JPS62199646A - Thermoplastic elastomer composition - Google Patents

Abstract

PURPOSE:A composition having improved compatibility with resins and rubber and excellent improving effects on impact resistance and wear resistance, obtained by blending a block copolymer consisting of a vinyl aromatic compound-conjugated diene compound with a specific block copolymer. CONSTITUTION:(A) 50-99wt% vinyl aromatic compound-conjugated diene block copolymer such as block copolymer shown by formula I-formula III (A1 is polymer block mainly comprising vinyl aromatic part; B1 is polymer block mainly comprising conjugated diene; n is >=1; X is coupling agent residue), preferably block copolymer shown by formula III, containing 25-95wt% vinyl aromatic compound is blended with (B) 50-1wt% block copolymer comprising a polymer block consisting of other vinyl compound, preferably alpha-monoolefin, vinyl cyanide, (meth)acrylic acid(alkyl ester), etc., except the vinyl aromatic compound and the conjugated diene compound and a polymer block of the vinyl aromatic compound to give a composition.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention has excellent compatibility with resins and foams, and has good impact resistance and abrasion resistance. The present invention relates to a thermoplastic elastomer composition containing a vinyl aromatic compound-conjugated diene compound block copolymer.

[Conventional technology]

A block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound obtained by anionic polymerization using an alkyllithium compound as an initiator in a hydrocarbon solvent can exhibit high rubber elasticity without vulcanization.

It can be molded using a regular thermoplastic resin molding machine.

Thermoplastic elastomers are in particular high demand in recent years because they are inexpensive and can be recycled from scrap.

For example, by blending an appropriate amount with a thermoplastic resin such as polystyrene as a physical property modifier such as impact resistance, or by blending it with an appropriate resin, gum, softener, filler, etc., it can be used for canvas jerseys, casual shoes, etc. It is widely used as a sole material for footwear, as well as in adhesives, asphalt modifiers, sheets, films, and molding materials.

[Problem that the invention is trying to solve] However,
This block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound is generally not said to have good compatibility with resins, rubbers, or other thermoplastic elastomers.
Currently, it is used as a modifier for resins based on polystyrene, such as polystyrene and high-impact polystyrene, but sufficient modifying effects can also be obtained when used as a modifier for other thermoplastic resins. As a result, the applications of block copolymers are greatly limited.

This block copolymer is also used in footwear applications by blending it with other resins, plums, softeners, fillers, etc., but polystyrene resins are mainly used as blended resins. It has limited compatibility with other resins, resulting in reduced wear resistance and other properties, so its uses are limited.

An object of the present invention is to provide a thermoplastic elastomer composition containing a vinyl aromatic compound-conjugated diene compound block copolymer, which has excellent compatibility with resins and rubber, and has a remarkable effect of improving impact resistance and abrasion resistance. There is a particular thing.

[Means for solving problems]

The present invention comprises a block copolymer (a) consisting of a vinyl aromatic compound and a conjugated diene compound, 50 to 99% by weight, and a polymer block portion of other vinyl compounds other than the vinyl aromatic compound and the conjugated diene compound, and a vinyl aromatic Block copolymer (b) having a polymer block portion of a group compound
It relates to a thermoplastic elastomer composition consisting of s o to 1% by weight.

The composition according to the present invention can be suitably used as a resin modifier, footwear material, sheet, film, molding material, adhesive/adhesive, etc.

The present invention will be explained in more detail below. First, the vinyl aromatic compound-conjugated diene block copolymer (a) used in the present invention contains at least one vinyl aromatic compound block and at least one conjugated diene compound block, and is linear. It may be of the radial type, or it may be of the so-called radial type, in which the vinyl aromatic compound gradually increases in the conjugated diene compound block.

As a block copolymer, (A, -8,)n, (A,
-B,) n-A1 (Mu 1-81) nXCXC formula A block mainly composed of aromatic vinyl, B is a block mainly composed of a conjugated diene, n is an integer of 1 or more, X is force, pulling agent (indicates a residue) and hydrogenated products thereof.

Among these block copolymers, A, -81-A, or (A, -B,)YX types are preferred. In particular, the block copolymer contains 25 to 95% by weight of a vinyl aromatic compound and has the general formula A, -B, -A, or (A, -B,)nX
(Shikichunin.

is a vinyl aromatic compound polymer block, the total amount of A includes 50 to 97% by weight of the entire vinyl aromatic compound, and B is preferably a copolymer of a conjugated diene and a vinyl aromatic compound. The B1 portion has 2 to 10 taper blocks in which the vinyl aromatic compound gradually increases, n is an integer of 2 to 6, The content of the vinyl aromatic compound constituting a chain of 1 to 4 units is preferably 5 to 25% by weight based on the total vinyl aromatic compound.

Examples of the vinyl aromatic compound of the block copolymer used in the present invention include styrene, α-methylstyrene, p-methylstyrene, m-methylstyrene, 0-methylstyrene, p-tert-butylstyrene, dimethylstyrene, Although vinylnaphthalene and the like can be used, styrene is preferred. Further, as the conjugated diene, butadiene, isoprene, piperylene, etc. can be used, but among these, butadiene is preferred.

The weight average molecular weight of the block copolymer used in the present invention is preferably i o, o from the viewpoint of strength retention and processability.
The range is preferably from o o to so o, o o o, more preferably from 50,000 to 500,000.

The block copolymer (b) used in the present invention is a polymer block (1) in which one block component is a vinyl aromatic compound, and the other block component is a vinyl aromatic compound and a conjugated diene compound. It may have any structure as long as it has a polymer block (2) obtained by polymerizing other vinyl compounds, for example, a block block obtained by the method disclosed in JP-A-55-75414. Examples include polymers.

An example of the method for producing the block copolymers of the present invention is to react dibasic acid dichloride obtained by reacting glycol with dibasic acid dichloride such as heptanopic acid or dof-canniic acid, and react with sodium peroxide to form a polymer. 7-oxide, then polymerize 7-mer-A (e.g. styrene) with I remer/f-oxide, and then polymerize 7-mer-A (e.g. styrene), then synthesize 7-mer B (
For example, by polymerizing ethylene), a block copolymer having a polystyrene block and a 4-ethylene glycol in the molecule can be obtained.

The weight ratio of the constituent units of the block components (1) and (2) in the block copolymer (b) is preferably 90 to 10 weight for (1) and 10 to 90 weight for (2). Outside this range, the compatibility with the block copolymer consisting of a vinyl aromatic compound-conjugated diene compound and the compatibility with the modified resin will deteriorate.

■ Vinyl monomer compounds other than conjugated diene compounds and aromatic vinyl compounds that constitute the component include, for example, ethylene, globylene, butene, cyanide vinyl such as α-monoolefin, vinyl chloride, vinylidene chloride, and acrylonitrile. , vinylidene cyanide, vinyl acetate, vinyl stearate, vinylpyridine, vinylpyrrolidone, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, ethyl methacrylate, etc. Examples include meth)acrylic acid alkyl esters.Among these, α-monoolefin, vinyl chloride, vinyl cyanide, vinyl acetate, (meth)acrylic acid, and (meth)acrylic acid alkyl esters are preferred; Homopolymer blocks or copolymer blocks of can be preferably used.

Next, the preferred blending ratio of each component of the present invention is 50 to 99% by weight of a block copolymer (a) consisting of a vinyl aromatic compound and a conjugated diene compound;
~50% by weight. Particularly preferred is a block copolymer 6) consisting of a vinyl aromatic compound and a conjugated diene compound.
70-90% by weight, block copolymer (b) io~
It is 30% by weight. If the amount of block copolymer (b) is less than 1%, the effect of compatibilization with other resins, which is the objective of the present invention, cannot be obtained, while if it exceeds 50%, the vinyl aromatic compound-conjugated diene compound block copolymer -) The original characteristics such as rubber elasticity and low-temperature properties are lost, and the cost is also increased, which is undesirable.

The thermoplastic elastomer composition of the present invention may contain conventional thermoplastic resins, rubbers, or additives.

For example, thermoplastic resins include polystyrene resins (e.g. GPPS, IPS, As resin, ABS resin, AES resin, MBS resin, MASAs resin) yfe9
Zf-based resin, polypropylene-based resin, / ribtene-based resin, polyvinyl chloride-based resin, polyvinyl acetate-based resin,
Polyamide resin, thermoplastic? Lyester resin, polyacetal resin,? Littadiene resin, thermoplastic polyurethane resin.

These include I-lyester resin, I-recarnate resin, and the like.

Rubbers include SBR, NBR, BR, EPR, and IR.

NR%CR, IIR%H8E<. Additives include plasticizers such as phthalate ester compounds, silica,
Merck, fillers or reinforcing agents for glass fiber, other antioxidants, ultraviolet absorbers, antistatic agents, flame retardants, lubricants, foaming agents, colorants, pigments, nucleating agents, crosslinking agents, crosslinking aids, etc. or a mixture of these.

In addition, when blending the composition of the present invention with the above-mentioned resin, rubber, etc., the block copolymer (b) which is a component of the present invention
Even better performance can be obtained by using a polypropylene copolymer having components that match or are slightly compatible with the resin K in which the block components are blended.

Also, mixing of each component of the present invention and these and the above-mentioned resin,
For mixing with various additives such as rubber, softeners, fillers, etc., any conventionally known method can be used, such as an extruder (single-screw or twin-screw), roll, Banbury mixer, Niegoo mixer, or Henschel mixer. good.

The thermoplastic resin composition obtained by the above method can be molded using conventionally known methods such as extrusion molding, injection molding, blow molding, compression molding, and calendering to produce practically useful molded products. It can be processed into Further, if necessary, processing such as painting or plating can be applied.

The composition of the present invention can be blended with the resins, rubbers, additives, etc. mentioned above and used for various purposes. In particular, the composition of the present invention is useful as a modifier for the above-mentioned resins and rubbers. These compositions have excellent impact resistance, processability, low-temperature properties, temperature dependence, compatibility, paintability, printability, tossability, adhesion, deep drawability, slip resistance, and rubber properties. Taking advantage of its elasticity, rubber feel, removability, stress scratch resistance, tear strength, and low gloss, it can be used for various plastics, rubber-modified materials, footwear sole materials, adhesive and adhesive materials, asphalt-modified materials, It can be used as a modifying material for vulcanizates, films, sheets, and molding materials. For example, trays for meat and fresh fish! Film applications such as sheeting for fruit/paper, frozen dessert food containers, molding applications, food packaging, daily goods packaging, industrial material packaging, sports shoes, leisure shoes, leather shoes, leather shoes, etc. Footwear applications such as TVs, stereos, vacuum cleaners and other home appliances, bumper parts, etc. Tea Gunnell,
Automotive parts such as sight shields, materials such as hot adhesives and pressure-sensitive adhesives, contact type adhesives, spray type adhesives, materials for asphalt prene P such as road paving materials, waterproof sheets, piping coatings, other daily necessities, leisure goods, It can be used for a wide range of purposes such as toys and industrial supplies.

The present invention will be described in detail below with reference to Examples, but the present invention is not limited to the Examples unless it goes beyond the gist of the present invention.

The vinyl aromatic/conjugated diene block copolymer used in the following examples was prepared by the following method.

(Production method of block copolymer (1)) A1-8. -A type block copolymer was prepared by the following method.

In a washed and dried autoclave equipped with a stirrer and a jacket, 4.500 g of cyclohexane and 1 g of tetrahydro 7 run were charged under a nitrogen atmosphere, and the internal temperature was then brought to 70°C.

Next, a hexane solution containing 0.5 p of n-butyllithium was added, and then 155 g of styrene was added and polymerized for 60 minutes. Next, 460 g of butadiene was added and polymerized for 60 minutes.

Finally, styrene 155I was added and polymerized for 60 minutes. The polymerization conversion rate of styrene and butadiene in each operation was 10
It was 0%. Note that during the polymerization, the temperature was always adjusted to 70°C. After polymerization, 2,6-not-tert-butyl p-cresol was added, and then cyclohexane was removed by heating to obtain a block copolymer.

(Production method of block copolymer ("l[)] Tapered type A
-B-A type block copolymer was produced by the following method.

Add 4,500 cyclohexane to the same autoclave as above.
After charging g, the internal temperature was set to 70°C.

Next, a hexane solution containing 0.59% of n-butyllithium was added, and then 130g of styrene was added and polymerized for 60 minutes. The polymerization conversion rate of styrene was low. Next, a mixture of 15 I styrene and 115 g of tutadiene was added to
Separation polymerization was carried out. styrene.

The polymerization conversion rate of butadiene was 100%. This operation was repeated two more times. Next, 115 g of tutadiene was added and polymerized to a polymerization conversion rate of 100%. After that, styrene was added to the page at 130F and polymerized for 60 minutes. The conversion rate is 1
It was 00%.

During the polymerization, the temperature was always adjusted to 70°C. After the polymerization was completed, 2,6-di-tart-butyl p-cresol was added to the polymer solution, and then cyclohexane was removed by heating to obtain a block copolymer.

(Production method of block copolymer (III)) Next, an A, -B, -A type block copolymer having a high styrene content was produced by the following method.

Add 4,500 cyclohexane to the same autoclave as above.
After adding 1 g of tetrahydrofuran, the internal temperature was reduced to 7.
The temperature was set to 0°C.

Next, n-butyllithium o,s! After adding the hexane solution containing i, 265 g of styrene was added and polymerized for 60 minutes.

The polymerization conversion rate of styrene was 100%. Next, a mixture of 15 g of styrene and 50 g of tutadiene was added to
Separation polymerization was carried out. The polymerization conversion rate of styrene/getadiene is 10
It was 0%. This operation was repeated two more times. Next, 50 g of butadiene was added and polymerization was carried out at a polymerization conversion rate of 100 ts.

Thereafter, 265 II of styrene was further added and polymerized for 60 minutes. The conversion rate was 100%.

During the polymerization, the temperature was always adjusted to 70°C. After the polymerization was completed, 2,6-sheet t@rt-butyl p-cresol was added to the polymer solution, and then cyclohexane was removed by heating to obtain a block copolymer.

(Production method of block copolymer CIVI) Radial block copolymers (A1-8, )nX type were produced by the following method.

Add 4,500 cyclohexane to the same autoclave as above.
After adding 1 g of tetrahydrofuran, the internal temperature was reduced to 70
It was set to ℃.

Next, after adding a hexane solution containing 1 g of n-butyllithium, 380.0% of styrene was added. p was added and polymerized for 60 minutes. The polymerization conversion rate of styrene was 100%.

Next, a mixture of 10 p of styrene and 300 g of butadiene was added and polymerized for 60 minutes. The polymerization conversion rate of styrene and butadiene was 100%. After repeating this operation once, 1 g of butadiene was added and polymerized. After that, add 10.6611 of tetrachlorosila and force for 20 minutes.
During the polymerization, the temperature was always adjusted to 70°C. After the polymerization was completed, 2,6-sheet tert-butyl p-cresol was added to the polymer solution, and then cyclohexane was removed by heating to obtain a block copolymer.

Table 1 shows the properties of the obtained block copolymer.

The styrene chain was based on the method developed by Professor Ohnaka et al. of Agriculture and Technology (Proceedings of the Society of Polymer Science and Technology, Vol. 29, No. 7, 2055). The total styrene bond amount was determined by an infrared method.

Table-1 Examples 1 to 7. Comparative Examples 1 to 4 Each component of the present invention was prepared according to the formulation shown in Table 2, kneaded and pelletized using a 50-fill φ single screw extruder, and then subjected to DIN abrasion and Izot impact test pieces using a 5 oz injection molding machine. was prepared and subjected to evaluation. The results are shown in Table-2.

Note that DIN abrasion was measured according to DIN53516, and Izot impact strength was measured according to ASTM D256.

Examples 8 to 14 The compositions of the present invention shown in Examples 1 to 7 in Table 2 were blended at 15% with the resins shown in Table 3, molded in the same manner as Examples 1 to 7, and test pieces were prepared. was created and submitted for evaluation.

The results are shown in Table-3.

The following block copolymer (b) was used.

The following resins were used.

PE: High-density polyethylene (Mitsubishi Yuka: Yucalon EZ)
-40) PP: Polypropylene (Mitsubishi Yukafi: Noblen FG-38) EVA: Ethylene, vinyl acetate copolymer (Mitsui Polychemical Unipaflex P-190)
7) MMA: Polymethyl methacrylate resin (Kyowa Gas Chemical Co., Ltd.) Arupet G) AS: Acrylonitrile-ru-styrene copolymer (Japan Synthetic Rubber Co., Ltd.: JSRAS240)
) Table 3 Comparative Examples 5 to 9 Table 4 shows the results of kneading, molding and measurement in the same manner as in the above Example except that the block copolymer (b) was not blended.

Table 4 [Effects of the Invention] As is clear from the above description and examples, the thermoplastic elastomer composition of the present invention has a remarkable effect of improving impact strength and abrasion resistance when blended with a resin, which is superior to conventional methods. This is a new composition that could not be obtained previously.

Claims (3)

[Claims] (1) A block copolymer consisting of a vinyl aromatic compound and a conjugated diene compound (a) 50 to 99% by weight, and a polymer block portion of other vinyl compounds excluding the vinyl aromatic compound and the conjugated diene compound and vinyl aromatic A thermoplastic elastomer composition comprising 50 to 1% by weight of a block copolymer (b) having a polymer block portion of a group compound. (2) The vinyl compound of the block copolymer (b) is
The thermoplastic elastomer composition according to claim 1, which is at least one selected from α-monoolefin, vinyl cyanide, (meth)acrylic acid, alkyl (meth)acrylate, vinyl acetate, and vinyl chloride. . (3) The above block copolymer (a) is (A_1-B_1
)_n, (A_1-B_1)_n-A_1 type or (A
_1-B_1)_nX type (here, A_1 is a polymer block whose biological body is a vinyl aromatic, B_1 is a polymer block whose main body is a conjugated diene, n is an integer of 1 or more, and X is a coupling The thermoplastic elastomer composition according to claim 1, which is a block copolymer represented by the following: