JP3102842B2 - Method for producing thermoplastic elastomer resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a novel thermoplastic elastomer resin which is rich in flexibility, excellent in rubber properties, mechanical strength and moldability, and free of stickiness.

[0002]

2. Description of the Related Art In recent years, thermoplastic elastomer resins, which are rubber-like materials and do not require a vulcanization step and have the same moldability as thermoplastic resins, have been used in automobile parts, home appliance parts, wire coatings, footwear. , Has been attracting attention in the field of miscellaneous goods.

As such thermoplastic elastomer resins, various types of polymers such as polyolefin, polyurethane, polyester, polystyrene and polyvinyl chloride have been developed and are commercially available.

Of these, styrene-butadiene-
Polystyrene-based thermoplastic elastomer resins such as block copolymer (SBS) and styrene-isoprene-block polymer (SIS) are rich in flexibility, have good rubber elasticity at room temperature, and can be obtained from these. The composition is excellent in processability.

However, these polymers have a double bond as a conjugated diene block in the molecule, and therefore have a problem in heat aging resistance (thermal stability) and weather resistance.

[0006] In order to solve this problem, an elastomer resin composition having improved thermal stability can be obtained by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene.

Several thermoplastic elastomer resin compositions using these hydrogenated products have been proposed. For example, Japanese Patent Application Laid-Open Nos. 50-14742 and 52-72 have been proposed.
No. 26551, and the like. And
For example, Japanese Patent Application Laid-Open No. 58-13203 discloses such improved methods.
No. 2, JP-A-58-145751, JP-A-58-145751,
JP-A-9-53548, JP-A-59-131613 and JP-A-62-48757 disclose a method of adding a hydrocarbon and an α-olefin polymer resin to a hydrogenated styrene-conjugated diene-block copolymer. A blended composition or a method for producing the same is disclosed.

[0008] However, conventional thermoplastic elastomer resin compositions using these hydrogenated block copolymers have problems in rubber-like properties, such as deformation under heat and pressure (compression set) and rubber elasticity at high temperatures. Was.

To improve this point, a crosslinkable composition obtained by subjecting a composition containing such a hydrogenated derivative of a block copolymer to silane modification, or a hydrogenated derivative of such a block copolymer is provided. In the presence of an organic peroxide, there has been proposed a crosslinked product obtained by crosslinking in the presence of an organic peroxide. For example, JP-A-59-6236, JP-A-62-57662, and Japanese Patent Publication No. Hei. 49
927, Japanese Patent Publication 3-112291, Japanese Patent Publication 3-5838
1, Japanese Patent Publication No. Hei 6-13628.

However, the crosslinked composition of the hydrogenated block copolymer disclosed by these proposals still has insufficient compression set at high temperatures, particularly at 100 ° C., and has been conventionally required for vulcanized rubber applications. The current performance level has not been reached. For example, good workability cannot be obtained, and mechanical strength decreases.

The compositions obtained by these proposals are as follows:
At present, the use of an organic peroxide causes stickiness on the surface of a molded article of the composition due to decomposition of the peroxide-decomposable polymer during compounding, and presents problems such as being unfavorable for practical use.

[0012]

According to the present invention, there are provided (1) (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least two polymer blocks B mainly composed of a conjugated diene compound. One block copolymer and / or a hydrogenated block copolymer obtained by hydrogenating the block copolymer 100 parts by weight (b) Softener for non-aromatic rubber 40 to 300 parts by weight (c) Oxide-crosslinked olefin-based resin, and / or
Or a copolymer rubber containing the same 1.0 to 100 parts by weight (d) a peroxide-decomposable olefin-based resin, and / or
Alternatively, in the method for producing a thermoplastic elastomer resin composition containing 10 to 150 parts by weight of a copolymer containing the same, at least a part of the components (a) and (b), the component (c), and one of the components (d). Part is heat-treated in the presence of an organic peroxide to cause crosslinking, and then the crosslinked product is blended with the remainder of component (d) or the remainder of components (c) and (d). This is a method for producing an elastomer resin composition.

Preferred embodiments of the present invention include: (2) further comprising (e) 0 to 130 parts by weight of a polyester thermoplastic elastomer and (f) an inorganic filler (0).
(1) The production method according to (1), wherein 100 parts by weight are blended at an optional stage. (3) At least 3 parts by weight of the component (d) is subjected to a heat treatment in the presence of an organic peroxide, and at least 5 parts by weight. (4) The method according to any one of (1) to (3), wherein at least half of the component (c) is subjected to the heat treatment. (5) The production method according to any one of (2) to (4), wherein the heat treatment in the presence of the organic peroxide is performed in the presence of at least a part of the component (e). (6) The production method according to any one of (1) to (5), wherein the crosslinking is performed in the presence of a crosslinking aid that is a monomer having an ethylenically unsaturated group. g) Electron donor: 0 to 15 parts by weight is heated in the presence of an organic peroxide. The method according to any one of claims 1 to 6, which is added before or during the treatment. (8) Further, (g) a heat treatment in the presence of an organic peroxide in an amount of 0 to 25 parts by weight of the electron donor. Before, components (a)-
The production method according to any one of claims 1 to 6, wherein the mixture is heated and mixed (including melt kneading) with (f).

According to the present invention, there is provided a resin composition having excellent rubber-like properties and mechanical strength as compared with conventional thermoplastic elastomer resin compositions, and having no stickiness.

In addition, the resin composition of the present invention is excellent with almost no formation of a crosslinked gel.

Furthermore, molded articles obtained from the resin composition of the present invention have excellent appearance.

Hereinafter, each component and the production method will be described in detail.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION (a) Component Block Copolymer Component (a) of the present invention comprises at least two polymer blocks A mainly composed of a vinyl aromatic compound and a polymer mainly composed of a conjugated diene compound. A block copolymer comprising at least one united block B, a block copolymer obtained by hydrogenating the block copolymer, or a mixture thereof;
A vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as -BA, BABA, ABABA, or a hydrogenated product thereof; Can be mentioned. (Hydrogenated) block copolymer (hereinafter, (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer)
Contains 5 to 60% by weight, preferably 20 to 50% by weight of a vinyl aromatic compound. The polymer block A based on vinylaromatics preferably consists of vinylaromatics alone or with more than 50% by weight, preferably more than 70% by weight, of conjugated dienes (hydrogenated). It is a copolymer block with a compound (hereinafter, the (hydrogenated) conjugated diene compound means a conjugated diene compound and / or a hydrogenated conjugated diene compound). The polymer block B based on (hydrogenated) conjugated diene compounds preferably consists only of (hydrogenated) conjugated diene compounds or comprises more than 50% by weight of (hydrogenated) conjugated diene compounds, Preferably, it is a copolymer block of 70% by weight or more and a vinyl aromatic compound. In each of the polymer block A mainly containing the vinyl aromatic compound and the polymer block B mainly containing the (hydrogenated) conjugated diene compound, the vinyl compound in the molecular chain or the (hydrogenated)
The distribution of the conjugated diene compound is random, tapered (the monomer component increases or decreases along the molecular chain),
It may be partially block-shaped or any combination thereof. When there are two or more polymer blocks A mainly containing a vinyl aromatic compound or two or more polymer blocks B mainly containing a (hydrogenated) conjugated diene compound, they have different structures even if they have the same structure. There may be.

As the vinyl aromatic compound constituting the (hydrogenated) block copolymer, for example, one or more selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene and the like are selected. Of which styrene is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like.
Isoprene and combinations thereof are preferred.

The microstructure of the polymer block B mainly composed of a conjugated diene compound can be arbitrarily selected.
In the butadiene block, the 1,2-microstructure is preferably from 20 to 50%, particularly preferably from 25 to 45%. In the polyisoprene block, 70% of the isoprene compound
-100% by weight has a 1,4-microstructure and at least 9 aliphatic double bonds based on the isoprene compound.
Those in which 0% is hydrogenated are preferred.

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, More preferably, 1
It is in the range of from 00,000 to 550,000, particularly preferably from 10,000 to 400,000. The molecular weight distribution (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 is as follows:
It may be linear, branched, radial or any combination thereof.

Numerous methods have been proposed as methods for producing these block copolymers. Typical methods include, for example, a method described in Japanese Patent Publication No. 40-23798, which uses a lithium catalyst or a lithium catalyst. It can be obtained by performing block polymerization in an inert solvent using a Ziegler 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, SEBS, and SEPS. 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 at least 90 of aliphatic double bonds based on the isoprene
% Is a hydrogenated block copolymer having a weight average molecular weight of 50,000 to 550,000 and a polymer block B to which hydrogen has been added. More preferably, 90 to 100% by weight of isoprene is the above hydrogenated block copolymer having a 1,4-microstructure.

(B) Component Softener for Non-Aromatic Rubber As the component (b) of the present invention, a non-aromatic mineral oil or a liquid or low molecular weight synthetic softener can be used. The mineral oil softener used for rubber is a mixture of an aromatic ring, a naphthene ring, and a paraffin chain in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms. Those having 30 to 40% of naphthenic ring carbons are called naphthenics, and those having 30% or more aromatic carbons are called aromatics.

The mineral oil-based rubber softener used as the component (b) of the present invention is a paraffinic or naphthenic type in the above category. The use of an aromatic softening agent is not preferred because its use makes the component (a) soluble and inhibits the cross-linking reaction, so that the physical properties of the obtained composition cannot be improved.
The component (b) is preferably a paraffinic one,
Further, among paraffins, those having a small amount of aromatic ring components are 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
Indicates 70 to 300 ° C.

The amount of the component (b) is 100%.
40 to 300 parts by weight, preferably 8 parts by weight
0 to 150 parts by weight. If the amount exceeds 300 parts by weight, the softener tends to bleed out, may give tackiness to the final product, and deteriorate the mechanical properties. If the amount is less than 40 parts by weight, the moldability of the obtained composition will be lost (see Table 10). Part of component (b) can be added after heat treatment in the presence of peroxide, but this is not preferred because it causes bleed-out. Component (b) preferably has a weight average molecular weight of 100 to 2,000.

(C) Component Peroxide Crosslinked Ole
Fin-based resin and / or copolymer rubber containing the same As the component (c) of the present invention, one which mainly causes a cross-linking reaction by heat treatment in the presence of a peroxide to reduce its fluidity is used. Can be.
For example, polyethylene having a polymer density in the range of 0.88 to 0.94 g / cm ³ , such as high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene, or ethylene-propylene copolymer It is an elastic body of an amorphous random copolymer containing an olefin as a main component, such as a united rubber or an ethylene / propylene / non-conjugated diene copolymer rubber. Among them, polyethylene or ethylene-propylene copolymer rubber is preferable,
Among them, linear low-density polyethylene is particularly preferable in that an appropriate crosslinked structure can be obtained.

For example, when the component (c) is a rubber, the Mooney viscosity and ML1 + 4 (100 ° C.) are preferably 10 to 10.
120, more preferably 40-100. If the Mooney viscosity is less than 10, rubber properties of the obtained elastomer composition are inferior. On the other hand, when the amount exceeds 120, the moldability deteriorates, and particularly, the appearance of the molded product deteriorates.

The ethylene content in the copolymer is suitably from 5 to 50% by weight. Preferably it is 6 to 20% by weight, more preferably 10 to 15% by weight. When the ethylene content is less than 5% by weight, the flexibility of the obtained elastomer composition is insufficient, and when it is more than 50% by weight, the mechanical strength is reduced.

The weight average molecular weight of the peroxide-crosslinked olefin resin and / or the copolymer rubber containing the same is preferably in the range of 50,000 to 1,000,000, more preferably 70,000 to 500,000. . When a peroxide-crosslinked olefin resin having a weight-average molecular weight of less than 50,000 and / or a copolymer rubber containing the same is used, the obtained elastomer composition has poor rubber-like properties. Further, the weight average molecular weight is 1,000,000
When the amount exceeds the above range, the moldability deteriorates, and particularly the appearance of the molded product deteriorates.

The amount of component (c) is 100 parts
1.0 to 100 parts by weight, preferably 3.
0 to 50 parts by weight. When the amount is less than 1.0 part by weight, the mechanical properties of the obtained elastomer composition are reduced. 10
If the amount exceeds 0 parts by weight, the flexibility of the obtained elastomer composition decreases, and the moldability deteriorates.

Preferably, at least half, especially more than 3 parts by weight, of the amount of component (c) is incorporated before the heat treatment in the presence of the peroxide. The remainder is blended after the heat treatment, whereby various physical properties can be adjusted as described later.

(D) Component Peroxide Decomposition Type Ole
Fin-based resin and / or copolymer containing the same The component (d) of the present invention has an effect of improving the rubber dispersion in the obtained composition and improving the appearance of a molded article. The amount of component (d) is 10 to 150 parts by weight, preferably 25 to 100 parts by weight, per 100 parts by weight of component (a). When the amount is less than 10 parts by weight, the moldability of the obtained elastomer composition is deteriorated, and when it exceeds 150 parts by weight, the flexibility and rubber elasticity of the obtained elastomer composition are deteriorated.

The peroxide-decomposable olefin-based resin suitable as the component (d) of the present invention has a homo part of DS
According to C measurement, Tm was 150 ° C to 167 ° C, ΔHm was 2
It is in the range of 5 mJ / mg to 83 mJ / mg. The crystallinity can be estimated from Tm and ΔHm. Tm
When ΔHm is out of the above range, the rubber elasticity of the obtained elastomer composition at 100 ° C. or higher is not improved.

The peroxide-decomposable olefin resin is preferably used in combination of the following two types.

The peroxide-decomposable olefin-based resin to be added before the crosslinking reaction is a high-molecular-weight homo-type polypropylene such as isotactic polypropylene or propylene and a small amount of α-olefin such as ethylene or 1-olefin.
Copolymers with butene, 1-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
-10 g / 10 min, more preferably 0.1-5 g / 10
Min, more preferably 0.1 to 3 g / 10 min. The peroxide-decomposable olefin-based resin to be added after the crosslinking reaction may be one or more of good-flow block, random, and homo-type PP, for example, isotactic polypropylene, or propylene and other small amount of α-olefin such as ethylene, 1- Butene, 1-hexene, 4-methyl-1
-Copolymers with pentene and the like are preferred. MFR of the resin
Is preferably 5 to 200 g / 10 min, more preferably 8 to 150 g / 10 min, and still more preferably 10 to 100 g.
/ 10 minutes.

When compounded before the crosslinking reaction, if the MFR of the peroxide-decomposable olefin resin is less than 0.1 g / 10 minutes, the moldability of the obtained elastomer will be reduced,
When the FR exceeds 10 g / 10 minutes, the rubber elasticity of the obtained elastomer composition deteriorates, which is not preferable.

When blended after the crosslinking reaction, if the MFR of the peroxide-decomposable olefin-based resin is less than 5 g / 10 minutes, the moldability of the obtained elastomer is reduced, and the MFR is reduced.
If it exceeds 200 g / 10 minutes, the rubber elasticity of the obtained elastomer composition is undesirably deteriorated.

The amount of component (d) is 100 parts (a).
10 to 150 parts by weight, preferably 20 to 100 parts by weight with respect to parts by weight
80 parts by weight. If the amount is less than 10 parts by weight, the moldability deteriorates. If the amount exceeds 150 parts by weight, the hardness of the obtained elastomer composition becomes too high, the flexibility is lost, and a rubber-like product cannot be obtained.

In the present invention, a portion, preferably at least 3 parts by weight, of component (d) is subjected to a heat treatment in the presence of an organic peroxide, and the remainder of component (d), preferably at least 5 parts by weight, It is blended after heat treatment. By dividing and adding the component (d) in this way, each component is uniformly dispersed, so that the stickiness on the surface of the molded article is eliminated and the moldability is improved.

It is preferable that the ratio of the amount (X) to be added before the crosslinking reaction and the amount (Y) to be added after the crosslinking reaction is X <Y because a resin having more excellent rubber elasticity can be obtained. The above addition ratios X and Y can be determined by respective final molding methods such as injection molding and extrusion molding.

Component (e) Polyester-based thermoplastic resin
Lastomer The elastomer resin composition of the present invention can contain a polyester-based thermoplastic elastomer as component (e), if necessary. As the component (e) of the present invention, polybutylene terephthalate is used as a main hard segment,
Polyetherester block copolymers using poly (tetramethylene oxide) glycol as a soft segment or polyesterester block copolymers using polybutylene terephthalate as a main hard segment and poly-ε-caprolactone as a soft segment Even if heat treatment is performed in the presence of an oxide, a material that does not crosslink and does not decrease fluidity can be used. Component (e) is used in an amount of 0 to 130 parts by weight, preferably 10 to 60 parts by weight, per 100 parts by weight of component (a). If the amount exceeds 130 parts by weight, the flexibility of the obtained elastomer composition is reduced, and the moldability is also deteriorated.
In particular, the component (e) preferably has a Tm of 160 to 220 ° C and a D hardness of 35 or more. By blending the component (e), the oil resistance and heat resistance of the obtained elastomer composition are improved. The term “heat resistance” as used herein refers to the temperature dependence of compression set and hardness.

[0045] As the component (f) an inorganic filler if necessary with component (f), it can be blended an inorganic filler. This filler has the effect of improving some physical properties such as compression set of the molded article, and has the economical advantage of increasing the amount. Conventional inorganic fillers can be used satisfactorily, for example, calcium carbonate, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white carbon), titanium oxide,
And carbon black. Of these, calcium carbonate or talc is particularly preferred.

The amount of the component (f) is 100
0-100 parts by weight, preferably 0-6 parts by weight, relative to parts by weight
0 parts by weight. If the amount exceeds 100 parts by weight, the resulting elastomer composition is not preferred because the mechanical strength of the obtained elastomer composition is remarkably reduced, and the hardness is increased so that flexibility is lost and a rubbery product cannot be obtained.

(G) Component Electron Donor The (g) electron donor used in the present invention refers to an electron donor having an atom, ion or molecule in its structure that can easily give an electron to a partner. For example, aromatic hydrocarbons such as benzene and naphthalene and their substituted products, various amines, carboxylic acids, carboxylic anhydrides, carboxylic esters, alcohols, ethers, ketones, aldehydes, alcoholates and the like. can give. Examples of the electron donating atoms and ions include chlorine ions, fluorine ions, and iodine ions. As an electron donating group, an amino group, an imino group,
Examples include a hydroxyl group, a halogen group, an alkyl group and an allyl group. Examples of the electron donating monomer include ethyleneimine.

Specific examples of the aromatic hydrocarbon include benzene, toluene, o-xylene, m-xylene, p-xylene, hemimaritin, pseudocumene, prenitene, isodulen, durene, pentamethylbenzene, hexamethylbenzene, ethylbenzene, and propylbenzene. ,
Styrene, cumene, mesitylene, cymene, biphenyl,
Naphthalene, anthracene, indene, phenanthrene, indane, p-terphenyl, diphenylmethane,
Triphenylmethane, bibenzyl, stilbene, tetralin and the like.

Specific examples of the carboxylic acid include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, capionic acid, vivalic acid, acrylic acid, methacrylic acid and crotonic acid, and malonic acid. Acid, succinic acid,
Glutaric acid, adipic acid, sebacic acid, maleic acid, aliphatic dicarboxylic acids such as fumaric acid, cyclohexane monocarboxylic acid, cyclohexene monocarboxylic acid, cis-1,
Alicyclic carboxylic acids such as 2-cyclohexanedicarboxylic acid, cis-4-methylcyclohexene-1,2-dicarboxylic acid, benzoic acid, toluic acid, anisic acid, p-tert-butylbenzoic acid, naphthoic acid, and cinnamon Aromatic polycarboxylic acids such as aromatic monocarboxylic acids such as acids, phthalic acid, isophthalic acid, terephthalic acid, naphthalic acid, trimellitic acid, hemi-mellitic acid, trimesic acid, pyromellitic acid, and merit acid; .

As the carboxylic acid anhydride, the acid anhydrides of the above carboxylic acids can be used.

As the carboxylic acid ester, mono- or polyvalent esters of the above carboxylic acids can be used.
Specific examples thereof include butyl formate, ethyl acetate, butyl acetate, isobutyl isobutyrate, propyl bivalate, isobutyl bivalate, ethyl acrylate, ethyl methacrylate, isobutyl methacrylate, diethyl malonate, diisobutyl malonate, dibutyl succinate, Diethyl succinate, diethyl glutarate, dibutyl glutarate, diisobutyl glutarate, diisobutyl adipate, dibutyl maleate, diisobutyl maleate, dibutyl sebacate, diethyl sebacate, monomethyl maleate, diethyl tartrate, dibutyl tartrate, diisobutyl tartrate,
Ethyl cyclohexanecarboxylate, methyl benzoate, ethyl benzoate, methyl p-toluate, ethyl p-tert-butyl benzoate, ethyl p-anisate, ethyl α-naphthoate, isobutyl α-naphthoate, cinnamic acid Ethyl, monomethyl phthalate, monobutyl phthalate, dibutyl phthalate, diisobutyl phthalate, dihexyl phthalate, dioctyl phthalate, di-2-ethylhexyl phthalate, diallyl phthalate, diphenyl phthalate, diethyl isophthalate, dibutyl isophthalate, terephthalate Dibutyl acid, diethyl naphthalate, dibutyl naphthalate, triethyl trimellitate, butyl trimellitate, tetramethyl pyromellitate, tetraethyl pyrolitate,
And tetrabutyl pyromellitate.

As the carboxylic acid halide, acid halides of the above carboxylic acids can be used.
Specific examples thereof include acetic acid glolide, acetic acid bromide, acetic acid iodide, propionic acid chloride, butyric acid chloride,
Butyric bromide, Butyric acid iodide, Vivalic acid chloride, Vivalic acid bromide, Acrylic acid chloride, Acrylic acid bromide, Acrylic acid iodide, Methacrylic acid iodide, Crotonic acid chloride, Malonic acid chloride, Succinic bromide, Glutaric acid chloride, Glutaric acid bromide, Adipic acid chloride, adipic acid bromide, sebacic acid chloride, sebacic acid bromide, maleic acid chloride, maleic acid bromide, fumaric acid chloride, fumaric acid bromide, tartaric acid chloride, cyclohexanecarboxylic acid chloride, 1-cyclohexenecarboxylic acid chloride, cis-4 -Methylcyclohexenecarboxylic acid chloride, cis-4-methylcyclohexenecarboxylic acid bromide, benzoyl chloride, benzoyl bromide, p-toluic acid chloride, p-toluic acid Bromic acid, p-anisic acid chloride, p-anisic acid bromide, α-naphthoic acid chloride, cinnamic acid chloride, cinnamic acid bromide, phthalic dichloride, phthalic dibromide, isophthalic dichloride, isophthalic dibromide, terephthalic acid Dichloride, naphthalic acid dichloride and the like. Further, monoalkyl halides of dicarboxylic acids such as adipic acid monomethyl chloride, maleic acid monoethyl chloride, maleic acid monomethyl chloride, and butyl phthalate chloride can also be used.

Alcohols are represented by the general formula ROH.
In the formula, R is an alkyl, alkenyl, cycloalkyl, aryl, aralkyl or the like having 1 to 12 carbon atoms. Specific examples include methanol, ethanol, propanol, isopropanol, butanol, pentanol,
Hexanol, octanol, 2-ethylhexanol, cyclohexanol, benzyl alcohol, allyl alcohol, phenol, cresol, xylenol,
Examples thereof include ethylphenol, isopropylphenol, p-tert-butylphenol, and n-octylphenol.

The ethers are represented by the general formula ROR '. In the formula, R and R 'are alkyl, alkenyl, cycloalkyl, aryl, aralkyl and the like having 1 to 12 carbon atoms. R and R 'may be the same or different, and may together form a ring. Specific examples include diethyl ether, diisopropyl ether, dibutyl ether, diisoamyl ether, di-2-ethylhexyl ether, diallyl ether, ethyl allyl ether, diallyl ether, diphenyl ether, anisole, and ethylphenyl ether.
Cyclic ethers such as tetrahydrofuran, pyran and dioxane; chain ethers such as dimethoxyethane, diethylene glycol dimethyl ether and triethylene glycol dimethyl ether; 2,3-dihydrofuran;
Cyclic vinyl ethers such as 3,4-dihydro-2H-pyran, vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, 2,5-dihydrofuran,
Cyclic allyl ethers such as 5,6-dihydro-2H-pyran, aliphatic amines such as triethylamine and triethylenediamine, aromatic amines such as pyridine and picoline, 2-oxazoline, 6H-1,2,4- Heterocyclic compounds such as oxadiazine and the like can be mentioned.

In the present invention, preferred as the electron donor are toluene and methanol, and particularly preferred is toluene.

In the production method of the present invention, by using an electron donor in addition to the above components (a) to (f), the production of a crosslinked gel in the produced thermoplastic elastomer resin composition is reduced. Produces an effect. That is,
It is considered that the use of an electron donor in the present invention causes a reduction in the crosslinking rate and produces the above-described effect. The amount of the electron donor used in the present invention can vary depending on the electron donating ability of the electron donor used, but when it is added before heat treatment or during heat treatment in the presence of peroxide, it is generally used. , With respect to 100 parts by weight of component (a),
Not more than 0.5 parts by weight, preferably 0.5 to 6.0 parts by weight, more preferably 2.0 to 3.0 parts by weight, and before the heat treatment in the presence of peroxide, the component (g) is replaced with the component (a) to (F)
And heat-mixing (including melt-kneading),
The amount is 25 parts by weight or less, preferably 1.0 to 10 parts by weight based on 100 parts by weight of the component (a). In general, when the amount exceeds the upper limit, stickiness is caused in the molded product, which is not preferable. However, those with low electron donating ability
It is also possible to add more than parts by weight. The electron donating ability can be generally represented by a chain transfer constant of a polymer radical when an electron donor is used. The chain transfer constant varies depending on the type of the polymer used, the reaction temperature, and the like, but the chain transfer constant (Cs) of the styrene polymer radical at 60 ° C. when using an electron donor is 10 ⁻⁴ to 10 ^−6. Is preferred. For example, when toluene is used as the electron donor, the chain transfer constant of the styrene polymer radical is 1.25 × 10 ⁻⁵ .

Organic peroxide Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (te
rt-butylperoxy) hexane, 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 (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-butylperoxy Examples thereof include isopropyl carbonate, diacetyl peroxide, lauroyl peroxide, and tert-butylcumyl peroxide.

Of these, 2,5-dimethyl 2,5-di- (ter) is preferred in terms of odor, coloring, and scorch stability.
Most preferred are t-butylperoxy) hexane and 2,5-dimethyl2,5-di- (tert-butylperoxy) hexyne-3.

The amount of peroxide added is preferably in the range of 0.1 to 3.0 parts by weight, more preferably 100 parts by weight of the composition comprising components (a) to (e) at the time of peroxide addition. Is 0.5 to 2.5 parts by weight, more preferably 1.0 to 2.5 parts by weight.

In the method for producing the thermoplastic elastomer composition of the present invention, a polyfunctional vinyl monomer such as divinylbenzene or triallyl cyanurate, or ethylene glycol dimethacrylate or diethylene glycol Polyfunctional methacrylate monomers such as methacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, and allyl methacrylate can be blended as a crosslinking aid. With such a compound, a uniform and efficient crosslinking reaction can be expected.

In particular, in the present invention, triethylene glycol dimethacrylate is easy to handle and has good compatibility with the peroxide-crosslinked olefin polymer rubber (c) which is the main component of the object to be treated. In addition, it has a peroxide solubilizing effect and acts as a peroxide dispersing agent, so the cross-linking effect by heat treatment is uniform and effective, and a cross-linked thermoplastic elastomer with a balance between hardness and rubber elasticity can be obtained. preferable. Furthermore, triethylene glycol dimethacrylate has good compatibility with the polyester-based thermoplastic elastomer, and can suppress surface peeling of a molded product.

The amount of the crosslinking aid used in the present invention is
Composition 10 comprising components (a) to (e) at the time of addition
The range is preferably from 0.1 to 10 parts by weight, more preferably from 1.0 to 8 parts by weight, and even more preferably from 2 to 6 parts by weight, per 0 parts by weight. The addition amount of the crosslinking assistant is preferably about 2 to 2.5 times the addition amount of the peroxide.

Examples of antioxidants that may be used include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4
-Dimethyl-6-tert-butylphenol, 4,4
-Dihydroxydiphenyl, tris (2-methyl-4-
There are phenolic antioxidants such as hydroxy-5-tert-butylphenyl) butane, phosphite antioxidants and thioether antioxidants. Among them, phenolic antioxidants and phosphite antioxidants are preferred.

The amount of the antioxidant added is based on 100 parts by weight of the composition comprising components (a) to (e) at the time of addition.
The range is preferably 3 parts by weight or less, more preferably 1 part by weight or less. The antioxidant is preferably added to the first step of the production method described below in order to prevent hydrolysis resistance such as TPEE.

The mixing ratio of the components (a) to (g) is arbitrarily determined in consideration of the degree of crosslinking which particularly affects the quality of the obtained thermoplastic elastomer composition.

[Production Method] As a means for heat treatment and compounding in the method for producing the resin composition of the present invention, a conventional method can be used satisfactorily. For example, the following 3
It can be manufactured by a process, but is not limited to this.

In the first step, components (a) and (b), at least a portion of component (c), and a portion of component (d), and optionally, an antioxidant, a light stabilizer, a colorant, Various additives such as a flame retardant and components (e) to (g) are melt-kneaded in advance. As the kneading method, a method usually used for rubber, plastics and the like can be used satisfactorily. For example, a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer, various kneaders and the like are used. By this step, a composition in which each component is uniformly dispersed can be obtained.

In the second step, a peroxide and, if desired, a crosslinking aid are added to the composition obtained in the first step, and the mixture is further kneaded under heating to cause crosslinking. As described above, it is particularly preferable that the components (a) to (d) are melt-kneaded in advance to cause micro-dispersion, and then the organic peroxide is added to cause cross-linking.
This step can be generally performed by kneading using a twin-screw extruder, a Banbury mixer, or the like.

In the third step, the remaining components are added to the crosslinked composition obtained in the second step and kneaded. Kneading is
Generally, it can be carried out using a single-screw extruder, a twin-screw extruder, a roll, a Banbury mixer or various kneaders. In this step, the reaction is completed at the same time as the dispersion of each component further proceeds.

As a kneading method, it is preferable to use a twin-screw extruder or a Banbury mixer having an L / D of 47 or more, since all the steps can be performed continuously. Further, for example, when kneading with a twin-screw extruder, the rotation speed of the screw is 80 to 250 rpm, preferably 80 to 100 rpm.
When the reaction is performed under the condition of m, each component has good dispersion and good physical properties can be obtained.

The kneading temperature is desirably set in the first step so that each component is completely melted and easily mixed. In the second step, it is desirable to set the temperature so that a shearing force is applied to the organic peroxide and each component and the reaction proceeds uniformly. In the third step, it is desirable to set the temperature so that the reaction is completed at the same time as the mixing of the components proceeds.

The component (a) must be blended in the first step or at the latest in the second step. Thereby, a part of the component (a) causes a crosslinking reaction, and as a result, an effect is obtained that the dispersibility of each component is improved. JP-A-59-6
Unlike 236, as is apparent from the embodiment of the present invention,
The resin composition obtained by the method of the present invention has an effect of improving heat resistance. Component (b) is preferably blended in the first step. If the component (b) is blended in the third step, it causes bleed-out, which is not preferable. The entire amount of component (c) can be blended in the first step, but in order to adjust processing characteristics, fluidity, mechanical strength, etc., an appropriate amount is blended in the first step and the remaining amount is blended in the third step. You can also. In the latter case, the partially crosslinked composition in the presence of peroxide and a part of the component (c) blended in the third step are compatible with each other and microdispersed in the composition, and the resulting elastomer composition is mechanically dispersed. It is preferable because it has an effect of improving physical properties such as strength. As described above, the component (d) is blended in an appropriate amount in the first step and the remaining amount is blended in the third step. As a result, the composition partially crosslinked in the presence of the peroxide and a part of the component (d) blended in the third step are compatible with each other and microdispersed in the composition. This has the effect of improving physical properties such as properties and mechanical strength. Component (e) is blended when the resulting elastomer composition is required to further have heat resistance and oil resistance. In the compounding method, the entire amount can be compounded in the first step, but it is preferable to mix an appropriate amount in the first step and the remaining amount in the third step in order to obtain better function expression. Component (f) can be blended in any one or both of the first step and the third step. The component (g) is used in the first step and the second step,
Either one or both can be blended. For better function expression and effective use, it is preferable to mix in the second step. When the component (g) is blended in the first step, it is desirable that the component (g) be blended in a larger amount than in the case of blending in the second step, because the electron donor can volatilize by melt-kneading.

The degree of crosslinking of the thermoplastic elastomer composition obtained by crosslinking as described above can be represented by the gel fraction and the dynamic elastic modulus. The gel fraction was 100 g for 1 g of the sample.
After wrapped in a mesh wire mesh and extracted in boiling xylene using a Soxhlet extractor for 10 hours, it can be expressed by the ratio of the weight of the residual solid content to 1 g of the sample. The dynamic elastic modulus can be represented by a storage elastic modulus of melt viscoelasticity using a parallel plate.

In the present invention, the degree of crosslinking is preferably 30 to 45% by weight, more preferably 40 to 45% by gel fraction.
It is preferably 105 to 107 Pa in terms of weight% and storage modulus. Below this range, the resulting thermoplastic elastomer composition has poor high-temperature compression set and oil resistance. If the ratio exceeds this range, the moldability deteriorates, and at the same time, the tensile properties decrease.

The thermoplastic elastomer composition obtained in this way has a greater effect than the composition obtained according to the prior art.
Since the components are uniformly micro-dispersed, the composition is stable and has good physical properties such as compression set and tensile strength.

[0076]

The present invention will be described in detail with reference to examples and comparative examples, but the present invention is not limited to these examples. The evaluation method used in Examples and Comparative Examples was as follows. 1) Hardness: According to JIS K 6301, a 6.3 mm pressed sheet was used as a test piece. 2) Tensile strength: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick pressed sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. 3) Tensile elongation: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick pressed sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. 4) 100% elongation stress: According to JIS K 6301, a test piece was prepared by punching a 1 mm thick pressed sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. 5) 100% permanent elongation: Based on JIS K 6301, a test piece was prepared by punching a 1 mm thick press sheet into a No. 3 die using a dumbbell. The tensile speed was 500 mm / min. After holding at 100% elongation for 10 minutes, the chuck was opened, left for 10 minutes, and the length between the marked lines was measured. 6) Rebound resilience: Based on BS903, a 4 mm-thick press sheet was used as a test piece. 7) Compression set: Based on JIS K6262, a 6.3 mm-thick press sheet was used as a test piece. 70 ° C
It was measured under the conditions of × 22 hours, 100 ° C. × 22 hours, 120 ° C. × 22 hours, 140 ° C. × 11 hours, and 25% deformation. 8) Taber abrasion: JIS K 7204,
The test piece used was a 3 mm-thick press sheet. 1000
The wear mass after rotation was measured. 9) Spiral flow: Spiral flow test mold having a thickness of 1 mm, resin temperature 220 ° C, injection pressure 800 kg /
Injection molding was performed under the condition of cm ² , and the flow distance of the resin composition was measured. 10) Tear strength: According to JIS K 6301, a test piece was prepared by punching a 2.5 mm-thick press sheet into a B-shape with a dumbbell. The tensile strength was 500 mm / min. 11) Oil resistance: According to JIS K 6301, a test piece was prepared by punching a 1 mm-thick press sheet into a No. 3 die using a dumbbell. Using ASTM No. 2 oil, weight change and volume change at 70 ° C. for 24 hours, residual tensile strength, and 100% elongation stress were measured.

12) Formability: An 8.5 ton × 3 mm thick sheet is molded under predetermined conditions using an 80-ton injection molding machine, and a flow mark that does not cause delamination or deformation and significantly deteriorates the appearance is obtained. If not, the moldability was determined to be good. 13) Stickiness: When no bleeding or bloom of a low molecular weight product was observed in the above molded product and there was no stickiness even when touched by hand, it was determined that stickiness was good. 14) Crosslinked gel: using a Labo Plastomill (manufactured by Toyo Seiki Co., Ltd.), extruding a strip having a width of 20 mm and a thickness of 0.5 mm, length 2
The number of gels (0.5 mm ² or more in a foreign matter measurement chart manufactured by the Ministry of Finance, a foreign matter measurement chart) in 0 m was visually confirmed and evaluated. The extrusion temperature is 220 ° C. The evaluation stages are as follows. ◎: No crosslinked gel (0), ○: 1 to 5 crosslinked gels △: 6 to 10 crosslinked gels, ×: Many crosslinked gels (11 or more)

The following were used as each component. Component (a): hydrogenated block copolymer Septon 4055 manufactured by Kuraray Co., Ltd. Content of styrene: 30% by weight Content of isoprene: 70% by weight Weight average molecular weight: 130,000 Molecular weight distribution: 1.3 Hydrogenation rate: 90 % Or more Component (b): Non-aromatic rubber softener Diana Process Oil PW-90 manufactured by Idemitsu Kosan Co., Ltd. Type: paraffinic oil Weight average molecular weight: 540 Content of aromatic component: 0.1% or less Component (c) : Peroxide cross-linked olefin resin PE-1 V-0398CN manufactured by Idemitsu Petrochemical Co., Ltd. Type: LLDPE Weight average molecular weight: 80,000 EP-1 EP961SP manufactured by Nippon Synthetic Rubber Co., Ltd. Type: EPR Weight average molecular weight: 150,000 components ( d): Peroxide-decomposable olefin-based resin PP-1 E1100 manufactured by Asahi Kasei Corporation Type: PP MFR: 0.5 g / 10 min PP-2 Type: Low crystalline polypropylene with Tm = 160 ° C., ΔHm = 45 mJ / mg MRF: 2.5 g / 10 min PP-3: BC03B manufactured by Mitsubishi Yuka Type: PP MFR: 30 g / 10 min Component (e): polyester thermoplastic elastomer ELA4110N manufactured by Teijin Limited Type: ester-ester Component (f): inorganic filler RS400 manufactured by Sankyo Seiko Co., Ltd. Type: calcium carbonate Component (g): electron donation Body Toluene: Special grade manufactured by Kanto Chemical Co., Ltd. Methanol: Special grade manufactured by Kanto Chemical Co., Ltd. Peroxide: Perhexa 25B manufactured by NOF CORPORATION Type: 2,5-Dimethyl-2,5-di (t-butylperoxy) -hexane Agent: NK ester 3G manufactured by Shin-Nakamura Chemical Co., Ltd. Type: triethylene glycol dimethacrylate Antioxidant: manufactured by Asahi Denka PEP-36.

Example 1 A resin composition was manufactured according to the first to third steps. In the first step, 100 parts by weight of Septon 4055 as the component (a), 104 parts by weight of PW-90 as the component (b), 4.2 parts by weight of PE-1 (V-0398CN) as the component (c), 21 parts by weight of PP-2 (low crystalline PP) as component (d)
31 parts by weight of RS400 was used as the component (f), and 0.2 parts by weight of PEP-36 was used as an antioxidant. In the second step, perhexane 25B was used as peroxide.
One part by weight and 4.7 parts by weight of NK ester 3G were used as a crosslinking aid. In the third step, component (d) is PP
-3 (BC03B) in 10.4 parts by weight. In each step, a twin-screw kneader was used at a screw rotation of 100 rpm under the following temperature conditions. First step kneading temperature: 230
-240 ° C, kneading temperature in the second step: 180-220 ° C, kneading temperature in the third step: 200-220 ° C. Physical properties of the obtained resin were measured in accordance with the above evaluation methods. The composition is shown in Table 1 and the results are shown in Table 2.

Example 2 A resin composition was prepared in the same manner as in Example 1 except that 10.4 parts by weight of PP-1 (E1100) was used instead of PP-2 of the component (d). ,
Physical properties were evaluated. The composition is shown in Table 1 and the results are shown in Table 2.

(Example 3) PE-1 of component (c) (V-
0398CN), 14.6 parts by weight of the component (d) PP-
1 (E1100), 16 parts by weight of PP-3 (BC03
A resin composition was produced and the physical properties were evaluated in the same manner as in Example 2 except that B) was changed to 21 parts by weight. Table 1 shows the composition
And the results are shown in Table 2.

(Example 4) PE-1 of component (c) (V-
0398CN), 19.8 parts by weight of the component (d) PP-
1 (E1100), 16 parts by weight of PP-3 (BC03
A resin composition was prepared and the physical properties were evaluated in the same manner as in Example 2 except that B) was changed to 31 parts by weight. Table 1 shows the composition
And the results are shown in Table 2.

(Example 5) PE-1 (V-
0398CN), PP-1 of component (d)
(E1100) 21 parts by weight, PP-3 (BC03B)
Was changed to 42 parts by weight in the same manner as in Example 2,
A resin composition was manufactured and physical properties were evaluated. The composition is shown in Table 1 and the results are shown in Table 2.

Example 6 A resin composition was manufactured according to the first to third steps. In the first step, component (a)
10055 parts by weight of Septone 4055, 104 parts by weight of PW-90 as component (b), and PE as component (c)
4.2 parts by weight of -1 (V-0398CN) and EP-1
25 parts by weight of (EP931SP) and P as component (d)
10.1 parts by weight of P-1 (E1100), 31 parts by weight of ELA4110N as component (e), 31 parts by weight of RS400 as component (f), and PEP-36 as antioxidant
Was used in an amount of 0.2 part by weight. In the second step, 2.1 parts by weight of perhexa 25B was used as a peroxide, and 4.7 parts by weight of NK ester 3G was used as a crosslinking aid. In the third step, PP-3 (BC03B) as component (d)
Was used in an amount of 21 parts by weight. A resin composition was manufactured in the same manner as in Example 1, and the physical properties were evaluated. The composition is shown in Table 1 and the results are shown in Table 2.

(Example 7) EP-1 of component (c) (EP
961SP), PP-1 of component (d)
(E1100) 16 parts by weight, PP-3 (BC03B)
Was changed to 42 parts by weight in the same manner as in Example 6,
A resin composition was manufactured and physical properties were evaluated. The composition is shown in Table 1 and the results are shown in Table 2.

Example 8 ELA41 was used as the component (e).
A resin composition was manufactured and the physical properties were evaluated in the same manner as in Example 2 except that 63 parts by weight of 10N was blended. The composition is shown in Table 1 and the results are shown in Table 2.

(Example 9) A resin composition was prepared and the physical properties were evaluated in the same manner as in Example 6, except that the component (f) RS400 was not blended. The composition is shown in Table 1 and the results are shown in Table 2.

[0088]

[Table 1]

[0089]

[Table 2]

Example 10 A resin composition was manufactured according to the first to third steps. In the first step, 100 parts by weight of Septon 4055 as the component (a), 104 parts by weight of PW-90 as the component (b), 9.4 parts by weight of PE-1 (V-0398CN) as the component (c), 21 parts by weight of PP-2 (low crystalline PP) as component (d)
As the component (e), 31 parts by weight of ELA4110N was used. In the second step, 3.1 parts by weight of perhexa 25B as a peroxide, 4.7 parts by weight of NK ester 3G as a crosslinking aid, and 0.2 parts by weight of PEP-36 as an antioxidant were used. In the third step, component (d)
And 10.3 parts by weight of PP-3 (BC03B). A resin composition was manufactured in the same manner as in Example 1, and the physical properties were evaluated. The composition is shown in Table 3 and the results are shown in Table 4.

Example 11 A resin composition was prepared and the physical properties were evaluated in the same manner as in Example 10 except that the amount of the peroxide was changed to 1 part by weight and the amount of the crosslinking aid was changed to 9 parts by weight. The composition is shown in Table 3. Table 4 shows the results. (Example 12) A resin composition was produced and the physical properties were evaluated in the same manner as in Example 10, except that the peroxide was 2.1 parts by weight and the crosslinking aid was 10.5 parts by weight. Table 3 shows the composition
And the results are shown in Table 4.

Example 13 A resin composition was manufactured according to the first to third steps. In the first step, 100 parts by weight of Septon 4055 as the component (a), 104 parts by weight of PW-90 as the component (b), 9.4 parts by weight of PE-1 (V-0398CN) as the component (c), 21 parts by weight of PP-3 (BC03B) as the component (d),
0.2 parts by weight of PEP36 was used as an antioxidant. In the second step, perhexa 25B is used as the peroxide.
Was used and 4.7 parts by weight of NK ester 3G was used as a crosslinking aid. In the third step, 10.4 parts by weight of PP-3 (BC03B) was used as the component (d). A resin composition was manufactured in the same manner as in Example 1, and the physical properties were evaluated. The composition is shown in Table 3 and the results are shown in Table 4.

(Example 14) PE-1 of component (c) was added to 1
A resin composition was prepared and the physical properties were evaluated in the same manner as in Example 13 except that the amount was changed to 4.6 parts by weight. Table 3 shows the composition
Table 4 shows the results. (Example 15) A resin was prepared in the same manner as in Example 13 except that 19.8 parts by weight of PE-1 of the component (c) and 31.2 parts by weight of the component (d) blended in the third step were changed. Compositions were prepared and physical properties were evaluated. The composition is shown in Table 3 and the results are shown in Table 4.

Example 16 A resin composition was prepared in the same manner as in Example 10 except that the peroxide was changed to 2.1 parts by weight, and the physical properties were evaluated. The composition is shown in Table 3 and the results are shown in Table 4.

[0095]

[Table 3]

[0096]

[Table 4]

Example 17 A resin composition was manufactured according to the first to third steps. In the first step, 100 parts by weight of Septon 4055 as the component (a), 104 parts by weight of PW-90 as the component (b), 4.2 parts by weight of PE-1 (V-0398CN) as the component (c), 21 parts by weight of PP-2 (low crystalline PP) as component (d)
31 parts by weight of RS400 was used as the component (f), and 0.2 parts by weight of PEP-36 was used as an antioxidant. In the second step, perhexane 25B was used as peroxide.
One part by weight, 4.7 parts by weight of NK ester 3G as a crosslinking aid, and 2 parts by weight of toluene as a component (g) were used. In the third step, PP-3 (BC03
5.2 parts by weight of B) were used. In each step, the twin-screw kneader was rotated with a screw at 100 rpm under the following temperature conditions.
Used in First step kneading temperature: 230 to 240 ° C, Second step kneading temperature: 180 to 220 ° C, Third step kneading temperature: 200 to 2
20 ° C. Physical properties of the obtained resin were measured in accordance with the above evaluation methods.
The composition is shown in Table 5 and the results are shown in Table 6.

(Example 18) Component (d) PP-3 in which 9.4 parts by weight of PE-1 of component (c) was blended in the third step
Was changed to 10.4 parts by weight, and a resin composition was produced in the same manner as in Example 17, and the physical properties were evaluated. The composition is shown in Table 5 and the results are shown in Table 6. (Example 19) A resin composition was prepared in the same manner as in Example 17 except that 14.6 parts by weight of the component (c) PE-1 and 21 parts by weight of the component (d) PP3 blended in the third step were used. Products were manufactured and their physical properties were evaluated. The composition is shown in Table 5 and the results are shown in Table 6.

(Example 20) PE-1 of component (c) was added to 1
9.8 parts by weight, the same as Example 17 except that the component (d) PP3 blended in the third step was changed to 31 parts by weight.
A resin composition was manufactured and physical properties were evaluated. The composition is shown in Table 5 and the results are shown in Table 6.

Example 21 A resin composition was manufactured according to the first to third steps. In the first step, 100 parts by weight of Septon 4055 as the component (a), 104 parts by weight of PW-90 as the component (b), 25 parts by weight of PE-1 (V-0398CN) as the component (c), 21 parts by weight of PP-2 (low crystalline PP) was used as d), 31 parts by weight of RS400 was used as component (f), and 0.2 parts by weight of PEP-36 was used as an antioxidant. In the second step, 2.1 parts by weight of perhexa 25B as a peroxide, 4.7 parts by weight of NK ester 3G as a crosslinking aid, and 2 parts by weight of toluene as a component (g) were used. In the third step, PP-3 (BC03
B) was used in an amount of 42 parts by weight. A resin composition was produced in the same manner as in Example 17, and the physical properties were evaluated. The composition is shown in Table 5 and the results are shown in Table 6.

Example 22 A resin composition was manufactured according to the first to third steps. In the first step, 100 parts by weight of Septon 4055 as the component (a), 104 parts by weight of PW-90 as the component (b), 4.2 parts by weight of PE-1 (V-0398CN) as the component (c) and 5.2 parts by weight of EP-1 (EP931SP), 10.4 parts by weight of PP-1 (E1100) as component (d), 31 parts by weight of ELA4110N as component (e),
0.2 parts by weight of PEP-36 was used as an antioxidant. In the second step, perhexa 25 is used as a peroxide.
2.1 parts by weight of B, 4.7 parts by weight of NK ester 3G as a crosslinking aid, and 2 parts by weight of toluene as a component (g). In the third step, PP-3 is used as component (d).
10.4 parts by weight of (BC03B) was used. Example 17
In the same manner as in the above, a resin composition was produced, and physical properties were evaluated. The composition is shown in Table 5 and the results are shown in Table 6. (Example 23) In the same manner as in Example 22, except that the component (c) PE-2 was changed to 15.6 parts by weight and the component (d) PP-3 blended in the third step was changed to 31 parts by weight, A resin composition was manufactured and physical properties were evaluated. The composition is shown in Table 5 and the results are shown in Table 6.

[0102]

[Table 5]

[0103]

[Table 6]

Example 24 A resin composition was prepared and its physical properties were evaluated in the same manner as in Example 18, except that the amount of the toluene component (g) was changed to 0.5 part by weight. The composition is shown in Table 7 and the results are shown in Table 8. (Example 25) Component (g)
A resin composition was produced and the physical properties were evaluated in the same manner as in Example 18 except that the toluene was changed to 4 parts by weight. The composition is shown in Table 7 and the results are shown in Table 8.

Example 26 Toluene of component (g) was added to 6
A resin composition was manufactured and the physical properties were evaluated in the same manner as in Example 18 except that the amount was changed to parts by weight. The composition is shown in Table 7 and the results are shown in Table 8. (Example 27) A resin composition was produced and the physical properties were evaluated in the same manner as in Example 18, except that the amount of the toluene component (g) was changed to 10 parts by weight. The composition is shown in Table 7 and the results are shown in Table 8. (Example 28) A resin composition was prepared and the physical properties were evaluated in the same manner as in Example 18 except that the toluene of the component (g) was changed to 15 parts by weight. The composition is shown in Table 7 and the results are shown in Table 8.

Example 29 Example 18 was repeated except that 2 parts by weight of toluene of the component (g) was changed to 2 parts by weight of methanol.
In the same manner as in the above, a resin composition was produced and physical properties were evaluated. The composition is shown in Table 7 and the results are shown in Table 8. (Example 30) A resin composition was prepared and the physical properties were evaluated in the same manner as in Example 18 except that 2 parts by weight of toluene of the component (g) was changed to 4 parts by weight of methanol. The composition is shown in Table 7 and the results are shown in Table 8.

[0107]

[Table 7]

[0108]

[Table 8]

Comparative Example 1 A resin composition was manufactured according to the first to third steps. In the first step, component (a)
10055 parts by weight of Septon 4055, 38 parts by weight of PW-90 as component (b), and PE-
9.4 parts by weight of 1 (V-0398CN), 21 parts by weight of PP-2 (low crystalline PP) as component (d), component (e)
31 parts by weight of ELA4110N and 0.2 parts by weight of PEP-36 as an antioxidant. In the second step, 2.1 parts by weight of perhexa 25B was used as a peroxide, and 4.7 parts by weight of NK ester 3G was used as a crosslinking aid. In the third step, PP-3 is used as component (d).
10.4 parts by weight of (BC03B) was used. A resin composition was manufactured in the same manner as in Example 1, and the physical properties were evaluated. Table 9 shows the composition and Table 10 shows the results.

(Comparative Example 2) PW-90 of the component (b) was changed to 3
A resin composition was produced and the physical properties were evaluated in the same manner as in Comparative Example 1 except that the amount was changed to 08 parts by weight. Table 9 shows the composition and Table 10 shows the results. (Comparative Example 3) PW- of component (b)
90 to 125 parts by weight of the component (c) PE-1 (V-03
98CN) was changed to 104 parts by weight, and a resin composition was produced in the same manner as in Comparative Example 1, and the physical properties were evaluated. Table 9 shows the composition and Table 10 shows the results.

(Comparative Example 4) PW-90 of the component (b) was 1
25 parts by weight of component (c) PE-1 (V-0398C
N), 104 parts by weight of the component (d) PP-3 (BC03
A resin composition was prepared and the physical properties were evaluated in the same manner as in Comparative Example 1 except that B) was changed to 21 parts by weight. Table 9 shows the composition
Table 10 shows the results.

(Comparative Example 5) PW-90 of the component (b) was 1
04 parts by weight of PE-1 of component (c) (V-0398C
N) in 25 parts by weight and component (e) ELA4110N in 1 part
A resin composition was produced in the same manner as in Comparative Example 1 except that the amount was changed to 34 parts by weight, and instead of PP-2 of the component (d), 10.4 parts by weight of PP-1 (E1100) was used. Physical properties were evaluated. Table 9 shows the composition and Table 10 shows the results.

(Comparative Example 6) PE-1 (V-
0398CN), PP-3 of component (d)
Comparative Example 5 except that (BC03B) was changed to 21 parts by weight.
In the same manner as in the above, a resin composition was produced and physical properties were evaluated.
Table 9 shows the composition and Table 10 shows the results.

(Comparative Example 7) PW-90 of the component (b) was changed to 1
The resin composition was manufactured in the same manner as in Comparative Example 1 except that the amount was changed to 04 parts by weight and no peroxide was used.
Physical properties were evaluated. Table 9 shows the composition and Table 10 shows the results.

Comparative Example 8 A resin composition was produced according to the first to third steps. In the first step, component (a)
10055 parts by weight of Septone 4055, 104 parts by weight of PW-90 as component (b), and PE as component (c)
-1 (V-0398CN) in 4.2 parts by weight and EP-1
5.2 parts by weight of (EP961SP), 10.4 parts by weight of PP-1 (E1100) as component (d) and PP-3
21 parts by weight of (BC03B) and ELA as component (e)
3110 parts by weight of 4110N, PEP-36 as an antioxidant
Was used in an amount of 0.2 part by weight. In the second step, 2.1 parts by weight of perhexa 25B was used as a peroxide, and 4.7 parts by weight of NK ester 3G was used as a crosslinking aid. In the third step, the components were not blended. A resin composition was manufactured in the same manner as in Example 1, and the physical properties were evaluated. Table 9 shows the composition and Table 10 shows the results.

[0116]

[Table 9]

[0117]

[Table 10]

Comparative Example 9 A resin composition was produced in the same manner as in Example 2, except that no peroxide was used. (Comparative Example 10) Except that no peroxide was used,
A resin composition was produced in the same manner as in Example 4.

For the resin compositions produced according to Examples 2 and 4 and Comparative Examples 9 and 10, the temperature dependence of hardness was examined in order to examine heat resistance. The measurement was performed according to the method described above, but the temperature was set to room temperature, 70 ° C, and 110 ° C. Table 11 shows the results.

[0120]

[Table 11]

(Comparative Example 11) A resin composition was prepared in the same manner as in Example 17 except that the component (g) was not used.
Physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13. (Comparative Example 12) A resin composition was produced in the same manner as in Example 18 except that the component (g) was not used, and physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13.

(Comparative Example 13) A resin composition was prepared in the same manner as in Example 19 except that the component (g) was not used.
Physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13.

(Comparative Example 14) A resin composition was prepared in the same manner as in Example 20, except that the component (g) was not used.
Physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13.

(Comparative Example 15) A resin composition was prepared in the same manner as in Example 21 except that the component (g) was not used.
Physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13.

(Comparative Example 16) A resin composition was prepared in the same manner as in Example 22 except that the component (g) was not used.
Physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13.

(Comparative Example 17) A resin composition was prepared in the same manner as in Example 23 except that the component (g) was not used.
Physical properties were evaluated. The composition is shown in Table 12, and the results are shown in Table 13.

(Comparative Example 18) Toluene as the component (g) was mixed with 2
Except having changed to 0 weight part, it carried out similarly to Example 18, and produced the resin composition and evaluated the physical property. The composition is shown in Table 12, and the results are shown in Table 13.

[0128]

[Table 12]

[0129]

[Table 13]

[0130]

The resin composition obtained by the method of the present invention is excellent in rubber properties such as compression set, excellent in mechanical strength and moldability, and free of stickiness, so that it can be used in various fields such as automobile parts. It is useful in.

Continuation of the front page (51) Int.Cl. ⁷ identification code FI C08L 23/00 C08L 23/00 67/00 67/00 (58) Field surveyed (Int.Cl. ⁷ , DB name) C08L 53/02 C08J 3/20 C08K 3/00 C08K 5/01 C08K 5/14 C08L 23/00 C08L 67/00

Claims (8)

(57) [Claims] 1. A block copolymer comprising (a) at least two polymer blocks A mainly composed of a vinyl aromatic compound and at least one polymer block B mainly composed of a conjugated diene compound, and And / or hydrogenated block copolymer obtained by hydrogenating the same 100 parts by weight (b) Softener for non-aromatic rubber 40 to 300 parts by weight (c) peroxide-crosslinked olefin resin, and / or
Or a copolymer rubber containing the same 1.0 to 100 parts by weight (d) a peroxide-decomposable olefin-based resin, and / or
Alternatively, in the method for producing a thermoplastic elastomer resin composition containing 10 to 150 parts by weight of a copolymer containing the same, at least a part of the components (a) and (b), the component (c), and one of the components (d). Part is heat-treated in the presence of an organic peroxide to cause crosslinking, and then the crosslinked product is blended with the remainder of component (d) or the remainder of components (c) and (d). A method for producing an elastomer resin composition. 2. A polyester thermoplastic elastomer (e) in an amount of 0 to 130 parts by weight and (f) an inorganic filler.
The production method according to claim 1, wherein 0 to 100 parts by weight is added at an optional stage. 3. The method according to claim 1, wherein at least 3 parts by weight of the component (d) is subjected to a heat treatment in the presence of an organic peroxide, and at least 5 parts by weight are blended after the heat treatment. 4. The method according to claim 1, wherein at least half of the component (c) is subjected to the heat treatment. 5. The method according to claim 2, wherein the heat treatment in the presence of the organic peroxide is performed in the presence of at least a part of the component (e). 6. The cross-linking is carried out in the presence of a cross-linking aid which is a monomer having an ethylenically unsaturated group.
The production method according to any one of the above. 7. The method according to claim 1, further comprising adding (g) 0 to 15 parts by weight of an electron donor before or during heat treatment in the presence of an organic peroxide. 8. The method according to claim 1, wherein (g) 0 to 25 parts by weight of the electron donor is heat-mixed (including melt-kneading) with the components (a) to (f) before the heat treatment in the presence of the organic peroxide. Item 7. The manufacturing method according to any one of Items 1 to 6.