JPH07113027A - Olefin resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition having excellent coating adhesion even on a surface neither washed nor modified with e.g. primer coating and useful for an industrial purpose by compounding an olefin resin mixture having a specific composition with an elastomer at a specific ratio. CONSTITUTION:The composition is obtained by compounding (A) a modified olefin resin mixture consisting of (i) a low-modified olefin resin containing 0.01-1.5wt.% of at least one kind of compound selected from unsaturated carboxylic acids and their derivatives and (ii) a high-modified olefin resin containing 3-20wt.% of the above mentioned compound at the weight ratio [component (i)/component (ii)] of 0.01-1000 and (B) an elastomer, wherein component A and component B are contained in an amount of 1-90wt.% and 99-10wt.% respectively based on the total of component A and component B. Further, 100 pts.wt. of the composition is preferably compounded with (C) 1-1000 pts.wt. of a non-modified olefin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an olefin resin composition suitable for coating a surface. More specifically, the present invention relates to an olefin resin composition that exhibits excellent paint adhesion even without surface cleaning with a halogen organic solvent, primer coating, plasma treatment, or other surface modification.

[0002]

2. Description of the Related Art Conventionally, when coating the surface of a resin molded product, a halogen-based organic solvent has been used before the coating in order to wash and remove dirt, machine oil, etc. adhering to the surface of the molded product. Steam cleaning is being performed. Further, the olefin resin does not have a polar group in its structure, and since the crystallinity is high, the adhesion of the paint is extremely poor and the coating performance is inferior. ,
The surface was modified by plasma treatment or the like to improve the adhesion, and then the coating was applied.

[0003]

However, in such a method, there have been the following problems conventionally. That is, from the viewpoint of environmental protection, it is necessary to pay sufficient attention to the use of the halogen-based organic solvent, and various alternative techniques are being studied under the circumstances where the prohibition of the use is considered. In addition, in the method of applying the primer, there is a drawback in that an expensive primer must be used, and the cost is increased due to the large number of steps, and it is necessary to further exhibit 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 device must be installed, and the cost increase cannot be avoided because it is a batch method.
Further, the surface after the plasma treatment is unstable, and when it comes into contact with a foreign substance, the adhesiveness of the paint is lowered, and therefore the adhesive performance may vary, which makes the handling very inconvenient.

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. Much research has also been done to improve these problems. However,
After all, this target has not yet been fully achieved, and with olefin resins, such primer coating and plasma treatment cannot be omitted, and in many cases, coating is applied after such treatment.

There have been some reports that a resin composition using a modified resin obtained by graft-modifying an olefin resin with an unsaturated carboxylic acid or an anhydride thereof improves the adhesion of a coating material. For example, although there are many reports of graft-modifying an elastomer component, when the elastomer component is graft-modified to an amount within the range where the paint adhesion performance can be exhibited, a gel component is inevitably generated, and when this composition is molded, its molding is performed. There is a problem that the surface of the body is not smooth and the appearance of the finished surface is poor. The same applies when the resin component and the elastomer component are simultaneously graft-modified. Also,
There are many reports of graft-modifying only the resin component, but for example, JP-A-57-76041 and JP-A-4-1548.
No. 50 discloses that a tackifying component is required, and JP-A No. 61-40345 discloses only the modifying effect of one type of polyethylene. Further, the compositions disclosed in JP-A-48-20824, JP-A-58-49736, JP-A-61-89239, JP-A-5-59231, etc., may differ depending on the type of paint. The adhesion is insufficient, and there is still a problem in terms of versatility (see Comparative Examples 5 to 9).

[0006]

[Means for Solving the Problems]

[Summary of the Invention] The present inventors have conducted extensive studies in view of the above problems, and as a result, have obtained the finding that the above problems can be solved by using a specific resin composition. The invention has been completed. That is,
The olefin resin composition of the present invention comprises the following component (A)
And (B), and containing 1 to 90% by weight of the component (A) and 99 to 10% by weight of the component (B) based on the total amount of the components (A) and (B). It is what Component (A): Modified olefin resin mixture in which the following components (a) and (b) coexist at a weight ratio (a) / (b) of 0.01 to 1,000 Component (a): Low concentration modified olefin resin containing 0.01 to 1.5% by weight of at least one compound selected from unsaturated carboxylic acids or derivatives thereof Component (b): at least one selected from unsaturated carboxylic acids or derivatives thereof High-concentration modified olefin resin component (B) containing 3 to 20% by weight of compound : elastomer

[Detailed Description of the Invention] [I] Olefin Resin Composition (1) Constituent Components The olefin resin composition of the present invention basically comprises the following components (A) and (B). It is what is done. (A) Component (A): Modified olefin-based resin The modified olefin-based resin used as the component (A) of the olefin-based resin composition of the present invention includes a low-concentration modified olefin-based resin and a component of the following component (a): It is important that the high-concentration modified olefin-based resin (b) is present and these components coexist.

(A) Component (a): Low-concentration modified olefinic resin At least one compound selected from unsaturated carboxylic acids and derivatives thereof used as the component (a) constituting the component (A) of the present invention is 0. The low concentration modified olefin-based resin (hereinafter simply referred to as "low concentration modified olefin-based resin") containing 0.01 to 1.5% by weight is selected from unsaturated carboxylic acids and derivatives thereof in the olefin-based resin. At least one compound is 0.01 to 1.5% by weight, preferably 0.05 to 1.3% by weight, particularly preferably 0.1.
Graft copolymerized within the range of 1 to 1% by weight. When the graft amount is outside the above range, only the effect of the present invention is extremely low.

The olefin resin used here is an α-olefin represented by ethylene, propylene, butene-1,3-methylbutene-1, pentene-1,4-methylpentene-1, hexene-1 and the like. Examples thereof include a homopolymer, a mutual copolymer of these α-olefins, a copolymer of the above α-olefin and an organic silicon compound, or a graft polymer onto the olefin resin. These polymers have a flexural modulus of 1,000 to 30,0 measured according to JIS-K7203.
00 kg / cm ² , preferably 2,000 to 20,000
0 kg / cm ² , particularly preferably 3,000 to 15,0
It is the one of 00 kg / cm ² . The melt flow rate (MFR) of the polymer is not particularly limited, but the value measured according to ASTM-D1238 is usually 0.001 to 200 g / 10 minutes, preferably 0.01 to
Optimally, it is within the range of 100 g / 10 minutes. Examples of the olefin resin include polyethylene resins such as so-called low-pressure polyethylene, medium-pressure polyethylene, high-pressure polyethylene, and linear low-density polyethylene,
Stereoregular polypropylene, Stereoregular polybutene-
1, stereoregular poly α-, such as stereoregular poly 3-methylbutene-1 and stereoregular poly 4-methylpentene-1
An olefin resin can be mentioned. Among these olefin resins, stereoregular polypropylene (hereinafter simply referred to as “propylene resin”) is preferable because of its versatility, basic physical properties, and easy handling.

As the propylene resin, a propylene homopolymer or a propylene component is 70 mol%.
As described above, the copolymer is a copolymer of propylene and the α-olefin, preferably 80 mol% or more, and has a flexural modulus measured in accordance with JIS-K7203 of 1,000 to 30,000 kg / cm ^2, and preferably 5,000~20,000kg / cm ^2, particularly preferably those of 8,000~15,000kg / cm ^2. The melt flow rate (MFR) of the polymer is not particularly limited, but the value measured according to ASTM-D1238 is usually 0.001 to 50 g / 10.
Min, preferably 0.01 to 10 g / 10 min, is optimum because the effects of the present invention are more effectively exhibited. Among these propylene-based resins, propylene homopolymers and propylene / ethylene copolymers are preferable, and propylene homopolymers and propylene / ethylene random copolymers are particularly preferable. These propylene-based resins can be used alone or as a mixture of a plurality of types of the above-mentioned resins, and usually, they can be appropriately selected and used from commercially available resins.

The unsaturated carboxylic acid or its derivative used here is acrylic acid, methacrylic acid, 3-butenoic acid, crotonic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid, maleic acid. Unsaturated carboxylic acids such as acids, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, or anhydrides and esters, amides, imides, metal salts, etc. of these unsaturated carboxylic acids Can be mentioned. Among these, acrylic acid, methacrylic acid, maleic acid, or their anhydrides are preferable,
Maleic anhydride is particularly preferable in terms of performance and cost.

The method for producing the low-concentration modified olefin resin used as the component (a) of the present invention is not particularly limited. For example, at least one selected from the above-mentioned propylene resin and unsaturated carboxylic acid or its derivative. It is produced by a method of producing a compound by a graft reaction with an organic peroxide in the presence of a suitable solvent or under heating and melting.

[0013] The organic peroxide also can be specific examples of the organic peroxide used in the production, di -t- butyl peroxide, dicumyl peroxide, t- butyl cumyl peroxide, 2,5
Dialkyl peroxides such as dimethyl-2,5-bis (t-butylperoxy) hexane; acetyl peroxide, isobutyryl peroxide, octanoyl peroxide, decanoyl peroxide, lauroyl peroxide, benzoyl peroxide, 2 , 4
-Diacyl peroxides such as dichlorobenzoyl peroxide; t-butyloxyacetate, t-butylperoxybutyrate, t-butylperoxy-2-
Ethyl hexanoate, t-butyl peroxylaurylate, t-butyl peroxybenzoate, di-t-butyl peroxyisophthalate, 2,5-dimethyl-
Peroxyesters such as 2,5-di (benzoylperoxy) hexane, t-butylperoxymaleic acid, t-butylperoxydiisopropyl carbonate, cumylperoxyoctate; 1,1-bis (t
-Butylperoxy) -3,5,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (t-butylperoxy) octane, 2,2-bis (t -Butyl peroxy) butane and the like; and t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5
And hydroperoxides such as dimethyl-2,5-dihydroperoxide. Among these, diacyl peroxides and peroxyesters are preferable, and diacyl peroxides are particularly preferable, from the viewpoint of grafting performance and handling.

The amount of the organic peroxide is 0.01 to 5 parts by weight, preferably 0.05 to 3 parts by weight, particularly preferably 0.1 to 1 part by weight, based on 100 parts by weight of the olefin resin. Used in a range. If the amount is less than the range, the graft modification is not sufficiently performed, and if the amount exceeds the range, the resin tends to be deteriorated.

A monomer copolymerizable with at least one compound selected from the above unsaturated carboxylic acids or derivatives thereof may be used in the low concentration modified olefin resin as long as the characteristics of the present invention are not impaired. It is possible. Specific examples include vinyl aromatic compounds such as styrene, α-methylstyrene and vinyltoluene; nitrile compounds such as acrylonitrile and methacrylonitrile; vinylpyridines such as 2-vinylpyridine and 4-vinylpyridine; methyl vinyl ether, 2- Vinyl ethers such as chloroethyl vinyl ether; vinyl halides such as vinyl chloride and vinyl bromide; halogenated vinyl such as nato; vinyl esters such as vinyl acetate.

(B) Component (b): Highly Concentrated Modified Olefin Resin At least one compound selected from the unsaturated carboxylic acids used as the component (b) constituting the component (A) of the present invention, or a derivative thereof. The high-concentration modified olefin-based resin (hereinafter abbreviated as "high-concentration modified olefin-based resin") containing 3 to 20% by weight is at least one compound selected from unsaturated carboxylic acids and their derivatives in the olefin-based resin. In the range of 3 to 20% by weight, preferably 4 to 15% by weight, particularly preferably 5 to 10% by weight. If the graft amount is outside the above range, the effect of the present invention is very low.

The olefin resin used here may be the same as the above-mentioned component (a), but among these olefin resins, a propylene resin is preferable, and the melt flow (MFR) of the resin is preferable. ) Is ASTM
The value measured according to -D1238 is usually 0.001 to
The range of 50 g / 10 min, preferably 0.01 to 10 g / 10 min is optimal for the effect of the present invention to be exhibited more effectively. Among these propylene-based resins, propylene homopolymers and propylene-ethylene copolymers are preferable, and propylene homopolymers and propylene / ethylene random copolymers are particularly preferable. These propylene-based resins can be used alone or as a mixture of a plurality of types of the above-mentioned resins, and usually, they can be appropriately selected and used from commercially available resins.

Examples of the unsaturated carboxylic acid or its derivative used here include acrylic acid, methacrylic acid, 3-butenoic acid, crotonic acid, pentenoic acid, heptenoic acid, octenoic acid, nonenoic acid, decenoic acid, undecenoic acid and maleic acid. Unsaturated carboxylic acids such as acids, itaconic acid, citraconic acid, tetrahydrophthalic acid, norbornene-5,6-dicarboxylic acid, or anhydrides and esters, amides, imides, metal salts, etc. of these unsaturated carboxylic acids Can be mentioned. Among these, acrylic acid, methacrylic acid, maleic acid, or their anhydrides are preferable,
Maleic anhydride is particularly preferable in terms of performance and cost.

The method for producing the high-concentration modified olefin resin used as the component (b) of the present invention is not particularly limited. For example, at least one selected from the above-mentioned propylene resin and unsaturated carboxylic acid or its derivative. A compound of the above, in the presence of a suitable solvent, or under heating and melting, a method for producing by a graft reaction using an organic peroxide, the above propylene-based resin is thermally decomposed, to the generated molecular terminal It is produced by a method of adding an unsaturated carboxylic acid, or at least one compound selected from an anhydride thereof and a derivative thereof, to a low molecular weight propylene resin having a double bond, using an azo radical initiator.

Specific examples of the organic peroxide used in the production include the same organic peroxides as those mentioned above. It is preferable to use oxides, dialkyl peroxides and peroxyesters, and it is particularly preferable to use dialkyl peroxides and peroxyesters.
Further, specific examples of the azo radical initiator include azobisisobutyronitrile and 2,2′-azobis- (2
-Amidinopropane) dibasic acid, 1,1'-azobis (cyclohexane-1-carbonitrile), 2,2'-
Azobis (2,4-dimethylvaleronitrile), 2,2
′ -Azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like can be mentioned, with preference given to azobisisobutyronitrile and 1,1′-azobis (cyclohexane-1-carbonitrile). The organic peroxide or azo radical initiator is 0.01 to 20 parts by weight, preferably 0.05 to 15 parts by weight, and particularly preferably 0.1 to 100 parts by weight of the propylene resin.
Used in the range of 10 parts by weight. If the amount is less than the range, the graft modification is not sufficiently performed, and if the amount exceeds the range, the resin tends to be deteriorated.

It is also possible to use a monomer copolymerizable with at least one compound selected from the above-mentioned unsaturated carboxylic acids or their derivatives in the high concentration modified olefin resin as long as the characteristics of the present invention are not impaired. Is.
Specific examples thereof include the same as the above-mentioned monomers.

(B) Component (B): Elastomer The elastomer used as the component (B) of the olefin resin composition of the present invention is a polymer exhibiting rubber elasticity at room temperature, and includes natural rubber and synthetic rubber. What is chosen. 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. Is mentioned. These elastomers may be used alone or in combination of two or more. Among these, styrene-based elastomers and olefin-based elastomers, urethane-based elastomers, silicon-based elastomers, and acrylic-based elastomers are preferable, and styrene-based elastomers and olefin-based elastomers are particularly preferable because the surface roughness of the molded body is unlikely to occur. Here is an example:

Styrenic Elastomer Examples of the styrenic elastomer include styrene and α-
An elastomeric random or block copolymer of a styrene compound such as methylstyrene and a conjugated diene such as 1,3-butadiene or isoprene, and a hydrogenated product of these copolymers. Among these styrene elastomers, a block copolymer of a styrene compound and a conjugated diene is preferable, and these block copolymers are linear and radial. For example, the general formula is represented by the following formula. General formula (AB) _{n + 1} , A- (BA) _n , B- (AB)
_{n + 1} , or A ′-[(BA) _n ] _m (in the above formula, A is a polymer block composed of a styrene compound, A ′ is a chemistry bonded to m (BA) n blocks) Seed, B is a conjugated diene polymer block, n is an integer of 1 to 20, m is an integer of 2 or more, A block and A
The ratio of ′ in the whole molecule is 1 to 50% by weight. ) The average molecular weight of these copolymers is 10,000 to 1,000.
50,000, preferably 50,000 to 250,000
Is.

Specific examples of these styrene elastomers are styrene / butadiene random copolymers, styrene / isoprene random copolymers, styrene / butadiene / styrene triblock copolymers, styrene / isoprene / styrene triblock copolymers. , Polystyrene block-terminated styrene-butadiene radial block copolymer, polystyrene block-terminated styrene-isoprene radial block copolymer, styrene-butadiene 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 from the viewpoints of stability and miscibility with olefin resins.

Olefin-based Elastomer The olefin-based elastomer is a copolymer of α-olefins such as ethylene, propylene, butene-1, and hexene-1, a copolymer of these with a non-conjugated diene, or hexene-1. A homopolymer of a higher α-olefin such as
Mooney viscosity ML _{1 + 4} measured at 0 ° C is usually 1-40
0, preferably 5 to 200, particularly preferably 7 to 100
It is in the range of. Among these olefin elastomers, ethylene elastomers are particularly preferable in terms of basic performance and miscibility with olefin resins. Specifically, ethylene / propylene copolymer rubber (EPM), ethylene / butene-1 copolymer rubber, ethylene / propylene /
Butene-1 copolymer rubber, ethylene / propylene / non-conjugated diene copolymer rubber (EPDM), ethylene / butene-1
-Non-conjugated diene copolymer rubber, ethylene-propylene-butene-1, non-conjugated diene copolymer rubber and the like are available. As specific examples of the non-conjugated diene, dicyclopentadiene, 1,4-hexadiene, cyclooctadiene, dicyclooctadiene, methylenenorbornene, 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.

(C) Component (C): Unmodified olefin resin In the present invention, an unmodified olefin resin may be added to the above components (A) and (B). The unmodified olefin resin used here may be the same as the olefin resin used in the component (a), but among these olefin resins, a propylene resin is preferable, and The melt flow rate (MFR) is usually 0.01 to 200 g / 10 as a value measured according to ASTM-D1238.
Optimally, it is in the range of minutes, preferably 0.1 to 100 g / 10 minutes. Further, among these unmodified propylene-based resins, a copolymer of propylene and another α-olefin is preferable in order to effectively obtain the effect of the present invention.
A copolymer with ethylene is particularly preferable. The copolymer may be a random copolymer or a block copolymer, but a block copolymer is particularly preferable. In addition, the combination of the components (a) and (b) of the component (A) constituting the olefin resin composition of the present invention with the component (B), or the component (C) optionally added thereto is preferable. As a matter of course, it goes without saying that the combination of the above components is optimal.

(D) Component (D): Additional component In addition to the component (A), the component (B), or the component (C) optionally mixed, the olefin resin composition of the present invention contains To the extent that the effects of the invention are not significantly impaired,
The following additional components may be added. Examples of the additional component include fillers. The fillers are convenient because the rigidity and dimensional stability can be adjusted.

[0028] Filler Here filler, any inorganic or organic fillers can be used, its shape, plate shape, spherical, those fibrous, or may be of irregular. Specifically, natural silica such as quartz, synthetic silica produced by a wet method or a dry method, kaolin, mica, talc, natural silicate such as asbestos, calcium silicate, synthetic silicate such as aluminum silicate, magnesium hydroxide, Metal hydroxide such as aluminum hydroxide, metal oxide such as alumina and titania,
Metal powder such as calcium carbonate, aluminum, bronze,
Wood powder, carbon black, glass fibers, carbon fibers, aramid fibers, fibrous substances such as alumina fibers, 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,
Examples include whiskers such as sapphire whiskers and beryllia whiskers. Among these, preferred are mica, talc, calcium carbonate, potassium titanate whiskers, magnesium sulfate whiskers, aluminum borate whiskers, calcium carbonate whiskers and glass fibers, and mica, talc, potassium titanate whiskers, sulfuric acid. Magnesium whiskers are particularly preferable in terms of surface smoothness of molded articles and adjustment of physical properties. These fillers may be surface-treated with a surfactant, a coupling agent or the like. The fillers may be used alone or in combination of two or more. Various fillers can be appropriately selected and used from the market.

Other additional components include, for example, additives. Specific examples thereof include plasticizers such as paraffin oil and petroleum resin, fluidity improvers, and olefin liquid rubbers. , Softening agents such as conjugated diene liquid rubber, coloring agents, antioxidants, neutralizing agents,
Light stabilizers, ultraviolet absorbers, antistatic agents, lubricants,
Examples thereof include dispersion aids, molecular weight modifiers, crosslinking agents, nucleating agents, flame retardants and the like.

(2) Amount Ratio The proportions of the above components constituting the olefin resin composition of the present invention are as follows. Component (A): Modified olefin-based resin The modified olefin-based resin is 1 to 90% by weight, preferably 5 to 85% by weight, particularly preferably 20 to 80% by weight, based on the total amount of the elastomer of the component (B). is there. Also,
The mixing ratio of the component (a) and the component (b) in the component (A) is 0.01 to 1,00 in terms of weight ratio ((a) / (b)).
0, preferably 0.1-100, particularly preferably 0.5
The range is from -50.

Component (B): Elastomer 99 to 10% by weight, preferably 95, of elastomer component based on the total amount of the modified olefin resin of component (A).
˜15% by weight, particularly preferably 80 to 20% by weight.

Alternatively, as the case may be, the component (C): an unmodified olefin resin is an unmodified olefin resin, which is the above-mentioned component (A) and component (B).
1 to 1,000 parts by weight, preferably 5 to 500 parts by weight, and particularly preferably 10 to 200 parts by weight per 100 parts by weight.
Parts by weight can be added. Furthermore, the total content of at least one compound selected from unsaturated carboxylic acids or derivatives thereof in the olefin resin composition when these components are blended in the above amount ratio is usually 0.1 to 2% by weight. %,
It is preferably 0.3 to 1.5% by weight, particularly preferably 0.1.
The olefin resin composition is preferably in the range of 5 to 1% by weight.

When the amount of the modified olefin resin as the component (A) is less than the above range, the adhesive strength of the paint is lowered. On the other hand, even if the amount exceeds the above range, the effect proportional to the added amount of the modified olefin resin is not obtained, and the adhesive strength of the coating is rather lowered. Further, when the range of the mixing ratio of the component (a) and the component (b) in the component (A) exceeds the above range or is less than the above range, the coating performance, which is an effect of the present invention, is extremely low. I can only get things. When the content of the elastomer component (B) is less than the above range, the adhesive strength of the coating composition is lowered. On the other hand, even if the amount exceeds the above range, the adhesive strength of the coating composition and the physical properties of the composition are degraded.
It is convenient to further add the unmodified olefin resin as the component (C) because the physical properties and moldability of the composition can be adjusted. However, if it exceeds the above range, the adhesive strength of the coating material will be reduced. Further, when the total content of at least one compound selected from unsaturated carboxylic acids or derivatives thereof in the olefin resin composition is less than the above range, the adhesive strength of the coating tends to be low. on the other hand,
If it exceeds the above range, the physical properties of the composition tend to be deteriorated, and the moldability, surface appearance and the like tend to be deteriorated.

(3) Composition (Production of Olefin Resin Composition) The olefin resin composition of the present invention is produced by mixing and kneading the above-mentioned respective components. The order of mixing these respective constituents is not particularly limited, and a method of simultaneously mixing the above constituents, any two or several components are mixed and kneaded in advance, and then the remaining components are mixed and mixed.
Any method such as a kneading method may be adopted. mixture·
As a kneading method, a conventionally known kneader such as a Brabender plastograph, a single or twin screw extruder, a strong screw type kneader, a Banbury mixer, a kneader and a roll can also be used.

[II] Molded Product In order to manufacture a molded product using the olefin resin composition of the present invention, injection molding, compression molding, vacuum molding, extrusion molding (sheet molding, blow molding, film molding), etc. Any known molding method can be applied. In particular, the characteristics of the olefin resin composition of the present invention can be effectively exhibited even in a molded article that is injection molded into a complicated shape. A molded product molded from the olefin resin composition of the present invention is directly used, that is, it is necessary to pay sufficient attention in use from the viewpoint of environmental protection, or a halogen-based organic compound whose use is partially prohibited. Coating can be performed without performing vapor cleaning with a solvent and without surface modification treatment such as primer coating and plasma treatment, and has a characteristic that good coating adhesion can be obtained. However, for the purpose of cleaning and removing hand dust and machine oil adhered to the surface of the molded product inevitably in the process from molding of the olefin resin composition to coating, cleaning with a cleaning liquid that does not contain a halogen-based organic solvent is a problem. There is no. Examples of cleaning liquids that do not contain these halogen-based organic solvents include:
A solvent type cleaning liquid, an emulsion type cleaning liquid, and an aqueous cleaning liquid can be mentioned.

Specifically, solvent-type cleaning liquids include kerosene, aliphatic hydrocarbons such as d-limonene, aromatic hydrocarbons such as toluene and xylene, methanol, ethanol,
Alcohols such as isopropyl alcohol can be mentioned. As an emulsion type cleaning liquid, kerosene,
Examples thereof include those obtained by emulsifying and dispersing a solvent such as d-limonene, silicon, or toluene in water with a surfactant. As the aqueous cleaning solution, an alkaline cleaning solution in which an alkaline component such as sodium hydroxide, potassium hydroxide, sodium silicate, and sodium carbonate is used in combination with a surfactant, an acidic cleaning solution in which an acid component such as phosphoric acid is used in combination with a surfactant, and a nonionic Examples thereof include a neutral cleaning liquid using a type surfactant and the like, pure water, water such as warm water, and the like.

[III] Coating When coating a molded article molded from the olefin resin composition of the present invention, a surface modification step such as primer coating or plasma treatment may be omitted from the conventional coating step. it can. That is, the coating composition can be directly applied directly to the molded body obtained by molding the resin composition. As a coating means, there are spray coating, spray coating, roller coating and the like, but any method can be adopted. As the paint that can be used in the painting step, generally used organic solvent-based paints and water-based paints such as water-soluble resin paints, water-dispersible resin paints and water-based emulsion paints can be used. Specific examples thereof include paints in which these resin components or cross-linking components are acrylic, epoxy, polyester, alkyd, urethane, melamine, and the like. Among these, acrylic paints, urethane paints and melamine paints are preferable as paints that effectively exhibit the effects of the present invention, and melamine paints are particularly preferable.

[IV] Application Example Since the molded article molded from the olefin resin composition of the present invention has good paint adhesion as described above,
Used as electric parts for pots, vacuum cleaners, washing machines, refrigerators, lighting fixtures, audio equipment, packaging materials such as packaging films, synthetic papers and laminated films, or various daily goods such as color boxes and storage cases. can do.

[0039]

EXAMPLES The present invention will be specifically described with reference to Examples and Comparative Examples below. The molding conditions, the coating method, and the test method for obtaining the test pieces for measurement from the compositions manufactured in the examples and comparative examples are as follows.
In these examples and comparative examples, the characteristics of the olefin resin composition of the present invention are shown by the coating performance of the molded product. The parts in the examples are parts by weight. (1) Molding conditions Molding machine: Toshiba Machine, IS170 injection molding machine Molding temperature: 230 ° C Molded product: Flat plate (100 mm x 100 mm x 3 mm) MFR: Measured in accordance with ASTM-D1238.

(2) Coating Coating was carried out using a one-pack type organic solvent-based melamine cross-linking coating. (a) Coating Method A coating material was prepared and spray-coated using an air spray gun so that the coating film thickness was 30 μm. Then 14
It was baked and dried at a temperature of 0 ° C. for 20 minutes. (b) Paint Adhesion Evaluation Cross-cut test: Using a single-edged razor, 11 parallel and 11 vertical and horizontal lines running perpendicular to the surface of the test piece are drawn at 2 mm intervals to make 100 cross-cuts. On top of that, cellophane tape (JIS-Z1
522) was sufficiently pressure-bonded, kept at about 30 degrees from the coating surface, and peeled off at once in front, the state of the part surrounded by the grids was observed, and the number of grids that did not peel was recorded.

Examples 1 to 22 and Comparative Examples 1 to 10 (1) Manufacture of Resin Molded Body Each component shown in the following Table 1, Table 2, Table 3 and Table 4 was blended and the mixture was mixed by a twin-screw extruder. Pellets were obtained by melting and kneading at a temperature of 200 ° C. A flat plate test piece was injection-molded using this pellet. The results are shown in Table 1, Table 2, Table 3 and Table 4.
Shown in. In addition, the compounding components of the raw materials in Table 1, Table 2, Table 3 and Table 4 are as follows.

(A) Modified olefin-based resin: Component (A) (a) Low-concentration modified olefin resin: Component (a) LMPP (1) Maleic anhydride content of 0.
Maleic acid graft polypropylene having 7% by weight and MFR of 40 g / 10 minutes. (Manufacturing method) 5 kg of a propylene homopolymer having a flexural modulus of 11,600 kg / cm ² and an MFR of 1 g / 10 min.
Maleic anhydride 40g, benzoyl peroxide 4
Dry blend 0 g, set temperature 160-200 ℃,
Melt kneading was carried out in a twin-screw extruder set at a rotation speed of 300 rpm and a discharge rate of 10 kg / hr. The maleic acid content of the obtained product was 0.7% by weight. LMPP (2) 20 g of maleic anhydride was prepared in the same manner as in the above production method.
20 g of benzoyl peroxide and the charged amount were changed, and it manufactured. Maleic anhydride content 0.3% by weight, MFR
16 g / 10 min maleic anhydride grafted polypropylene. LMPP (3) By the same method as the above manufacturing method, a propylene-based resin containing 4% by weight of ethylene and a flexural modulus of 8,000 kg / cm.
² , and a maleic anhydride content of 0.8 produced by changing to random polypropylene having an MFR of 0.6 g / 10 min.
Maleic acid-grafted random polypropylene having 5% by weight and MFR of 25 g / 10 minutes.

(B) Highly modified olefin resin: Component (b) HMPP (1) Maleic anhydride-grafted polypropylene having a maleic anhydride content of 7% by weight, produced as follows. (Manufacturing method) Bending elastic modulus is 11,600 kg / cm ² and MFR is 1 g in an autoclave having a capacity of 1 liter.
/ 10 minutes propylene homopolymer 100 g xylene 3
50g, melt at 130 ° C. Maleic anhydride 8 there
The reaction was carried out while dropping a solution of 6.4 g of g, t-butylcumyl peroxide in 50 g of xylene for 2 hours. After the reaction was completed, the reaction mixture was allowed to cool, 200 g of acetone was added to the system to precipitate a product, which was filtered and dried to obtain 10
6 g were obtained. The maleic acid content of the obtained product was 7% by weight. MFR was too high to measure. HMPP (2) A maleic acid graft polypropylene having a maleic anhydride content of 5% by weight and an MFR of 900 g / 10 minutes, produced as described below. (Manufacturing method) 5 kg of a propylene homopolymer having a flexural modulus of 11,600 kg / cm ² and an MFR of 1 g / 10 min.
350g of maleic anhydride and 100g of t-butylperoxybenzoate are dry blended to a set temperature of 160
~ 200 ° C, rotation speed 300 rpm, discharge rate 10 kg / h
Melt kneading was carried out in a twin-screw extruder set to r. The maleic acid content of the obtained product was 5% by weight. HMPP (3) Maleic anhydride-grafted polypropylene having a maleic anhydride content of 8% by weight, produced as follows. (Manufacturing method) 5 kg of a propylene homopolymer having a flexural modulus of 11,600 kg / cm ² and an MFR of 1 g / 10 min.
At a set temperature of 300 to 350 ° C., a rotation speed of 300 rpm,
Pyrolysis was performed in a twin-screw extruder set to a discharge rate of 3 kg / hr. 4 kg of the obtained thermally decomposable organism was allowed to cool and pulverized, and then 350 g of maleic anhydride and 55 g of 1,1-azobis (cyclohexane-1-carbonitrile) were dry-blended, and the set temperature was 160 to 200 ° C. and the rotation speed was 300 rpm,
Melt kneading was performed in a twin-screw extruder set to a discharge rate of 5 kg / hr. The maleic acid content of the obtained product was 8% by weight. In addition, MFR was too high to measure.

(C) Medium-Concentration Modified Olefin Resin: MMPP for Comparative Example A maleic acid-grafted polypropylene having a maleic anhydride content of 2% by weight and an MFR of 600 g / 10 minutes, produced as follows. (Manufacturing method) 5 kg of a propylene homopolymer having a flexural modulus of 11,600 kg / cm ² and an MFR of 1 g / 10 min.
120 g of maleic anhydride and 40 g of t-butylperoxybenzoate are dry blended to a set temperature of 160-
200 ° C, rotation speed 300 rpm, discharge rate 10 kg / hr
Melt kneading was carried out in a twin-screw extruder set to. The maleic acid content of the obtained product was 2% by weight.

(B) Elastomer: Component (B) Ethylene having EPM Mooney viscosity L _{1 + 4} (100 ° C.) of 44, propylene content of 27% by weight and specific gravity of 0.86
Propylene copolymer rubber. EPDM Mooney viscosity L _{1 + 4} (100 ° C.) 88, propylene content 28% by weight and ethylidene norbornene content 11
Ethylene / propylene / ethylidene norbornene copolymer rubber having a weight percentage of 0.86. A hydrogenated product of a styrene / butadiene block copolymer rubber having an SEBS number average molecular weight of 53,000, a styrene content of 20% by weight, and a specific gravity of 0.91.

(C) Unmodified olefin resin: Component (C) BPP (1) Ethylene content 4% by weight, flexural modulus 14,000 k
Block polypropylene having g / cm ² and MFR of 60 g / 10 minutes. BPP (2) ethylene content is 8.2% by weight, flexural modulus is 10,000
Block polypropylene with 0 kg / cm ² and MFR of 33 g / 10 minutes. RPP ethylene content 3.4% by weight, flexural modulus 10,50
Random polypropylene having 0 kg / cm ² and MFR of 15 g / 10 minutes.

(D) Filler: Component (D) (additional component) Talc specific surface area is 39,000 cm ² / g and average particle size is 1.
Talc of 8 to 2.2 μm. Potassium titanate whiskers having an average particle size of mica of 0.2 to 0.5 μm and an average aspect ratio of 20 or more [K ₂ O.6
TiO]

(2) Coating of resin molded body Directly on the flat plate manufactured by the above-mentioned resin molded body,
The paint was applied using an air gun. After baking and drying,
It was left at room temperature for 48 hours and a cross-cut test was conducted. The weight ratio (a) / (b) of the low concentration modified olefin resin (component (a)) and the high concentration modified olefin resin (component (b)) in the modified olefin resin (component (A)) used. The results of the total maleic acid content of the obtained resin composition and the paint adhesion of the molded product are shown in Table 1, Table 2, Table 3 and Table 4.

[0049]

[Table 1]

[0050]

[Table 2]

[0051]

[Table 3]

[0052]

[Table 4]

According to the paint adhesion data shown in Tables 1, 2, 3 and 4, the low concentration modified olefin resin (component (a)) and the high concentration modified olefin resin (component (b It can be seen that the compositions which do not contain both) or one of them do not show paint adhesion at all or are extremely low (see Comparative Examples 4 to 7). For comparison, a study was conducted using only a medium-concentration modified olefin resin (maleic anhydride modified, graft amount 2% by weight).
The paint adhesion was very low (see Comparative Examples 8 and 9). Furthermore, although a low concentration modified olefin resin and a maleic anhydride monomer were used in combination, the combined use of maleic anhydride further reduced the paint adhesion (see Comparative Examples 5 and 10). On the other hand, a system using a modified olefin resin, which is a combination of a low-concentration modified olefin resin and a high-concentration modified olefin resin, which is composed of the olefin resin composition of the present invention, exhibits excellent paint adhesion. The fact was quite surprising (see Examples 1-22).

[0054]

Since the olefin resin composition of the present invention is composed of the above-mentioned specific components, a molded article molded from the resin composition must be used with sufficient care from the viewpoint of environmental protection. Yes, or direct coating is possible without vapor cleaning with a halogen-based organic solvent whose use is partially prohibited, or without primer coating or surface treatment such as plasma treatment. And good paint adhesion is obtained. Therefore, overturning the conventional wisdom that it is impossible to directly coat an olefin resin, a molded article molded from the olefin resin composition of the present invention is subjected to surface treatment such as primer coating and plasma treatment. Even if a paint is applied without applying it in advance, good paint adhesion is exhibited, which is extremely useful industrially.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Izumi Ishii 1 Toho-cho, Yokkaichi-shi, Mie Prefecture Yokkaichi Research Institute Ltd. (72) Inventor Yuichi Shimizu 1 Toho-cho, Yokkaichi-shi, Mie Mitsubishi Yuka Co., Ltd. Yokkaichi Research Institute

Claims (2)

[Claims] 1. A composition comprising the following components (A) and (B), wherein the component (A) is 1 to 90% by weight and the component (B) is based on the total amount of the component (A) and the component (B). An olefin resin composition comprising 99 to 10% by weight. Component (A): Modified olefin resin mixture in which the following components (a) and (b) coexist at a weight ratio (a) / (b) of 0.01 to 1,000 Component (a): Low concentration modified olefin resin containing 0.01 to 1.5% by weight of at least one compound selected from unsaturated carboxylic acids or derivatives thereof Component (b): at least one selected from unsaturated carboxylic acids or derivatives thereof High-concentration modified olefin resin component (B) containing 3 to 20% by weight of compound : elastomer 2. An olefin resin composition comprising 100 parts by weight of the composition of claim 1 and 1 to 1,000 parts by weight of the following component (C). Component (C): Unmodified olefin resin