JPS62241948A - Hydrogenated block copolymer composition having excellent oil resistance - Google Patents

Abstract

PURPOSE:To obtain a compsn. having excellent oil resistance and rubber elasticity, by blending two specified hydrogenated copolymers with a non-aromatic softener for rubber and a polyphenylene ether resin. CONSTITUTION:A compsn. consists of 100pts.wt. hydrogenated block copolymer (a) obtd. by hydrogenating a block copolymer consisting of a polymer block A mainly composed of at least two arom. vinyl compds. and a polymer block B mainly composed of at least one conjugated diene compd., 30-250pts.wt. hydrogenated block copolymer (b) obtd. by hydrogenating a block copolymer consisting of a hydrogenated polybutadiene obtd. by hydrogenating polybutadiene having a 1,2-bonded vinyl unit content of lower than 20% and at least one polymer block B' having a 1,2-bonded vinyl unit content of lower than 20%, mainly composed of butadiene, 50-500pts.wt. non-aromatic softener (c) for rubber and a polyphenylene ether resin (d) which is a homopolymer and/or a copolymer composed of a repeating unit of the formula.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a thermoplastic nidistomer that is highly flexible, has excellent elasticity (compression set) at high temperatures, mechanical strength, and moldability. The present invention relates to a hydrogenated block copolymer composition which has excellent oil resistance comparable to that of Chlorobu-4 Renzam and which can be used as a material for various molded products.

(Prior art) In recent years, thermoplastic nystomers, which are rubber-like soft materials that do not require a vulcanization process and have moldability similar to thermoplastic resins, have been used in automobile parts, home appliance parts, electric wire covering materials, and medical parts. It is useful in the fields of miscellaneous goods, footwear, etc. Under these circumstances, vinyl aromatic compound-conjugated diene compound block copolymers of thermoplastic nidistomers, for example? Although block copolymers having a listerene-bolybutadiene-polystyrene structure are useful as soft materials with excellent processability, their range of use has been limited due to their poor heat resistance, weather resistance, and oil resistance. Hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers) of thermoplastic elastomers that have improved these drawbacks have been recognized to have improved weather resistance and heat resistance. However, in terms of oil resistance, the performance level was the same as that of conventional products.

Several proposals have been made regarding elastomeric compositions using this hydrogenated block copolymer.

For example, JP-A-50-14742, JP-A-52-65
No. 51 and JP-A No. 58-206644 disclose a di-stomer-like composition in which a hydrogenated block copolymer is blended with a hydrocarbon oil and an olefinic polymer. Japanese Patent Publication No. 59-131613
In the No. 1 issue, a hydrogenated block copolymer, a hydrocarbon oil, an olefin polymer, and an inorganic filler are blended into a nidistomer-like composition, which is partially crosslinked in the presence of an organic gas oxide and a crosslinking agent. Proposals have been made to improve the rubber elasticity (compression set) of elastomeric compositions at high temperatures.

However, the hydrogenated block copolymer compositions obtained by these proposals have excellent rubber elasticity but are poor in oil resistance.

(Problems to be Solved by the Invention) When improving oil resistance, the rubber elasticity (compression set) of the hydrogenated block copolymer composition obtained by the above-mentioned prior art proposal deteriorates. Improving the elasticity (compression set) does not result in poor oil resistance, and the directionality of performance is determined by the ingredients in the composition, and the two performances of oil resistance and Zum elasticity (compression set) are contradictory. there were. Therefore, it is currently impossible to obtain a hydrogenated block copolymer composition in the form of a hydrogenated block copolymer excellent in both properties using conventional techniques, and this has been taken for granted.

(Means for Solving the Problems) The present invention was made to solve the problems that were difficult with the conventional elastomer molding materials described above, and in particular, the processability as a thermoplastic elastomer. Rubber elasticity at high temperatures (100
This was made based on the desire for a molding material that could satisfy properties that had never been achieved, such as excellent compression set (at 100°C) and excellent oil resistance comparable to that of chlorozolene. It has been discovered that this can be satisfactorily achieved by a di-stomer-like composition, and furthermore, it has been discovered that this is a practically useful composition.

That is, the present invention provides: (1) (,) a block polymer consisting of a polymer block B mainly consisting of at least two vinyl aromatic compounds and a polymer block B mainly consisting of at least one conjugated diene compound; Hydrogenated block copolymer obtained by hydrogenating a polymer 100 parts by weight (b) Hydrogenated polybutadiene obtained by hydrogenating a polybutadiene having a 1.2 vinyl bond content of less than 20.7 and/or at least 1 Polymer block A' mainly composed of vinyl aromatic compounds
and at least one polybutadiene-based polymer block B' having a 1,2 vinyl bond content of less than 20%.
Hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of 30 to 250 parts by weight (e) Non-aromatic shim softener 50 to 500 parts by weight (here %
R1+ R4e R4 and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group), reduced viscosity (o, sy
/dft chloroform solution, measured at 30°C) is 0.15~
The polyphenylene ether resin (d) which is a homopolymer and/or copolymer having a molecular weight in the range of 0.70 is the (-)
For (a)/(d) = 90/10~30/70
To provide a hydrogenated block copolymer composition having excellent oil resistance and having a total weight ratio within the range of (total weight ratio).

The present invention will be described in detail below.

The hydrogenated block copolymer used as the (-) component in the present invention is a polymer block mainly composed of at least two vinyl aromatic compounds and a polymer block mainly composed of at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of B, for example,
A-B-A, B-A-B-A, (A-B→♂i,
It is a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer having a structure such as AB-A-B-A. This hydrogenated block copolymer contains 5 to 60% by weight, preferably 10 to 5% by weight of a vinyl aromatic compound.
Furthermore, referring to the block structure, the polymer block A mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block, or contains more than 50% by weight, preferably 70% by weight of a vinyl aromatic compound. It has a copolymer block structure of a vinyl aromatic compound containing the above and a hydrogenated conjugated diene compound,
Furthermore, the polymer block B mainly composed of a hydrogenated conjugated diene compound contains more than 50% by weight of a conjugated diene compound polymer block to which no water has been added or a hydrogenated conjugated citric compound, preferably 70% by weight. It has a structure of a copolymer block of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing at least % by weight. In addition, a polymer block mainly composed of these vinyl aromatic compounds A1 a polymer block mainly composed of a hydrogenated conjugated diene compound ntt, a hydrogenated conjugated diene compound in the molecular chain of each polymer block Or, even if the distribution of the vinyl aromatic compound is random, highly dispersed (the monomer component increases along the molecular chain), partially block-like, or any combination of these, the vinyl aromatic When there are two or more polymer blocks mainly composed of a group compound and two or more polymer blocks mainly composed of the hydrogenated conjugated diene compound, each polymer block may have the same structure or may have different structures. It may be a structure.

As the vinyl aromatic compound constituting the hydrogenated block copolymer, for example, one selected from styrene, α-methylstyrene, vinyltoluene, p-tertiary methylstyrene, etc.
One or more types can be selected, and styrene is preferred among them. In addition, examples of the conjugated citric compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, imprene, 1,3-pentadiene, 2,3-dimethyl-1,3-buta-citene, etc. 1 or 2 from
One or more species are selected, among which butadiene, isoprene and combinations thereof are preferred. The microstructure of the polymer block mainly composed of a conjugated diene compound before being hydrogenated can be arbitrarily selected. For example, ? In the liptadiene block, the 1.2 vinyl content is 20-50%, preferably 25-45%.

Further, the number average molecular weight of the hydrogenated block copolymer used in the present invention having the above structure is s, ooo to 1.000,
00G, preferably 10,000 to 800,000, more preferably 3G, 000 to soo, ooo, molecular weight distribution [ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw/ Mn ) ] is 1
It is less than or equal to 0. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

These block copolymers may be produced by any method as long as they have the structure described above. For example,
3798, a vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst, and then the vinyl aromatic compound-conjugated diene compound block copolymer is synthesized using a lithium catalyst or the like. As a method for producing hydrogenated products of polymers, for example, Japanese Patent Publication No. 42
Although it can also be obtained by the method described in Japanese Patent Publication No. 8704 and Japanese Patent Publication No. 43-6636, titanium-based water exhibits particularly excellent weather resistance and heat deterioration resistance of the hydrogenated block copolymer obtained. Hydrogenated block copolymers synthesized using an added catalyst are most preferred, for example, as disclosed in JP-A-59-133
The hydrogenated block copolymer used in the present invention is synthesized by hydrogenation in the presence of a titanium-based hydrogenation catalyst in an inert solvent according to the nine methods described in JP-A No. 203 and JP-A-60-79005. can do. At that time, at least 60% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and the polymer block mainly composed of the conjugated diene compound is transformed into an olefin. The compound can be converted into a polymer block. In addition, the hydrogen of the aromatic double bond based on the vinyl aromatic compound copolymerized into the polymer block B mainly consisting of a vinyl aromatic compound and, if necessary, the polymer block B mainly consisting of a conjugated diene compound. Although there is no particular restriction on the addition rate, it is preferable that the hydrogenation rate is 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like.

Next, the hydrogenated polybutadiene and/or hydrogenated block copolymer used as component (b) in the present invention are as follows: 1.
It is effective in improving the oil resistance and processability of the resulting composition.

In addition, a polymer block mainly composed of butarenin before hydrogenation of hydrogenated (vinyl aromatic compound/butadiene block copolymer) that can be provided with the hydrogenated block copolymer of the above-mentioned (-) component. 1 of Pig Quen in・2 bond amount and hydrogenated polybutadiene and/or hydrogenated polybutadiene provided in component (a) is the 1.2 bond amount of butadiene in the polybutadiene and/or butadiene-based polymer block before hydrogenation of the hydrogenated block copolymer. This difference in structure is due to the effect of the present invention. In other words, in a hydrogenated block copolymer using butadiene as the conjugated diene component of the hydrogenated block copolymer provided in component (,), the amount of 1 and 2 vinyl bonds in the polymer block mainly composed of butadiene before hydrogenation is 20%
In the above, sb shows poor oil resistance performance l), (b
The hydrogenated polybutadiene and/or hydrogenated block copolymer provided in component ) has less than 20% of the 1/2 vinyl bond, which is the bond form of butadiene before hydrogenation, and exhibits excellent oil resistance. It is.

Therefore, the hydrogenated polybutadiene used as component (b) in the present invention is known and easily available high-cis polybutadiene, and 1 and 2 polybutadiene synthesized using an organolithium catalyst.
It is obtained by hydrogenating polybutadiene with a vinyl bond content of less than 20%. The number average molecular weight of IJ butadiene is in the range of s,ooo to 1.000,00G, preferably 10,000 to 800,000, more preferably 3G,000 to soo,ooo, and the molecular weight distribution [weight average molecular weight ( MY) and number average molecular weight (Mn
) (My/Mn)) is 10 or less.

As a method for producing a 9-value additive, the 1.2-vinyl content obtained by a known method is 20%.
For example, Japanese Patent Publication No. 42-8704
Although hydrogenated polybutadiene can be obtained by hydrogenation using the method described in Japanese Patent Publication No. 43-6636, titanium-based hydrogenated polybutadiene exhibits particularly excellent weather resistance and heat deterioration resistance of the resulting hydrogenated polybutadiene. Hydrogenation synthesized using a catalyst, j?
, lJ butadiene is most preferred, for example, JP-A-59
Hydrogenated polybutadiene used in the present invention is synthesized by hydrogenation in the presence of a titanium-based hydrogenation catalyst in an inert solvent according to the method described in Japanese Patent Publication No. 133203 and Japanese Patent Application Laid-Open No. 60-79005. be able to.

Furthermore, the hydrogenated block copolymer used as component (b) in the present invention has a polymer block A' mainly composed of at least one vinyl aromatic compound and at least one butadiene mainly composed of a polymer block A' mainly composed of at least one vinyl aromatic compound. It is obtained by hydrogenating a block copolymer consisting of a polymer block B', for example, λ'-h', A'-B'-A', B'
- to -B'-, (A'-B' large si, to -n/- to -
It is assumed that a vinyl aromatic compound-butadiene block copolymer having a structure such as B'- is hydrogenated. This hydrogenated block copolymer contains 5 to 6 vinyl aromatic compounds.
0% by weight, preferably 10 to 50% by weight.Moreover, referring to the block structure, the polymer block A' mainly composed of a vinyl aromatic compound is a vinyl aromatic compound polymer block or a 501i polymer block containing a vinyl aromatic compound.
It has a copolymer block structure of hydrogenated butadiene and a vinyl aromatic compound containing more than 70% by weight, preferably 70% by weight or more, and furthermore, The combined block B' is a hydrogenated butadiene polymer block or contains more than 50% by weight of hydrogenated butadiene, preferably 70% by weight.
It has a structure of a copolymer block of hydrogenated buta-citric compound and a vinyl aromatic compound containing 1i% or more.

In addition, the polymer block A1 mainly composed of these vinyl aromatic compounds and the polymer block B' mainly composed of hydrogenated butadiene contain hydrogenated butadiene or vinyl aromatic compounds in the molecular chain of each polymer block. The distribution of group compounds is random, Theno # IF (
The monomer component may increase or decrease along the molecular chain), partially block-like, or any combination thereof; When there are two or more polymer blocks mainly composed of butadiene, each polymer block may have the same structure,
It may have a different structure.

As the vinyl aromatic compound constituting the hydrogenated block copolymer, one or more types can be selected from, for example, styrene, α-methylstyrene, vinyltoluene, p@3-butylstyrene, etc. Among them, styrene is preferred. .

The microstructure of the butadiene-based polymer block before hydrogenation can be arbitrarily selected, but in order to bring out the effect of oil resistance,
・The amount of 2-vinyl bond is less than 20%, preferably 2 to 20%.
It is 18%.

Further, the number average molecular weight of the hydrogenated block copolymer of the component (b) used in the present invention having the above-mentioned nine structures is s, ooo ~
1,000,000, preferably 10,000-800
,000, more preferably 30,000 to 500,00
0 range, molecular weight distribution [weight average molecular weight (Mvr
) and number average molecular weight (Mn) (possible W/Mn > )
is 10 or less. Furthermore, the molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

These block copolymers may be produced by any method as long as they have the structure described above. For example,
According to the method described in Japanese Patent No. 3798, a vinyl aromatic compound-butadiene block copolymer is synthesized in an inert solvent using a lithium catalyst, and then the vinyl aromatic compound-butadiene block copolymer is synthesized. As a method for producing the hydrogenated product, it can be obtained, for example, by the method described in Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43-6636, but in particular, the weather resistance of the hydrogenated block copolymer obtained Hydrogenated block copolymers synthesized using titanium-based hydrogenation catalysts that exhibit excellent heat deterioration resistance and good friend performance are most preferred, such as those disclosed in JP-A-59-133203 and JP-A-60-79005. The hydrogenated block copolymer to be used as component (b) of the present invention can be synthesized by hydrogenation in the presence of a titanium-based hydrogenation catalyst in an inert solvent according to the method described in . At that time, at least 80% of the aliphatic double bonds based on butadiene in the vinyl aromatic compound-butadiene block copolymer are hydrogenated, and the polymer block mainly composed of butadiene is transformed into an olefinic compound polymer. Can be converted into a combined block. (9) Aromatic double bonds based on a vinyl aromatic compound copolymerized with a polymer block A' mainly composed of a vinyl aromatic compound and, if necessary, a polymer block B' mainly composed of butadiene. Although there is no particular presbyopia regarding the hydrogenation rate, it is preferable to keep the hydrogenation rate to 20% or less. The amount of unhydrogenated aliphatic double bonds contained in the hydrogenated block copolymer can be easily determined using an infrared spectrophotometer, nuclear magnetic resonance apparatus, or the like.

The blending amount of component (b) is 30 to 250 parts by weight, preferably 40 to 200 parts by weight, per 100 parts by weight of component (a). If the amount is more than 250 parts by weight, the hardness of the resulting diastereomeric composition will be too high, resulting in a loss of flexibility, resulting in a product with a sticky feel. The rubber elasticity (compression set) in this case is extremely deteriorated, which is undesirable.

In addition, when the amount is less than 30 parts by weight, the resulting nidistomer-like composition has excellent tum elasticity (compression set) at high temperatures;
The poor oil properties of the test oils at 70°C are poor and undesirable.

Next, the non-aromatic tsum softener used as component (C) in the present invention is an essential component for making the resulting composition into a flexible tsum-like composition, and is made of reed, non-aromatic mineral oil, etc. Alternatively, liquid or low molecular weight synthetic softeners are suitable.

Among them, mineral oil-based softeners called process oils or extender oils, which are generally used to soften, increase volume, and improve processability of Tsum, are mixtures of aromatic rings, naphthenic rings, and paraffin chains. Those in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total carbons are called paraffin series, and those in which the number of carbon atoms in the naphthene ring is 30
~45% are naphthenic, with an aromatic carbon number of 3
Those containing more than 0% are considered aromatic. Ingredients of the present invention (
The mineral oil-based softener used as C) is preferably a naphthenic or paraffinic softener in the above category,
Aromatic compounds having an aromatic carbon number of 30% or more are not preferred in terms of dispersibility and solubility in the composition with component (a). The properties of these non-aromatic softeners include a kinematic viscosity of 20 to 500 cst at 37.8°C, a pour point of -10 to -15°C, and a flash point of 170 to 300 cst.
Indicates °C.

As the synthetic softener, polybutene, low molecular weight polybutadiene, etc. can be used, but the mineral oil-based softener mentioned above gives better results.

The amount of the softener (component (c)) is 50 to 500 parts by weight per 100 parts by weight of the component (,), preferably 1
00 to 400 parts by weight. 500! If more than 1 part is added, the softener may cause a pull-out, which may cause stickiness in the final product, and may also reduce mechanical properties. If the amount is less than 50 parts by weight, the resulting composition becomes close to a resin composition, increases in hardness, loses flexibility, and is also unfavorable from an economic point of view.

Next, the phenylene ether resin used as component (d) of the present invention is an essential component for improving the oil resistance and compression set of the resulting composition. (Here, R1+ Rle R3 and R4 are each selected from the group consisting of hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, and may be the same or different from each other). It is a combination,
The reduced viscosity measured at 30°C in a 0.5 f/dft chloroform solution is in the range of 0.15 to 0.70, more preferably in the range of 0.20 to 0.60. It will be done. As this polyphenylene ether resin, known ones can be used.

Specific examples include poly 2,6-cumyl-1,4-phenylene ether 7j@IJ 2-methyl-6ethyl-1-47 dinilene ether, /su2-6--/phenyroot 4-phenylene ether, yt? 2-methyl-6-phenyl-1,4-phenylene ether, poly2
・6--) Chloroto 4-phenylene ether, etc., and 2,6-dimethylphenol and other phenols (such as 2,3,6-dimethylphenol and 2-dimethylphenol).
Also mentioned are polyphenylene ether copolymers such as copolymers with (methyl-6-butylphenol). Among them (poly(2,6-dimethyl-1,4-)2elm ether, 2,6-dimethylphenol and 2,3,6-)
! A copolymer with j-methylphenol is preferred, and poly(2,6-di)thi-f-1,4-phenylene) ether is more preferred.

In the case of poly(2,6-dimethyl-1,4-phenylene ether), its reduced viscosity (0.5t/dX, chloroform solution, measured at 30°C) is preferably in the range of 0.15 to 0.70. More preferably 0.30 to 0.60
I will do it within the range of.

The blending amount of component (d) can be suitably selected in the range of the weight ratio of component (=) hydrogenated block copolymer/component (d) polyphenylene ether in the range of 90/10 to 30/70. . If the weight ratio is less than 30/70, the hardness of the resulting elastomeric composition will be too high, resulting in loss of flexibility, resulting in a resinous composition and a product with a sticky feel. Idiotly, rubber elasticity [compression set] at high temperatures
(100°C x 22 hours)] is poor and unfavorable. Further, in a blend in which the quantitative ratio exceeds 90/10, no improvement in rubber elasticity (compression set) at high temperatures is observed as an effect of adding polyphenylene ether, which is not preferable.

In addition to the above-mentioned components (,) to (d), the composition of the present invention may further contain a polystyrene resin, a polyolefin resin, and an inorganic filler, if necessary.

As the polystyrene resin that can be added as necessary, those obtained by known radical polymerization methods and ionic polymerization methods, which are effective in improving the processability of the resulting composition, can be suitably used, and the number average molecular weight is 5,000. ~ soo, ooo, preferably from 10,000 to 200,000, and molecular weight distribution [weight average molecular weight (MW') and number average molecular f! Ratio to t (Mn) (Mw/Mn) ]
ij s or less is preferable. The blending amount of the testyrene resin is 100% of the hydrogenated block copolymer of component (-).
It can be suitably selected in the range of 5 to 100 parts by weight.

If the amount exceeds 100 parts by weight, the oil resistance of the resulting nidistomer composition will deteriorate, and the rubber elasticity (compression set) at high temperatures will be extremely deteriorated, which is undesirable. Furthermore, when the amount is less than 5 parts by weight, the performance is equivalent to the case where the 4-listyrene resin of the present invention is not added. In addition, polyolefin resins, which can be added as necessary, are effective in improving the oil resistance, processability, and/or heat resistance of the resulting composition, such as polyethylene, isotactic polypropylene, propylene and other polyolefin resins. Small amounts of copolymers of α-olefins, such as propylene-ethylene copolymers, propylene-1-hexene copolymers, propylene-4-methyl-1-pentene copolymers, and poly-4-methyl-1
-Pentene, poly, butene-1, etc. can be mentioned. MFR when using isotactic polypropylene or its copolymer as polyolefin resin (
AS'rM-D-1238-L conditions, 230°C) was 0.
1 to 5 (1/10 min., particularly 0.5 to 30 f/10 min.) can be suitably used.

The blending amount of the polyolefin resin can be suitably selected within the range of 5 to 100 parts by weight based on 100 parts by weight of the hydrogenated block copolymer as component (-). If the amount exceeds 100 parts by weight, the rubber elasticity (compression set) at high temperatures of the resulting nidistomer composition deteriorates, which is not preferable. In addition, when the amount is less than 5 parts by weight, the performance is equivalent to the case where the 2-lyolefin resin of the present invention is not added.

Furthermore, inorganic fillers, which can be added as necessary, are not only beneficial in reducing product costs as fillers, but also have positive effects on quality improvement (oil resistance, compression set, elongation). There are also advantages to doing so. Examples of inorganic fillers include calcium carbonate, casen black, Merck, clay, magnesium hydroxide, mica, nororium sulfate, natural silicic acid, synthetic silicic acid (white casen), titanium oxide, etc. As the black, channel black, furnace black, etc. can be used. Among these inorganic fillers, talc, calcium carbonate and furnace black are economically advantageous and preferred. It is also possible to add a conductive filler to impart conductivity; for example, conductive filler such as Ketjenblack etc.
You may also use

The amount of the inorganic filler to be blended can be suitably selected within the range of 1 to 300 parts by weight based on 100 parts by weight of the hydrogenated block copolymer of component (2).

The hydrogenated block copolymer composition of the present invention having excellent oil resistance can be obtained by polymerizing the above-mentioned components, and may further include flame retardants, glass fibers, carzene fibers, antioxidants, A heat stabilizer, an ultraviolet absorber, a hinder P amine light stabilizer, and a coloring agent can be added.

As a method for compounding the hydrogenated block copolymer composition with excellent oil resistance of the present invention, methods used in the production of ordinary resin compositions or rubber compositions can be adopted.
Compounding can be carried out using a melt mixer such as a single screw extruder, a twin screw extruder, a conventional mixer, a heating roll, a blender, and various kneaders. At this time, there is no restriction on the order in which each component is added; for example, all the components are premixed using a mixer such as a Henschel mixer or blender, and then melted and composited using the above-mentioned mixer. It is possible to adopt an addition method such as melting and compounding one by one, and then adding the remaining components and melting and compounding.

The composite composition of the present invention can be molded using a commonly used thermoplastic resin molding machine, and can be molded by various molding methods such as injection molding, extrusion molding, blow molding, and calendar molding. is applicable.

(Effects of the Invention) The composition obtained by the present invention has excellent oil resistance, flexibility, heat resistance, mechanical strength, and rubber elasticity at high temperatures comparable to that of chloroprene bim, as well as excellent moldability and electrical insulation properties. Its fields of use include automobile parts, home appliance parts, and various electric wire coatings (insulation, sheathing), where improvements in oil resistance, rubber elasticity, molding speed, molding yield, etc. are desired.
, and can be suitably molded and used in various industrial parts. Specific uses include various gaskets, flexible tubes, hose coverings, etc.

(Examples) The present invention will be explained in more detail by Examples, but the present invention is not limited to these Examples.

In addition, in these Examples and Comparative Examples, the following test methods were used for various evaluations.

(1) Hardness [-] JI8--6301, A type (2) Tensile strength (87cm") and tensile elongation [%]
JI8-6301, a 2 m thick injection sheet was used as the sample, and a 3-sho dumbbell was used as the test piece.

(3) Oil resistance JIS-6301 specified Mu3 test oil was used, and 70
A test piece of 50 gourds x 5 ta x 2 yao was immersed at ℃ for 2 hours,
The weight change (%) before and after immersion was determined.

(4) Compression set [%] JI8-K 6301. 25% deformation at 70°C and 100°C for 22 hours.

In addition, the blended components are as follows.

(1) <Component (!-1)> Has a structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene,
Bound styrene content 30%, number average molecular weight 172,000,
Molecular weight distribution 1.05, 1.2 of polybutadiene before hydrogenation
A hydrogenated block copolymer with a vinyl bond content of 39% and a hydrogenation rate of 99% was prepared using T
It was synthesized using an i-based hydrogenation catalyst and designated as component (,-1).

Component (a-2) > Has a polystyrene-hydrogenated monoliptadiene-polystyrene structure, with a bound styrene content of 43%, a number average molecular weight of 203,000, a molecular weight distribution of 1.07, and a polybutadiene content before hydrogenation. 1/2 vinyl bond amount is 29%, hydrogenation rate is 9
8% hydrogenated block copolymer in JP-A-59-13320
Synthesized using the Ti-based hydrogenation catalyst described in Publication No. 3,
It was referred to as component (a-2).

Ingredient (a-3) > Pristyrene-puri (styrene/butadiene 210 F9
0 weight 2)-poly(styrene/butadiene = 10/90
3% by weight)-poly(styrene/butadiene = 10/90% by weight)-polystyrene structure, and in which styrene is increased in the pre(styrene/butadiene = 10/90% by weight) portion. A block copolymer having a total bonded styrene content of 37%, a block styrene content of 30%, a number average molecular weight of 196,000, and a molecular weight distribution of 1.06.1/2 vinyl bond content of 44% was synthesized. A hydrogenation reaction was carried out using the Ti-based hydrogenation catalyst described in JP-A-133203 to obtain a hydrogenated block copolymer (a-3) with a hydrogenation rate of 99%.

Component (a-4) > (Polystyrene-hydrogenated polybutadiene÷si
It has a structure with a bound styrene content of 20% and a number average molecular weight of 3.
79,000, a molecular weight distribution of 1.55, a hydrogenated block copolymer with a 1.2-vinyl bond content of pributadiene before hydrogenation of 45%, and a hydrogenation rate of 99%, as described in JP-A-60-79005. Synthesized using a Ti-based hydrogenation catalyst, the components (, -
4).

<Component (a-5)> Shell Chemical Company KRATON-G 1651 (2
) <Component (b-1) > 1.2 vinyl bond amount 13%, number average molecular weight 63,00
0, polybutadiene with a molecular weight distribution of 1.95 was
A hydrogenation reaction was carried out using a Ti-based hydrogenation catalyst described in JP 9-133203, to obtain hydrogenated liptadiene (b-1) with a hydrogenation rate of 98%.

Component (b-2) > 1.2 vinyl bond amount 16%, number average molecular weight 73,00
Polybutadiene having a structure of (polybutadiene÷8i) with a molecular weight distribution of 1.43 was hydrogenated using a 7'j Ti-based hydrogenation catalyst described in JP-A-60-79005, resulting in hydrogenation with a hydrogenation rate of 94%. Polybutadiene (b-2) was obtained.

<Ingredient (b-3)> Commercially available high-cis with 1/2 vinyl bond content of 2.6%? Liptadiene TAKINB 1202 (manufactured by Polycer) was subjected to a hydrogenation reaction using a Ti-based hydrogenation catalyst described in JP-A-60-79005, resulting in hydrogenated polybutadiene (b-3) with a hydrogenation rate of 97%. I got it.

<Component (b-4)> Has a structure of pystyrene-hydrogenated polybutadiene, bound styrene ito%, number average molecular weight 157.0
00, a molecular weight distribution of 1.04, a hydrogenated block copolymer with a 1.2-vinyl bond content of polycitaquene before hydrogenation of 12%, and a hydrogenation rate of 98%, which is described in JP-A-59-133203 and is a fief system. Synthesized using a hydrogenation catalyst, component (b-4
).

<Component (b-5)> Polystyrene-hydrogenated polybutadiene-polystyrene structure, amount of bound styrene 30%, number average molecular weight 14♀,000, molecular weight distribution 1.04, 1 of polybutadiene before hydrogenation・A hydrogenated block copolymer with a 2-vinyl bond content of 13% and a hydrogenation rate of 98% was published in JP-A-59-1332.
Component b-5) was synthesized using the 'rl hydrogenation catalyst described in Japanese Patent No. 03.

<Component (b-6)> Has a structure of hydrogenated polybutadiene-polystyrene-hydrogenated polybutadiene-polystyrene,
Bound styrene content 45%, number average molecular weight 193,000,
Molecular weight distribution 1.06, 1.2 of polybutadiene before hydrogenation
A hydrogenated block copolymer having a vinyl bond content of 13.6% and a hydrogenation rate of 99% was synthesized using a 7tTi hydrogenation catalyst as described in JP-A-60-79005, and (component b-6) And so.

<Component (b-7)> (Polystyrene-hydrogenated polybutadiene÷si
It has a structure of 18% bound styrene, several thousand-11! +
IAヱJ! L qna nn1'1 ΔEmoku Yame
1 [ri-, L-? A hydrogenated block copolymer of 6My M prbutadiene with a 1.2-vinyl bond content of 17% and a hydrogenation rate of 98% was synthesized using a Ti-based hydrogenation catalyst described in JP-A-60-79005, (Component (b-7
).

<Component (b-8)>Polystyrene-poly(styrene/butadiene; 10/9
0% by weight)-Poly(styrene/butadiene 310F90
3% by weight)-Bori (styrene/butadiene 310% by weight 90% by weight)-polystyrene structure, and in which styrene gradually increases in the poly(styrene/butadiene = 10/90% by weight) part. Totally bonded styrene content: 37%, block styrene content: 30%, number average molecular weight: 1:44,000, molecular weight distribution: 1. Synthesize a block copolymer with 12.4% of o5, l and 2 vinyl bonds,
Furthermore, fc
The hydrogenation reaction is carried out using a Ti-based hydrogenation catalyst, and the hydrogenation rate is 98%.
A hydrogenated block copolymer (bs) was obtained.

(3) Component (c) Diana process oil P8-32 manufactured by Idemitsu Kosan [paraffinic process oil 2 volumes: 31.42cst]
(40°C), 5.42 cst (100°C), average molecule 1408, ring analysis; 0A=0.1%, 0N=32.
8%, 0P=67.1X) (4) <Component (d-1)>? Poly(2,6-dimethyl-1,4-phenylene) ether (reduced viscosity;
0.30.0.58) was synthesized and used as component (d-1).

Component (d-2) > PoI) As a phenylene ether resin, 2, 3, 6-
From 2,6-dimethylphenol containing 5% dolimethylphenol, 2,6-dimethylphenol/2,3,6
- Dolimethylphenol copolymer (reduced viscosity 0.54
) was synthesized and used as component (d-2).

Examples 1 to 11 Each component shown in Table 1 was mixed with a Henschel mixer, and 50
The mixture was melt-kneaded in a twin-screw extruder with a diameter of rnM at 250° C. to obtain nidistomer-like pellets with a good surface texture. Test pieces were obtained by injection molding using these pellets, and various evaluations were carried out and the results are listed in Table 1.

From this result, it is clear that the composition of the present invention has excellent oil resistance and rubber elasticity (compression set). Furthermore, no stickiness was observed on the surface of the sample after the oil resistance test.

Margin Comparative Examples 1 to 4 Below, the components shown in Table 2 were mixed using a Henschel mixer, compounded in the same manner as Examples 1 to 11, and further molded and evaluated. The results are listed in Table 2.

These results revealed that among compositions outside the scope of the present invention, those with excellent oil resistance had poor rubber elasticity (compression set), and those with excellent rubber elasticity had poor oil resistance. In addition, Comparative Examples 1 and 2 each contained (a-1) as the (b) component.
component, (--5) component was used.

The samples of Comparative Examples 1 and 2 after the oil resistance test had significant surface flatness.

Below is a blank table 2 Example 12 The same composition as in Example 1 was used except that component (a-2) was used as the polyphenylene ether, and the mixture was melt-kneaded under the same conditions and further injection molded to obtain a test piece. . When physical properties were evaluated, hardness was 69 and tensile strength was 140 words/crn.
2. Elongation 640%, oil resistance 16%, 70℃ compression set 3
A hydrogenated block copolymer having a compression set of 0% and a compression set of 452 at 100° C. and excellent oil resistance and tum elasticity was obtained.

Example 13, i? The same composition as in Example 1 was used, except that component (d-1) with a reduced viscosity of 0.30 was used as the IJ phenylene ether, and the same composition was melt-kneaded, and then injection molded and tested. Got the piece. When the physical properties were evaluated,
Hardness 68, tensile strength 140) cf/(7)2, elongation 7
20%, oil resistance 13%, 70℃ compression set 30%, 10
A hydrogenated block copolymer having a compression set of 41% at 0° C. and excellent oil resistance and elasticity was obtained.

Examples 14-18 Each component shown in Table 3 was mixed with a Henschel mixer, and 50
The mixture was melt-kneaded at 250° C. in a large-sized twin-screw extruder to obtain elastomeric pellets with a good surface texture. This pellet was injection molded to obtain a test piece, and various evaluations were performed and the results are listed in Table 3.

These results revealed that even if a polystyrene resin and a polyolefin resin are used in combination, a composition excellent in oil resistance and tum elasticity can be obtained within the composition range of the present invention. Moreover, no flatness was observed on the sample surface after these oil resistance tests.

The polystyrene resin used here was obtained by anionic polymerization and had a number average molecular weight of 29,000 and a molecular weight distribution of 1.02.

Margin below

Claims (1)

[Claims] (1) (a) Hydrogenating a block copolymer consisting of a polymer block A mainly composed of at least two vinyl aromatic compounds and a polymer block B mainly composed of at least one conjugated diene compound. 100 parts by weight of hydrogenated block copolymer obtained by (b) Hydrogenated polybutadiene obtained by hydrogenating polybutadiene having a 1/2 vinyl bond content of less than 20% and/
Alternatively, a polymer block A' mainly composed of at least one vinyl aromatic compound and a 1/2 vinyl bond amount of 20
30 to 250 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of at least one butadiene-based polymer block B' that is less than % (c) Non-aromatic type Rubber softener 50 to 500 parts by weight (d) Bond unit ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1, R_2, R_3 and R_4 are hydrogen, halogen, hydrocarbon group, substituted hydrocarbon group, respectively) ) and has a reduced viscosity (0.5 g/dl chloroform solution, measured at 30°C) of 0.
．． The polyphenylene ether resin (d), which is a homopolymer and/or copolymer, has a polyphenylene ether resin (d) in the range of 15 to 0.70 compared to the above (a) (a)/(d) = 90/10 to 30/
Hydrogenated block copolymer composition with excellent oil resistance consisting of a weight ratio of 70 (weight ratio)