JP2002105264A - Thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic elastmer composition capable of rotary powder molding and producing a molded article excellent in smoothness of a back side. SOLUTION: In the thermoplastic resin composition, (a) a saponified ethylene- vinyl acetate copolymer resin contains 40-95 wt.% ethylene, the saponification degree is 80 wt.% or more based on vinyl acetate component, and (b) at least one selected from a group consisting of an aromatic vinyl compound-conjugated diene compound copolymer and the hydrogenated polymer is at least one selected from a group consisting of (b-1) an aromatic vinyl compound-conjugated diene compound block copolymer and the hydrogenated polymer and (b-2) a hydrogenated aromatic vinyl compound-conjugated diene compound random copolymer which contains 50 wt.% or less of an aromatic vinyl compound and of which the contents of vinyl bonds based on conjugated diene compound is 10% or more to bond based on conjugated diene compound.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a thermoplastic resin composition. More specifically, the present invention relates to a thermoplastic resin composition containing a specific saponified ethylene-vinyl acetate copolymer resin and an aromatic vinyl-conjugated diene copolymer and / or a hydrogenated product thereof. The composition has excellent moldability and is suitably used for toys and automobile interior parts.

[0002]

2. Description of the Related Art Rotary powder molding is widely used for toys, automobile interior parts, etc. because of its suitability for molding of complicated shapes, high material yield, and easy uniform thickness. I have. In the powder molding, the powder raw material that does not adhere to the mold is collected and reused in the next molding, but a part of the surface of the collected resin is melted by the heat history at the time of the previous molding, thereby Agglomeration of powders (hereinafter referred to as blocking) is likely to occur. When such blocked particles are subjected to molding, in the molded article,
It is easy to cause pinhole problems. Pinholes can also arise from unmelted parts if the melting temperature of the material is higher than the molding temperature. In addition, if gas is generated from the material,
Transferability is poor. Therefore, it is necessary to use a raw material resin that not only satisfies the required characteristics of the product but also does not cause any trouble in molding.

[0003] As raw material resins for rotary powder molding, polyvinyl chloride resins, polyolefin elastomers, and thermoplastic polyurethane elastomers are used. Since the polyvinyl chloride resin contains a large amount of a low molecular weight plasticizer, there is a problem that a soft feeling is lost below the freezing point of the plasticizer. In addition, there is a problem that the matte effect and the softness disappear due to the transfer of the plasticizer to the surface of the molded product in long-term use. Polyolefin-based elastomers are inexpensive and have excellent weather resistance, but have the drawback of being inferior in moldability and scratch resistance. Although a composition in which the scratch resistance is improved by a compounding composition or surface decoration such as painting has been studied, the cost is high and it is not practical. The thermoplastic polyurethane elastomer has a problem that a molding cycle is long and stringing and blocking are likely to occur during molding. Also, the back side of the molded product is not smooth,
In the post-processing, when the foamable resin is molded on the back surface, there is a problem that the foamed gas leaks from the uneven portion. Furthermore, there is a problem that it is expensive and is inferior in weather resistance and flame retardancy.

Incidentally, ethylene-vinyl acetate copolymer (EVA) or a saponified product thereof, and ethylene-ethyl acrylate copolymer (EEA) can be molded at a lower temperature than the above resins. A composition containing the saponified ethylene-vinyl acetate copolymer resin and an aromatic vinyl compound-conjugated diene compound copolymer or a hydrogenated product thereof is disclosed (Japanese Patent Publication No. 2-60687). However, the present inventors have studied and found that the composition is not suitable for rotary powder molding. If a specific thermoplastic polyurethane-based elastomer is blended, molding can be performed at a temperature similar to that of the saponified ethylene-vinyl acetate copolymer, but as described above, the molded product is inferior in weather resistance and has a lower surface. Poor smoothness.

[0005]

Accordingly, the present invention solves the above-mentioned problems in the rotary powder molding, has no problems such as gasification, pinholes and blocking during molding, and has weather resistance and flame retardancy. It is an object of the present invention to provide a thermoplastic elastomer composition which gives a molded article having excellent smoothness and a smooth back surface.

[0006]

As a result of various studies, the present inventors have found that a saponified ethylene-vinyl acetate copolymer having a specific ethylene content and saponification rate (hereinafter referred to as "EVOH").
Abbreviated. The present inventors have found that the above problems can be solved by using a copolymer of a specific aromatic vinyl compound and a conjugated diene compound. That is, the present invention relates to (a) a saponified ethylene-vinyl acetate copolymer resin.
In a thermoplastic resin composition containing 40 to 95 parts by weight, and (b) 60 to 5 parts by weight of at least one selected from the group consisting of an aromatic vinyl compound-conjugated diene compound copolymer and a hydrogenated product thereof , (A) the ethylene-vinyl acetate copolymer saponified resin has an ethylene content of 40 to 95%;
%, And the degree of saponification is at least 80% by weight of the vinyl acetate component, and is selected from the group consisting of (b) an aromatic vinyl compound-conjugated diene compound copolymer and a hydrogenated product thereof. At least one of (b-1) an aromatic vinyl compound-conjugated diene compound block copolymer, a hydrogenated product thereof, and (b-2) an aromatic vinyl compound content of 50% by weight or less; Number average molecular weight (M
n) is 5,000 to 1,000,000 and the polydispersity (Mw / M
hydrogenation of an aromatic vinyl compound-conjugated diene compound random copolymer wherein n) is 10 or less and the content of vinyl bonds based on the conjugated diene compound is 10% or more of the bonds based on the conjugated diene compound A thermoplastic resin composition, which is at least one member selected from the group consisting of: Component (b) is a hydrogenated styrene-isoprene-styrene block copolymer having a weight average molecular weight of 5,000 to 1,500,000, wherein 70 to 100% by weight of the isoprene is 1,4-micron. Preferably, it has a structure and at least 90% of the aliphatic double bonds based on the isoprene are hydrogenated. Alternatively, component (b) is preferably a hydrogenated styrene-butadiene random copolymer in which at least 70% of the olefinically unsaturated bonds have been hydrogenated. According to the present invention, there is provided a thermosetting composition further comprising (c) 0.01 to 3 parts by weight of an organic peroxide and (d) 0.01 to 5.5 parts by weight of a crosslinking aid, based on 100 parts by weight of the total of components (a) and (b). It also relates to a plastic resin composition. Further, the present invention provides a composition comprising the component
(E) (poly) with respect to the total of 100 parts by weight of (e) and (b)
The thermoplastic resin composition according to any one of claims 1 to 4, further comprising 1 to 20 parts by weight of a hydroxyalkyl (meth) acrylate. Sum of components (a) and (b)
(F) 5-150 parts by weight of thermoplastic polyurethane resin (g) 0.1-20 parts by weight of liquid polybutadiene (h) 0.05-5 parts by weight of unsaturated carboxylic acid or derivative thereof (i) peroxide decomposition Type polyolefin resin 0.05
To 30 parts by weight and (j) peroxide-crosslinked polyolefin resin 0.05
Preferably, the composition further contains at least one component selected from the group consisting of -30 parts by weight.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Each component constituting the composition of the present invention will be described. (A) Saponified ethylene-vinyl acetate copolymer The composition of the present invention is characterized by containing a saponified ethylene-vinyl acetate copolymer resin (hereinafter, referred to as “EVOH”). By blending EVOH, the weather resistance of the composition and the smoothness of the back surface of the molded product are improved. The EV
OH has an ethylene content of 40-95 wt%, preferably 60-95 wt%.
~ 90 wt%, and the degree of saponification of the vinyl acetate component is 80
wt% or more, preferably 90 wt% or more. If the ethylene content is less than 40 wt%, the heat resistance is poor, and 95 wt%
%, It is inferior in flexibility. When the saponification degree of the vinyl acetate component is less than 80%, the heat resistance decreases.

[0008] The EVOH is 190 in accordance with JIS K6924-2.
The melt flow rate (MFR) measured at a load of 21.18 N at 10 ° C. is 10 to 400 g / 10 min, preferably MFR 2
0 to 250 g / 10 min. If the MFR is less than 10, the fluidity of the composition is poor, and if it exceeds 400, the mechanical strength and heat resistance are poor.

( B) Aromatic vinyl compound-conjugated diene compound
Compound copolymer and / or hydrogenated product thereof Component (b) in the present invention comprises (b-1) a block copolymer of an aromatic vinyl compound and a conjugated diene compound, a hydrogenated product thereof, and (b-2) At least one selected from the group consisting of a hydrogenated random copolymer of an aromatic vinyl compound and a conjugated diene compound.

As the aromatic vinyl compound in the component (b), for example, styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylstyrene, N, N-diethyl-
p-aminoethylstyrene, vinyltoluene, p-third
One or more of butylstyrene and the like can be selected, and among them, styrene is preferable.

As the conjugated diene compound, for example,
Butadiene, isoprene, 1,3-pentadiene, 2,
One or more kinds are selected from 3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable.

(B-1) The block copolymer and / or its hydrogenated product (hereinafter referred to as (hydrogenated) block copolymer) comprises at least one polymer block A mainly composed of an aromatic vinyl compound. And at least one polymer block B mainly composed of a conjugated diene compound, for example, AB, ABA, BABA, ABAA
Having a structure such as -BA. A and B are each 2
If there are more than one, each may have the same structure or different structures. Component (b-1) contains 5 to 60% by weight of an aromatic vinyl compound, preferably 20 to 50% by weight.
% By weight. The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of only the aromatic vinyl compound, or the amount of the aromatic vinyl compound exceeds 50% by weight,
Preferably 70% by weight or more of the conjugated diene compound and / or
Or a hydrogenated conjugated diene compound (hereinafter referred to as (hydrogenated)
A conjugated diene compound). The polymer block B mainly composed of a (hydrogenated) conjugated diene compound is preferably composed of only the (hydrogenated) conjugated diene compound or the (hydrogenated) conjugated diene compound exceeds 50% by weight, preferably 70% by weight. It is a copolymer block of not less than weight% and an aromatic vinyl compound. Polymer block A mainly composed of these aromatic vinyl compounds, (hydrogenated)
In each of the polymer blocks B mainly composed of a conjugated diene compound, the distribution of the aromatic vinyl compound or the (hydrogenated) conjugated diene compound in the molecular chain is random or tapered (the monomer component increases or decreases along the molecular chain). ), Partially in the form of a block, or an arbitrary combination thereof. The microstructure of the polymer block B mainly composed of a conjugated diene compound can be arbitrarily selected. When block B is composed of butadiene alone,
In the butadiene block, the 1,2-microstructure is preferably from 20 to 50%, particularly preferably from 25 to 45%. 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%, and even more preferably less than 15%. When the block B is composed of isoprene alone, 70 to 100% by weight of the isoprene compound is 1,4.
Preference is given to those having a microstructure and at least 90% of the aliphatic double bonds based on the isoprene compound being hydrogenated.

[0013] Numerous methods have been proposed for producing these block copolymers. Representative methods include, for example, a method described in Japanese Patent Publication No. 23798/1971 using a lithium catalyst or Ziegler catalyst. It can be obtained by performing block polymerization in an inert solvent using a type catalyst. 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, SIBS, SEBS, and SEP.
S, SEEPS 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, And a weight average molecular weight of at least 90% of the isoprene-based aliphatic double bond and the polymer block B obtained by hydrogenation of 5,000 to
1,500,000, more preferably 10,000-5
50,000, most preferably 10,000 to 15
It is a 000 hydrogenated block copolymer. The polydispersity (ratio (Mw / Mn) of weight average molecular weight (Mw) to 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 may be linear, branched, radial, or any combination thereof. More preferably, 90 to 100% by weight of isoprene
Is a hydrogenated block copolymer having a 1,4-microstructure.

(B-2) The hydrogenated random copolymer comprises 50% by weight of a conjugated diene compound and an aromatic vinyl compound.
A random copolymer having a number average molecular weight of 5,000 to 1,000,000 and a polydispersity (M
w / Mn) is 10 or less, and the vinyl bond content of 1, 2, or 3, 4 or the like in the conjugated diene portion is 10% or more, preferably 20 to 90%, particularly preferably 40%. ~ 90%. If it is less than 10%, the resulting molded article has a hard feel, which does not meet the purpose of the present invention. Here, the content of the aromatic vinyl compound constituting the component (b-2) is 50% by weight or less, preferably 5 to 35% by weight.
It is. If the content exceeds 50% by weight, the resulting molded article has a hard feel, which does not meet the purpose of the present invention. As the aromatic vinyl compound in the component (b-2), the component (b-
The same one as in 1) is used. The aromatic vinyl compound is randomly linked and is known as Korsoff [IM Kolthof].
f, J. Polymer Sci., Vol. 1 p.429 (1946)], the content of the block-shaped aromatic vinyl compound is 10% by weight or less, preferably 5% by weight or less in the total bound aromatic vinyl compound.

Further, the conjugated diene compound is also used as the component (b)
The same ones as in -1) are used, and examples thereof include butadiene, isoprene, 2,3-dimethylbutadiene, and pentadiene. Preferably, at least 90% of the aliphatic double bonds based on the conjugated diene compound are hydrogenated.

The ratio of component (a) to component (b) is from 40 to 95 parts by weight of component (a), from 60 to 5 parts by weight of component (b), preferably from 50 to 90 parts by weight of component (a). Component (b) 50
To 10 parts by weight, more preferably 60 to 80 parts by weight of component (a) and 40 to 20 parts by weight of component (b).

(C) Organic peroxide By performing dynamic crosslinking using an organic peroxide, the heat resistance and scratch resistance of the composition are improved. Examples of the organic peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2, 5-di (ter
t-butylperoxy) hexyne-3, 1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy)-
3,3,5-trimethylcyclohexane, n-butyl-
4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, t
tert-butyl peroxyisopropyl carbonate,
Examples thereof include diacetyl peroxide, lauroyl peroxide, tert-butylcumyl peroxide and the like.

Of these, 2,5-dimethyl-2,5-di- (te) is preferred in terms of odor, coloring and scorch stability.
Most preferred are rt-butylperoxy) hexane, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene.

The amount of the peroxide to be added depends on the amount of the component (a)
The lower limit of the total of 100 parts by weight of (b) and (b) is 0.
01 parts by weight, preferably 0.05 parts by weight, the upper limit is 3 parts by weight,
Preferably it is 2 parts by weight. In the amount less than the lower limit,
The required crosslinking is not obtained. On the other hand, if it exceeds the upper limit, crosslinking proceeds too much, the fluidity of the resin composition decreases,
Poor moldability.

(D) Crosslinking Aid In the present invention, a crosslinking aid is used to increase the efficiency of crosslinking by the component (c). Examples of the crosslinking assistant include polyvinyl monomers such as divinylbenzene and triallyl cyanurate, or ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl. Examples include polyfunctional methacrylate monomers such as methacrylate, 1,9-nonanediol dimethacrylate, and 2-methyl-1,8-octanediol dimethacrylate. In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle, has an organic peroxide solubilizing effect, and acts as a dispersion aid for the organic peroxide, so that the crosslinking effect by heat treatment is uniform and effective. Thus, a crosslinked thermoplastic elastomer having a good balance between hardness and rubber elasticity can be obtained, which is the most preferable. The range of the addition amount of the crosslinking aid is 0.01 parts by weight, preferably 0.05 parts by weight, and the upper limit is 5.5 parts by weight, based on 100 parts by weight of the total of components (a) and (b). Preferably it is 4 parts by weight. If the amount is less than the lower limit, the effect of improving crosslinking is not sufficient. On the other hand, if the amount exceeds the upper limit, the crosslinking proceeds excessively, the dispersion of each component is poor, and the moldability of the composition is poor. The addition amount of the crosslinking aid is preferably about 1.0 to 3.0 times the peroxide addition amount.

(E) (poly) hydroxyalkyl (meth)
The acrylate component (e) (poly) hydroxyalkyl (meth) acrylate has an effect of improving the compatibility between the components (a) and (b). Examples include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, 3-hydroxybutyl acrylate, ethyl-2-hydroxyethyl fuma Rate, 2-hydroxybutyl acrylate, 4-hydroxybutyl acrylate, and a polymer, copolymer, or copolymer with another monomer comprising the same can be used. Here, the copolymerizable monomers include ethylene, propylene,
Styrene, vinyl acetate and vinyl chloride can be mentioned. Preferably, 2-hydroxyethyl methacrylate is used. When the component (e) is blended, the blending amount is based on 100 parts by weight of the total of the components (a) and (b).
The lower limit is 1 part by weight, preferably 1.3 parts by weight, and the upper limit is 2 parts by weight.
0 parts by weight, preferably 10 parts by weight. If the amount is less than the lower limit, the effect of improving compatibility is insufficient. on the other hand,
If the amount exceeds the upper limit, a large amount of gas is generated during molding.

(F) Component Thermoplastic polyurethane elastomer
Tomer In the present invention, the thermoplastic polyurethane elastomer improves the scratch resistance and heat resistance of the composition. The thermoplastic polyurethane resin is generally prepared from a polyol, a diisocyanate, and a chain extender. Polyols include polyester polyols, polyester ether polyols, polycarbonate polyols and polyether polyols.

Examples of the polyester polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. A cyclic dicarboxylic acid such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or an acid ester or anhydride thereof, and ethylene glycol, 1,3
-Propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5
-Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, etc.
Or, a polyester polyol obtained by a dehydration condensation reaction with a mixture thereof; a polylactone diol obtained by ring-opening polymerization of a lactone monomer such as ε-caprolactone, and the like.

As the polycarbonate polyol, ethylene glycol, 1,3-propylene glycol, 1,2-
Propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8- Examples thereof include those obtained by reacting one or more polyhydric alcohols such as octanediol, 1,9-nonanediol, and diethylene glycol with diethylene carbonate, dimethyl carbonate, diethyl carbonate, and the like.

Examples of the polyester ether polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid. Alicyclic dicarboxylic acids, such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or acid esters or acid anhydrides thereof, and glycols such as diethylene glycol or propylene oxide adducts; or Products obtained by a dehydration condensation reaction with these mixtures are mentioned.

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran, respectively, and copolyethers thereof. Among the above various polyols, polyether polyols are preferred from the viewpoint of hydrolysis resistance.

Examples of the isocyanate include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate, tolidine diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate. Isocyanate (XDI), hydrogenated XD
I, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanatomethyloctane, lysine ester triisocyanate, 1,
Examples include 3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, and the like. Among them, 4,4'-diphenylmethane diisocyanate (M
DI) is preferably used.

As the chain extender, a low molecular weight polyol is used. For example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanediene Examples include aliphatic polyols such as methanol and glycerin, and aromatic glycols such as 1,4-dimethylolbenzene, bisphenol A, and ethylene oxide or propylene oxide adducts of bisphenol A.

When the component (f) is blended, the blending amount is based on 100 parts by weight of the total of the components (a) and (b).
The lower limit is 5 parts by weight, preferably 8 parts by weight, and the upper limit is 15 parts by weight.
0 parts by weight, preferably 100 parts by weight, more preferably 8 parts by weight
0 parts by weight. If the amount is less than the lower limit, the effect of improving the scratch resistance and heat resistance is insufficient. On the other hand, if the amount exceeds the upper limit, the obtained molded product is inferior in weather resistance.
In addition, there is a problem that the smoothness of the back surface of the formed molded product is poor, and when the foamable resin is molded on the back surface in the post-processing, gas foamed from the uneven portion leaks. If the composition containing the polyurethane elastomer is used as a skin of an automobile interior part comprising an olefin core material and an intermediate foamed layer of urethane foam, the composition can be pulverized and recycled.

Component (g) Liquid Polybutadiene By blending liquid polybutadiene, the heat resistance and scratch resistance of the composition are improved. Liquid polybutadiene is a liquid polymer that is transparent at room temperature and has a main chain fine structure of vinyl 1,2-linked, trans 1,4-linked, and cis 1,4-linked. Where vinyl 1,
The 2-bond content is preferably 30% by weight or less, and the vinyl 1,2-bond content exceeding 30% by weight is not preferred because the low-temperature properties of the resulting composition are deteriorated.

The number average molecular weight of the liquid polybutadiene is:
The upper limit is preferably 5,000, more preferably 4,000.
0, and the lower limit is preferably 1,000, more preferably 2,000. If the amount is less than the lower limit, the heat-deformation resistance of the obtained composition decreases, and if it exceeds the upper limit, the compatibility in the obtained composition decreases.

The liquid polybutadiene is preferably a copolymerizable compound having one or more groups selected from an epoxy group, a hydroxyl group, an isocyanate group, a carboxyl group and a carbonyl group. Among them, those having a hydroxyl group and a copolymerizable unsaturated double bond are particularly preferable, and examples of commercially available products include R-45HT (trademark) manufactured by Idemitsu Petrochemical Co., Ltd.

When the component (g) is blended, the blending amount is based on 100 parts by weight of the total of the components (a) and (b).
The upper limit is 20 parts by weight, preferably 10 parts by weight, and the lower limit is 0.1 part by weight, preferably 1 part by weight. If the amount is less than the above lower limit, the effect of improving heat resistance and scratch resistance is insufficient, and if the amount exceeds the above upper limit, bleed out may occur.

Component (h) unsaturated carboxylic acid or derivative thereof
By blending the conductive unsaturated carboxylic acid or its derivative, the compatibility between the component (b) and the component (f) is improved. Preferably, acrylic acid, methacrylic acid, maleic acid, dicarboxylic acid or derivatives thereof such as acids, halides, amides, imides, anhydrides and esters are exemplified. Particularly preferably, maleic anhydride (MAH) is used. Preferably, polypropylene or the like is modified with the unsaturated carboxylic acid or derivative thereof. That is, the soft-segment component of the hydrogenated block copolymer in the component (b-1) or the hydrogenated conjugated diene compound portion of the hydrogenated random copolymer in the component (b-2), and the peroxide decomposable type of the component (i) It is believed that the polyolefin resin is modified.

When the component (h) is blended, the blending amount is based on 100 parts by weight of the total of the components (a) and (b).
The upper limit is 5 parts by weight, preferably 1 part by weight, and the lower limit is 0.1 part by weight.
05 parts by weight, preferably 0.1 part by weight. If the amount is less than the lower limit, the effect of improving compatibility is insufficient. If the amount exceeds the upper limit, a large amount of gas is generated during molding, fogging occurs in the molded body, and pinholes are further increased.

(I) Component Peroxide decomposable poly
Olefin Resin The component (i) of the present invention has the effect of improving the dispersion of the component (b) in the composition, improving the appearance of a molded article, and improving heat resistance. When component (i) is compounded, the lower limit is 0.05 part by weight, preferably 1 part by weight, based on 100 parts by weight of the total of components (a) and (b).
The upper limit is 30 parts by weight, preferably 10 parts by weight. If the amount is less than the lower limit, the effect of improving heat resistance is insufficient, and if the amount exceeds the upper limit, the composition becomes hard and moldability deteriorates. The peroxide decomposable polyolefin resin suitable as the component (i) in the present invention has a melting peak temperature (Tm) determined by differential scanning calorimetry.
Is 150 ° C or higher and melting enthalpy (△ Hm) 100
J / g or less. Preferably, Tm is 150 ° C.
１６167 ° C., ΔHm is 25 mJ / mg to 83 mJ / mg
Of the range. The crystallinity can be estimated from Tm and ΔHm. When Tm and ΔHm are out of the above ranges, the rubber elasticity of the obtained composition at 100 ° C. or higher is not improved.

The peroxide-decomposable polyolefin resins include high-molecular-weight homo-type polypropylenes such as isotactic polypropylene and propylene and other small amounts of α-olefins such as ethylene, 1-butene and 1-butene.
Copolymers with hexene, 4-methyl-1-pentene and the like are preferred. The MFR of the resin (ASTM-D-1238,
L condition, 230 ° C.) is preferably 0.1 to 10 g / 1.
0 minutes, more preferably 3 to 8 g / 10 minutes.

If the MFR of the peroxide decomposable polyolefin resin is less than 0.1 g / 10 minutes, the moldability of the resulting composition is poor, and if the MFR exceeds 10 g / 10 minutes,
It is not preferable because the rubber elasticity of the obtained composition is deteriorated.

If necessary, a peroxide decomposable polyolefin resin may be modified with maleic anhydride, modified with glycidyl methacrylate, modified with allyl glycidyl ether, modified with oxazolyl methacrylate, modified with allyl oxazolyl ether, ) Hydroxyalkyl (meth) acrylate modified products, carboxyl methacrylate modified products, allyl carboxyl ether modified products, alkyl methacrylate modified products, and alkyl acrylate modified products can be used.

In addition to the peroxide decomposable polyolefin resin, the number average molecular weight (Mn) is 25,000 or more, and the weight average molecular weight (Mw) and the number average molecular weight (M
n) and a boiling heptane-soluble polypropylene having a ratio (Mw / Mn) of 7 or less and a melt index of 0.1 to 4 g.
Peroxide decomposable olefin resin composed of / 10 minute boiling heptane-insoluble polypropylene, boiling heptane-soluble polypropylene having an intrinsic viscosity [η] of 1.2 dl / g or more, and intrinsic viscosity [η] of 0.5 to 9.0 dl / g. g
A peroxide-decomposable olefin resin comprising a boiling heptane-insoluble polypropylene of the formula (I) can also be used.

Component (j) Peroxide crosslinked polio
When the olefin resin peroxide-crosslinked polyolefin resin is blended, the tensile strength of the composition is improved. Peroxide-crosslinked polyolefin resins include high-density polyethylene (low-pressure polyethylene), low-density polyethylene (high-pressure polyethylene), and linear low-density polyethylene (ethylene and a small amount, preferably 1 to 10 mol% of butene-1 and hexene). -1, copolymers with α-olefins such as octene-1), ethylene-propylene copolymers, ethylene-vinyl acetate copolymers, ethylene-
1 selected from acrylic ester copolymers
Species or two or more species are preferably used. Particularly preferred are produced with a metallocene catalyst (single site catalyst), a density of 0.90 g / cm ³ or less of ethylene-octene copolymers or density 0.90 g / cm ³ or more ethylene-hexene copolymers. Those having a Tm of 100 ° C. or lower need to be added and crosslinked at the latest at the time of crosslinking. Due to the crosslinking, Tm disappears and octene and hexene do not melt. When the addition is performed after the crosslinking, the melting of octene and hexene at 30 to 60 ° C. remains, and the heat resistance decreases.

For example, according to the method described in JP-A-61-296008, the support and 4b of the periodic table
Comprising a reaction product of a metallocene containing at least one metal of Group 5, 5b and 6b with alumoxane;
An olefin polymer polymerized by an olefin polymer catalyst, wherein the reaction product is formed in the presence of a support.

Group 3 (other than scandium) of the periodic table of elements described in JP-A-3-163008,
A metal coordination complex comprising a Group 10 or lanthanide series metal and a delocalized π-bonded moiety substituted with a constraint inducing moiety, wherein the complex has a constrained geometry around the metal atom and The metal angle between the center of the localized substituted π-bond moiety and the center of the at least one remaining substituent is smaller in such a comparison complex in which the only difference is that the constraint-induced substituent is replaced by hydrogen. And one more
For such complexes containing one or more delocalized substituted π-bonded moieties, wherein each of the complexes has, for each metal atom, only one of them is a cyclic delocalized substituted π-bonded moiety. An olefin polymer polymerized from a coordination complex is exemplified.

If necessary, modified with maleic anhydride, modified with glycidyl methacrylate, modified with allyl glycidyl ether, modified with oxazolyl methacrylate, modified with allyl oxazolyl ether, (poly) hydroxyalkyl (meth) acrylate Modified products, carboxyl methacrylate modified products, allyl carboxyl ether modified products, alkyl methacrylate modified products, and alkyl acrylate modified products can be used. Among them, ethylene-glycidyl methacrylate copolymer and maleic anhydride-modified polyethylene are preferable.

Component (j) is preferably at a temperature of 190 ° C.
MFR at a load of 2.16 kg is preferably 0.1 to
300 g / 10 min, more preferably 0.3 to 200 g /
10 minutes. When the component (j) is blended, the blending amount is based on 100 parts by weight of the total of the components (a) and (b).
The upper limit is 30 parts by weight, preferably 20 parts by weight, and the lower limit is
0.05 parts by weight, preferably 1 part by weight. If the amount is less than the lower limit, the effect of improving mechanical properties is insufficient, and if the amount exceeds the upper limit, the composition becomes hard and moldability deteriorates.

Other Ingredients In addition to the above components, the resin composition of the present invention may contain a releasing agent such as stearic acid and silicone oil, a lubricant such as polyethylene wax, and a pigment, as long as the object of the present invention is not impaired. , An inorganic filler such as alumina, an antioxidant, a blowing agent (organic or inorganic), a flame retardant (hydrated metal compound, red phosphorus, ammonium polyphosphate, antimony, silicone), and the like.

The thermoplastic resin composition of the present invention can be produced by melt-kneading the above components in any order or simultaneously. Preferably, in the first step, all components other than the component (a) EVOH are melt-kneaded, and in the second step, the component (a) is added and melt-kneaded. At that time, the component (c) the organic peroxide and (d) the crosslinking aid are added in a part in the first step, and the remainder is added in the second step.
The method of melt kneading is not particularly limited, and a known method can be used. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders, or the like can be used. 2
When a shaft kneader is used, for example, melt kneading is performed at a screw rotation speed of 100 rpm and a kneading temperature of 180 to 240 ° C, preferably 200 to 220 ° C. Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[0049]

EXAMPLES Evaluation method (1) Pinhole in molded article The surface of the molded article obtained by rotary powder molding was observed with a 5-fold loupe. ：: There is no pinhole at all. Δ: Pinholes are partially present. ×: There is a pinhole as a whole. (2) Smoothness of the back surface of the molded product Using a gloss meter (GMX-202 manufactured by Murakami Color Research Laboratory),
Light was applied to the back surface of the molded product after the rotational molding with a light source of incident light of 60 degrees, the gloss value of the reflected light was measured, and evaluated according to the following evaluation criteria. ◎: Gloss value of 50 or more ○: Gloss value of 10 or more ×: Gloss value of less than 10 (3) Blocking At the time of rotary powder molding, it was observed whether or not the material collected in the powder box was blocked by heat history. ：: Not at all. (0%) Δ: Slightly blocked. ×: Remarkably blocked. (4) Heat resistance: A change in shape after placing the resin composition molded into a No. 3 dumbbell shape in a gear oven at 110 ° C. for 168 hours was confirmed. ◎: Deformation amount 0% ○: Deformation amount less than 5% ×: Deformation amount 5% or more (5) Taber abrasion resistance: According to JIS K 7204, a 2 mm thick press sheet was used as a test piece, and a worn wheel H-22 , 10
The amount of wear (mg) after 00 rotations was measured. (6) Hardness (HDD): Based on JIS K 7215. The test piece was prepared by heating the pellets obtained by melt-kneading at 240 ° C.
A sheet pressed to a thickness of 6.3 mm was used. (7) Tensile strength (TS): According to JIS K 7161, the test piece was a 1 mm thick pressed sheet punched out with a dumbbell into a No. 3 die. The pulling speed was 500 mm / min. (8) 100% elongation stress (100% M): A 1 mm-thick press sheet of a test piece was punched out with a dumbbell into a No. 3 type and a No. 3 type according to JIS K 7161. The pulling speed was 500 mm / min. (9) Elongation at break (EL): Specimen 1 according to JIS K 7161
A mm-thick press sheet was punched out with a dumbbell into a No. 3 type and used. The pulling speed was 500 mm / min. (10) Tear strength: based on JIS K6252,
As the test piece, a No. 3 dumbbell-shaped test piece having a thickness of 2 mm was prepared from a 2 mm-thick press sheet and used. The tearing speed is
It was 500 mm / min.

Substances used (a) EVOH (1) Mersen HH6922X, manufactured by Tosoh Corporation Ethylene content: 72% by weight Saponification degree: 90% by weight (2) Mersen HH6920, manufactured by Tosoh Corporation Ethylene content : 72% by weight Saponification degree: 90% by weight Component (b) Aromatic vinyl compound-conjugated diene compound copolymer and / or hydrogenated product thereof (b-1) Septon 2002, Kuraray Co., Ltd. Styrene content: 30% by weight Isoprene content: 70% by weight Mn: 55,000 Mw: 60,000 Mw / Mn: 1.09 Hydrogenation rate: 90% or more (b-2): hydrogenated random copolymer (SBR) Dynaron 1320P (trademark) manufactured by JSR Styrene content: 10% by weight Mn: 300,000 Mw / Mn: 1.1 Hydrogenation rate: 90% or more Component (c): Organic peroxide Manufacturer: Nippon Yushi Co., Ltd. Made Product name: Perhexa 25B Type: 2,5-dimethyl-2,5-di (t-butylperoxy) hexane component (d): Crosslinking assistant NK ester 3G manufactured by Shin-Nakamura Chemical Co., Ltd. Type: triethylene glycol dimethacrylate component ( e): (poly) hydroxyalkyl (meth) acrylate 2-hydroxyethyl methacrylate (HEMA), light ester HO (trademark), manufactured by Kyoeisha Chemical Co., Ltd. Component (f): thermoplastic polyurethane resin Pandex T-8180 (trademark) ), Dainippon Ink Industry Co., Ltd. Component (g): Liquid polybutadiene R-45HT (trademark), manufactured by Idemitsu Petrochemical Industry Co., Ltd. Component (h): Unsaturated carboxylic acid or derivative thereof Maleic anhydride, manufactured by Kanto Chemical Co., Ltd. Component (i): peroxide decomposable olefin resin polypropylene, BC03C (trademark) Component (j): Peroxide-crosslinked olefin resin manufactured by Mitsubishi Chemical Corporation Linear low-density polyethylene, FS370 (trademark), Sumitomo Chemical Optional components: heavy calcium carbonate, NS400 (trademark), silicone oil manufactured by Shiraishi calcium , SH-200 1000CS (trademark), manufactured by Toray Dow Corning Silicone Co., Ltd. Materials used in Comparative Examples: ethylene-vinyl acetate copolymer, Ultracene 680
Tosoh Corporation Ethylene content: 80% by weight MFR: 160 g / 10 min Ethylene-vinyl acetate copolymer, Ultracene 760
Ethylene content: 58% by weight, manufactured by Tosoh Corporation MFR: 70 g / 10 minutes EVOH, Mersen H H6251 Ethylene content: 72% by weight, manufactured by Tosoh Corporation Saponification degree: 21.4% by weight MFR: 5 g / 10 minutes

Preparation of Resin Composition In each ratio shown in Tables 1 and 2, first, the component (a) EVO
The components other than H are kneaded by a twin-screw extruder, and if (c) peroxide and (d) a part of the crosslinking aid are added, kneading temperature 210 ° C., screw rotation 350 rpm, extruder discharge rate Dynamic crosslinking was performed at 20 kg / hr. Next, the component (a) is side-fed, and if there is a residue of the peroxide (c) and the crosslinking assistant (d), the residue is added to the residue.
Kneaded at 0 ° C. Each evaluation was performed about the obtained resin composition.

[0052]

[Table 1]

[0053]

[Table 2]

As can be seen by comparing Tables 1 and 2, the resin composition of the present invention does not cause blocking, has no pinholes, and gives a molded article having a smooth back surface. The molded article is also excellent in heat resistance and wear resistance.

[0055]

As described above, since the thermoplastic resin composition of the present invention uses a saponified ethylene-vinyl acetate copolymer having a specific ethylene content and a saponification rate, the moldability in rotary powder molding is reduced. Provides molded products with excellent weather resistance, flame retardancy, smoothness on the back surface, and heat resistance. Further, since a copolymer of an aromatic vinyl compound and a conjugated diene compound is used, toys and automobile members having a soft touch can be obtained. Further, since it does not contain a volatile softener, no gas is generated at the time of molding, and there is no molding failure due to the gas.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/14 C08K 5/14 C08L 23/04 C08L 23/04 23/10 23/10 25/10 25 / 10 47/00 47/00 53/02 53/02 75/04 75/04 // B29K 55:00 B29K 55:00 B29L 31:52 B29L 31:52 31:58 31:58 F term (reference) 4F205 AA19K AA31K AA46J AA46K AB03 AB04 AC04 GA01 GB01 GC04 GE17 GE24 GF02 4J002 BB035 BB055 BB125 BB145 BB22W BC05X BE03W BL014 BP01X CK023 CK033 CK043 EF049 EF069 EF129 EH0 EF EF079 EF029 EH0148 EH0148 EH0148 EH0148 EF049

Claims (6)

[Claims] 1. A method comprising: (a) 40 to 95 parts by weight of a saponified ethylene-vinyl acetate copolymer resin, (b) an aromatic vinyl compound-conjugated diene compound copolymer, and a hydrogenated product thereof. In a thermoplastic resin composition containing at least one selected from 60 to 5 parts by weight, the ethylene content of (a) the saponified ethylene-vinyl acetate copolymer resin is 40 to 95% by weight of the resin, and The saponification degree is 80% by weight or more of the vinyl acetate component, and at least one selected from the group consisting of (b) an aromatic vinyl compound-conjugated diene compound copolymer and a hydrogenated product thereof is (b) −
1) An aromatic vinyl compound-conjugated diene compound block copolymer and a hydrogenated product thereof, and (b-2) the content of the aromatic vinyl compound is 50% by weight or less, and the number average molecular weight (Mn) is 5,000. 11,000,000 and polydispersity (M
w / Mn) is 10 or less, and the content of the vinyl bond based on the conjugated diene compound is 10% or more of the bond based on the conjugated diene compound. A thermoplastic resin composition, which is at least one member selected from the group consisting of hydrogenated products. 2. Component (b) having a weight average molecular weight of 5,000
0 to 1,500,000 hydrogenated styrene-isoprene-styrene block copolymers, wherein 70-100% by weight of the isoprene has a 1,4-microstructure and the isoprene-based fat The thermoplastic resin composition according to claim 1, wherein at least 90% of the group II double bonds are hydrogenated. 3. The thermoplastic resin composition according to claim 1, wherein component (b) is a hydrogenated styrene-butadiene random copolymer in which at least 70% of olefinically unsaturated bonds are hydrogenated. object. 4. The composition further comprises (c) 0.01 to 3 parts by weight of an organic peroxide and (d) 0.01 to 5.5 parts by weight of a crosslinking aid, based on 100 parts by weight of the total of the components (a) and (b). The thermoplastic resin composition according to claim 1. 5. (e) (poly) hydroxyalkyl (meth) based on 100 parts by weight of the total of components (a) and (b)
The thermoplastic resin composition according to any one of claims 1 to 4, further comprising 1 to 20 parts by weight of an acrylate. 6. A total of 100 parts by weight of components (a) and (b), (f) 5-150 parts by weight of a thermoplastic polyurethane resin (g) 0.1-20 parts by weight of liquid polybutadiene (h) unsaturated Carboxylic acid or its derivative 0.05 to 5 parts by weight (i) peroxide decomposable polyolefin resin 0.05
To 30 parts by weight and (j) peroxide-crosslinked polyolefin resin 0.05
The thermoplastic resin composition according to any one of claims 1 to 5, further comprising at least one component selected from the group consisting of: 30 to 30 parts by weight.