JP2002128970A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition excellent in mechanical characteristics, and thermal fusibility with various resins, causing no bleed of a softening agent, and, therefore, capable of easily controlling the flexibility of its molding, and a laminated molding containing a layer therefrom. SOLUTION: This thermoplastic composition contains 100 pts.wt. polypropylene and/or its copolymer (a), 5-350 pts.wt. polyethylene and/or its copolymer (b) polymerized with a single site catalyst, 10-200 pts.wt. (co-)polymer (c) of 0-95 pts.wt. ethylenic ionomer resin (c-1) and/or ethylene (c-2) and 100-5 pts.wt. monomer (c-3) represented by formula (I): CH2=C(R1)-COOR2 (wherein R1 represents a hydrogen or a methyl group, and R2 represents hydrogen or a 1-10C alkyl group), 0-200 pts.wt. polyethylene and/or its copolymer (d), 0-400 pts.wt. block copolymer (e), and 0-500 pts.wt. non-aromatic softening agent (f) for rubber.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, and more particularly to a thermoplastic resin composition useful for composite molded articles, for example, automobile molding.

[0002]

2. Description of the Related Art Conventionally, composite molding (for example, two-color molding) of different resins has been performed in automobile members, building members, and weak electric appliances. For automotive parts, for example, window frames and lamp packing for automobiles, for building parts, for example, sash frames, for light electrical products, for example, push molding of telephones, radios, TV remote controllers, VTR remote controllers, etc. (2)
Color molding).

In order to obtain a composite molded product of different resins, it is common to bond the molded products separately molded for each resin with an adhesive, or to mold and fit both resins with irregularities. is there.

[0004] However, the method using an adhesive has increased the cost due to the complexity of the step of applying the adhesive and required skill for applying the adhesive effectively. In addition, the method of providing the fitting portion has a drawback that the cost is increased due to the complexity of the mold, and the fitting process deteriorates the workability.

Therefore, Japanese Patent Application Laid-Open Nos. 61-213145, 63-115711, and 1-139240 are disclosed.
JP-A-1-139241 and JP-A-2-1392
As described in Japanese Patent Publication No. 32, it has been proposed that a specific resin is used and a molded article is composited by heat fusion. However, it has been difficult to control the flexibility of a molded article with any of the compositions described in these publications. Oil is usually added for the purpose of making it easier to control the flexibility of the molded article. However, when oil is added to the above-mentioned conventional composition, a phenomenon in which the oil bleeds from the surface of the obtained molded article or the interface between individual resins is observed. Therefore, there has been a problem that the adhesive strength between the respective resins is reduced, and thus peeling occurs when the molded article is used for a long time.

[0006] In addition, various types of moldings for automobiles, such as wind moldings, roof moldings, protector moldings, weather moldings, strip moldings, and the like, which are one of the composite molded products, are such that the portions exposed on the outer surface are tough and scratch-resistant. It is required to have excellent adhesion, weather resistance and chemical resistance. In recent years, olefin-based resins, styrene-based resins, and the like have been used for these automobile moldings. However, since these have a very large bending restoring force, it is very difficult to bend the molded product and mount it on an automobile, and since the skin layer is easily damaged, there is a problem that a clean gloss cannot be obtained. Was.

Japanese Utility Model Laid-Open No. 5-32152 and Japanese Utility Model Laid-Open No.
As described in JP-A-26217, a hard olefin polymer such as an ionomer, an ethylene-acrylic acid copolymer, an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid ester copolymer, an ethylene -The use of a methacrylate copolymer or the like has an effect on scratch resistance, weather resistance, and chemical resistance. However, when a thermoplastic elastomer composition having a small bending restoring force is used as a base material, there is a problem that the thermoplastic elastomer composition peels off without being adhered to a skin layer made of a hard olefin polymer.

Further, it is desired that these thermoplastic elastomer compositions have good heat-fusibility with various resins in various composite molded articles. Conventionally, a polyolefin-based thermoplastic elastomer (TPO) can be heat-fused to a polyolefin resin of the same series, but an ethylene-acrylic acid-based copolymer having a polar group, an ethylene-methacrylic acid-based copolymer and It is difficult to heat-bond to an ionomer resin or the like, which has been an obstacle to expanding its use. In particular, when using TPO as a core material in an automobile molding member or the like,
Only a polyolefin-based resin can be used as the skin, and there is a problem that the resin is limited.

[0009]

DISCLOSURE OF THE INVENTION The present invention has excellent mechanical properties, is excellent in heat-sealing properties with various resins, and has no bleeding of a softening agent. To provide a resin composition capable of easily controlling the flexibility of the resin composition, and a laminated molded article including a layer composed of the resin composition.

[0010]

Means for Solving the Problems The present inventors have conducted various studies in order to solve the above problems. As a result, they have found that if the components (a) to (f) are blended in the following predetermined amounts, all of the above problems can be solved.

That is, the present invention relates to (1) (a) polypropylene and / or a copolymer mainly composed of propylene.
0 parts by weight, (b) polymerized with a single-site catalyst,
5 to 350 parts by weight of a copolymer mainly composed of polyethylene and / or ethylene, (c) (c-1) an ethylene ionomer resin, and / or (c-2) ethylene 0 to 95
% By weight and the following formula (I)

Embedded image CH ₂ ＣC (R ¹ ) —COOR ² (I) (wherein R ¹ represents hydrogen or a methyl group, and R ² represents hydrogen or an alkyl group having 1 to 10 carbon atoms). 5 to 200 parts by weight of a (co) polymer with 100 to 5% by weight of the indicated monomer, (d) a copolymer mainly composed of polyethylene and / or ethylene (excluding those polymerized with a single-site catalyst) A block copolymer consisting of 0 to 200 parts by weight, (e) at least two polymer blocks A mainly made of an aromatic vinyl compound, and at least one polymer block B mainly made of a conjugated diene compound, and And / or (f) a thermoplastic resin composition containing 0 to 400 parts by weight of a block copolymer obtained by hydrogenating the same and (f) 0 to 500 parts by weight of a softening agent for non-aromatic rubber.

As a preferred embodiment, (2) the thermoplastic resin according to the above (1), which contains 10 to 250 parts by weight of polyethylene and / or a copolymer (b) mainly composed of ethylene, which is polymerized by a single-site catalyst. The composition, (3) the thermoplastic resin composition according to the above (1), which contains 10 to 200 parts by weight of a copolymer (b) mainly composed of polyethylene and / or ethylene, which is polymerized by a single-site catalyst, 4)
The heat according to any one of the above (1) to (3), wherein the copolymer (b) mainly composed of polyethylene and / or ethylene polymerized by a single-site catalyst is an ethylene-octene copolymer. The thermoplastic resin composition according to any one of the above (1) to (4), which contains 10 to 180 parts by weight of the thermoplastic resin composition, (5) component (c-1) and / or (c-2). (6) any one of the above (1) to (5), which contains 10 to 150 parts by weight of polyethylene and / or a copolymer mainly composed of ethylene (excluding those polymerized by a single-site catalyst) (d). (7) A thermoplastic resin composition comprising (7) at least two polymer blocks A mainly made of an aromatic vinyl compound and at least one polymer block B mainly made of a conjugated diene compound. Click copolymers, and / or, 30 the block copolymer obtained by hydrogenating the (e) which
The thermoplastic resin composition according to any one of the above (1) to (6) containing 350 parts by weight, and (8) the softening agent for non-aromatic rubber (f) containing 40 to 200 parts by weight of the above (1). ) ~
(7) the thermoplastic resin composition according to any one of the above,
(9) A laminated molded article including a layer comprising the thermoplastic resin composition according to any one of (1) to (8), (10)
The thermoplastic resin composition according to any one of the above (1) to (8), an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, an ethylene / acrylic acid ester copolymer, and an ethylene / acrylic acid copolymer. Polar resin consisting of methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer and ionomer resin, and non-polar resin consisting of non-polar polyolefin resin and non-polar polystyrene resin A molded article obtained by laminating one or more members selected from the group consisting of
(11) Non-polar polyolefin resin is polypropylene, propylene / α-olefin copolymer, polyethylene, ethylene / α-olefin copolymer rubber, polybutene, polyisobutylene, polybutadiene (BR), poly-4-methylpentene (1) The molded article according to the above (10) comprising a resin and an olefin-based thermoplastic elastomer, and (12) the non-polar polystyrene-based resin comprising a polystyrene, a styrene-based copolymer rubber, and a styrene-based thermoplastic elastomer. 10) The molded article described in (1)
3) Styrenic copolymer rubber is SBR, SBS, SI
(14) The molded article according to the above (12), comprising S, SIBS, SEBS, SEBS and SEEPS.
(8) A molded product in which the thermoplastic resin composition according to any one of (1) and (2) is a core material, and a polar resin is laminated on a skin and a non-polar resin is laminated on a lip. (15) The polar resin is an ethylene-acrylic acid copolymer. , Ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer, ethylene / methacrylic acid ester copolymer, ethylene / vinyl acetate copolymer,
The molded article according to the above (14), wherein the molded article is selected from the group consisting of a saponified ethylene / vinyl acetate copolymer and an ionomer resin, and the nonpolar resin is selected from the group consisting of a nonpolar polyolefin resin and a nonpolar polystyrene resin. , (1
6) The molded article according to the above (14), wherein the polar resin is an ionomer resin and the nonpolar resin is a polyolefin-based thermoplastic elastomer and / or a styrene-based thermoplastic elastomer; The molded article according to any one of) to (16),
(18) The molded article according to the above (17), wherein the molding for an automobile is wind molding, roof molding, protector molding, weather molding or strip molding.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The components constituting the thermoplastic resin composition of the present invention are as follows.

Component (a): essential component

Examples of the copolymer mainly composed of polypropylene and / or propylene include propylene homopolymer,
Copolymer of propylene and ethylene, propylene and α-
Examples thereof include a copolymer with an olefin or a copolymer of propylene with ethylene and an α-olefin.
The α-olefin in the copolymer has 4 carbon atoms.
~ 8 are preferred. For example, butene-1, hexene-1, 4-methyl-1-pentene, octene-1 and the like can be mentioned. At least one kind of α-olefin selected from these is copolymerized.

The copolymer of propylene and ethylene, the copolymer of propylene and α-olefin, and the copolymer of propylene with ethylene and α-olefin may be any of random or block copolymers. Good. Preferably, it is a random copolymer.

In the above copolymer, the ethylene content is preferably 50% by weight or less, more preferably 0 to 50% by weight.
It is 15% by weight, more preferably 1 to 13% by weight, particularly preferably 2 to 10% by weight. Here, the ethylene content can be determined by an infrared spectrum analysis method or the like. The α-olefin content is preferably 0 to 40% by weight, more preferably 1 to 40% by weight.

Component (b): essential component

Examples of the copolymer mainly composed of polyethylene and / or ethylene polymerized with a single-site catalyst include high-density polyethylene (low-pressure polyethylene) polymerized with a single-site catalyst (metallocene catalyst).
Low-density polyethylene (high-pressure polyethylene), linear low-density polyethylene (ethylene and a small amount, preferably 1 to
10 mol% butene-1, hexene-1, octene-1
One or two or more selected from polyethylene, ethylene-propylene copolymer, and the like are preferably used. More preferably, it is an ethylene-octene copolymer produced using a single-site catalyst (metallocene catalyst). One of these can be used, and preferably two or more can be used in combination. In the case of a copolymer mainly composed of polyethylene and / or ethylene polymerized with a catalyst other than the single-site catalyst, the compatibility with the component (a) is poor, and the mechanical properties of the obtained composition are deteriorated.

The amount of the component (b) is 100 parts (a)
The upper limit is 350 parts by weight, preferably 25 parts by weight.
0 parts by weight, more preferably 200 parts by weight, and the lower limit is 5 parts by weight, preferably 10 parts by weight. If it is less than the above lower limit, the dispersion of the components (c-1) and (c-2) will be poor, and if it exceeds the above upper limit, the heat resistance of the obtained thermoplastic resin composition will be poor.

Component (c): essential component

(C-1) Ethylene ionomer resin

The ethylene ionomer resin is an ethylene / α, β-unsaturated carboxylic acid copolymer or ethylene /
The carboxyl groups of the α, β-unsaturated carboxylic acid / α, β-unsaturated carboxylic acid ester copolymer are partially neutralized and cross-linked by metal ions.

The proportion of ethylene units in the ethylene copolymer before neutralization is preferably 75 to 99.5 mol%, more preferably 88 to 98 mol%, and α, β-
The proportion occupied by unsaturated carboxylic acid units is preferably 0.1%.
5 to 15 mol%, more preferably 1 to 6 mol%,
The proportion of the α, β-unsaturated carboxylic acid ester unit is preferably 0 to 10 mol%, more preferably 0 to 10 mol%.
6 mol%. When the proportion of the α, β-unsaturated carboxylic acid in the ethylene copolymer is less than 0.5 mol%, the adhesiveness of the obtained ethylene ionomer resin is impaired, and
If it exceeds 5 mol%, the heat resistance of the resulting ethylene ionomer resin will decrease. α, β-unsaturated carboxylic acid ester unit is present in the above proportion,
Flexibility can be imparted to the obtained ethylene ionomer resin. If it exceeds 10 mol%, the heat resistance of the resulting ethylene ionomer resin will be reduced.

As the α, β-unsaturated carboxylic acid constituting the copolymer, those having 3 to 8 carbon atoms are preferably used, and more preferably, acrylic acid, methacrylic acid,
Maleic acid, fumaric acid, maleic anhydride and the like are used. As the α, β-unsaturated carboxylic acid ester, those having 4 to 8 carbon atoms are preferably used, and more preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isobutyl acrylate , Butyl methacrylate, dimethyl phthalate and the like are used. As the α, β-unsaturated carboxylic acid, acrylic acid and methacrylic acid are particularly preferably used.
As the unsaturated carboxylic acid ester, isobutyl acrylate is particularly preferably used.

The ratio of the carboxyl groups in the ethylene copolymer neutralized by metal ions (neutralization degree)
Is preferably 5 to 80%, more preferably 10 to 75%
%. If the degree of neutralization of the carboxyl groups by the metal ions is less than 5%, the surface gloss and chemical resistance of the obtained ethylene ionomer resin will be reduced, and if it is 80% or more, the fluidity of the obtained ethylene ionomer resin will be small.

Examples of the metal ion include metal ions having a valence of 1 to 3, especially I, I in the periodic table of the elements.
It is a metal ion having a valence of 1 to 3 of groups I, III, IV and VII. For example, Na ⁺ , K ⁺ , Li ⁺ , Cs ⁺ , A
g ⁺ , Hg ⁺ , Cu ⁺ , Be ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , S
r ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , Cd ⁺⁺ , Hg ⁺⁺ , Sn ⁺⁺ , Pb
^{++, Fe ++, Co ++,} Ni ++, Zn ++, Al +++, Sc
⁺⁺⁺ , Fe ⁺⁺⁺ , Y ^{+++ and the} like. These metal ions may be a mixed component of two or more types, or may be a mixed component with an ammonium ion. Among these metal ions, Zn ⁺⁺ and Na ⁺⁺ are particularly preferable.

(C-2) 0 to 95% by weight of ethylene and the following formula (I)

Embedded image CH ₂ ＣC (R ¹ ) —COOR ² (I)
(Wherein, R ¹ represents hydrogen or a methyl group, and R ² represents hydrogen or an alkyl group having 1 to 10 carbon atoms) (co) polymer with 100 to 5% by weight of a monomer represented by the following formula:

The content of ethylene and the monomer represented by the formula (I) in the (co) polymer is preferably 20 to 95% by weight of ethylene and the monomer 8 represented by the formula (I).
0 to 5% by weight, more preferably 50 to 9% ethylene.
5% by weight and 50 to 5% by weight of the monomer represented by the formula (I)
And particularly preferably 80 to 95% by weight of ethylene and 20 to 5% by weight of the monomer represented by the formula (I). When the content of the monomer represented by the formula (I) is less than the above lower limit, the obtained composition is mixed with an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, and an ethylene / acrylate copolymer. , Ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, and the adhesive force with the ionomer resin becomes insufficient. The bending restoring force of the object tends to increase. The monomer represented by the above formula (I) is preferably methyl methacrylate, methyl acrylate, ethyl methacrylate,
Examples include methacrylic acid and acrylic acid. Of these, methacrylic acid is particularly preferred.

The above (co) polymer is used in an amount of 0.5 to 15
g / 10 min melt flow rate (JIS K 676)
0, measured at a temperature of 190 ° C. and a load of 2160 g).

The amount of the component (c) is 100%.
The upper limit is 200 parts by weight, preferably 18 parts by weight.
0 parts by weight, and the lower limit is 5 parts by weight, preferably 10 parts by weight. Below the lower limit, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / methacrylic acid copolymer
A problem arises in that the adhesive strength with an acrylic ester copolymer, an ethylene / methacrylic ester copolymer, an ethylene / vinyl acetate copolymer, a saponified ethylene / vinyl acetate copolymer, and an ionomer resin is poor. In addition, when it exceeds the above upper limit, a problem that the heat resistance of the composition is inferior occurs.

Component (d) (optional component)

[0033] Polyethylene and / or copolymers based on ethylene (excluding those polymerized with a single-site catalyst) are mainly used as extenders. Component (d)
Are high-density polyethylene (low-pressure polyethylene), low-density polyethylene (high-pressure polyethylene), linear low-density polyethylene (ethylene and a small amount, preferably 1 to 10 mol%) synthesized with a catalyst other than a single-site catalyst. Copolymers with α-olefins such as butene-1, hexene-1 and octene-1), ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-acrylate copolymers and the like. Alternatively, two or more kinds are preferably used. Particularly preferably, linear low-density polyethylene is used.

Component (d) is added in an amount of 0 to 200 parts by weight, preferably 1 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of component (a).
When the amount of the component (d) exceeds 200 parts by weight, a problem occurs in that the heat resistance of the resin composition is poor.

Component (e) (optional component)

The block copolymer is a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. Or a product obtained by hydrogenating it, or a mixture thereof. For example, ABA, BABA, ABAA
And an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as -BA, or a hydrogenated product thereof. Above (hydrogenated)
The block copolymer (hereinafter, the (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer) contains 5 to 60% by weight of an aromatic vinyl compound, preferably , 20 to 50% by weight. The polymer block A mainly composed of an aromatic vinyl compound preferably comprises only an aromatic vinyl compound. Alternatively, more than 50% by weight, preferably 70% by weight or more of the aromatic vinyl compound and optional components, for example, a (hydrogenated) conjugated diene compound (hereinafter, a (hydrogenated) conjugated diene compound is a conjugated diene compound and / or Or a hydrogenated conjugated diene compound). The polymer block B based on a (hydrogenated) conjugated diene compound preferably consists only of the (hydrogenated) conjugated diene compound. Alternatively, it is a copolymer block of more than 50% by weight, preferably 70% by weight or more, of a (hydrogenated) conjugated diene compound and an optional component such as an aromatic vinyl compound. In each of the polymer block A mainly containing the aromatic vinyl compound and the polymer block B mainly containing the (hydrogenated) conjugated diene compound, the vinyl compound or the (hydrogenated) conjugate in the molecular chain is used. The distribution of the diene compound may be random, tapered (the monomer component increases or decreases along the molecular chain), partially blocky, or any combination thereof. When there are two or more polymer blocks A mainly composed of an aromatic vinyl compound or polymer blocks B mainly composed of a (hydrogenated) conjugated diene compound, they may have the same or different structures.

As the aromatic vinyl compound constituting the (hydrogenated) block copolymer, for example, one or more of styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like are selected. Of which styrene is preferred. As the conjugated diene compound, for example,
Butadiene, isoprene, 1,3-pentadiene, 2,
One or more of 3-dimethyl-1,3-butadiene and the like are selected. Among them, butadiene, isoprene and a combination thereof are preferred.

The microstructure of the polymer block B mainly composed of a conjugated diene compound can be arbitrarily selected.
When the block B is composed of butadiene alone, the 1,2-microstructure of the butadiene block is 20 to
50%, especially 25-45% is preferred. When block B is composed of a mixture of isoprene and butadiene,
The 1,2-microstructure is preferably less than 50%, more preferably less than 25%, even more preferably less than 15%. When block B is composed of isoprene alone, in the polyisoprene block, 70 to 100% by weight of the isoprene compound has a 1,4-microstructure and at least 90% of aliphatic double bonds based on the isoprene compound are present. % Is preferably hydrogenated.

The weight average molecular weight of the (hydrogenated) block copolymer of the present invention having the above-mentioned structure is preferably from 5,000 to 1,500,000, more preferably from 10,000 to 550,000. Yes, more preferably from 100,000 to 550,000, particularly preferably from 10,000 to 400,000. The molecular weight distribution (the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less.

The molecular structure of the (hydrogenated) block copolymer is as follows:
It may be linear, branched, radial or any combination thereof.

Numerous methods have been proposed for producing these block copolymers. As a typical method, it can be obtained by performing block polymerization in an inert solvent using a lithium catalyst or a Ziegler-type catalyst, for example, according to the method described in Japanese Patent Publication No. 40-23798. By hydrogenating the block copolymer obtained by the above method in the presence of a hydrogenation catalyst in an inert solvent, a hydrogenated block copolymer is obtained.

Specific examples of the (hydrogenated) block copolymer include SBS, SIS, SEBS, SEPS, and SEE.
PS and the like. In the present invention, a particularly preferred (hydrogenated) block copolymer is a polymer block A mainly composed of styrene, and mainly composed of isoprene, and 70 to 100% by weight of isoprene has a 1,4-micro structure, Further, it is a hydrogenated block copolymer comprising a polymer block B in which at least 90% of an aliphatic double bond based on isoprene is hydrogenated. The weight average molecular weight of the hydrogenated block copolymer is from 50,000 to 550,000.
It is. More preferably, 90 to 100% by weight of isoprene is the above hydrogenated block copolymer having a 1,4-microstructure.

The component (e) is used in an amount of 0 to 400 parts by weight, preferably 30 to 350 parts by weight, based on 100 parts by weight of the component (a). Thereby, flexibility can be imparted to the resin composition. If the component (e) exceeds 400 parts by weight, there arises a problem that workability is poor.

Component (f): (arbitrary component)

As the softener for non-aromatic rubber, non-aromatic mineral oil or liquid or low molecular weight synthetic softener can be used. Mineral oil softeners used for rubber are a combined mixture of aromatic rings, naphthene rings and paraffin chains. Those having 50% or more of the total number of carbon atoms in the paraffin chain are called paraffinic, those having 30 to 40% naphthenic ring carbon are called naphthenic, and those having 30% or more aromatic carbon are called aromatic. Is distinguished by

The mineral oil-based rubber softener used as the component (f) in the present invention is a paraffin-based or naphthene-based one in the above category. If an aromatic softening agent is used, the component (d) becomes soluble and inhibits the crosslinking reaction, and the physical properties of the resulting composition are not improved, which is not preferable. As the component (f), a paraffin-based component is preferable, and a paraffin-based component having a small amount of an aromatic ring component is particularly preferable.

The properties of these softeners for non-aromatic rubbers have a dynamic viscosity at 37.8 ° C. of 20 to 500 cS.
t, pour point is -10 to -15 ° C, flash point (COC) is 1
70-300 ° C.

Component (f) is added in an amount of 0 to 500 parts by weight, preferably 0 to 200 parts by weight, based on 100 parts by weight of component (a). If the upper limit is exceeded, bleed-out of the softener tends to occur, which may give tackiness to the final product, and also deteriorates mechanical properties. When the softening effect is to be obtained, if the amount is less than 40 parts by weight, the required flexibility of the obtained composition may not be obtained in some cases. Component (f)
Preferably have a weight average molecular weight of 100 to 2,000.

Component (g): inorganic filler (optional component)

The resin composition of the present invention may contain, as an optional component, component (g) an inorganic filler. As the inorganic filler, for example, calcium carbonate, talc, clay, carbon black, magnesium hydroxide, mica,
Barium sulfate, natural silicic acid, synthetic silicic acid, titanium oxide,
Examples include magnesium oxide and zinc oxide.

The component (g) is used in an amount of preferably 0 to 500 parts by weight, more preferably 0 to 4000 parts by weight, particularly preferably 0 to 300 parts by weight, based on 100 parts by weight of the component (a). If the upper limit is exceeded, bleed-out of the softener tends to occur, which may give tackiness to the final product, and also deteriorates mechanical properties. By blending the component (g) inorganic filler, rigidity can be imparted to the resin composition. It is also effective in reducing the cost as an extender and improving the appearance (gloss) of a molded product.

When oil resistance and heat resistance are required for the thermoplastic resin composition, an organic peroxide and a crosslinking aid can be used in combination.

Component (h): organic peroxide (optional component)

Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-
Butyl peroxy) hexane, 2,5-dimethyl-2,
5-di (tert-butylperoxy) hexyne-3,
2,5-dimethyl-2,5-di (tert-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3 , 3,5-trimethylcyclohexane, n-butyl-4,4-bis (te
rt-butylperoxy) valerate, benzoylpar-
Oxide, p-chlorobenzoyl peroxide,
2,4-dichlorobenzoyl peroxide, tert
-Butylperoxybenzoate, tert-butylperoxyisopropylcarbonate, diacetylperoxide, lauroylperoxide, tert-butylcumylperoxide, and the like. These may be used alone or in combination of two or more. Can be used. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane and 2,5-dimethyl-2,5 are preferable in terms of odor, coloring and scorch stability. −
Di (tert-butylperoxy) hexyne-3 is most preferred.

The amount of the component (h) is 100 parts (a).
It is preferably 0.1 to 3 parts by weight with respect to parts by weight.

Component (i): Crosslinking aid (optional component)

Examples of the crosslinking aid include divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and trimethylol. Polyfunctional methacrylate monomers such as propane trimethacrylate, allyl methacrylate, or polyfunctional vinyl monomers such as vinyl butyrate or vinyl stearate can be used. By using this component, a uniform and efficient crosslinking reaction can be expected.

The amount of the component (i) is 100%.
The lower limit is preferably 0.1 part by weight, and the upper limit is preferably 10 parts by weight, more preferably 5 parts by weight with respect to parts by weight.

In addition to the above components, the resin composition of the present invention may contain various antiblocking agents, sealant improvers, heat stabilizers, antioxidants, antioxidants, ultraviolet absorbers, depending on the intended use.
Lubricants, coloring agents and the like can also be included.

The method for producing the composition of the present invention described above is not particularly limited. The composition of the present invention can be produced by melt-kneading the components at once. Any conventional melt-kneading method and apparatus (single or twin screw extruder, roll, Banbury mixer, various kneaders, etc.) can be used.

The above-mentioned resin composition of the present invention can be favorably thermally fused with various resins to form various laminated products. The resin capable of being heat-fused with the resin composition of the present invention is preferably an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, an ethylene / acrylic ester copolymer, or an ethylene / methacrylic ester copolymer. Copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, a polar resin composed of an ionomer resin, and the like, and preferably a nonpolar polyolefin resin, and a nonpolar polystyrene resin, etc. Resins. Examples of the ionomer resin include, in addition to the above-mentioned ethylene ionomer resin, other α-olefin ionomer resins such as propylene. As the non-polar polyolefin resin, preferably, polypropylene, propylene / α-olefin copolymer, polyethylene (low density polyethylene resin, linear low density polyethylene resin, medium density polyethylene resin, high density polyethylene resin, etc.), ethylene / α -Olefin copolymer rubber, polybutene, polyisobutylene, polybutadiene (BR), poly-4-methylpentene-1 resin,
Olefinic thermoplastic elastomer (TPO) (an elastomer composition composed of ethylene / α-olefin copolymer rubber / polypropylene) and the like. Non-polar polystyrene resins include polystyrene (general polystyrene resin, high impact polystyrene resin) and styrene copolymer rubber (SBR, SBS, SIS, SIB)
S, SEBS, SEBS, SEEPS, etc.) and styrene-based thermoplastic elastomer (styrene-based copolymer rubber /
Elastomer composition comprising a polyolefin-based resin). Particularly preferably, ionomer resins and polypropylene are used. As a preferred embodiment, a molded article can be produced in which the above resin composition of the present invention is used as a core material and a polar resin is laminated on the skin and a non-polar resin is laminated on the lip. Here, the same polar resin and non-polar resin as described above can be used. Preferably, the polar resin is an ionomer resin, and the non-polar resin is a polyolefin-based thermoplastic elastomer and / or a styrene-based thermoplastic elastomer.

Such a laminated molded article can be used for various uses such as automobile parts, building parts, light electric appliances and the like. Among other things, automotive moldings, for example, wind moldings, roof moldings mounted on automobiles,
It is useful for various moldings such as protector molding, weather molding, and strip molding. In particular, by using a laminate having an ionomer resin as a surface layer, the surface portion exposed to the outer surface of various moldings can be made tough and excellent in scratch resistance, weather resistance, and chemical resistance. Lamination can be performed using, for example, coextrusion molding, insert molding, transfer molding.

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0064]

EXAMPLES In the examples and comparative examples, the following substances were used.

Component (a): a polypropylene homopolymer,
CJ700 (trademark) manufactured by Mitsui Chemicals, Inc., crystallinity: Tm16
6 ° C, ΔHm 82mJ / mg

Component (b): ethylene-octene copolymer, Engage EG8100 (trade name, manufactured by Dow Chemical Japan Co., Ltd.), density: 0.870 g / cm ³ , melt index (190 ° C., load 2.16 kg): 0. 5g /
10 minutes, comonomer content: 24%

Component (c): (c-1) Ionomer of ethylene-acrylic acid copolymer, Himilan 1554 (trademark), manufactured by Mitsui / Dupont, MAA (methacrylic acid) content: 9.0% by weight, density:
0.94 g / cm ³ , melting point: 99 ° C., melt index (measuring temperature 190 ° C., measuring load 2.16 kg): 1.
3 g / 10 min, ion-crosslinked product Metal salt: zinc-based (c-2) ethylene-acrylic acid copolymer, Nucrel N0903HC (trademark), manufactured by Mitsui / DuPont, MAA
(Methacrylic acid) content: 9.0% by weight, density: 0.93
g / cm ³ , melting point: 99 ° C., melt index (measuring temperature 190 ° C., measuring load 2.16 kg): 1.3 g / 1
0 minutes

Component (d): LLDPE, V-0398C
N (trademark) manufactured by Idemitsu Petrochemical Co., Ltd., weight average molecular weight: 80,
000, density: 0.907 g / cm ³ , melt index (measuring temperature 190 ° C., measuring load 2.16 kg):
3.3 g / 10 minutes

Component (e): Septon 4077 ™
Kuraray Co., Ltd., styrene content: 30% by weight, isoprene content: 70% by weight, number average molecular weight: 260,000,
Weight average molecular weight: 320,000, molecular weight distribution: 1.2
3. Hydrogenation rate: 90% or more

Component (f): paraffinic oil, Diana process oil PW-90 (trade name, manufactured by Idemitsu Kosan Co., Ltd.)
Weight average molecular weight: 540, content of aromatic component: 0.1
%Less than

Component (g): filler calcium carbonate, NS-400 (trade name) manufactured by Nitto Powder Chemical Industry Co., Ltd.

Component (h): Peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) -hexane, Perhexa 25B (trade name, manufactured by NOF Corporation)

Component (i): Crosslinking aid Triethylene glycol dimethacrylate, NK ester 3G (manufactured by Shin-Nakamura Chemical Co., Ltd.)

Various tests and evaluations performed in Examples and Comparative Examples were performed as follows.

(1) Specific gravity According to JIS K 6301, the test piece was measured using a 6.3 mm thick press sheet.

(2) Hardness According to JIS K 6301, a 6.3 mm-thick pressed sheet was used as a test piece. The hardness after 15 seconds was measured.

(3) Tensile strength In accordance with JIS K 6301, a test piece was prepared by extracting a 1 mm thick press sheet into a dumbbell No. 3 mold. The tensile speed was 500 mm / min.

(4) 100% Elongation Stress According to JIS K 6301, a 1 mm thick press sheet was used as a test piece by pulling it out with a dumbbell No. 3. The tensile speed was 500 mm / min.

(5) Tensile Elongation In accordance with JIS K 6301, a test piece was prepared by extracting a 1 mm thick pressed sheet into a dumbbell No. 3 mold. The tensile speed was 500 mm / min.

(6) Compression set In accordance with JIS K6262, a 6.3 mm thick press sheet was used as a test piece. The measurement was performed at 70 ° C. for 72 hours under a condition of 25% deformation.

(7) Adhesion evaluation test Length moldability: A sheet was molded with an 80-ton injection molding machine under the following injection conditions I, and a length of 150 mm and a width of 2 were obtained from the sheet.
A resin plate having a thickness of 5 mm and a thickness of 4 mm was cut out. The resins used to make the resin plate are as follows. Ionomer resin (Mitsui DuPont HM2500BK) Polypropylene resin (CJ-700, manufactured by Mitsui Chemicals, Inc.) Injection molding machine: FS-120, manufactured by Nissei Plastics Co., Ltd. Molding temperature: 200 ° C Injection speed: 55 mm / sec Injection pressure: 1400 kg / C. ² Holding pressure: 400 kg / cm. ² Injection time: 6 seconds Cooling time: 45 seconds As shown in FIG. And the composition of the present invention was injection-molded under the following injection conditions II to prepare test pieces as shown in FIGS. Injection condition II Injection molding machine: FS-120 manufactured by Nissei Plastics Co., Ltd. Molding temperature: 200 ° C Injection speed: 55 mm / sec Injection pressure: 1400 kg / cm ² Holding pressure: 0 kg / cm ² Injection time: 6 seconds Cooling time: 45 Secondly, the 180 ° peel strength of the obtained test piece was measured. The measurement was performed by bending a resin plate made of the composition of the present invention as shown in FIG. 3 and pulling both ends of the resin plate and the plate-like material in the directions indicated by arrows. ○: Material destruction Δ: Interfacial destruction ×: Peeling immediately after starting measurement

(8) Bleed Evaluation Test A press sheet having a thickness of 1 mm and a length and a width of 50 mm each was placed in an atmosphere of 70 ° C. for 72 hours.
The surface condition of the test piece was observed. ：: No change is observed on the surface. ×: Bleed was observed on the surface.

[0083]

Examples 1 to 11 and Comparative Examples 1 to 8 Each composition shown in Tables 1 and 2 was kneaded at a kneading temperature of 200 to 2 using a twin-screw kneader.
Pellets were prepared by melt-kneading at 20 ° C. and a screw rotation of 100 rpm. The pellets were used for preparing test pieces and the like in the various tests described above. Various evaluations were performed on the pellets and molded articles thus obtained. The results are shown in Tables 1 and 2.

[0084]

[Table 1]

[0085]

[Table 2]

Examples 1 to 11 are resin compositions of the present invention. All of them had excellent adhesiveness to both the ionomer resin and the polypropylene resin, and also had excellent mechanical properties. In each case, no bleeding of the softener was observed, and the flexibility of the molded article could be easily controlled. In Example 1, (c)
-2), while Example 10 used
(C) uses (c-1). Both exhibited almost the same properties.

On the other hand, in Comparative Example 1, (b) was not added in Example 1. Poor adhesion to the ionomer resin and bleeding of the softener were observed. Comparative Example 2 is obtained by blending (b) in Example 1 beyond the scope of the present invention. Poor adhesion to the ionomer resin and bleeding of the softener were observed.
Also, a decrease in mechanical properties was observed. In Comparative Example 3, (c-2) was not added in Example 1. Adhesion to the ionomer resin was significantly reduced. Comparative Example 4 is obtained by blending (c-2) in Example 1 beyond the scope of the present invention. Poor adhesion to the polypropylene resin and bleeding of the softener were observed. Comparative Example 5 is obtained by blending (c-1) in Example 10 beyond the scope of the present invention. Poor adhesion to the polypropylene resin and bleeding of the softener were observed. In Comparative Examples 6 and 7, (e) or (f) in Example 1 was blended beyond the scope of the present invention. In each case, the adhesion to the ionomer resin was extremely poor. In Comparative Example 7, significant bleeding of the softener was also observed. Comparative Example 8 is obtained by blending (d) in Example 1 beyond the scope of the present invention. Adhesion to the ionomer resin was poor, and significant bleeding of the softener was observed.

[0088]

Industrial Applicability The present invention provides excellent mechanical properties and various resins, especially ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic ester copolymer, ethylene・ Polymer composed of methacrylate copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer and ionomer resin, and non-polar composed of non-polar polyolefin resin and non-polar polystyrene resin Including a resin composition which is excellent in heat-fusibility with a resin and further has no bleeding of a softening agent, so that the flexibility of a molded product can be easily controlled, and a layer composed of the resin composition An object of the present invention is to provide a laminated molded product, particularly a molded product obtained by laminating the resin composition and the polar resin and the non-polar resin.

[Brief description of the drawings]

FIG. 1 is a plan view of a test piece for evaluating adhesion.

FIG. 2 is a longitudinal sectional view of an adhesion evaluation test piece.

FIG. 3 is a diagram illustrating an adhesion evaluation method.

[Explanation of symbols]

1: Adhesion evaluation test piece 2: Resin plate (ionomer resin or polypropylene resin) 3: Plate-like material composed of the composition of the present invention (or comparative composition) 4: Paper A: Heat-sealed portion

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/26 C08L 23/26 53/02 53/02 91/00 91/00 (72) Inventor Ken Yuasa 3-11-5 Nihonbashi Honcho, Chuo-ku, Tokyo RIKEN VINYL INDUSTRY CO., LTD. F-term (reference) AL09C BA03 BA07 BA10A CA23B CA30B GB07 GB36 GB48 JB01 JK01 JK13 JL01 JL05 JL06 JL09 JL11 4J002 AE055 BB032 BB034 BB042 BB044 BB073 BB083 BB111 BB121 BB233 BP015 GN00

Claims (7)

[Claims] (1) 100 parts by weight of a copolymer mainly composed of polypropylene and / or propylene, and (b) a copolymer mainly composed of polyethylene and / or ethylene, which is polymerized with a single-site catalyst. 350 parts by weight,
(C) (c-1) an ethylene ionomer resin, and / or
Or (c-2) 0 to 95% by weight of ethylene and the following formula (I): CH ₂ ＣC (R ¹ ) —COOR ² (I) (wherein R ¹ represents hydrogen or a methyl group) , R ² represents hydrogen or an alkyl group having 1 to 10 carbon atoms) 5 to 200 parts by weight of a (co) polymer with 100 to 5% by weight of a monomer represented by the following formula: (d) polyethylene and / or ethylene (E) at least two polymer blocks A mainly made of an aromatic vinyl compound and 0 to 200 parts by weight of a conjugated diene compound (excluding those polymerized with a single-site catalyst) A block copolymer mainly composed of at least one polymer block B and / or a block copolymer obtained by hydrogenating the same, 0 to 400 parts by weight, (f) softening for non-aromatic rubber Agent 0-500 parts by weight The thermoplastic resin composition comprising. 2. A laminated molded article comprising a layer comprising the thermoplastic resin composition according to claim 1. 3. The thermoplastic resin composition according to claim 1,
Ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer, ethylene / acrylic acid ester copolymer,
Ethylene methacrylate copolymer, ethylene
One selected from the group consisting of a vinyl acetate copolymer, a polar resin consisting of a saponified ethylene / vinyl acetate copolymer and an ionomer resin, and a nonpolar resin consisting of a nonpolar polyolefin resin and a nonpolar polystyrene resin A molded product obtained by laminating more than that. 4. A molded article comprising the thermoplastic resin composition according to claim 1 as a core material and a polar resin on the skin and a non-polar resin on the lip. 5. A polar resin comprising an ethylene / acrylic acid copolymer, an ethylene / methacrylic acid copolymer, an ethylene / acrylic ester copolymer, an ethylene / methacrylic ester copolymer, an ethylene / vinyl acetate copolymer, The molded article according to claim 4, wherein the molded article is selected from the group consisting of a saponified ethylene / vinyl acetate copolymer and an ionomer resin, and the nonpolar resin is selected from the group consisting of a nonpolar polyolefin resin and a nonpolar polystyrene resin. 6. The molded article according to claim 4, wherein the polar resin is an ionomer resin, and the non-polar resin is a polyolefin-based thermoplastic elastomer and / or a styrene-based thermoplastic elastomer. 7. A molding for an automobile according to claim 2.
7. The molded article according to any one of items 6 to 6.