JPS6225149A - Highly elastic hydrogenated block copolymer composition - Google Patents

Abstract

PURPOSE:To obtain the titled copolymer composition having excellent moldability, high-temperature compression set and recycling moldability, by compounding a specific polyphenylene ether resin and a non-aromatic rubber softener to a hydrogenated block copolymer containing vinyl aromatic compound and conjugated diene compound. CONSTITUTION:The objective composition having a compression set of <=65% (100 deg.CX22hr) can be produced by compounding (A) 100pts.wt. of a hydrogenated block copolymer obtained by hydrogenating a copolymer consisting of the terminal polymer block A composed mainly of >=2 vinyl aromatic compounds and the intermediate polymer block B composed mainly of one or more conjugated diene compounds with (B) a polyphenylene ether resin which is a homopolymer and/or copolymer having the structure of formula (R1-R4 are H, halogen or hydrocarbon residue; n is sum of the number of monomer units and is 15-140) (the weight ratio of A/B is 90/10-30/70) and (C) 10-300pts.wt. of a non-aromatic rubber softener.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention is a highly elastic water material that is highly flexible, has excellent high-temperature compression set, mechanical strength, and moldability, and can be used as a material for various molded products. The present invention relates to a block copolymer composition.

(Prior art) In recent years, thermoplastic elastomers, which are rubber-like soft materials that do not require a vulcanization process and have moldability similar to thermoplastic resins, have been used for automobile parts, home appliance parts, electric wire coatings, and medical applications. It is useful in the fields of parts, miscellaneous goods, footwear, etc. Among such thermoplastic elastomers, there are several elastomeric compositions using hydrogenated derivatives of vinyl aromatic compound-conjugated diene compound block copolymers (hereinafter abbreviated as hydrogenated block copolymers). Suggestions have been made. For example, JP-A-50-14742, JP-A-52-
No. 65551 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 olefin polymer, and JP-A No. 59-131613 discloses , an elastomeric composition prepared by blending a hydrogenated block copolymer with a hydrocarbon oil, an olefin heavy agent, and an inorganic filler is partially crosslinked with an organic peroxide and a crosslinking aid, and the resulting nystomeric composition is heated at high temperatures. Proposals have been made to improve the rubber elasticity (compression set).

Furthermore, JP-A-54-88960, JP-A-59
No. 100159 and Japanese Patent Publication No. 57-56941 disclose hydrogenated block copolymer compositions containing hydrogenated block copolymer and polyphenylene ether as essential components and consisting of iriolefin resin and polystyrene resin. . However, these proposals are aimed at improving resin compositions, and the resulting compositions are thermoplastic resins, which can be used as elastomeric compositions that can be used as thermoplastic resins as described above. It had no rubber elasticity.

(Problems to be Solved by the Invention) Although the elastomeric composition of the hydrogenated block copolymer obtained by the above proposal has excellent 2M elasticity (compression set) at 70°C, the rubber elasticity at 100°C is 70% or more, it does not reach the level of compression set at high temperatures conventionally required for vulcanized rubber applications, and although it has the recyclable moldability that is a characteristic of thermoplastic elastomers,
At present, rubber properties at high temperatures are still inadequate, and this has been taken for granted.

(Means for Solving the Problems) The present invention was made to solve the problems that were difficult to solve with the above-mentioned conventional elastomer molding materials.
In particular, it was created based on the need for a molding material that can satisfy the previously unattainable properties of processability as a thermoplastic nidistomer, recycle moldability, and rubber elasticity at high temperatures (compression set at 100°C). It has been discovered that this hitherto unattainable desire can be fully achieved by selecting a specific nidistomer-like composition, and furthermore, it has been found that it is a practically useful composition. It is something that

That is, the present invention provides: (1) (a) a terminal polymer block polymer mainly composed of at least two vinyl aromatic compounds;
3,100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating a block copolymer consisting of an intermediate polymer block B mainly composed of conjugated diene compounds (b) General formula (where R1 + R2 + present, R and R4 are each
It is selected from the group consisting of hydrogen halogen and hydrocarbon groups, where n represents the total number of monomer units, and is 15 to 1.
Polyphenylene ether resin which is a homopolymer and/or copolymer having the structure (an integer of 40) is a/b=90/10 to 30/7Q (weight ratio) (C) non-aromatic Softener for group-based ZAM Formed from 10 to 300 parts by weight, compression set (100°C x 22 hours) is 6
A highly elastic hydrogenated block copolymer composition having a performance of 5% or less is also used in (a) l (b) ) (C) and (d)
A highly elastic hydrogenated block copolymer composition comprising 5 to 100 parts by weight of a polyolefin resin and having a compression set (00° C. x 22 hours) of 65% or less is a further embodiment, such as the above (a). , (b)
, (C), (d) and (1) A highly elastic hydrogenated block copolymer comprising 20 to 300 parts by weight of an inorganic filler and having a compression set (100°C x 22 hours) of 65% or less. The composition further comprises 20 to 300 parts by weight of the above (a), (b), (C) and (C) inorganic filler, and has a compression set (100°C x 22 hours) of 65% or less. The present invention provides highly elastic hydrogenated block copolymer compositions and the like.

The present invention will be described in detail below.

The hydrogenated block copolymer used as component (a) in the present invention consists of a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block A mainly composed of at least one conjugated diene compound. It is obtained by hydrogenating a block copolymer consisting of a combined block B, for example, A-B-A.

(A-B Shibetsu, A-B A-B-A, (A B+5i
- Vinyl aromatic compound with structure such as OH3 - Conjugated
It is a hydrogenated citric compound block copolymer. This hydrogenated block copolymer contains 5 to 60% by weight, preferably 10 to 50% by weight of a vinyl aromatic compound, and furthermore, referring to the block structure, the terminal polymer block A mainly composed of a vinyl aromatic compound is , having a structure of a vinyl aromatic compound polymer block or a copolymer block of a vinyl aromatic compound containing more than 50% by weight and preferably 70% by weight or more and a hydrogenated conjugated diene compound. and further, the intermediate polymer block B mainly composed of a hydrogenated conjugated diene compound contains more than 50% by weight of the hydrogenated conjugated diene compound polymer block or the hydrogenated conjugated diene compound. Preferably, it is one having a copolymer block structure of a hydrogenated conjugated diene compound and a vinyl aromatic compound containing 70% by weight or more.

In addition, the terminal polymer block A mainly composed of these vinyl aromatic compounds and the intermediate polymer block B mainly composed of a hydrogenated conjugated diene compound are The distribution of the diene compound or vinyl aromatic compound may be random, linear (the monomer component increases or decreases along the molecular chain), partially block-like, or any combination thereof; When there are two or more polymer blocks mainly composed of a vinyl aromatic compound and two or more polymer blocks mainly composed of the hydrogenated conjugated diene compound, each polymer block may have the same structure. , may have different structures.

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-tert-butylstyrene, etc. Among them, styrene is preferable.

Further, examples of the conjugated diene compound before hydrogenation constituting the hydrogenated conjugated diene compound include butadiene, isoprene, 2-3-pentadiene, 2-3-dimethyl-
One or more types are selected from 1,3-butadiene and the like, and among them, butadiene, isoprene, and a combination thereof are preferred. The microstructure of a polymer block mainly composed of a conjugated diene compound before being hydrogenated can be arbitrarily selected; for example, in a polybutadiene block, the 1,2-microstructure is 20 to 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 1.00.
0.000, preferably 10,000 to 800.000
, more preferably in the range of 30,000 to 500,000, and the molecular weight distribution [(Mw/Mn) between weight average molecular weight (number) and number average molecular weight (6)) 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,
A vinyl aromatic compound-conjugated diene compound block copolymer is synthesized in an inert solvent using a lithium catalyst or the like according to the method described in Japanese Patent Publication No. 3798, and then, for example, in Japanese Patent Publication No. 42-8704, The hydrogenated block copolymer used in the present invention is obtained by hydrogenation in the presence of a hydrogenation catalyst in an inert solvent by the method described in Japanese Patent Publication No. 43-6636 or Japanese Patent Application Laid-Open No. 59-133203. It is possible to synthesize combinations. In this case, at least 80% of the aliphatic double bonds based on the conjugated diene compound of the vinyl aromatic compound-conjugated diene compound block copolymer are hydrogenated, and one unitary block mainly composed of the conjugated diene compound is morphologically olefinic. The compound can be converted into a polymer block. In addition, hydrogenation of aromatic double bonds based on vinyl aromatic compounds copolymerized into polymer block A mainly composed of vinyl aromatic compounds and, if necessary, polymer block B mainly composed of conjugated diene compounds. There is no particular limit on the hydrogenation rate, but the hydrogenation rate is 20%.
It is preferable to do the following. 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 polyphenylene ether resin used as component (b) of the present invention has a compression set (1
00°C x 22 hours) to 65% or less, and has the general formula (where R1+ R2+ R3 and R4 are each selected from the group consisting of hydrogen halogen and hydrocarbon group, n represents the total number of monomer units, from 15 to
It is a polyphenylene ether resin which is a homopolymer and/or copolymer having a structure (which is an integer of 140). Examples of the polyphenylene ether resin include poly(2,6-dimethyl-1,4-phenyl)ether,'! J (2methyl-6ethyl-1,4-)22dine) ether, 2,6-dimethylphenol and 2,3.
Examples include copolymers of 6-dolinotylphenol.

Among them, poly(2,6-dimethyl-1,4-phenylene) ether, 2,6-7-methylphenylene/-#t2-
A copolymer with 3,6-dolimethylphenol is preferred, and poly(2,6--)methyl-1,4-phenylene)ether is more preferred.

used. j? Reduced viscosity (o, s r/dn ) of (2,6-dimethyl-1,4-)unicine ether).

700 form solution, measured at 30°C) is 0.15 to 0.7
It is preferably in the range of 0, more preferably from 0.30 to
It is in the range of 0.60.

The blending amount of component (b) is such that the weight ratio of hydrogenated block copolymer of component (a)/polyphenylene ether of component Φ) is 9.
It can be suitably selected within the range of 0/10 to 30/70. If the weight ratio exceeds 30/70, the hardness of the resulting nidistic composition will be high and the flexibility will be lost, resulting in a resinous composition, unless a product with a rubbery feel can be obtained. Or rubber elasticity at high temperature [compression set (100
℃ × 22 hours)] exceeded 65%, which is not preferable. In addition, when the weight ratio is less than 90/10, the effect of adding polyphenylene ether and the rubber elasticity at high temperature at l-
No improvement in compression set (compression set) was observed, which is unfavorable).

The rubber softener used as component (c) in the present invention is:
This is an essential component for making the resulting composition into a flexible rubber-like composition, and non-aromatic mineral oil or liquid or low molecular weight synthetic softeners are suitable. Among these, mineral oil-based rubber softeners, called process oils or extender oils, which are generally used to soften, increase volume, and improve processability of rubber, are mixtures of aromatic rings, naphthenic rings, and paraffin chains. So, those in which the number of carbon atoms in the sorafin chain accounts for 50% or more of the total carbons are called paraffinic, those in which the naphthene ring carbon number is 30 to 45% are called naphthenic, and those in which the number of aromatic carbons is 30%. Those with a larger amount are considered to be aromatic. The mineral oil-based rubber softener used as component (C) of the present invention is preferably a naphthenic or paraffinic one in the above category, and has an aromatic carbon number of 3.
Aromatic compounds containing 0% or more are not preferred in terms of dispersibility and solubility in the composition with component (a). The properties of these non-aromatic rubber softeners include a kinematic viscosity of 20 to 500 cst at 37.8°C and a pour point of -1.
It exhibits a temperature range of 0 to -15°C and a flash point of 170 to 300°C.

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

The blending amount of the softener as component (C) is 10 to 300 parts by weight, preferably 2 to 300 parts by weight, per 100 parts by weight of component (a).
It is 0 to 250 parts by weight. If the blend exceeds 300 parts by weight, the softener tends to bleed out and the final
It may cause stickiness in the product and also reduce mechanical properties. If the amount is still less than 10 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 polyolefin/fin type resin used as component (d) of the present invention is effective in improving the processability and/or heat resistance of the resulting composition, such as polyethylene, isotactic polyzoropylene, propylene, etc. and small amounts of other α-olefins, such as propylene-ethylene copolymer, propylene-1-hexene copolymer, propylene-4-methyl-1-pentene copolymer, and poly-4-methyl-1- Pentene, polybutene-1, etc. can be mentioned. MFR of olefin resin used
(ASTM-D-1238-L conditions, 230°C) is 0.
1~501/10 minutes, and <KO, 5~309710
A range of minutes is preferred.

The amount of component <d) to be blended is 5 to 100 parts by weight, preferably 10 to 70 parts by weight, per 100 parts by weight of component (a). If the amount exceeds 100 parts by weight, the hardness of the resulting elastomeric composition will become too high, resulting in a loss of flexibility, and a product with a rubbery feel will not be obtained.
Rubber elasticity (compression set) at high temperatures deteriorates extremely, which is undesirable. In addition, when the amount is less than 5 parts by weight, the polyolelain resin exhibits the same processability as the composition of the present invention to which it is not added.

Furthermore, the inorganic filler used as component (C) in Example 1-1 of the embodiment of the present invention not only has the benefit of reducing product cost as an extender, but also improves quality (
(compression set, etc.).

Examples of inorganic fillers include calcium carbonate, casen black, talc, magnesium hydroxide, mica, clay, barium sulfate, natural silicic acid, synthetic silicic acid (white casen), and titanium oxide. 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 casen such as Ketjen black may be used.

The amount of the inorganic filler blended is 20 to 300 parts by weight, preferably 30 to 250 parts by weight, per 100 parts by weight of the hydrogenated block copolymer of component (2). If the amount exceeds 300 parts by weight, the mechanical strength of the composition will drop significantly, and the hardness will increase, resulting in a loss of flexibility, making it impossible to obtain a product with a rubbery feel. Furthermore, when the amount is less than 20 parts by weight, the composition exhibits the same performance as the composition of the present invention obtained when the inorganic filler is not added.

The highly elastic elastomeric composition of the present invention may further include flame retardants, glass fibers, Rikizen fibers, antioxidants,
Heat stabilizers, ultraviolet absorbers, hindered amine light stabilizers, and colorants can be added.

As a method for compounding the highly elastic elastomeric composition of the present invention, methods used in the production of ordinary resin compositions or 2-molecular compositions can be employed, such as a single-screw extruder, a twin-screw extruder, etc. The composition can be compounded using a melt-kneading machine such as a saw mixer, a heating roll, a four-pounder, various kneaders, or the like.

At this time, there is no restriction on the order of addition of each component; for example, the product components may be premixed using a mixer such as a Henschel mixer or Zollender, premixed using the above kneading machine, and then melted and compounded using the above mixer; It is possible to adopt an addition method such as premixing the components, melting and compounding them using a master match, and then adding the remaining component υ and melting and compounding them.

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

(Effects of the Invention) The composition obtained by the present invention has excellent flexibility, heat resistance, mechanical strength, and rubber elasticity at high temperatures, and
Because of its excellent paintability and electrical insulation properties, it can be used in various electric wire coatings (
It can be suitably molded and used for insulation, sheaths), home appliance parts, automobile parts, and various industrial parts. Specific applications include various gaskets, flexible tubes, hose coverings, weather strips, flexible pantsaws, sleeves, moldings, filler panels, live housings, wire cable coverings, air intake hoses, and cushions. There are panels etc.

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

In addition, in these Examples and Comparative Examples, the test methods used for various evaluations are as follows.

(1) Hardness [-] JIS-6301, A type (2) Tensile strength [Hard/LM2] and tensile elongation [%] J
IS-6301, the sample used was an injection 7-piece with a thickness of 2m11, and the test piece was No. 3 type.

(3) Compression set [%] JIS -6301, 25% deformation at 70°C and 100°C for 22 hours.

The ingredients still blended are as follows.

(1) <Component (a-1)> Polystyrene-hydrogenated polybutadiene-polystyrene structure, bound styrene content 27%, number average molecular weight 157,000, molecular weight distribution 1.07, polybutadiene before hydrogenation A hydrogenated block copolymer having a 1/2 bond ratio of 34% and a hydrogenation rate of 98% was synthesized and was designated as component (II-1).

component (, -2)> (polystyrene-hydrogenated polybutadiene÷Si
It has a structure with a bound styrene content of 36% and a number average molecular weight of 3.
79,000. A hydrogenated block copolymer having a molecular weight distribution of 1.35, a polybutadiene 1.2 bond content of 27% before hydrogenation, and a hydrogenation rate of 99% was synthesized and was used as component (a-2).

Ingredient (a-3) > KTLATON-G1651 manufactured by Shell Chemical Company
Component (a4) > KRATON-G1650 (2) manufactured by Shell Chemical Co.
Component (b) Diana process oil PW-380 manufactured by Idemitsu Kosan [paraffinic, kinematic viscosity + 381-6 cst (40°C
), 30.1 cst (10°C), average molecular weight 746
, ring analysis; CN = 27%, CP = 73%] (3) Component (C) Polyzolopyrene resin manufactured by Mukasei Co., Ltd., M-1300CMFR
(230°C) Air 710 minutes] (4) Component (d) Calcium carbonate manufactured by Shiraishi Calcium Co., Ltd., Whitein 5B (5) Component (e) Poly(2゜6--
) mef-1,4-phenylene) ether (reduced viscosity;
0.37, 0.57> were synthesized.

Examples 1 to 6 Hydrogenated block copolymers (a-1) to (a-3) were used, and as polyphenylene ether, the reduced viscosity was 0.
The components shown in Table 1 were mixed using a Henschel mixer, and then melt-kneaded at 250°C in a twin screw extruder with a normal diameter of 50 to obtain a thermoplastic nidistomer pellet. This was evaluated as an injection molded product, and the results are listed in Table 1.

From this result, it can be seen that the nidistomer composition of the present invention has a
It is clear that the compression set at °C is 50% or less, and the rubber elasticity at high temperatures is excellent. Furthermore, these compositions also had excellent moldability.

Margin Comparative Examples 1 to 7 Below, hydrogenated block copolymers (, -1) to (--3) were used, and polyphenylene ether had a reduced viscosity of 0.
Using No. 57, each component shown in Table 2 was kneaded in the same manner as in Examples 1 to 6, and then molded and evaluated. The results are listed in Table 2.

These results revealed that compositions outside the scope of the present invention had excellent compression set at 70°C, but extremely poor compression set at 100°C and poor rubber elasticity at high temperatures. In addition, KRATON-G2705 and G-7, which are commercially available hydrogenated block copolymer compositions, are
Although the composition of 720 and G-7820 (both manufactured by Shell Chemical Company) is unknown, it has been revealed that the compression set at 100° C. is poor and the rubber elasticity at high temperatures is poor.

Examples 7 to 9 Comparative Examples 8 to 10 Using (, -4) as the hydrogenated block copolymer and polyphenylene ether with a reduced viscosity of 0.37, each component shown in Table 3 was carried out. The mixture was kneaded in the same manner as in Examples 1 to 6, and then molded and evaluated.

The results are listed in Table 3.

From this result, the hydrogenated block copolymer compositions using (a-4) (Comparative Examples 8 to 10) showed that polyphenylene ether was It is clear that the added hydrogenated block copolymer composition of the present invention has significantly improved compression set at 70°C and compression set at 100°C, and has improved rubber elasticity at high temperatures. There it was.

Below is a blank Example 10 Using a hydrogenated block copolymer and (--1) in 17, 2,6-dimethylphenol containing 5% of 2,3,6-dimethylphenol was polymerized as a polyphenylene ether resin. , 2,6-dimethylphenol/2,3,6-drimethylphenol copolymer (reduced viscosity 0.51) was obtained and used, but a test piece was prepared and evaluated using the same formulation as in Example 4. As a result, the hardness was 75 and the pore tensile strength was 1801.
4/lyn", elongation 390%, compression set (100℃
22HR8) A highly elastic hydrogenated block copolymer composition having properties of 38% was obtained.

Patent applicant: Asahi Kasei Industries, Ltd. Procedural amendment (voluntary) Showa 60th August 2nd

Claims (2)

[Claims] (1) (a) A block copolymer consisting of a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block B mainly composed of at least one conjugated diene compound is hydrogenated. Hydrogenated block copolymer a obtained by adding 100 parts by weight (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1, R_2, R_3 and R_4 are hydrogen halogen, hydrocarbon group, respectively) selected from the group consisting of n represents the total number of monomer units, and 1
polyphenylene ether resin b, which is a homopolymer and/or copolymer having the structure of
Weight ratio) (c) A highly elastic hydrogenated block copolymer composition comprising 10 to 300 parts by weight of a non-aromatic rubber softener and having a compression set (100°C x 22 hours) of 65% or less. thing (2) (a) A block copolymer consisting of a terminal polymer block A mainly composed of at least two vinyl aromatic compounds and an intermediate polymer block B mainly composed of at least one conjugated diene compound is hydrogenated. Hydrogenated block copolymer a obtained by adding 100 parts by weight (b) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (Here, R_1, R_2, R_3 and R_4 are hydrogen halogen, hydrocarbon group, respectively) selected from the group consisting of n represents the total number of monomer units, and 1
polyphenylene ether resin b, which is a homopolymer and/or copolymer having the structure of
weight ratio) (c) 10 to 300 parts by weight of non-aromatic rubber softener (d
) A highly elastic hydrogenated block copolymer composition comprising 5 to 100 parts by weight of a polyolefin resin and having a compression set (100°C x 22 hours) of 65% or less.