JP2001311012A - Softener composition and thermoplastic resin composition comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a softener composition extremely readily handleable in production of a thermoplastic resin composition and the thermoplastic resin composition comprising the softener composition. SOLUTION: This softener composition is obtained by compounding (a) 100 pts.wt. of one or more kinds selected from softeners for nonaromatic hydrocarbon-based rubbers, (b) 0.1-10 pts. wt. of an organic peroxide and (c) 0.1-50 pts.wt. of a cross-linking aid under conditions of <=1 weight ratio of the component (b)/component (c) and heat-treating the resultant compounded components.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a softener composition and a thermoplastic resin composition containing the same.

[0002]

2. Description of the Related Art Conventionally, a predetermined hardness is obtained by adding an oil as a plasticizer and an olefin resin as a resin component to a styrene resin composition or an ethylene-propylene resin composition. A thermoplastic elastomer resin composition having
Paraffin oil is often used as the oil.
However, by adding oil, lower hardness can be achieved,
Since a resin having a lower molecular weight than that of other resin components is used, heat resistance, weather resistance, mechanical strength, abrasion resistance and the like are reduced. In addition, when obtaining a very soft thermoplastic resin composition, when using a conventional uncrosslinked oil, there is a problem that oil bleeds on the surface of a molded product, and a satisfactory thermoplastic resin composition is obtained. Can not. Furthermore, since there is an upper limit on the amount of oil that can be absorbed by the thermoplastic resin composition (the amount of oil / the amount of thermoplastic resin composition is limited to slightly more than 3), bleeding of oil occurs when more oil is added. While the components other than oil are solid, the oil is liquid, which makes handling cumbersome and requires special equipment such as a pump to mix.

However, it has been found that by pre-crosslinking the oil, the oil alone becomes a solid (jelly-like) and handling becomes very easy. Also, by blending the above-mentioned substance (hereinafter, referred to as the softener composition of the present invention) obtained by pre-crosslinking the oil with a small amount of a thermoplastic elastomer resin or a thermoplastic resin, a very oil-free, very A thermoplastic resin composition as a soft elastic body was obtained. Since this elastic body has excellent shock absorbing properties, it has been found that it can be applied to a vibration damping material, a sound deadening material, and the like. Furthermore, when the softener composition of the present invention is used to obtain a conventional thermoplastic elastomer resin having a predetermined hardness, an effect of suppressing oil bleed during heat resistance evaluation is obtained, and mechanical strength and friction resistance are also improved. It was found to improve.

[0004]

According to the present invention, there are provided (a) 100 or more parts by weight of at least one selected from softeners for non-aromatic hydrocarbon rubber, and (b) 0.1 to 10 parts by weight of an organic peroxide. And (c) 0.1 to 50 parts by weight of a crosslinking assistant under the condition of the component (b) / component (c) weight ratio ≦ 1, and a heat treatment composition obtained by heat treatment. Also,
The present invention relates to a thermoplastic resin composition comprising 100 parts by weight of the softener composition of the present invention and (d) 0.1 to 1500 parts by weight of a thermoplastic resin. Furthermore, the present invention provides: (a) at least one member selected from the group consisting of softeners for non-aromatic hydrocarbon rubbers; 100 parts by weight; (b) 0.1 to 10 parts by weight of an organic peroxide; 0.1 to 50 parts by weight, and (d) 1500 parts by weight or less of a thermoplastic resin are blended under the condition of component (b) / component (c) weight ratio ≦ 1, and a thermoplastic resin composition obtained by heat treatment About things.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Each component used in the softener composition of the present invention will be described. Component (a): Softener for non-aromatic hydrocarbon rubber Component (a) is a softener for non-aromatic hydrocarbon rubber. As the softener for the non-aromatic hydrocarbon rubber used in the present invention, non-aromatic mineral oil or liquid, or,
And low molecular weight synthetic softeners. In general, a mineral oil softener for rubber is a mixture of an aromatic ring, a naphthene ring and a paraffin chain, and generally saturates a saturated hydrocarbon (paraffin) chain having a carbon number of 50% or more of the total carbon number. Hydrocarbons (paraffins) and those having 30 to 40% of naphthenic ring carbon atoms are called naphthenics, and those having 30% or more aromatic carbons are called aromatics. The mineral oil softener for rubber used in the present invention is preferably the above-mentioned saturated hydrocarbon (paraffin) type and naphthene type. Aromatic softeners are not preferred because of poor dispersibility. As the softener for the non-aromatic hydrocarbon rubber, a saturated hydrocarbon (paraffin) -based mineral oil softener is particularly preferable, and among the saturated hydrocarbon (paraffin) -based softeners, those having less aromatic ring components are particularly suitable. .

As the saturated hydrocarbon (paraffin), specifically, normal paraffin (methane, ethane, propane,
Butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tetradecane,
Pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, heneicosane, docosane, trichosane, tetracosane, pentacosane, hexacosane, heptacosane, octacosane, nonacosane,
Triacontane, hentriacontane, dotriacontane, pentatriacontane, hexacontane, heptacontane); isoparaffins (isobutane, 2-methylbutane (isopentane), neopentane, 2-methylpentane (isohexane), 3-methylbutane (isopentane), 2 , 2-dimethylbutane (neohexane), 2,
3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3-ethylpentane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2, 2,3-trimethylbutane (tributane), 3-methylheptane,
2,2-dimethylhexane, 2,3-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2,2,3-trimethylpentane, 2,2,4- Trimethylpentane (isooctane), 2,3,4-trimethylpentane, 2,
3,3-trimethylpentane, 2,3,4-trimethylpentane, 2-methyloctane (isononane), 2-methylnonane, isodecane, isoundecane, isododecane, isotridecane, isotetradecane, isopentadecane, isooctadecane, isonanodecane, isoeicosane, 4-ethyl-5-methyloctane) and derivatives of these saturated hydrocarbons. These saturated hydrocarbons are 4-155, preferably 4-
It has 50 carbon atoms.

Specifically, PW-90 manufactured by Idemitsu Kosan Co., Ltd.
(Normal paraffin-based process oil) and IP-solvent 2835 (synthetic isoparaffin-based hydrocarbon, 99.8 wt% or more isoparaffin) manufactured by Idemitsu Petrochemical Co., Ltd.

Further, a small amount of unsaturated hydrocarbon and a derivative thereof may coexist as another component. Examples of the unsaturated hydrocarbon include ethylene hydrocarbons (ethylene, propylene, 1-butene (α-butylene)) 2-butene (β-butylene), isobutylene (γ-butylene), 1-pentene (α-amylene), 2-pentene (β-amylene), 3-methyl-1-butene (γ-amylene), 3-methyl-1-butene (α-isoamylene), 2-methyl-2-butene (β-isoamylene),
1-hexene, 2,3-dimethyl-2-butene (tetramethylethylene), 1-heptene, 1-octene, 1-
Nonene, 1-decene), acetylene series hydrocarbons (acetylene, methylacetylene, 1-butyne, 2-butyne,
1-pentyne, 1-hexyne, 1-octin, 1-nonine, 1-decine).

Component (b): Organic peroxide Component (b) is an organic peroxide. Examples of the organic peroxide used in the present invention include dicumyl peroxide, di-tert-butyl peroxide, and 2,5-dimethyl-2,5-di- (tert-
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-butylperoxyisopropyl carbonate, diacetyl peroxide, lauroyl peroxide, tert- Butyl cumyl peroxide and the like can be mentioned.

Of these, 2,5-dimethyl-2,5-di (te) is preferred in terms of odor, coloring and scorch stability.
rt-butylperoxy) hexane and 2,5-dimethyl-2,5-di (tert-butylperoxy)
Hexin-3 is most preferred.

The upper limit of the amount of organic peroxide to be added is 10.0 parts by weight, preferably 5.0 parts by weight, and the lower limit is 0.1 part by weight, per 100 parts by weight of component (a).
It is selected so that the weight ratio to the component (c) (part (b) / component (c) weight ratio) described below is 1 or less. If the ratio exceeds the upper limit, the decomposition reaction by the peroxide is prioritized, and the resulting composition does not become a solid which is excellent in handling.

Component (c): Crosslinking Aid The component (c) used in the present invention has an effect of causing a uniform and efficient crosslinking reaction in the above-mentioned crosslinking treatment with the organic peroxide (b). By using a large amount, bleed out of a low molecular weight substance can be significantly suppressed. As the component (c), for example, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate,
Polyethylene glycol dimethacrylate having 9 to 14 repeating units of ethylene glycol, trimethylolpropane trimethacrylate, allyl methacrylate,
Polyfunctional methacrylate compounds such as 2-methyl-1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Examples include polyfunctional acrylate compounds such as propylene glycol diacrylate, and polyfunctional vinyl compounds such as vinyl butyrate, vinyl stearate, divinylbenzene, and triallyl cyanurate. These may be used alone or in combination of two or more. With such a compound, a uniform and efficient crosslinking reaction can be expected.

Among the above crosslinking aids, polyfunctional methacrylate compounds and polyfunctional acrylate compounds are preferred, and triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 2-methyl-
1,8-octanediol dimethacrylate, 1,9-
Nonanediol dimethacrylate is particularly preferred.

The upper limit of the amount of the crosslinking aid added is 50.0 parts by weight, preferably 45.0 parts by weight, and the lower limit is 0.1 part by weight, per 100 parts by weight of component (a). Parts by weight. If the amount is less than the lower limit, the effect of the addition is not recognized.If the amount exceeds the upper limit, the crosslinking of the composition proceeds excessively, and the crosslinking auxiliary does not partially disperse. Become.

The present invention also relates to a thermoplastic resin composition obtained by blending the following components (d) with a softener composition obtained by blending the above components (a) to (c) and heat treatment. . Component (d): Thermoplastic resin Component (d) is a thermoplastic resin. Examples of the thermoplastic resin used in the present invention include polystyrene (PS), high-impact polystyrene (HIPS), styrene-based resin (styrene-butadiene-styrene copolymer (SBS), and styrene-isoprene-styrene copolymer (SIS). ), Styrene-ethylene-butene-styrene copolymer (SEB)
S), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS), styrene-butadiene rubber (SBR), butadiene rubber (B
R), polybutadiene (syndiotactic 1,2-polybutadiene), isoprene rubber (IR), acrylonitrile-butadiene rubber (NBR), chloroprene rubber (CR), ethylene-propylene rubber (EPM), ethylene-propylene terpolymer ( EPDM), butyl rubber (IIR), acrylic rubber (ACM), polyolefin resin (polyethylene (PE), polypropylene (P
P)), thermoplastic polyester-based elastomers, thermoplastic polyurethane-based elastomers, thermoplastic amide-based elastomers, and the like. As the component (d), the above thermoplastic resins can be used alone or in combination of two or more kinds. Component (d) is preferably
It is composed of one or more components selected from component (d1) and component (d2) described below.

Component (d1): (hydrogenated) block copolymer
The body component (d1) is a block copolymer composed of 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, or What is obtained by hydrogenation, or a mixture thereof, for example, AB,
Aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABABA, and / or a hydrogenated product thereof And the like.

The above (hydrogenated) block copolymer (hereinafter referred to as “hydrogenated”)
The (hydrogenated) block copolymer means a block copolymer and / or a hydrogenated block copolymer. ) Comprises 5 to 60% by weight of an aromatic vinyl compound, preferably 20% by weight.
５０50% by weight.

The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of only the aromatic vinyl compound, or 50% by weight or more, preferably 70% by weight or more of the aromatic vinyl compound (hydrogenated). ) A copolymer block with a conjugated diene 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 a (hydrogenated) conjugated diene compound preferably consists only of the (hydrogenated) conjugated diene compound or comprises 50% by weight of the (hydrogenated) conjugated diene compound. %, Preferably 70% by weight or more, and a copolymer block of an aromatic vinyl compound.

In each of the polymer block A mainly containing an aromatic vinyl compound and the polymer block B mainly containing a (hydrogenated) conjugated diene compound,
The distribution of the aromatic vinyl compound or the (hydrogenated) conjugated diene compound in the molecular chain may be random, tapered (one in which the monomer component increases or decreases along the molecular chain), partially blocky, or any of these. It may be a combination.

When there are two or more polymer blocks A mainly containing an aromatic vinyl compound or two or more polymer blocks B mainly containing a (hydrogenated) conjugated diene compound, even if each has the same structure, Different structures may be used.

As the aromatic vinyl compound constituting the (hydrogenated) block copolymer, one or more of 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 micro bond in the polymer block B mainly composed of a conjugated diene compound can be arbitrarily selected.

In the butadiene block, 1,2-
The micro-bonding is preferably 20 to 50%, particularly preferably 25 to 45%.

In the isoprene block, 70 to 100% by weight of the isoprene compound has 1,4-micro bonds, and at least 90% of aliphatic double bonds based on the isoprene compound are hydrogenated. Are preferred.

The weight average molecular weight of the (hydrogenated) block copolymer used in 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 10
It is in the range of from 0.000 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 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. 40798/1972 using 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 a styrene-butadiene-styrene copolymer (S
BS), styrene-isoprene-styrene copolymer (S
IS), styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer (SEEPS)
And the like.

Component (d2): olefin resin and / or
The olefin-based copolymer rubber component (d2) is an olefin-based resin and / or an olefin-based copolymer rubber. The olefin-based resin and / or olefin-based copolymer rubber used in the present invention includes a peroxide-decomposed olefin-based resin and / or peroxide-decomposed olefin-based copolymer rubber, and a peroxide-crosslinked olefin-based resin. Resin and / or peroxide cross-linked olefin copolymer rubber may be used. The peroxide-decomposable olefin-based resin and / or peroxide-decomposable olefin-based copolymer rubber improve the rubber dispersion of the obtained composition, improve the appearance of the molded product, and adjust the hardness and shrinkage. It has an effect on. The component is an olefin-based polymer or copolymer that is thermally decomposed by heating in the presence of a peroxide to reduce the molecular weight and increase the fluidity during melting, for example, isotactic polypropylene or Mention may be made of copolymers of propylene with other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene and the like.

The peroxide-crosslinked olefin-based resin and / or the peroxide-crosslinked olefin-based copolymer rubber mainly undergoes a cross-linking reaction by heat treatment in the presence of the peroxide, and the fluidity thereof is reduced. is there. For example, as in high-density polyethylene, low-density polyethylene, linear low-density polyethylene, and ultra-low-density polyethylene, the polymer density is 0.88 to 0.94 g /
It is an elastic body of an amorphous random copolymer containing an olefin as a main component, such as polyethylene or an ethylene / propylene copolymer rubber or an ethylene / propylene / non-conjugated diene copolymer rubber in the range of cm ³ . Among them, polyethylene or ethylene / propylene copolymer rubber is preferred, and among them, linear low-density polyethylene is particularly preferred in that an appropriate crosslinked structure can be obtained.

The weight average molecular weight of the olefin resin and the olefin copolymer rubber is from 50,000 to 1,000,
000, more preferably 70,000 to 500,000. When a peroxide-crosslinked olefin-based resin and / or peroxide-crosslinked olefin-based copolymer rubber having a weight-average molecular weight of less than 50,000 is used, the resulting elastomer composition has poor rubber-like properties.
On the other hand, if the weight average molecular weight exceeds 1,000,000, the moldability is deteriorated and the appearance of the molded product is particularly deteriorated. The MFR (measured at 230 ° C. under a load of 2.16 kg) is 0.05 to 200 g / 10 min, and more preferably 0.1 to 50 g / 10 min.

The upper limit of the component (d) is 1500 parts by weight and the lower limit is 0.1 part by weight, preferably 1.0 part by weight, per 100 parts by weight of the softener composition of the present invention. Parts by weight. Preferably, when the thermoplastic resin is blended at 50 parts by weight or less, a very soft thermoplastic resin composition (elastic body) can be obtained. In addition, 100 or more, 300
JIS K7
A soft thermoplastic resin composition having an A hardness of 215 can be obtained without bleed-out. Three
If it exceeds 00 parts by weight, a thermoplastic resin composition having a D hardness shown in JIS K7215 is obtained. To obtain a harder thermoplastic resin composition, it is preferable to add 400 parts by weight or more of the thermoplastic resin composition. To obtain a harder thermoplastic resin composition, it is preferable to add the thermoplastic resin composition in an amount of 600 parts by weight or more.
If the upper limit is exceeded, the hardness of the resin composition becomes too high,
The flexibility is lost, and a rubbery product cannot be obtained, resulting in poor moldability.

The present invention also relates to the above components (a) to (c)
The present invention also relates to a thermoplastic resin composition obtained by blending the above component (d) and heat-treating the same. The amount of component (d) is 1500 parts by weight or less based on 100 parts by weight of component (a), and preferably 0.1 part by weight if a lower limit is set. Preferably, when the thermoplastic resin is blended at 50 parts by weight or less, a very soft thermoplastic resin composition (elastic body) can be obtained. In addition, 100 parts by weight or more, 3
When less than 00 parts by weight of thermoplastic resin is blended, JISK
A soft thermoplastic resin composition having an A hardness of 7215 can be obtained without causing bleed-out.
If it exceeds 300 parts by weight, a thermoplastic resin composition having a D hardness shown in JIS K7215 is obtained. To obtain a harder thermoplastic resin composition, it is preferable to add 400 parts by weight or more of the thermoplastic resin composition. To obtain a harder thermoplastic resin composition, it is preferable to add the thermoplastic resin composition in an amount of 600 parts by weight or more. If it exceeds the upper limit, the hardness of the resin composition becomes too high, the flexibility is lost, and a product having a rubbery feel cannot be obtained, and the moldability deteriorates. As the thermoplastic resin, preferably, styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene-ethylene-propylene-styrene copolymer ( SEEPS) is used.

The softener composition and the thermoplastic resin composition of the present invention contain, in addition to the above components, an antiblocking agent,
Heat stabilizers, antioxidants, light stabilizers, ultraviolet absorbers, lubricants, coloring agents, thickeners, antioxidants, fillers and the like can be added.

Production Method Next, a method for producing the softener composition and the thermoplastic resin composition of the present invention will be specifically described.

Method for Producing the Softener Composition of the Present Invention The softener composition of the present invention is obtained by the following method. Manufacturing conditions vary depending on the reactor. For example, the softener composition of the present invention is prepared by mixing the above components (a) to (c) and putting the mixture into a heatable reaction vessel such as an autoclave, and the reaction temperature is 100 to 250 ° C, preferably 120 to 250 ° C.
It is obtained by reacting at 200 ° C. for 10 minutes or more. If the temperature is lower than 100 ° C., no decomposition reaction of the organic peroxide occurs, and no crosslinking reaction occurs. On the other hand, when the temperature exceeds 250 ° C., a rapid decomposition reaction of the organic peroxide occurs, so that a uniform crosslinking reaction cannot be performed. The composition thus obtained is jelly-like, and preferably has an extraction residue after immersion in an acetone solvent at room temperature for 48 hours of 10% by weight or more.

Since the softener composition of the present invention is in the form of jelly, it can be handled according to solid matter when obtaining a thermoplastic resin composition. Further, since the softener composition of the present invention is in a jelly state, it can be independently applied to a shock absorbing material, a vibration damping material, a sound deadening material, and the like.

Thermoplastic resin containing the softener composition of the present invention
Method for Producing Composition The thermoplastic resin composition containing the softener composition of the present invention is obtained by blending the softener composition of the present invention with the component (d).
It is obtained by kneading using a kneading device.

First, the softener composition of the present invention and the component (d) are blended and melt-kneaded in a kneading apparatus at a kneading temperature of 160 to 230 ° C. to obtain a desired thermoplastic resin composition. Alternatively, a molded article can be formed by an extrusion molding machine or an injection molding machine having a kneading function. As the kneading device used in the present invention, a pressure kneader, a Banbury mixer,
A single-screw extruder, a twin-screw extruder, a multi-screw extruder and the like can be used. Preferably, a method of kneading with a batch kneading apparatus such as a pressure kneader or a Banbury is good. In the case of performing continuously, a method in which a batch-type kneading apparatus and an extruder are combined, for example, a method in which kneading is performed by an apparatus in which a pressure kneader and an extruder are combined (batch supply type continuous extruder) is preferable.
In addition, at the time of the above blending, if a relatively small amount of the component (d) is blended with the softener composition of the present invention, the hardness can be easily adjusted, and the thermoplasticity is very soft as compared with the conventional thermoplastic resin composition. A resin composition (elastic body) can be obtained (Examples 5 to 10).

Further, when oil resistance and heat resistance are to be obtained, the component (b) organic peroxide and the component (c) crosslinking aid added to the thermoplastic resin composition in the softener composition of the present invention are used. A thermoplastic resin composition having excellent oil resistance and heat resistance can be obtained by further adding an agent and kneading under heating and melting (Example 13). At this time, the lower limit of the addition amount of each of the component (b) the organic peroxide and the component (c) of the crosslinking aid is 0.1 part by weight with respect to 100 parts by weight of the softener composition of the present invention. The value is 10 parts by weight, preferably 8.0 parts by weight. If it exceeds the upper limit, the organic peroxide will not be uniformly dispersed and will be partially crosslinked, and although it can be produced, the appearance will be poor, and the compression set and oil resistance will be poor. If it is less than the lower limit, the effect of addition is not recognized, and the compression set and heat resistance are not improved.

In addition to the above method, the thermoplastic resin composition according to the present invention can also be produced by blending the component (d) with the components (a) to (c) and subjecting to heat treatment. When a relatively small amount of a thermoplastic resin, for example, up to 50 parts by weight of the thermoplastic resin (d) is blended with respect to 100 parts by weight of the component (a), heat treatment is performed in the same manner as in the above-described softener composition. As a result, a thermoplastic resin composition (elastic body) that is much softer than the conventional thermoplastic resin composition can be obtained (Example 4). When a relatively large amount of the thermoplastic resin, for example, 100 to 1500 parts by weight of the thermoplastic resin is blended with respect to 100 parts by weight of the component (a), the thermoplastic resin containing the above-described softener composition of the present invention is used. By melting and kneading in the same manner as in the case of the composition, a thermoplastic resin composition having a hardness of A to D shown in JIS K7215 can be obtained without causing bleed-out (Examples 14 to 18).

Various additives such as an antiblocking agent, a light stabilizer, a heat stabilizer, an antioxidant, an ultraviolet absorber, a lubricant, a colorant, a thickener, an antioxidant, and a filler are used in the present invention. It can be added when the agent composition or the thermoplastic resin composition is obtained, but is preferably added when the thermoplastic resin composition is obtained, since it can be uniformly dispersed.

[0043]

The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited to these examples.

Examples 1 to 4 and Comparative Examples 1 to 3 The components shown in Table 1 below were blended according to a predetermined blending amount, and crosslinked while blending in an autoclave heated to 140 ° C. Was obtained.

[0045]

[Table 1] (A-1) (Softener for non-aromatic rubber): PW-90 (manufactured by Idemitsu Kosan Co., Ltd.) Type: normal paraffinic process oil (a-2) (branched saturated hydrocarbon): IP-2835 (Idemitsu Petrochemical Co., Ltd.) Type: Synthetic isoparaffinic hydrocarbon (b) (organic peroxide): Perhexa25B (Nippon Oil & Fat Co., Ltd.) Type: 2,5-dimethyl-2,5-di (t- Butylperoxy) -hexane (c) (crosslinking aid): NK Ester IND (Shin Nakamura Chemical Co., Ltd.)
Type): Mixture of 2-methyl-1,8-octanediol dimethacrylate (85%) and 1,9-nonanediol dimethacrylate (15%) * 1 Thermoplastic resin: SEPS (Kuraray Co., Ltd., Septon 4)
077) Type: Styrene-ethylene propylene-styrene copolymer * 2 Composition state: Properties of softener composition at room temperature (23 ° C); jelly-like, which can be handled according to solids "Jelly-like". * 3 Extraction residue: Extraction residue after immersing the obtained composition in acetone solvent at room temperature for 48 hours (% by weight)

Examples 5 to 10 and Comparative Examples 4 to 6 As component (d), SEPS, EPR, Engage, PE, SEBS and S
After blending one or more of the IS with the softener composition of the present invention prepared in Example 3 according to the blending amount shown in Table 2 below, a pressure kneader (kneader temperature of 160 to
(230 ° C.) to produce a thermoplastic resin composition that is much softer than a conventional thermoplastic resin composition. In Comparative Examples 4 to 6, the conventional uncrosslinked oil (PW-9) was used instead of the softener composition of the present invention prepared in Example 3.
0) was used.

[0047]

[Table 2]

Table 2 shows that a solid elastic body can be obtained by adding a small amount of a thermoplastic resin to the softener composition of the present invention. In the comparative example using the conventional uncrosslinked oil, the oil remains liquid.

Examples 11 to 13 and Comparative Examples 7 to 8 In Examples 11 to 12, SEPS, EPR, E
ngage, PP and PS, and blended with the softener composition of the present invention prepared in Example 3 according to the compounding amount shown in Table 3 below, and then using a twin screw extruder. The mixture was kneaded (cylinder temperature 200 ° C.) to produce a thermoplastic resin composition. In Example 13, the thermoplastic resin composition obtained in Example 12 was heat-treated in the presence of an organic peroxide. In Comparative Examples 7 and 8,
Instead of the softener composition of the present invention prepared in Example 3,
Conventional uncrosslinked oil (PW-90) was used.

[0050]

[Table 3] PP: Tokuyama Corporation PN610S Type: Block type polypropylene PS: Denki Kagaku Kogyo Co., Ltd. GP 1-301 Type: HIPS Oil bleed: After producing 1mm sheet by pressing, 5
It was left at 0 ° C and evaluated by the time until oil bleeding was observed. ○ (1 week or more) △ (3 days or more) × (less than 3 days) Tensile strength: Evaluated with JIS No. 3 dumbbell according to JIS K6251 (tensile speed: 500 mm / min).

From Table 3, when the softener composition of the present invention is used in the production of a thermoplastic resin composition having an A hardness indicated in JIS K7215, the resulting thermoplastic resin composition has reduced oil bleeding, Further, it is understood that the mechanical strength is also improved.

Examples 14 to 18 Ingredients (a) to (d) were blended according to the blending amounts shown in Table 4, and kneaded using a pressure kneader (kneader temperature 16).
0-230 ° C.) A thermoplastic resin composition was obtained. as a result,
A thermoplastic resin composition having the hardness shown in Table 4 (measured according to JIS K7215) was obtained without causing bleed-out.

[0053]

[Table 4]

Examples 19 and 20 The components (a) to (d) were blended according to the blending amounts shown in Table 5, and kneaded using a pressure kneader (kneader temperature 16).
0-230 ° C.) A thermoplastic resin composition was obtained. Component (c)
By adding a large amount of, oil bleeding could be better prevented.

[0055]

[Table 5]

[0056]

The softener composition of the present invention is solid,
Handling in the production of the thermoplastic resin composition is very easy. When the softener composition of the present invention is used, a very soft thermoplastic resin composition without oil bleed can be produced. Furthermore, also in the production of a conventional thermoplastic resin composition having a predetermined hardness, the softener composition of the present invention exerts an effect of suppressing oil bleed and improves the mechanical strength of the resin composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C08L 91/00 C08L 91/00 F term (reference) 4J002 AC03W AC06W AC07W AC08W AC09W AE05X BB03W BB12W BB15W BB18W BC03W BC04W BG04W BL01W BN14W BP01W CF00W CK02W CL00W EA047 EH077 EK036 EK046 EK056 EK086 EU187 FD146 FD157

Claims (19)

[Claims] (A) at least one member selected from the group consisting of a softener for a non-aromatic hydrocarbon rubber, 100 parts by weight, (b) 0.1 to 10 parts by weight of an organic peroxide, and (c) a crosslinking aid. A softener composition obtained by blending 0.1 to 50 parts by weight under the condition of component (b) / component (c) weight ratio ≦ 1 and subjecting to heat treatment. 2. Component (a) is a saturated hydrocarbon having from 4 to 155 carbon atoms.
4. The softener composition according to item 1. 3. The softener composition according to claim 1, wherein component (a) is a saturated hydrocarbon having 4 to 50 carbon atoms. 4. The softener composition according to claim 1, wherein the component (a) is a linear saturated hydrocarbon. 5. The softener composition according to claim 1, wherein the component (a) is a branched saturated hydrocarbon. 6. The softener composition according to claim 1, wherein the component (a) is liquid at room temperature. 7. An extraction residue in an acetone solvent is 10% by weight.
The method according to any one of claims 1 to 6, wherein
Item 4. The softener composition according to item 1. 8. A thermoplastic resin composition comprising 100 parts by weight of the softener composition according to claim 1 and (d) 0.1 to 1500 parts by weight of the thermoplastic resin. 9. A block copolymer comprising component (d) comprising (d1) at least one polymer block A mainly made of an aromatic vinyl compound and at least one polymer block B mainly made of a conjugated diene compound. A polymer and / or a block copolymer obtained by hydrogenating the same, and (d2) an olefin-based resin and / or
9. The thermoplastic resin composition according to claim 8, comprising at least one selected from copolymer rubbers. 10. A thermoplastic resin composition obtained by heat-treating the thermoplastic resin composition according to claim 8 or 9 in the presence of an organic peroxide. 11. (a) at least one member selected from the group consisting of softeners for non-aromatic hydrocarbon rubbers, 100 parts by weight, (b) 0.1 to 10 parts by weight of organic peroxide, and (c) crosslinking aid 0 .1 to 50 parts by weight, and (d) 1500 parts by weight or less of a thermoplastic resin, under the condition of component (b) / component (c) weight ratio ≦ 1 and heat treatment, thereby obtaining a thermoplastic resin composition. . 12. The thermoplastic resin composition according to claim 11, wherein the amount of the component (d) is 100 to 1500 parts by weight. 13. The thermoplastic resin composition according to claim 11, wherein the component (a) is a saturated hydrocarbon having 4 to 155 carbon atoms. 14. The composition according to claim 1, wherein component (a) is a saturated hydrocarbon having 4 to 50 carbon atoms.
13. The thermoplastic resin composition according to 1 or 12. 15. The thermoplastic resin composition according to claim 11, wherein the component (a) is a linear saturated hydrocarbon. 16. The thermoplastic resin composition according to claim 11, wherein the component (a) is a branched saturated hydrocarbon. 17. The thermoplastic resin composition according to claim 11, wherein the component (a) is liquid at room temperature. 18. The thermoplastic resin composition according to claim 11, wherein an extraction residue with an acetone solvent is 10% by weight or more. 19. A block copolymer comprising component (d) comprising (d1) at least one polymer block A mainly made of a vinyl aromatic compound and at least one polymer block B mainly made of a conjugated diene compound. The polymer comprises at least one selected from the group consisting of a polymer and / or a block copolymer obtained by hydrogenating the same, and (d2) an olefin resin and / or a copolymer rubber. 19. The thermoplastic resin composition according to any one of 11 to 18.