JPH02269138A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:To obtain a thermoplastic elastomer composition having excellent oil resistance, moldability and heat resistance by dynamically treating a thermoplastic polymer, partially hydrogenated and conjugated diene based rubber polymer and as necessary other rubber polymer in the presence of a crosslinking agent. CONSTITUTION:The thermoplastic elastomer composition obtained by dynamically treating (A) 10-90wt.% thermoplastic polymer (preferably ABS resin, nylon 12, etc.), (B) 10-90wt.% partially hydrogenated and conjugated diene based rubber polymer (preferably hydrogenated SBR, hydrogenated NBR, etc.) in which 60-95wt.% of a conjugated diene component is partially hydrogenated and (C) 0-50wt.% other rubber polymer (e.g. acryl rubber or fluorine rubber) in the presence of a crosslinking agent, or preferably by carrying out the above- mentioned treatment using the component B previously blended with the crosslinking agent and being insoluble in cyclohexane in >=50wt.% of the component B contained in the composition and being within the range of 50wt.% in elongation set in the case of 100% elongation.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a thermoplastic elastomer composition comprising a thermoplastic polymer and a conjugated diene polymer and useful for automobile interior/exterior products, industrial parts, etc. .

[Prior Art] Plastic molded products are widely used as interior and exterior parts of automobiles and industrial parts. In recent years, thermoplastic elastomers, which are rubber-like soft materials that do not require a vulcanization process and can be molded using the same molding process as thermoplastic resins, have been attracting attention as materials, and are used in automobile parts, home appliance parts, and medical equipment. It is used in fields such as parts and daily necessities. These thermoplastic elastomers include thermoplastic elastomer compositions made of polypropylene and ethylene-propylene copolymer rubber (JP-A-52-13541, JP-A-52-841, JP-A-53-149241). , JP-A-58-34837, etc.), compositions consisting of polypropylene and acrylonitrile-butadiene copolymer rubber (JP-A-56-143233, JP-A-Sho 5),
5-46661), a composition consisting of polypropylene and vinyl acetate-ethylene copolymer (Japanese Patent Publication No. 55-2
No. 1050, JP-A-57-18748), compositions consisting of polypropylene and butyl rubber (JP-A-56-1987),
-122879, Japanese Patent Publication No. 61-18581), compositions consisting of polypropylene and chlorosulfonated polyethylene (Japanese Unexamined Patent Publication No. 138046/1982), polypropylene and styrene-butadiene-styrene block copolymers or their hydrogenation. (Japanese Patent Publication No. 55-18739, Japanese Patent Publication No. 49-4547, Japanese Patent Publication No. 56-44913, etc.), compositions consisting of polyamide and ethylene-acrylic acid ester copolymer (Japanese Patent Publication No. 1987-18739, Japanese Patent Publication No. 49-4547, Japanese Patent Publication No. 56-44913, etc.); 63-314256).

[Problems to be Solved by the Invention] Although these thermoplastic elastomer compositions have individual advantages, they also have problematic drawbacks. For example, a composition made of polypropylene and ethylene-propylene copolymer rubber exhibits excellent elastomer elasticity, but has the disadvantage of poor oil resistance. In addition, compositions made of polypropylene and acrylonitrile-butadiene copolymer rubber have excellent oil resistance, but have the drawbacks of poor elastomer elasticity and processability;
Compositions made of acrylic ester copolymers have excellent heat resistance, but have the disadvantage of poor elastomer elasticity.

Therefore, there has been a desire for a method of producing a thermoplastic elastomer that can meet a wide range of industrial demands, or a thermoplastic elastomer that can meet a wide range of industrial demands.

[Means for Solving the Problem] Taking this situation into consideration, as a result of intensive studies, we have developed a partially hydrogenated conjugated diene rubber polymer in which 70 to 95% of the thermoplastic polymer and conjugated diene components are hydrogenated. It has been found that the object of the present invention can be achieved by dynamically treating a polymer mixture consisting of a polymer in the presence of a crosslinking agent, and the present invention has been achieved.

That is, the present invention comprises: (1) (A) 10 to 90% by weight of a thermoplastic resin; (B) 10 to 90% by weight of a partially hydrogenated conjugated diene-based rubbery polymer;
and (C) other rubbery polymer by dynamically treating 0 to 50% by weight in the presence of a crosslinking agent, and 50% by weight of component (B) in the composition.
A thermoplastic elastomer composition in which at least % by weight is insoluble in cyclohexane and has a permanent elongation at 100% elongation of 50% or less, (2) in (1) above, (B) is a partially hydrogenated conjugated diene-based random conjugate; A thermoplastic elastomer composition that is a polymer, and (3) a thermoplastic elastomer composition in (1) above, in which (A) is a thermoplastic elastomer and (C) is another thermoplastic polymer. It is something.

[Description of the invention (1)] The thermoplastic polymer used in the above invention (1) of the present invention is:
It includes thermoplastic polymers and thermoplastic polymer compositions.

Thermoplastic polymers include, for example, ABS resin, AES resin,
Aromatic vinyl polymers such as MBS resin, AS resin, polystyrene, HIPS, styrene-maleic anhydride copolymer, styrene-acrylonitrile-N-substituted maleimide copolymer, styrene-methacrylic acid copolymer, polymethyl methacrylate , acrylic polymers such as methyl methacrylate-styrene copolymer, methyl methacrylate-styrene-N-substituted maleimide copolymer, 6-nylon, 46-nylon, 6-row nylon, 11-nylon, 12-nylon, 610- Polyamide polymers such as nylon and 612-nylon, polyester polymers such as polyethylene terephthalate and polybutylene terephthalate, polyethylene, polypropylene, and polybutene.
Polyolefin polymers such as 1, polycarbonate, polyvinyl chloride, polyphenylene ether, polyoxymethylene, polyphenylene sulfide, thermoplastic resins such as fluororesins, and polyester elastomers, polyamide elastomers, polyamide polyester elastomers, hydrogenated styrene-butadiene-styrene tris. Block polymers, styrene-butadiene-styrene triblock polymers, hydrogenated styrene-isoprene diblock polymers, thermoplastic elastomers such as thermoplastic polyurethane, polymer compositions consisting of polystyrene and polyphenylene ether, ABS resin and thermoplastic polyurethane A polymer composition consisting of ABS resin and polyamide, a polymer composition consisting of ABS resin and polycarbonate, a polymer composition consisting of polyamide and polyester, a polymer consisting of polypropylene and ethylene-propylene copolymer rubber All thermoplastic polymers and polymer compositions, such as compositions, can be preferably used as the thermoplastic polymer of the present invention.

Preferred thermoplastic polymers as component (A) include aromatic vinyl polymers, acrylic polymers, polyamide polymers, polyester polymers, polycarbonate resins, polyether polymers, polyurethane polymers, and polyvinyl chloride. It is at least one thermoplastic polymer selected from the group consisting of resin, polyvinylidene chloride resin, and fluororesin. Particularly preferred are ABS resin, AES resin, MBS resin, AS resin, styrene-maleic anhydride copolymer, 11-nylon, 12-nylon, 610-nylon, polyamide elastomer, polyester elastomer, polycarbonate, polyethylene terephthalate, Examples include polybutylene terephthalate, polyphenylene ether, polyoxymethylene, thermoplastic polyurethane, polyvinyl chloride, polyvinylidene chloride, and the like.

The amount of these thermoplastic polymers used is usually 10 to 90% by weight, preferably 20 to 80% by weight, and more preferably 30 to 70% by weight. Thermoplastic polymer 30-70
It is most preferable to use within the range of % by weight because a composition with excellent balance between processability and mechanical strength can be obtained.

If the amount of thermoplastic polymer used is less than 10% by polymerization, thermoplasticity will not be developed and processability will be significantly inferior, which is not preferable. Furthermore, if it is used in an amount exceeding 90% by weight, the performance as an elastomer will be poor, which is not preferable.

Next, the partially hydrogenated conjugated diene rubbery polymer which is the component (B) of the present invention (1) will be explained in detail.

Partially hydrogenated conjugated diene-based rubbery polymers (hereinafter referred to as partially hydrogenated rubber) are polymers of conjugated diene compounds, or random copolymers or graft copolymers of conjugated diene compounds and other monomers that can be copolymerized. A polymer or block copolymer obtained by hydrogenating some of the unsaturated bonds in the (co)polymer.

Examples of the conjugated diene compound include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Other monomers that can be copolymerized with the conjugated diene compound include:
For example, α such as aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene, acrylonitrile, and methacrylonitrile.

β-unsaturated nitrile compounds, acrylic esters such as methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl methyl acrylate, methacrylic esters such as methyl methacrylate, ethyl methacrylate, and cyclohexyl methacrylate, N-substituted maleimide compounds, acrylic acid, methacrylic acid , maleic anhydride, and the like.

The hydrogenation rate is 60 to 95%, preferably 70 to 95%, more preferably 75 to 95% of the unsaturated bonds in the (co)polymer. If the hydrogenation rate is less than 60%, it is not preferable because weather resistance, heat aging resistance, etc. may deteriorate due to residual unsaturated bonds. Further, hydrogenation exceeding 95% is not preferable because crosslinking becomes insufficient, mechanical strength tends to decrease, and permanent elongation at 100% elongation tends to deteriorate.

The method of hydrogenation is a normal method (for example,
No. 9275, JP-A-52-32095, JP-A-56-
133291, etc.).

A typical example of these partially hydrogenated rubbers is 60% of the butadiene component of a styrene-butadiene random copolymer.
~95% partially hydrogenated (hereinafter referred to as hydrogenated SB)
60-95% of the butadiene component of a block copolymer in which a block segment made of polystyrene is bonded to a block segment made of a styrene-butadiene random co-assembly (abbreviated as R) is partially hydrogenated (abbreviated as R).
(hereinafter abbreviated as hydrogenated S-8BR), a block copolymer in which a block segment made of polybutadiene is bonded to a block segment made of polystyrene, and 60 to 95% of the butadiene component of the block copolymer is partially hydrogenated (hereinafter referred to as hydrogenated S-8BR). 5-BR), a block segment made of polystyrene, a block segment made of a styrene-butadiene random copolymer, and a pro-tsk segment made of polybutadiene are combined as a part of 60 to 95% of the butadiene component of the block copolymer. partially hydrogenated (hereinafter abbreviated as S-8BR-BR), 60 to 75% of the isoprene component of a block copolymer in which a block segment made of polystyrene is bonded to a block segment made of polyisoprene. Hydrogenated (hereinafter abbreviated as hydrogenated 5-IP), 60 to 9 of the butadiene component of acrylonitrile-butadiene random copolymer
5% partially hydrogenated (hereinafter abbreviated as hydrogenated NBR), 60 to 95% of the butadiene component of acrylic acid ester-butadiene random copolymer partially hydrogenated (hereinafter referred to as hydrogenated NBR) (abbreviated as hydrogenated NABR), acronitrile-acrylic acid ester-butadiene random copolymer in which 60 to 95% of the butadiene component is partially hydrogenated (hereinafter abbreviated as hydrogenated NABR), etc. , these can be used alone or in combination, but are not limited to these.

Among these partially hydrogenated rubbers, hydrogenated SBR.

Hydrogenated S-3BR, Hydrogenated 5-BR, Hydrogenated S-8BR-8R
Monohydrogenated 5-IP, hydrogenated NBR, and the like are examples of those preferably used.

The amount of conjugated diene in the conjugated diene rubbery polymer before undergoing partial hydrogenation is usually 1 to 100% by weight.
be selected as appropriate within the range. When the copolymerized monomer is a resin-like polymer, such as styrene, acrylonitrile, methyl methacrylate, etc., the amount of conjugated diene used is 30 to 99% by weight. is preferred, and most preferably used within the range of 50 to 99% by weight. When the polymer consisting only of copolymerized polymers uses a monomer that becomes a rubber-like polymer, such as ethyl acrylate or butyl acrylate, it is preferably used in an amount of 3 to 80% by weight. 5-70
It is most preferable to use within a range of % by weight.

In invention (1), it is extremely useful to use a partially hydrogenated rubber as component (B) mixed with a crosslinking agent in advance (hereinafter referred to as a rubber composition). Compared to elamadomer, it can provide better properties in terms of breadth and physical properties.

The crosslinking agent is one that is commonly used for crosslinking rubber, such as “
Crosslinking agent handbook (written by Shinzo Yamashita and Tosuke Kaneko, Taiseisha)
” can be used.

Preferred crosslinking agents include sulfur, sulfur compounds, p-benzoquinone dioxime, p, p'-dibendiylquinone dioxime, 4,4'-dithiobis-dimorpholine, poly-p-dinitrosobenzene, and tetrachloro. benzoquinone, alkylphenol-formaldehyde resin,
Brominated alkylphenol-formaldehyde resin, ammonium benzoate, bismaleimide compound, jepoxy compound, diisocyanate compound, diamine compound, dicarboxylic acid compound, diol compound, amino resin, organometallic salt, metal alkoxide, organometallic compound, organic peroxide, etc. be.

These crosslinking agents can be used alone or in combination. Furthermore, it is known that crosslinking can proceed more efficiently depending on the crosslinking agent when used in combination with other compounds.

In particular, when sulfur or a sulfur compound is used as a crosslinking agent, it is desirable to use a vulcanization accelerator, a vulcanization accelerator, and an activator that promote the crosslinking reaction of sulfur.

Examples of vulcanization accelerators include aldehyde ammonias such as hexamethylenetetramine, aldehyde amines which are reaction products of n-butyraldehyde and aniline, diphenylguanidine, di-o-tolylguanidine, and 0-tolyrubiguanidine. Guanidines, thiocarbanilide, N,N'diethylthiourea, dibutylthiourea,
dilaurylthiourea, 2-mercaptoimidacillin,
Thioureas such as trimethylthiourea, mercaptobenzothiazole, sodium salt of mercaptobenzothiazole, N-tert-butyl-2-benzothiazoyl-sulfeamide, N.

N'-dicyclohexyl-2-benzothiazoyl sulfamide, dibenzothiazoyl disulfide, 2-(4
-morpholinodithio)benzothiazole, 2- (2
, 4-dinitro-phenyl)-mercapto-benzothiazole, dithiocarbamates such as iron dimethyldithiocarbamine, zinc dimethyldithiocarbamine, zinc diethyldithiocarbamine, copper copper dimethyldithiocarbamate, zinc butylxanthogen, sodium isopropylxanthogen, zinc isopropylxanthogen, etc. Xanthates, thiurams such as tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide, and mixtures of several of these vulcanization accelerators are preferably used.

Vulcanization accelerators and activators include zinc oxide, activated zinc white, surface-treated zinc white, zinc carbonate, magnesium oxide, litharge, red lead, white lead, steolic acid, oleic acid, lauric acid, zinc stearate, These include triethanolamine, and other organic amines.

Further, when using an organic peroxide as a crosslinking agent, a method of using a crosslinking aid in combination is preferred. As a crosslinking aid,
Sulfur, sulfur compounds such as dipentamethylenethiuram pentasulfide, mercaptobenzothiazole, oxime nitroso compounds, ethylene glycol dimethacrylate, aryl methacrylate, triaryl cyanurate, diaryl phthalate, polyethylene glycol dimethacrylate, divinyl adipate, maleic anhydride,
Monomers such as bismaleimide compounds, trimethylolpropane trimethacrylate, divinylbenzel, liquid polybutadiene, liquid styrene-butadiene copolymers,
There are polymers such as poly-1,2-butadiene.

The rubber composition used in (1) of the present invention is a partially hydrogenated rubber containing a crosslinking agent and a vulcanization accelerator, a vulcanization accelerator, an activator, or a crosslinking auxiliary to be used in combination as necessary. Refers to something that has been done.

It is desirable that these crosslinking agents and other compounds used in combination as necessary be thoroughly masticated with the partially hydrogenated rubber before use. In particular, when using a system consisting of sulfur or a sulfur compound and a vulcanization accelerator as a crosslinking system, it is important to add these to partially hydrogenated rubber and thoroughly masticate it before use to prevent local overvulcanization. It is desirable to avoid this and obtain uniform vulcanization. Although all of the crosslinking agents may be mixed in advance, it is preferable to blend a portion of the crosslinking agent into the rubber using the method described above, and use the rest by triblending or post-adding.

Alternatively, a method is also used in which a plurality of crosslinking agents (systems) are used, one type is masticated and blended into the rubber, and the other types are triblended or added later. For example, when using an organic peroxide as a crosslinking agent, all the organic peroxide particles used may be masticated in partially hydrogenated rubber, or
Alternatively, a portion may be masticated into partially hydrogenated rubber, and the remaining portion may be attached to the surface of the partially hydrogenated rubber pulverized product by triblending, or may be post-added during melt mixing of the polymer mixture. In some cases, it is also an embodiment of the present invention to use the entire amount of the crosslinking agent used by applying it to the surface of the polymer mixture by triblending.

As a guideline when selecting a crosslinking agent (system), it is preferable to consider the following points.

Mixtures of different polymers are essentially incompatible. Simply dynamically crosslinking the rubber component in a mixture of incompatible polymers results in poor performance of the composition. The reason for this is poor adhesion at the interface between the crosslinked rubber and the resin phase.

In the present invention, it has become possible to use various thermoplastic polymers as the resin phase by using partially hydrogenated rubber that leaves unsaturated bonds. Some of the agents cause crosslinking reactions with functional groups in other polymers, and the concept of co-crosslinking of rubber and resin will be put into practical use.

Specifically, there are the following examples of co-crosslinking agents (systems).

Dithiol compounds cause addition reactions to double bonds to form crosslinks, and are also effective as crosslinking agents for chlorinated or brominated polymers. Therefore, it can be used in a co-crosslinking reaction between partially hydrogenated rubber and vinyl chloride resin, vinylidene chloride resin, etc.

Alkylphenol-formaldehyde resins perform crosslinking reactions with double bonds as well as amide bonds, chlorides, bromides, carboxyl groups, thiol groups, and nitrile groups. Therefore, it can be used for co-crosslinking reactions between partially hydrogenated rubber and polyamide, vinyl chloride resin, vinylidene chloride resin, polyester, acrylonitrile copolymer resin, etc.

In addition, the jepoxy compound performs a crosslinking reaction with a carboxyl group, a hydroxyl group, an isocyanate group, etc., as well as an addition reaction with a double bond. Therefore, it can be used for co-crosslinking reactions between partially hydrogenated rubber and polyamide, polyester, polyurethane, etc.

Further, organic peroxides are preferably used for crosslinking unsaturated or saturated polymers.

Some saturated polymers, such as polypropylene, are decomposed by organic peroxides, but by using an appropriate crosslinking aid, decomposition can be stopped and crosslinking can be achieved. For example, polypropylene and partially hydrogenated rubber can be co-crosslinked by using an organic peroxide together with bismaleimide, divinylbenzene, a quinone dioxime compound, thiuram sulfide, or the like.

In the case of co-crosslinking of polypropylene, p-benzoquinone dioxime, p, p'-dibenzoylquinone dioxime, dipentamethylene lentiaum tetrasulfide, dibentamethylene lentiaum pentasulfide, etc. are preferred. A particularly preferred system is dicumyl peroxide, di-t
- This is a system that uses a monofunctional high-temperature decomposition type organic peroxide such as butyl peroxide in combination with a thiuram sulfide compound.

Although the amount used is not particularly limited, it is preferable to use 1/2 equivalent mole or more of the crosslinking aid relative to the organic peroxide.

There are many types of crosslinking agents that can be applied to other types of inversion. In particular, when a partially hydrogenated rubber copolymerized with a polymer having a functional group is used, the selection of applicable co-crosslinking agents becomes wider.

For example, when using a partially hydrogenated rubber copolymerized with a polymer having carboxyl groups, carboxylic acid ester groups, hydroxyl groups, epoxy groups, etc. as functional groups, unsaturated double bonds in the partially hydrogenated rubber are A crosslinking reaction between these functional groups can be used in combination with the crosslinking reaction used.

Dynamic crosslinking of the composition of the present invention may be carried out using only the above-mentioned co-crosslinking agent, or a crosslinking agent that only crosslinks double bonds and a co-crosslinking agent may be used in combination. For example, a method in which double bonds are crosslinked using a sulfur-vulcanization accelerator system and an appropriate amount of co-crosslinking agent is used in combination can crosslink rubber evenly and highly, and can also crosslink thermoplastic polymers and partially hydrogenated rubber. Co-crosslinking improves the miscibility of the two, which is preferable.

The amount of crosslinking agent used can be adjusted as appropriate depending on the performance required of the final composition. Selection of an appropriate crosslinking system and amount to be used are preferably determined with reference to the above-mentioned bottom setting and the like. Usually, the crosslinking agent is 0.1 to 8 parts by weight per 100 parts by weight of partially hydrogenated rubber.
Vulcanization accelerator: 0.1~10 parts, vulcanization accelerator: 0.5~
10 parts by weight, activator 0.5-10 parts by weight, crosslinking aid 0.
It is used appropriately within the range of 1 to 20 parts.

The amount of partially hydrogenated rubber used is usually 10 to 90% by weight,
Preferably 20 to 80% by weight, more preferably 30 to 80% by weight
It is 70% by weight. If the amount used is less than 10% by weight, the performance as an elastomer will be poor and the elasticity etc. will be insufficient, which is not preferable. Furthermore, if it is used in an amount exceeding 90% by weight, it is difficult to impart thermoplasticity and the processability is poor, which is not preferable.

Further, other rubbery polymers can be blended into the composition of the present invention. The other rubbery polymers used are any other rubbery polymers that do not fall under the partially hydrogenated rubber of the present invention, such as ethylene-propylene copolymer rubber, ethylene-butylene copolymer rubber, and the rubbery polymers of the present invention. A rubbery polymer in which the conjugated diene component of a conjugated diene rubbery polymer, which is a precursor of partially hydrogenated rubber, is almost completely hydrogenated, acrylic rubber, partially crosslinked acrylic rubber, chlorosulfonated polyethylene, epichlorohydrin rubber , essentially saturated rubbery polymers such as polyester urethane rubber, fluororubber, ethylene-vinyl acetate copolymer rubber, ethylene-acrylate copolymer rubber, chlorinated polyethylene, silicone rubber, fluorosicone rubber, or ethylene-propylene. - Diene component ternary copolymer rubber, ethylene-butylene-terpolymer rubber, the conjugated diene rubbery polymer itself which is the precursor of the partially hydrogenated rubber of the present invention, or one with a hydrogenation rate of less than 70% Essentially unsaturated rubbery polymers such as , partially crosslinked nitrile rubber, partially crosslinked acrylate-butadiene copolymer rubber are preferably used. The amount of these other rubbery polymers used is appropriately within the range of 0 to 50% by weight.

When adding other rubbery polymers to the polymer composition of the present invention for the purpose of imparting new performance, for example, acrylic rubber, chlorosulfonated Adding polyethylene, silicone rubber, fluororubber, etc. is an effective means. When adding other rubbery polymers for such purposes, the amount of the other rubbery polymers used is usually 0.05 to
50% by weight, preferably 0.1-40% by weight, more preferably 0.5-35% by weight. If the amount is less than 0.05% by weight, the desired new performance will not be imparted, which is not preferable. Further, if it is used in an amount exceeding 50% by weight, it is not preferable because processability may be impaired. Further, these other rubbery polymers may be used in a form containing a vulcanizing agent, a vulcanization aid, or a vulcanization accelerator, if necessary.

The cyclohexane-insoluble portion of the partially hydrogenated rubber in the polymer composition of the present invention is expressed as a value calculated as follows from the cyclohexane-insoluble portion of the composition of the present invention.

where: Total weight of the composition after cyclohexane extraction n Weight of thermoplastic polymer insoluble in cyclohexane in the composition Wadd is total weight of components insoluble in cyclohexane among additives Wrb is partial water in the composition The weight WpI) of the added rubber is W8X.

The test involves extraction in cyclohexane at 60°C for 4 hours.

When using other rubbery polymers in the present invention, it is necessary to consider the insoluble content of the other rubbery polymers.
1) It cannot be determined by formula. Therefore, when using another rubbery polymer, a composition excluding this polymer is prepared on a trial basis, and the insoluble portion of the partially hydrogenated rubber is calculated from the cyclohexane insoluble portion of the test material.

The cyclohexane insoluble content of the thermoplastic elastomer composition of the present invention is calculated according to formula (1), and is usually 50% or more,
Preferably 55-100%, more preferably 60-1
It is desirable that it be crosslinked to 00%. Insoluble content is 5
If it is less than 0%, the degree of crosslinking is insufficient and mechanical strength and elastomer elasticity are poor, which is not preferable.

Furthermore, the composition of the present invention has a permanent elongation of 5 at 100% elongation.
It is within 0%. For permanent elongation, a JISI dumbbell-shaped test piece with a marked line for elongation measurement was measured at 500 mm/
After pulling at a speed of 100 cm and holding at 100% elongation for 10 minutes, do not rebound (suddenly contract and measure the elongation after 10 minutes).

Permanent elongation (%) is calculated by the following formula.

LO, gauge distance (mm) τ1; Length between gauge lines after shrinking and leaving for specified time (no
++) Preferably the permanent elongation is within 45%, more preferably 40%.
Within %. If the permanent elongation exceeds 50%, the elasticity as an elastomer will be poor, and therefore it is not preferable.

[Description of invention (2)] The thermoplastic polymer of component (A) used in the invention (2) is a polyolefin resin, an aromatic vinyl polymer, an acrylic polymer, a polyamide polymer, a polyester polymer. , polycarbonate resin, polyether polymer,
At least one thermoplastic polymer selected from the group consisting of polyurethane polymers, polyvinyl chloride resins, and fluororesins, and suitable examples include those described in the description of the thermoplastic polymer in invention (1). You can select the appropriate one.

For example, polyethylene, polypropylene, ABS resin,
AES resin, MBS resin, As resin, styrene-maleic anhydride copolymer, 11-nylon, 12-nylon,
Preferred examples include 6,10-nylon, polyamide elastomer, polyester elastomer polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyphenylene ether, polyoxymethylene, thermoplastic polyurethane, polyvinyl chloride, and polyvinylidene chloride.

The amount of thermoplastic polymer used is the same as in the present invention (1).

The partially hydrogenated rubber used in invention (2) essentially contains a conjugated diene, and at least one monomer selected from the group consisting of tolyllic acid ester for α, β-unsaturation, aromatic vinyl, and as necessary. A rubbery undertone copolymer obtained by copolymerizing at least one polymer selected from the group consisting of other radically polymerizable monomers according to the
60 to 95% of the conjugated diene component in the copolymer is partially hydrogenated, and the preferred hydrogenation rate is the same as in invention (1).

Specifically, styrene-butadiene random copolymer,
Butyl acrylate-butadiene random copolymer, ethyl acrylate-butadiene random copolymer, butyl acrylate-ethyl acrylate-butadiene random copolymer, acrylonitrile-butadiene random copolymer, acrylonitrile-butadiene random copolymer Coalescence, acrylonitrile-butyl acrylate-phtadiene random copolymer, acrylonitrile-
Examples include ethyl acrylate-butadiene random copolymer, butyl acrylate-styrene-butadiene random copolymer, and the like, in which 60 to 95% of the unsaturated bonds in each polymer are partially hydrogenated.

In the composition of invention (2), the cyclohexane insoluble content of the partially hydrogenated rubber is calculated according to the method described in the explanation of invention (1), and the appropriate amount of insoluble content is the same as that of invention (1). Furthermore, the description in invention (1) applies to the method of measuring permanent elongation at 100% elongation and the appropriate value.

Invention (2) is particularly industrially useful among the thermoplastic elastomer compositions that can be produced in Invention (1) in that a composition with excellent oil resistance can be obtained.

Further, the other rubbery polymers used in invention (2) and their usage amounts are the same as those in invention (1), and the crosslinking agent, its selection method, usage, etc. are also the same as in invention (1).

[Description of invention (3)] The thermoplastic elastomer used in invention (3) is a material that can be plasticized and molded at high temperatures, and the molded product behaves as a rubber-like elastic body at room temperature. A substance that has a hard phase and a soft phase.

Thermoplastic elastomers are classified according to the properties of the hard phase, for example, Koei Komatsu, Plastic Age, 23 (3).
, 1982''. For example, polystyrene thermoplastic elastomer, polyester thermoplastic elastomer, polyurethane thermoplastic elastomer, polyamide thermoplastic elastomer, fluororesin thermoplastic elastomer, polyolefin plastic elastomer. etc. are representative examples.

As a styrene thermoplastic elastomer, styrene-
Typical examples include butadiene-styrene block copolymers and hydrogenated products thereof, styrene-isoprene-styrene block copolymers and hydrogenated products thereof.

As the thermoplastic polyester elastomer, a high melting point crystalline segment (A) consisting of an aromatic polyester unit is used.
and a low melting point polymer segment (B) mainly consisting of aliphatic polyether or aliphatic polyester units.

The above (A) and (
The ratio of B) is (A)/(B)-10~95/90~5
Weight%.

The aromatic polyester unit (A) has a molecular weight of 300
one or more dicarboxylic acids smaller than 300
It consists of at least one type of alkylene glycol or cycloalkylene glycol having a smaller molecular weight, and the above (B) consists of at least one type of long chain glycol having a molecular weight of 400 to 6,000 alone, or this long chain. It consists of one or more long-chain glycols and at least one dicarboxylic acid having a molecular weight of less than 300.

Dicarboxylic acids with a molecular weight lower than 300 are cycloaliphatic dicarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid, 2,6- and 1,5-naphthalenedicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, oxalic acid. , aliphatic dicarboxylic acids such as glutaric acid, adipic acid, azelaic acid, and sebacic acid, and ester-forming derivatives thereof, and two or more of these may be copolymerized and used.

Alkylene glycols having a molecular weight of less than 300 that react with these cigarboxylic acids to form short-chain polyesters include ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, and the like. Examples include alkylene glycol and cycloalkylene glycol such as 1°4-cyclohexane dimetatool.

Examples of long chain diols with a molecular weight of 400 to 6,000 include polyethylene glycol, poly(1,2- and 1.3-
Examples include poly(alkylene oxide) glycols such as propylene oxide) glycol, poly(tetramethylene oxide) glycol, and copolymers of ethylene oxide and propylene oxide.

Preferred compositions of thermoplastic polyester elastomers include polybutylene terephthalate-poly(tetramethylene oxide) glycol, polybutylene terephthalate-polybutylene isophthalate-poly(tetramethylene oxide) glycol, polybutylene terephthalate-polybutylene terephthalate-poly(tetra methylene oxide) glycol, polybutylene terephthalate-polyhexamethylene terephthalate-polyethylene glycol, polyhexamethylene terephthalate-poly(tetramethylene oxide) glycol, and the like.

As the polyamide elastomer, one synthesized by a condensation reaction of a polyether having a hydroxyl group at the chain end and a polyamide is used.

The polyether having a hydroxyl group at the end of the chain may be a linear or branched polyoxyalkylene glycol, such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol or a mixture thereof, or a compound derived from the above-mentioned compounds. It is a copolyether.

The average molecular weight of the polyether is generally 200 to 6,
000, preferably 400-3. It is 000. The weight ratio of polyoxyalkylene glycol to the weight of all components is usually 5 to 85%, preferably 10 to 50%.
It is.

In addition, as a polyamide, the number of carbon atoms in the hydrocarbon chain is 4 to 4.
Starting from a lactam or amino acid that is 14, such as caprolactam, enantlactam, dodecalactam, undecanolactam, todecanolactam, 11-amino-undecanoic acid or 12-aminododecanoic acid,
or condensation products of dicarboxylic acids and diamines, such as the condensation products of hexamethylene diamine and adipic acid, azelaic acid, sebacic acid and 1,12-dodecanedioic acid, and the condensation products of menamethylene diamine and adipic acid. Nylon 6-6.6-9.6-10.6-
12 and 9-6.

The average molecular weight of dicarboxylic acid polyamide is usually 300-
15,000, preferably 800 to 5,000.

A polyolefin thermoplastic elastomer has a polyolefin resin, preferably polypropylene or polyethylene, as a hard phase, and includes a blend of polypropylene and ethylene-propylene copolymer rubber, and a blend of polypropylene and ethylene-vinyl acetate copolymer rubber. , blends made of polyolefin resins and rubbery polymers such as blends made of polypropylene and chlorinated polyethylene, and graft polymers in which polypropylene is grafted onto ethylene-propylene rubber.

Thermoplastic elastomers can be used alone or in combination of two or more. The amount of thermoplastic elastomer used is usually 10 to 90% by weight, preferably 20 to 80% by weight.
It is n% by weight, more preferably 30 to 70% by weight. If the amount of thermoplastic elastomer used is less than 1.0% by weight, thermoplasticity will not appear and processability will be poor, which is not preferable. Furthermore, if it is used in an amount exceeding 90% by weight, the softening caused by the introduction of rubber will be insufficient, resulting in insufficient flexibility, which is not preferable.

The rubber component (B) used in invention (3) is at least one rubber selected from the group consisting of natural and synthetic rubbers. Specific examples include natural rubber, partially hydrogenated rubber described in invention (1), other rubbery polymers described in invention (1), or chemical treatment of the above rubber. Modified rubber modified with substances, etc.
Rubbers exhibiting a glass transition temperature of 0° C. or less are preferred. Preferably, the rubber has a glass transition temperature of 0°C or lower, and more preferably one having a glass transition temperature of -5°C or lower. Materials with a glass transition temperature exceeding 10° C. can be used depending on the purpose, but are not preferred because they have poor flexibility at low temperatures.

Examples of preferred rubbers include the partially hydrogenated rubbers described in invention (1) and other rubbery polymers.

The amount of rubber used is usually 10 to 90% by weight, preferably 2% by weight.
It is 0 to 80% by weight, more preferably 30 to 70% by weight. If the amount used is less than 10% by weight, it is not preferable because softening by adding rubber is insufficient and flexibility cannot be imparted.

Furthermore, if it is used in an amount exceeding 90% by weight, it is undesirable because it tends to lose its thermoplasticity and has poor processability.

The selection and appropriate amount of the crosslinking agent used in invention (3) are in accordance with those described in invention (1).

Preferred crosslinking agents include those that partially co-crosslink rubber and thermoplastic elastomer, and it is preferable to use a crosslinking agent that crosslinks only rubber and one that co-crosslinks rubber and thermoplastic elastomer.

When using highly unsaturated diene rubber, sulfur and a vulcanization accelerator are mixed into the rubber as a crosslinking agent for the rubber, and an alkylphenol-formaldehyde resin is used as a co-crosslinking agent for the rubber and thermoplastic polyamide elastomer. A method of using a jepoxy compound as a co-crosslinking agent for rubber and a thermoplastic polyester elastomer; A method of using an organic peroxide and a crosslinking aid as a co-crosslinking agent for rubber and a styrenic thermoplastic elastomer or an olefinic thermoplastic elastomer There is a way.

In the composition of invention (3), the method for measuring the cyclohexane insoluble content of the rubber, the appropriate amount of insoluble content, and the method for measuring permanent elongation at 100% elongation and its appropriate value are the same as those in invention (1).

Further, in the invention (3), other polymers, particularly thermoplastic resins, can be added and used as necessary.

A thermoplastic resin is one having a glass transition temperature equal to or higher than room temperature, and a corresponding thermoplastic resin can be found among the thermoplastic polymers described in the explanation of invention (1).

Other polymers used in invention (3) are added as necessary for the purpose of improving the weather resistance, oil resistance, chemical resistance, heat resistance, etc. of the thermoplastic elastomer of the invention.

Therefore, it is desirable to select a polymer that has excellent properties. For example, fluororesin is effective in improving weather resistance, oil resistance, and chemical resistance, and polyethylene, polypropylene, etc. are effective in improving chemical resistance. Further, polyester, polyamide, etc. are effective in improving heat resistance and oil resistance.

The amount of these other polymers used is usually 0 to 50% by weight, but when used for the above purpose,
0.05-50% by weight, preferably 0.1-40% by weight
, more preferably within the range of 0.5 to 35% by weight. If the amount used is less than 0.05% by weight, the desired new performance will not be imparted, which is not preferable. Also, 5
If it is used in excess of 0 weight percent, it becomes inflexible and hard, which is not preferable.

Invention (3) provides a flexible composition with excellent mechanical strength that is particularly industrially useful among thermoplastic elastomers produced by the method according to Invention (1).

The composition of the present invention is most preferably manufactured using a manufacturing method that uses component (B) described in invention (1) mixed with a crosslinking agent in advance, but it is not limited to this method. isn't it.

Regarding the production of the polymer composition of the present invention, ordinary masticating equipment such as a rubber mill, Brabender mixer, Banbury mixer 1 pressurized double-screw extruder, etc. can be used. Even if there is a gas, it is preferable to use a type that can be replaced with an inert gas. The kneading temperature needs to be a temperature at which all the components to be mixed are melted, and is preferably within the range of usually 160 to 300°C, preferably 170 to 280°C. The kneading time cannot be discussed unconditionally because it depends on the type and amount of the constituent components and the masticating device, but when using a pressure kneader, Banbury mixer, etc. as the masticating device, it is usually about 10 to 40 minutes. A mixing time of minutes is preferred.

[Examples] Next, the present invention will be explained in more detail by showing examples.

Examples 1 to 10, Comparative Examples 1 to 6 The polymer compositions of the present invention were produced by melt-mixing the thermoplastic polymers, rubber compositions, etc. shown in Table 1. The physical property values are shown in Table-1.

(All numbers are parts by weight. Crosslinking agent and compounding agent are rubber 1
The amount added is shown in parts by weight relative to 00 parts by weight. ) In Table 1, each component of the crosslinking agent is the following *A1*B, *
It was blended by either method of C.

*A: The crosslinking agent was blended with rubber in advance and mixed with a thermoplastic resin, etc. *B: The crosslinking agent was attached to the surface of the polymer mixture by Nidry blending *C: The thermoplastic resin, rubber, etc. were added after melt mixing In *A above, when the crosslinking agent was blended into the rubber in advance, it was mixed at a low temperature of 60° C. or lower to prevent crosslinking from proceeding during blending. The composition of each component in Table 1 is determined using a pressure kneader.
(described as N in Table 1) or a twin-screw extruder (described as E in Table 1). Since the specific manufacturing procedure differs depending on each of the above-mentioned wire drawing apparatuses, each will be explained below using typical examples.

[Production example using a pressure kneader] Using a pressure kneader whose temperature is controlled at an oil bath temperature of 200°C, hydrogenated SBR containing polypropylene, a vulcanizing agent, and a vulcanization accelerator is heated with nitrogen gas. The mixture was melted and mixed under a stream of air. After about 12 to 15 minutes, the mixture became a constant homogeneous mixture, after which mixing was continued for an additional 10 minutes and then discharged. The resulting mixture was passed through a heated roll, formed into a sheet, and press-molded into a square plate with sides of 10 cm.
It was cut out with a dumbbell cutter and used as a test piece for measurement.

[Example of production using a twin-screw extruder] A rubber composition containing a vulcanization aid is produced in advance using a roll, and this is pulverized into granules, and 2,5-dimethyl is added as a vulcanizing agent. A rubber composition to which -2,5-di(t-butylperoxy)hexane was attached was produced.

Next, the cylinder temperature was set to 240° C., and the thermoplastic resin and the rubber composition obtained above were melt-mixed using a twin-screw extruder. The operation was carried out at a screw rotation speed of 250 revolutions, and the average residence time of the contents was 30 to 40 seconds. The obtained pellet was dried and injection molded to obtain a test piece for measurement.

Evaluation tests for physical properties were conducted according to JIS K6301. The evaluation of weather resistance is shown by the change in the appearance of the test piece after being exposed to a weather tester at 70°C for 7 days. ○ means almost no coloring, △ means slightly colored, Shows cracks.

Below margin *10 *11 N,N'-m-phenylene bismaleimide manufactured by Taoka Chemical Industry ■, brominated alkylphenol formaldehyde resin agent Nouriy ■, 2,5-dimethyl-2゜5-di(t
-butylperoxy)hexanization agent Nourii ■, di-
t-Butyl peroxide dipentamethylenethiuram tetrasulfide N-t-metabutyl-2-penzothiazole sulfeinamide 2-bis-benzothiazyl disulfide Manufactured by Iruuchi Kagaku ■,
4.4' (α, α-dimethylbenzinoviphenylamine) Iriuchi Chemical ■, 2-Mercaptobenzimidazole Idemitsu Kosan ■, Diana Process Oil W-90 Nippon Synthetic Rubber ■, AES 665 *12 8' d 5T20 %, styrene-butadiene diblock' polymer with hydrogenation rate of 87% *13 Ethylene-propylene copolymer rubber EP02P manufactured by Japan Synthetic Rubber *14 ABS resin/thermoplastic polyurethane composition*
15 B' d 5T 25%, hydrogenation rate 90% styrene-isoprene diblock polymer *1 B Urethane rubber *17 Mitsubishi Gas Chemical ■, polycarbonate knee pilon S-1000 $18 8' d 5T 28%, hydrogenation rate 88 % of styrene (styrene-butadiene random copolymer)
Butagent triblock polymer *19 Manufactured by Asahi Kasei ■,
Modified polyphenylene ether Zylon 300H *20 8' d Acrylonitrile-butadiene random copolymer with 35% AN and 90% hydrogenation $21 Manufactured by Du Pont, fluororubber Piton-A *22 Manufactured by Mitsubishi Yuka ■, Polypropylene *23 *24 *25 *26 *27 *28 *29 *30 Shi PBT
1401-XO6 Acrylonitrile-butyl acrylate-butadiene random copolymer with B' d AN 20%, B' dBA 35%, hydrogenation rate 90% Manufactured by Toshi ■, polyamide 12 Rilsan MN O B'dBA 40%, hydrogenation rate 92% butyl acrylate-butadiene random copolymer Toshi Silicone ■ Silicone rubber manufactured by DUTRAL, polyester elastomer PIBII'LEX
35 CM Ethyl acrylate-butadiene random copolymer with B'dEA 50% and hydrogenation rate 90% *31 Partially crosslinked acrylic rubber, 80% methyl ethyl ketone insoluble content *32 Manufactured by Japan Synthetic Rubber Company, B' d AN4
5%, acrylonitrile-butadiene rubber 23O8 *33 Manufactured by Hoechst, fluororesin Ho5ta f
lonTF 9205 *34 Manufactured by Daicel Huls, Diamid PAE
E-40L *35 Ethylene-propylene rubber EP57P manufactured by Nihon Gosei Rubber Company *36 8' d Styrene-butadiene random copolymer with 5T20% and hydrogenation rate of 98%*37 B' d AN35% and hydrogenation rate 30% acrylonitrile-butadiene random copolymer *38 8' d 5T 25%, hydrogenation rate 25% styrene-isoprene diblock copolymer B'dST: Total styrene amount B' AN: Total acrylonitrile amount B' BA .

EA: Total acrylate amount shows.

As is clear from Table 1 below, the composition obtained by the present invention is soft and has an excellent balance of mechanical strength, and also has excellent elastomer elasticity.

Furthermore, functions such as weather resistance and oil resistance can be imparted by selecting the thermoplastic polymer and partially hydrogenated rubber used. Therefore, it is an excellent thermoplastic elastomer composition that can meet a wide range of required performances.

Comparative Examples 1.2.3 are examples in which vulcanization was not performed. Weather resistance is good, but mechanical strength is poor. 100%
Permanent elongation during elongation is also poor, making it unsuitable for use as an elastomer.

Comparative Example 4.5 is an example in which partially hydrogenated rubber with a low hydrogenation rate was vulcanized. Mechanical strength is improved and elastomer elasticity is good, but weather resistance is poor due to residual unsaturated bonds.

Comparative Example 6 does not have the composition of the present invention (3).

Although it has good mechanical strength and weather resistance, it is hard resin-like and is not suitable for use as an elastomer.

[Effects of the Invention] The polymer composition of the present invention can meet a wide variety of performance demands from the industrial world due to the wide range of applicable polymers, and is particularly capable of meeting the various performance requirements of the industry. This makes it possible to provide a unique thermoplastic elastomer composition not found anywhere else.

Specific applications include rack and pinion boots, bellows, vacuum connectors, tubes, side moldings, headrests, regulators, armrests, shift lever boots, weather strips, side moldings, air spoilers, suspension boots, belt covers, and other automotive vehicle parts. Foil covers, knobs, bumpers, sight shields, bumper moldings, and other industrial parts include hydraulic hoses, air tubes, rubber hoses, outcovers, various gaskets, containers, O-rings, and backing materials.

Patent applicant: Japan Synthetic Rubber Co., Ltd.

Claims (3)

[Claims] (1) (A) At least one thermoplastic polymer 10-9
0% by weight (B) Partially hydrogenated conjugated diene rubbery polymer 1 in which 60 to 95% of the conjugated diene component is partially hydrogenated
0 to 90% by weight, and (C) 0 to 50% by weight of another rubbery polymer, dynamically treated in the presence of a crosslinking agent, and is a partially hydrogenated conjugated diene rubbery polymer that occupies the composition. (B) 50
A thermoplastic elastomer composition in which at least % by weight is insoluble in cyclohexane and has a permanent elongation at 100% elongation of 50% or less. (2) Component (B) essentially contains a conjugated diene, at least one monomer selected from the group consisting of α, β-unsaturated nitriles, acrylic esters, and aromatic vinyl, and other monomers as necessary. 60 to 95% of the unsaturated bonds based on the conjugated diene component in the rubbery random copolymer obtained by copolymerizing with at least one monomer selected from the group consisting of radically polymerizable monomers The thermoplastic elastomer composition according to claim 1, which is a partially hydrogenated conjugated diene-based rubbery polymer. (3) (A) Thermoplastic elastomer 10 to 90% by weight (
B) 10 to 90% by weight of at least one rubber selected from natural and synthetic rubbers and 0 to 50% by weight of another thermoplastic polymer are dynamically processed under heating and melting in the presence of a crosslinking agent to form a composition. A thermoplastic elastomer composition in which 50% by weight or more of the rubber component thereof is insoluble in cyclohexane, and the permanent elongation at 100% elongation is 50% or less.