present invention can be effectively exhibited even in a molded product injection-molded into a complicated shape.

[III] Surface Treatment of Molded Product A molded product formed from the resin composition of the present invention can be directly coated with a paint as described above, but it is relatively simple as shown below. By applying the surface treatment, it is often possible to obtain stronger adhesion in a wide variety of paints and the like. Surface treatment with halogen-free organic solvent-free cleaning liquids Halogen-free organic solvent-free cleaning liquids are various fluorocarbons widely used today as cleaning solvents.
1-Trichloroethane, perchlorethylene, and all cleaning liquids excluding halogen-based organic solvents such as trichlene. Examples of such a cleaning liquid include a solvent type cleaning liquid, an emulsion type cleaning liquid and an aqueous cleaning liquid.

Specifically, 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 in which a solvent such as kerosene, d-limonene, silicon, or toluene is emulsified and dispersed 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, and 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. Of these cleaning liquids, water-based cleaning liquids and emulsion-type cleaning liquids are preferable, and particularly preferable are
It is an aqueous cleaning solution.

The cleaning method using these cleaning solutions is the surface treatment method referred to herein, and includes the immersion cleaning method, 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 body inevitably in the steps from molding of the resin composition to coating. Is. However, in the molded body 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. A 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 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) in which the molded body is placed in the 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 and hot gases is only required, and a broader range can be obtained without applying a primer coating or surface treatment such as plasma treatment. It is very surprising that stronger paint adhesion can be obtained in various paint types.

[IV] Coating When 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 the surface treatment with a cleaning liquid containing no halogen-based organic solvent or the surface treatment with 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, acrylic paints, epoxy paints, urethane paints and melamine paints are preferable, and acrylic paints, urethane paints and melamine paints are particularly preferable.

[V] Application Example Since the molded product formed from the resin composition of the present invention has good suitability for painting, adhesion and printing as described above, it is suitable for automobile bumpers, mudguards and side moldings. ,
Automotive exterior parts such as wheel caps and spoilers;
Automotive interior parts such as instrument panels, levers, knobs and linings; electric products such as pots, vacuum cleaners, washing machines, refrigerators, lighting equipment, audio equipment; packaging films,
It can be used as a packaging material such as a synthetic paper or 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.

[0118]

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 according to JIS K-7203. MFR : Measured according to ASTM D-1238.

<Surface treatment> No treatment : The molded test piece was not subjected to any treatment,
Painted directly. Alkali treatment : The test piece was immersed in warm water at 60 ° C. for 30 seconds, and then, an alkaline detergent (CL551 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.).
The 5% aqueous solution of 3) 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. 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 of 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. Hot gas treatment : The molded test piece was treated at 80 ° C. for 30 minutes while flowing nitrogen in an oven.

<Coating> One-component organic solvent-based acrylic paint, two-component organic solvent-based urethane paint, one-component organic solvent-based acrylic metallic base paint and two-component organic solvent-based urethane clear paint were used. And painted. Coating method : Each coating material was prepared and spray-coated with an air spray gun so that the coating film thickness was 100 μm. However, for metallic paint, metallic base paint is 15μm, and clear paint is 85μm.
m was sprayed in a wet-on-wet state. Then, 60 minutes at 100 ° C. for the one-component organic solvent-based acrylic paint, 60 minutes at 80 ° C. for the two-component organic solvent-based urethane paint, and 80 ° C. for the one-component organic solvent-based acrylic metallic base paint system. It was baked and dried under the condition of 30 minutes.

<Evaluation of Paint Adhesion> Peel Strength : After treatment for preventing the paint from adhering to the upper half of the test piece, each paint was applied to a coating film thickness of 100 μm and baked and dried. Adhere the cellophane adhesive tape (eg Nichiban width 24mm) on the entire surface of the test piece,
With a width of 1 cm, make a cut in the vertical direction to reach the substrate. The side without the coating film was peeled off 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 44 and Comparative Examples 1 to 11 (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 test piece for measuring three-point bending elastic modulus were injection-molded using the pellet. The ingredients used in Tables 1 and 2 are as follows.

<Olefin Resin: (a) Component> Block PP (1) : Ethylene Content of 4% by Weight, JIS-
Flexural modulus measured according to K7203 is 1400
Propylene / ethylene block copolymer having an 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-K6760.
The low pressure polyethylene (high density polyethylene) having an MFR of 20 g / 10 min.

<Copolymer resin containing non-conjugated dienes:
Component (b)> copolymer (1) 7-methyl-1,6-octadiene content 7.
Propylene-7-methyl-1,6-octadiene random copolymer having 3 wt%, flexural modulus of 6,250 kg / cm ² , and MFR of 3.5 g / 10 min.

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

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

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

<Polymer (c) Component Having Hydroxyl Group > EHM (1) Ethylene-2-hydroxyethyl methacrylate obtained by a high pressure radical polymerization method having a 2-hydroxyethyl methacrylate content of 10% by weight and an MFR of 7 g / 10 min. Copolymer. EHM (2) 2-hydroxyethyl methacrylate content of 10% by weight, methyl acrylate content of 10% by weight, MFR of 13 g / 10 minutes obtained by high pressure radical polymerization method ethylene 2-hydroxyethyl methacrylate methyl acrylate Original copolymer.

PUD Propylene-10-undecen-1-ol copolymer produced as follows (Production method) 100 ml of heptane was placed in a 300 ml glass flask, and then 10-undecen-1-ol was added.
After adding 6.8 g and 34 ml of a heptane solution of diethylaluminum chloride (20% by weight), the temperature was raised to 70 ° C. and the mixture was stirred for 1 hour. Add 250 ml to this solution.
Heptane was added so that In a stainless steel autoclave with an internal volume of 1 liter equipped with a stirrer and temperature controller, 14.4 ml of the previously prepared heptane solution of diethylaluminum chloride and Ti manufactured by Marubeni Solvay
After introducing 0.7 g of Cl ₃ catalyst and adding 110 ml of hydrogen,
Supply so that the propylene pressure is 0.5 kg / cm ² G, and
Polymerization was carried out at 5 ° C for 2 hours.

After completion of the polymerization, 50 ml of butanol was added to the polymerization solution.
And 800 ml of methanol were added, and the mixture was stirred and filtered to collect the resin. The recovered resin was put into a 500 ml glass flask equipped with a stirrer, and isopropanol 2 was added.
80 ml and 20 ml of hydrochloric acid (36%) were added, and the mixture was stirred at 55 ° C for 2 hours. The reaction product obtained was filtered off, washed with isopropanol, and dried under reduced pressure to obtain a copolymer 95.1.
g was obtained. Infrared spectroscopic analysis showed absorption at 3340 cm ^-1 due to the hydroxyl group. The MFR of this resin is 1.7g
It was / 10 minutes, and the content of 10-undecen-1-ol was 2.97 mol% by ¹ H-NMR.

HMEPM 2-Hydroxyethyl Methacrylate Graft-Propylene-Ethylene-7-methyl-1,6-octadiene Copolymer Resin Produced as Follows : (Production Method) Propylene
50 g of an ethylene / 7-methyl-1,6-octadiene copolymer (the above-mentioned copolymer (3)), 40 g of 2-hydroxyethyl methacrylate and 1000 ml of chlorobenzene were added, and the mixture was heated and stirred at 130 ° C. to dissolve. In this solution,
1.5 g of benzoyl peroxide dissolved in 200 ml of chlorobenzene was added dropwise over 2 hours, and the mixture was mixed at 130 ° C for 3 hours.
The reaction was carried out over time. After completion of the reaction, the product was precipitated in acetone, filtered and dried to obtain the desired product. The 2-hydroxyethyl methacrylate content of the obtained polymer is
It was 1.7% by weight.

<Phosphorus oxyacid compound: (d) component> PAMOE: 1: 1 mixture of phosphoric acid mono (2-ethylhexyl) ester and di (2-ethylhexyl) phosphate EPAMOE (1): Polyethylene of the backbone polymer Acid mono (2-methacryloyloxyethyl) ester,
A graft copolymer in which phosphoric acid di (2-metacroyloxyethyl) ester and styrene are grafted, and the sum of phosphoric acid mono (2-metacloyloxyethyl) ester and phosphoric acid di (2-metacloyloxyethyl) ester. A graft copolymer obtained by the impregnation graft polymerization method shown below, which has a physical property value of a content of 12% by weight, a styrene content of 20% by weight, and a number average molecular weight of 11,000.

(EPAMOE by Impregnation Graft Polymerization Method
(Synthesis of (1)) In an autoclave having a capacity of 10 liters, 1080 g of pellets of low molecular weight linear low density polyethylene having a number average molecular weight of 2,500, phosphoric acid mono (2-methacryloyloxyethyl) ester: phosphoric acid di (2- (Methacroyloxyethyl) ester 1: 1 mixture 360 g, styrene 360 g, benzoyl peroxide 6.5 g,
Calcium phosphate [Ca ₃ (PO ₄ ) ₂ ] 2 as a dispersant
1 g was suspended in 4 liters of water. Then, by maintaining the temperature of the suspension at 50 ° C. for 3 hours, the phosphoric acid mono (2-metacroyloxyethyl) ester, phosphoric acid di (2-metacroyloxyethyl) ester, styrene, and benzoylperester are prepared. Oxide was impregnated into the polyethylene pellets. Then, the reaction was performed while gradually raising the temperature to 94 ° C. over 8 hours. After the reaction was completed, the obtained pellets were washed with water, removed of water with a centrifuge, and dried at 80 ° C. for 12 hours to obtain a target graft polymer.

EPAMOE (2): Phosphoric acid mono (2-methacryloyloxyethyl) ester and phosphoric acid di (2)
-Methacryloyloxyethyl) ester total content of 15% by weight, number average molecular weight of 17,000 obtained by a high-pressure radical polymerization method ethylene-phosphoric acid mono (2-methacryloyloxyethyl) ester diphosphate ( 2-methacryloyloxyethyl) ester copolymer.

PAPTE: Phosphoric Acid-Modified Diene Polymer Hydrogenated Product Produced as Follows (Production Method) 100 g of the diene polymer hydrogenated product (2) and 300 ml of dry toluene were placed in an autoclave having a capacity of 1 liter, and nitrogen was added. The temperature was kept at 40 ° C under the atmosphere. A solution prepared by dissolving 16.7 g of phosphorus oxychloride in 50 ml of dry toluene was added dropwise thereto over 20 minutes, followed by stirring for 2 hours. After allowing to cool to room temperature, a mixed solution of 22 g of pyridine, 10 g of water and 30 g of isopropanol was added, and the mixture was further stirred for 2 hours. After completion of the reaction, the product was precipitated in methanol, filtered and dried to obtain the desired product. The phosphorus atom content was 1.5% by weight.

PANPE: 1: 1 mixture of phosphoric acid mono (nonylphenoxyethyl) ester and phosphoric acid di (nonylphenoxyethyl) ester.

<Tertiary amine compound: (e) component> EDMA (1) : 2- (dimethylamino) ethyl methacrylate content of 30% by weight, MFR measured according to JIS-K6760 is 2 g / 10 min. Ethylene 2- (dimethylamino) obtained by the high-pressure radical polymerization method of
Ethyl methacrylate copolymer.

EDMA (2) : A graft copolymer in which 2- (dimethylamino) ethyl methacrylate and styrene are grafted on polyethylene, which is a trunk polymer, has a 2- (dimethylamino) ethyl methacrylate content of 15% by weight and a styrene content of 25% by weight, JIS-K6760
A graft copolymer obtained by the following impregnation graft polymerization method, which shows a physical property value of MFR measured according to 1.

(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, and the polyethylene pellets were impregnated 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 centrifuge.
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 showed g / 10 minutes.

DMAPEM: Propylene of the trunk polymer
A graft polymer obtained by grafting ethylene (7-methyl-1,6-octadiene random copolymer resin) with 2- (dimethylamino) ethyl methacrylate, which has a 2- (dimethylamino) ethyl methacrylate content of 5.2% by weight. %, The MFR measured according to JIS-K6760 is
Graft polymer obtained by the following kneading graft method at 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 are dry blended, and the temperature is 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 MFR, which was 2.2 g / 10 minutes.

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

[0149]

[Chemical 12]

(R ²⁷ , R ²⁸ , R ²⁹ , and R ³⁰ in the formula are as follows.

[0151]

[Chemical 13]

Or —C ₁₃ H ₂₇ , wherein at least one of R ²⁷ , R ²⁸ , R ²⁹ , and R ³⁰ is N-methyl-2,2,2 represented by the above formula [Formula 13]. 6,6
-Tetramethyl-4-piperidyl group, the rest is -C
₁₃ H ₂₇ is shown. )

<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 : A hydrogenated product of a styrene / butadiene block copolymer rubber having a number average molecular weight of 70,000 and a specific gravity of 0.91.

<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.

[0156]

[Table 1]

[0157]

[Table 2]

[0158]

[Table 3]

[0159]

[Table 4]

[0160]

[Table 5]

[0161]

[Table 6]

[0162]

[Table 7]

[0163]

[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 diene polymer having a hydroxyl group and the hydrogenated product thereof (component (c)), or both does not show paint adhesion at all or is extremely low (Comparative Example 1-9). Further, it can be seen that the composition containing the phosphorus oxyacid compound (component (d)) has improved paint adhesion as compared with the composition not containing this (see Example 34 and Comparative Example 10). Furthermore, a phosphorus oxyacid compound and a tertiary amine compound ((e)
It is understood that the paint adhesion is further improved by using the components together (Examples 28 and 29).

[0165]

EFFECT OF THE INVENTION Since the polyolefin resin composition of the present invention is composed of the above-mentioned specific components, a molded article formed from the resin composition is vaporized by a halogen-based organic solvent which may cause environmental damage. It is possible to directly apply paints, adhesives, etc. and print printing inks, etc. without performing cleaning, etc., and without applying surface modification treatment such as primer application or plasma treatment. Adhesiveness, adhesiveness and printability can be obtained. Further, the surface of the molded body formed from the resin composition is further strengthened by 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, etc. are obtained, but also good paint adhesion etc. are obtained for a wider range of paint types and the like.

Further, even if the resin composition of the present invention is further added with additives such as light stabilizers, lubricants, and antioxidants of the resins which are usually used, it is possible to obtain coatings, adhesives and printing inks. Adhesion does not decrease and good adhesion is exhibited.
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 industrially very useful.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display location C08L 53/00 LLY 7142-4J 101/06 LSZ 7242-4J

Claims (4)

[Claims] 1. A component (a), a component (b), a component (c), a component (d) and a component (e) described below, wherein the component (b) is added to 100 parts by weight of the component (a). .1 to 90
0 parts by weight, 0.01 to 400 parts by weight of the component (c), 0.01 to 300 parts by weight of the component (d) and 0 of the component (e).
~ 200 parts by weight of an olefin resin composition. Component (a) : Olefin-based resin component (b) : At least one selected from α-olefins having 2 to 12 carbon atoms and at least one of non-conjugated dienes represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer component having hydroxyl group (d) : Phosphorus oxyacid compound component (e) : Tertiary amine compound 2. A component (a), a component (b), a component (c), a component (d), a component (e) and a component (f) described below, which are added to 100 parts by weight of the component (a). 0.1 to 900 parts by weight of (b) and 0.01 to 750 of component (c)
Parts by weight, 0.01 to 550 parts by weight of component (d), 0 to 400 parts by weight of component (e) and 1 to 90 parts of component (f).
An olefin resin composition containing 0 part by weight. Component (a) : Olefin-based resin component (b) : At least one selected from α-olefins having 2 to 12 carbon atoms and at least one of non-conjugated dienes represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer component having a hydroxyl group (d) : Phosphorus oxyacid compound component (e) : Tertiary amine compound component (f) : Elastomer 3. A component (a), a component (b), a component (c), a component (d), a component (e) and a component (g) described below, which are added to 100 parts by weight of the component (a). 0.1 to 900 parts by weight of (b) and 0.01 to 500 of component (c).
Parts by weight, 0.01 to 400 parts by weight of the component (d), 0 to 250 parts by weight of the component (e) and 0.1 to 100 parts of the component (g).
An olefin 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) : Polymer component having hydroxyl group (d) : Phosphorus oxyacid compound component (e) : Tertiary amine compound component (g) : Filler 4. A component (a), a component (b), a component (c), a component (d), a component (e), a component (f) and a component (g), which are 100 parts by weight of the component (a). 0.1 to 900 parts by weight of the component (b) and 0.0 to the component (c) with respect to the parts.
1-900 parts by weight, component (d) 0.01-650 parts by weight, component (e) 0-450 parts by weight, component (f) 1-
An olefin resin composition containing 900 parts by weight 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 of non-conjugated dienes represented by the following general formula (I) Block and / or random copolymer resin ^{(Wherein, R 1, R 2, R} 3, R 4 and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms and, n is an integer of 1 to 10.) Component (C) : Polymer component having hydroxyl group (d) : Phosphorus oxyacid compound component (e) : Tertiary amine compound component (f) : Elastomer component (g) : Filler