JP5249548B2 - Thermoplastic resin blend, composite material, and method for producing composite material - Google Patents

Description

  The present invention relates to a thermoplastic resin compound used for imparting flexibility to the surface of a base resin molding, and a composite in which the thermoplastic resin compound molding is melt bonded to the surface of the base resin molding. The present invention relates to a method for manufacturing a material and a composite material.

  For example, automotive instrument panels, center console boxes, door trims, pillar covers, automotive parts such as assist grips, building materials such as doors and window frames, and electrical switch parts such as polycarbonate (PC) and styrene -Based resin (PS), polyvinyl chloride (PVC), modified polyphenylene ether (modified PPE) and other hard resins are used as the material, but the above-mentioned members, materials, parts, etc. have a soft hand, elasticity, vibration resistance, A resin molded body having flexibility and elasticity is joined to provide soundproofing, damage prevention functions, and the like.

Conventionally, as the resin molding, a block copolymer having a styrene block and a diene block and a styrene elastomer that is a hydrogenated product thereof have been used, but the styrene elastomer has low polarity. Insufficient melt adhesion with polar base resins such as PC, PS, PVC, and modified PPE used as materials for the above-mentioned members, materials and parts.
Therefore, as a means for improving the melt adhesion of the styrene-based elastomer, it has been proposed to blend polar elastomers such as polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers.

In order to melt-bond the elastomer molded body to the polar base resin molded body, a method of generally using a two-layer extruder and extruding the base resin melt and the elastomer melt together to perform melt bonding It has been adopted.
In the case of the above conventional elastomer compounding, there is a drawdown phenomenon in which the elastomer melt hangs down from the die of the extruder during extrusion molding, or the so-called “eye phenomenon” in which the solidified product of the elastomer melt adheres to the die. May occur.

The present invention has an object to prevent the occurrence of a drawdown phenomenon and a phenomenon in the eyes during the extrusion molding . As means for solving the above problems, a styrene polymer (S) block and a butadiene-styrene system are used. A block copolymer (S-EB / S-S) comprising a controlled distribution copolymer (B / S) block and a styrenic polymer (S) block, which is selectively hydrogenated, The end region adjacent to the S block of the EB / S block is rich in conjugated butadiene units, and the region not adjacent to the S block is a block copolymer rich in styrene (S-EB / S-S). ) And a softening agent having a kinematic viscosity at 40 ° C. of 40 cSt or more and 1000 cSt or less, and 100 parts by mass of the mixture of 40:60 to 95: 5 mass ratio, the polyurethane-based thermoplastic elastomer 30 to 25 Parts by weight, a formulation was admixed compatibilizer 5-100 parts by weight, and at least one conjugated diene of U.S. Patent Application Publication No. 2007/0225429 Pat described, consisting of at least one alkenyl arene controlled distribution An acrylic soft multilayer structure for a total of 100 parts by mass of the S-EB / S-S block copolymer and the softening agent in the blend, which is a blend that does not contain a soft improver comprising a copolymer a formulation resin excluding formulations are added in an amount exceeding 200 parts by weight, it is used for subjecting the flexibility and melt bonded by extrusion to the surface of the molded article of the blend base resin A thermoplastic resin formulation is provided.
The number average molecular weight of the S block in the block copolymer (S-EB / S-S) ranges from 6,500 to 45,000, and the number average molecular weight of the EB / S block ranges from 40,000 to 275. The total amount of styrene in the block copolymer (S-EB / S-S) is preferably 35 to 70% by mass, and the compatibilizer is a polyurethane block copolymer, And / or an acid-modified polyolefin and / or an acid-modified styrenic elastomer. Furthermore, in the thermoplastic resin blend, 200 parts by weight of the acrylic soft multilayer structure resin is further added to 100 parts by weight of the total of the S-EB / S-S block copolymer and the softener in the blend. It is desirable to add and mix in the following amounts, and in the thermoplastic resin blend, with respect to a total of 100 parts by weight of the S-EB / S-S block copolymer and the softener in the blend, It is desirable to add acrylic modified polytetrafluoroethylene in an amount of 30 parts by mass or less.
In the present invention, further by extruding a melt of the thermoplastic resin formulation on the surface of the molded body of the base resin, melted junction a thermoplastic resin formulation on the surface of the substrate resin composite Material is provided. The base resin is preferably at least one polar resin selected from polycarbonate, styrene resin, polyvinyl chloride, modified polyphenylene ether, acrylic resin, polyamide, and polyester.
In the present invention, a two-layer extruder is further used to extrude the base resin from one extruder, and the thermoplastic resin composition is extruded from the other extruder to be extruded from the one extruder. Also provided is a method for producing a composite material in which the base resin and the thermoplastic resin blend extruded from the other extruder are melt-bonded.

[Action]
In the resin blend of the present invention, S-EB / S-S having good thermal processability is used as the styrene elastomer. In the elastomer, since the styrene monomer S is interposed in the controlled distribution ethylene-butylene copolymer block (EB) to form the ethylene-butylene-styrene copolymer block (EB / S), The polarity of the elastomer is improved and the melt adhesion with the base resin is improved. Here, the control distribution EB / S is rich in conjugated butadiene units in the end region of EB / S adjacent to the styrenic polymer block S and rich in styrene monomer in the region not adjacent to the S block. Thus, it can be said that EB and S are distributed. Here, “rich” is defined as having an amount greater than average, preferably 50% greater than average.
In the resin composition of the present invention, a styrene elastomer (S-EB / S) is used by using a softener having a good compatibility with the styrene elastomer and a kinematic viscosity at 40 ° C. of 40 cSt or more and 1000 cSt or less. -S) facilitates gelation, adjusts the hardness, and further adds a polar polyurethane thermoplastic elastomer (TPU) to improve the melt adhesion with the base resin. Add a compatibilizer such as a polymer, acid-modified polyolefin, or acid-modified styrene elastomer to uniformly dissolve S-EB / S-S and TPU, and generate phenomena in the eyes during extrusion. It prevents and roughens the surface of the resulting molded product to provide an excellent appearance.
Furthermore, when an acrylic soft multilayer structure resin is added to the resin composition of the present invention, the viscosity of the melt of the thermoplastic resin composition is increased, and the drawdown phenomenon and the phenomenon in the eyes during extrusion are further suppressed. In addition, weather resistance is improved.
If desired, acrylic modified polytetrafluoroethylene (acrylic modified PTFE) is added to the thermoplastic resin formulation of the present invention. The acrylic-modified PTFE improves the surface tension of the melt of the thermoplastic resin composition of the present invention, and the drawdown phenomenon or nozzle where the melt of the thermoplastic resin composition hangs down from the die of the extruder during extrusion molding. In addition, the occurrence of a phenomenon in the eyes where the solidified product of the resin compound melt is fixed is suppressed.

〔effect〕
The thermoplastic resin composition of the present invention exhibits good melt adhesion particularly to polar base resin, but the thermoplastic resin composition exhibits a drawdown phenomenon or a phenomenon in the eyes when it is extruded. Does not occur.

The present invention is described in detail below.
[Styrene elastomer]
In the resin blend of the present invention, an S-EB / S-S block copolymer is used as a styrene elastomer. Here, S is a styrene polymer block, for example, styrene, o-methylstyrene, p-methylstyrene, p-tertiarybutylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, vinylanthracene. EB / S is a selective hydrogenation product of a butadiene / styrene copolymer block (B / S). The EB / S is a controlled distribution copolymer block, the terminal region adjacent to the S block is rich in EB, and the region not adjacent to the S block has a monomer distribution rich in S. doing. Usually, the number average molecular weight of the S block ranges from 6,500 to 45,000 (6,000 to 45,000), and the number average molecular weight of the EB / S block ranges from 40,000 to 275,000 (4 The styrene content is 5 to 45 mass%, and the total amount of styrene in S-EB / S-S is 35 to 70 mass%.

[Softener]
Examples of the softener used in the resin composition of the present invention include rubber softeners such as paraffinic oil, naphthenic oil, and aromatic oil, and those having a kinematic viscosity of 40 cSt or more and 1000 cSt or less at 40 ° C. select. More preferably, the kinematic viscosity is 40 cSt or more and 600 cSt or less at 40 ° C. When the kinematic viscosity of the softening agent is less than 40 cSt at 40 ° C., a drawdown phenomenon occurs during extrusion molding of the thermoplastic resin compound.

[Polyurethane thermoplastic elastomer]
The polyurethane thermoplastic elastomer used in the resin blend of the present invention includes a hard segment composed of diisocyanate and a short-chain glycol having a molecular weight of about 50 to 500, and a soft segment composed of a diisocyanate and a long-chain polyol. I have it.
Examples of the short chain glycol include ethylene glycol, propylene glycol, 1,4-butanediol, bisphenol A, and the like. As the long chain polyol, a molecular weight of 500 to 10,000 (500 to 10,000) is used. Ether-based polyols or polyester-based polyols are used. Examples of the polyether-based polyols include polyalkylene glycols, and examples of the polyester-based polyols include polyalkylene adipates, polycaprolactones, and polycarbonates.

[Compatibilizer]
Examples of the compatibilizer used in the resin blend of the present invention include polyurethane block copolymers, acid-modified polyolefins, and acid-modified styrene elastomers.
The polyurethane block copolymer is prepared by melting and kneading a styrene-ethylene-propylene block copolymer (SEPS-OH) having a hydroxyl group at one end and the polyurethane thermoplastic elastomer (TPU) to form an OH group in the SEPS. It is a block copolymer in which TPU is bound via
Examples of the acid-modified polyolefin include polyethylene, polypropylene, ethylene-propylene copolymer, maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and endo-cis-bicyclo (2,2 1) Dicarboxylic acids such as-5-heptene-2,3-dicarboxylic acid, or anhydrides, esters, amides and imides of the above dicarboxylic acids, monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid, or the above Some of them have monocarboxylic acid esters and amides added.
Examples of the acid-modified styrenic elastomer include a styrenic polymer block and a styrene elastomer that is a hydrogenated conjugated diene compound such as butadiene, isoprene, or 1,3 pentadiene, and the dicarboxylic acid, monocarboxylic acid, or dicarboxylic acid. And monocarboxylic acid esters, amides, imides and the like.

[Acrylic soft multilayer resin]
An acrylic soft multilayer resin may be further added to the resin composition of the present invention. The acrylic soft multilayer structure resin has an acrylic rubber component inside and a copolymer containing a methacrylic ester at the outermost part (Japanese Patent Laid-Open No. 11-292940), and has a glass transition point (Tg). A copolymer layer containing an acrylic acid alkyl ester and a methacrylic acid alkyl ester that are 30 ° C. or lower as an inner layer, and a Tg of −20 to −50 ° C. acrylic acid alkyl ester and methacrylic acid alkyl ester Is the outer layer.
The acrylic soft multilayer structure resin is added in an amount of 200 parts by mass or less with respect to a total of 100 parts by mass of the S-EB / S-S block copolymer and the softening agent in the thermoplastic resin blend. It is desirable. When the addition amount exceeds 200 parts by mass, the effect on the draw-down phenomenon and the eye phenomenon at the time of extrusion molding reaches a peak state, and the fusion strength with the base resin tends to decrease.

[Acrylic modified PTFE]
The acrylic-modified PTFE used in the resin composition of the present invention is a PTFE-modified product (Japanese Patent No. 2942888) comprising PTFE (A) and an alkyl (meth) acrylate polymer (B) having 5 to 30 carbon atoms, or The content of PTFE (A) is 40 to 70 parts by mass, and includes a methacrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms, and an acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms. It is a PTFE modified product (Patent No. 3909020) having a content of 30 to 60 parts by mass of a (meth) acrylic acid alkyl ester polymer (B) containing 70% by mass or more of structural units.

[Third component]
In addition to the above components, the resin composition of the present invention includes a propylene homopolymer, a propylene-ethylene random copolymer, a propylene-based resin such as a propylene-ethylene block copolymer (PP), an aromatic polyester block, and the like. Block copolymer composed of non-aromatic polyester block, block copolymer composed of aromatic polyester block and polyether block, block copolymer composed of aromatic polyester block, non-aromatic polyester block and polyether block Polyester thermoplastic elastomer (TPEE) such as may be added. The TPEE has polarity and has good melt adhesion with the polar base resin, and therefore can be used in combination with TPU.

[Filler]
Furthermore, in the resin composition of the present invention, a filler may be used. Examples of the filler include talc, calcium carbonate, magnesium carbonate, barium sulfate, calcium sulfate, calcium sulfite, calcium phosphate, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, magnesium oxide, titanium oxide, iron oxide, zinc oxide, Alumina, silica, diatomaceous earth, dolomite, gypsum, calcined clay, asbestos, mica, calcium silicate, bentonite, white carbon, carbon black, iron powder, aluminum powder, stone powder, blast furnace slag, fly ash, cement, zirconia powder, etc. Fillers, organic fillers such as linter, linen, sisal, wood flour, palm flour, walnut flour, starch, wheat flour, rice flour, or natural fibers such as cotton, hemp, wool, polyamide fibers, polyester fibers, acrylic fibers, Viscose fiber, acete Organic synthetic fibers such as preparative fibers, asbestos fibers, glass fibers, carbon fibers, ceramic fibers, metal fibers, can be mentioned fibrous fillers, such as whisker fibers, particularly preferred, talc or calcium carbonate. By adding a filler, the effect of improving the drawdown during extrusion molding can be seen. The addition amount can be added up to 20% at the upper limit. When the above range is exceeded, the fusion strength decreases.

[Combination]
In the resin blend of the present invention, the mixing ratio of S-EB / S-S and the softening agent is set in the range of 40:60 to 95: 5 (mass ratio). When more softening agent is mixed than the above range, the fusion strength of the resin compound to the polar base resin is lowered, and during the extrusion molding, a draw-down phenomenon or a defect in the eyes occurs. When less softening agent is added, gelation of S-EB / S-S becomes difficult. In the present invention, since S-EB / S-S having good heat processability is used as the styrene-based elastomer, the amount of softening agent used can be reduced.
In order to suppress the occurrence of a drawdown phenomenon during extrusion molding, it is preferable to select a softener having a kinematic viscosity of 40 cSt or higher at 40 ° C. However, when a softener having a kinematic viscosity exceeding 1000 cSt at 40 ° C. is used, the workability at the time of blending this composition is deteriorated.
The polyurethane-based thermoplastic elastomer (TPU) is added in the range of 30 to 250 parts by mass with respect to 100 parts by mass in total of the S-EB / S-S and the softening agent. When TPU is added in an amount less than the above range, the fusion strength with the polar base resin is lowered, whereas when TPU is added in an amount greater than the above range, extrusion molding is performed. In this case, a drawdown phenomenon occurs, and the weather resistance of the resin composition also deteriorates.
The compatibilizing agent is added in the range of 5 to 100 parts by mass with respect to 100 parts by mass in total of the S-EB / S-S and the softening agent. When the compatibilizer is added in an amount less than the above range, a phenomenon occurs in the eyes, the surface of the molded product is roughened, and the appearance is deteriorated. On the other hand, when the compatibilizing agent is added in an amount larger than the above range, the compatibilizing effect reaches its peak and the material cost increases.
When the acrylic soft multilayer structure resin is added, it is added in an amount of 200 parts by mass or less with respect to a total of 100 parts by mass of the S-EB / S-S and the softening agent. The addition of the acrylic soft multilayer structure resin suppresses the occurrence of a drawdown phenomenon or an eye phenomenon at the time of extrusion molding. However, if the addition amount exceeds 200 parts by mass, the fusion strength with the polar base resin decreases, Also the odor becomes stronger.
When adding acrylic modified PTFE, it adds in the quantity of 30 mass parts or less with respect to a total of 100 mass parts of said S-EB / S-S and a softening agent. The addition of the acrylic-modified PTFE suppresses the occurrence of a drawdown phenomenon or a phenomenon in the eyes, but if the addition amount exceeds 30 parts by mass, the melt viscosity of the resin composition becomes too high and the moldability deteriorates.

  PP improves the pellet moldability of the resin composition and is added for the purpose of adjusting the hardness. The addition amount is 100 parts by mass or less with respect to 100 parts by mass in total of the S-EB / S-S and the softening agent. If the amount of PP added exceeds 100 parts by mass, the hardness of the resin composition increases and the fusion strength also decreases.

  Although TPEE is not as high as TPU, it improves the fusion strength of the resin blend with the polar base resin, but the amount added is less than 1/2 of TPU. If the amount of TPEE added is too large, a phenomenon occurs in the eyes.

The filler is effective in improving the drawdown phenomenon during extrusion molding, but if the addition amount in the resin composition exceeds 20% by mass, the fusion strength is lowered.

[Base resin]
Base resins targeted in the present invention are mainly styrene resins such as polycarbonate (PC), styrene homopolymer, styrene-acrylonitrile copolymer (AS), acrylonitrile-butadiene-styrene copolymer (ABS), Examples thereof include acrylic resins such as polyvinyl chloride, modified polyphenylene ether, polymethyl methacrylate, polyethyl methacrylate, and methyl methacrylate-ethyl acrylate copolymer, polyamide, polyester, and the like, and these thermoplastic resins have polarity.

(Co-extrusion)
In the present invention, in order to produce a composite material composed of a molded body of a base resin and a molded body of the thermoplastic resin blend, a two-layer extruder is used, and the above base resin is melted from one extruder. While extruding the product, the melt of the thermoplastic resin composition is extruded from the other extruder, and the extruded base resin and the extruded thermoplastic resin composition are melt bonded. However, in the present invention, the melt of the thermoplastic resin composition may be extruded and melt bonded to the surface of the molded body of the base resin.

Examples and comparative examples for describing the present invention more specifically will be described below.
〔Example〕
〔material〕
As S-EB / S-S, Kraton RP6935 (trade name, manufactured by Kraton Polymer Co., Ltd .: mass average molecular weight of about 200,000 and styrene content of 58% by mass) was used.
Septon 4099 (trade name, manufactured by Kuraray Co., Ltd .: styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS)) was used as a comparative styrene-based thermoplastic elastomer. The SEEPS has a mass average molecular weight of 422,000 and a styrene content of 30% by mass.
As a softening agent, PW380 (trade name, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity 40 ° C., 383.4 cSt) as a softening agent and PW90 (trade name, manufactured by Idemitsu Kosan Co., Ltd., kinematic viscosity 40 ° C.) which is also a paraffinic oil. 95.54 cSt).
As a comparative softener, high-col K-290 (trade name, manufactured by Kaneda Corp., kinematic viscosity 40 ° C., 32.3 cSt (<40 cSt)), which is a paraffinic oil, was used.
As the polyurethane-based thermoplastic elastomer, Elastollan ET-880 (trade name, manufactured by BASF, ether-based TPU (HsA80) using a polyether-based polyol as a soft segment material) was used.
As a compatibilizing agent, Kuraray TU-S5865 (trade name, manufactured by Kuraray Co., Ltd., polyurethane block copolymer (HsA70) having a TPU block and a styrene-ethylene-propylene-styrene block copolymer (SEPS) block), Kraton G1901X (trade name, manufactured by Kraton Polymer, maleic anhydride-modified SEBS (maleic anhydride content 1.7% by mass)) and Tuffmer MP0620 (trade name, manufactured by Mitsui Chemicals, maleic anhydride-modified ethylene-propylene) A polymer was used.
As the acrylic modified PTFE, Metablen A3000 (trade name, manufactured by Mitsubishi Rayon Engineering Co., Ltd.) was used.
Parapet NW-001 (trade name, manufactured by Kuraray Co., Ltd .: HsA80) was used as the acrylic soft multilayer structure resin.
As PP, PB222A (trade name, manufactured by Sun Allomer, flexural modulus of 1000 MPa, MFR 0.8 g / 10 min) was used.
As TPEE, Perprene P-75M (trade name, manufactured by Toyobo Co., Ltd .: ether-based TPEE, HsA96) was used.
Super SSS (trade name, manufactured by Maruo Calcium Co., Ltd., heavy calcium carbonate) was used as the filler.

[Resin compound pellet manufacturing conditions]
A premixture is prepared by dry blending materials other than the softener, and the premixture is impregnated with the softener to make a mixture. The mixture is melt-mixed by an extruder under the following conditions to produce resin blend pellets.
Extruder: Technobel K2W32TW-60MG-NG
Cylinder temperature: 180-220 ° C
Screw rotation speed: 220-400rpm

[Conditions for molding samples for hardness measurement]
Injection molding machine: Mitsubishi Industrial Co., Ltd. 100MSIII-10E
Injection molding temperature: 190 ° C
Injection pressure: 50%
Injection time: 5 seconds Mold temperature: 40 ° C
A plate having a thickness of 2 mm, a width of 125 mm, and a length of 125 mm is produced under the above conditions.

[Co-extrusion conditions with base resin]
Double-layer extruder: Ikegai Co., Ltd.
Extruder (FS40-25, VS40-25)
Die shape: Plate shape with width 20mm x thickness 1mm Molding temperature: Polar base resin side 220-250 ° C
Resin compound side 140 to 160 ° C
Dice junction 200 ° C
Polar base resin: ABS resin (Cebian V-500SF, trade name, manufactured by Daicel Polymer Ltd.)
A molded product sample is prepared by heat-sealing a base resin having a thickness of 1 mm and a width of 20 mm under the above-mentioned conditions (see FIG. 1, where 1 is the base resin, 2 is the resin composition, 3 Is the fused surface).

〔Evaluation method〕
Hardness: Hardness measurement was performed according to JIS K6253A using a 6 mm thick test piece.
Fusion strength: A fusion-molded piece produced under the above-mentioned production conditions is cut into a length of 20 mm. Fusing it
Pull in the direction perpendicular to the surface and measure its strength.
As a measured value, less than 5.0 N / mm ² is x, 5.0 to 6.0 N / mm ² is ○,
6.0 N / mm ² or more is evaluated as ◎.
Eye corner: When creating a fusion-molded piece under the above conditions, visually evaluate the amount of the eye deposit deposited at the die outlet in three stages.
Eye volume: High>Medium> Small Drawdown: The following criteria are used for drawdown when creating a fusion-molded piece under the above conditions.
Evaluation.
○: Drawdown is not seen and moldability is good.
Δ: Some drawdown is observed.
X: Remarkable drawdown Appearance of molded product: The appearance of the fusion-molded piece prepared under the above conditions was evaluated according to the following criteria.
◯: There is no rough surface, poor melting, or the like, and a smooth surface is good.
Δ: Some rough skin on the surface and poor melting are observed.
X: Remarkable surface roughness and poor melting are observed.

  Tables 1 and 2 show the results of formulation and performance evaluation of Examples 1 to 16, and Table 3 shows results of formulation and performance evaluation of Comparative Examples 1 to 9.

The blends of Examples 1 to 16 in Tables 1 and 2 are within the scope of the present invention, the fusion strength is clear at 5 (N / mm ² ) or more, the eyes are few, and the draw during extrusion molding The down phenomenon does not occur and the appearance of the molded product is good.

  Comparative Example 1 is a sample using SEEPS as a styrene-based elastomer instead of S-EB / S-S. Compared to the samples of Examples, the eyes are more visible and the appearance of the molded product is deteriorated.

Comparative Example 2 is a sample using a softener having a kinematic viscosity of 32.3 cSt (<40 cSt) at 40 ° C., and a drawdown phenomenon during extrusion molding is slightly observed as compared with each sample of Examples.

  Comparative Example 3 is a sample without the addition of a softening agent, and the gelation of the blend is not smoothly carried out, and some surface roughness and melting due to poor melting are observed on the surface of the molded product.

Comparative Example 4 is a sample in which the mixing ratio of S-EB / S-S: softening agent is 20:80 mass ratio (> 40:60) and the softening agent is excessively added, and the fusion strength is 3.5 N / mm. ² (<5 N / mm ² ), which is lower than that of each sample in the examples, causes a drawdown phenomenon during extrusion molding , and causes rough skin and poor melting on the molded product surface. Occurrence is seen.

Comparative Example 5 is a sample in which the amount of TPU added was 30 parts by mass or less (20 parts by mass) with respect to 100 parts by mass of the total amount of S-EB / S-S and softener, and the fusion strength was 4 It shows a low value of .7 N / mm ² (<5 N / mm ² ), and the surface of the molded product is slightly rough and has fuzz due to poor melting.

In Comparative Example 6, the amount of TPU added was 25 with respect to 100 parts by mass of the total amount of S-EB / S-S and the softener.
It is a sample used in an amount exceeding 0 parts by mass (300 parts by mass), a lot of eyes are generated, and a drawdown phenomenon is remarkably seen.

Comparative Example 7 is a sample to which no compatibilizing agent is added, and the eyes and eyes are considerably generated, and the surface of the molded product is slightly roughened.

Comparative Example 8 is a sample in which the amount of the compatibilizer is added in an amount exceeding 150 parts by mass (150 parts by mass) with respect to 100 parts by mass of the total amount of S-EB / S-S and the softener. A slight drawdown phenomenon is observed during extrusion molding .

In Comparative Example 9, the addition amount of the acrylic soft multilayer structure resin is S-EB / S-S and the total amount of the softening agent 1
00 is a sample being added in an amount of more than 200 parts by weight relative to the weight section (250 parts by weight), fusion strength is ^{4.5N / mm 2 (<5N /} mm 2) and low, and the surface of the molded article The appearance of rough skin and bumps is slightly seen.

The thermoplastic resin composition of the present invention is particularly excellent in melt adhesion with a polar base resin, and does not cause a slight drop-down phenomenon at the time of extrusion, so that it is coated or bonded to the surface of the base resin layer. In addition, a resin product having a soft surface and imparted with elasticity, vibration proofing, soundproofing, damage prevention functions and the like can be obtained.

Partial perspective view of co-extruded product

1 Base resin 2 Resin composition 3 Fusion surface

Claims (8)

A block copolymer consisting of a styrene polymer (S) block, a butadiene-styrene controlled distribution copolymer (B / S) block, and a styrene polymer (S) block, which is selectively hydrogenated. Coalescence (S-EB / S-S),
The end region adjacent to the S block of the EB / S block is rich in conjugated butadiene units, and the region not adjacent to the S block is a block copolymer rich in styrene (S-EB / S-S). ) And a softening agent having a kinematic viscosity at 40 ° C. of 40 cSt or more and 1000 cSt or less is 100 parts by mass of a mixture of 40:60 to 95: 5 mass ratio, 30 to 250 parts by mass of a polyurethane thermoplastic elastomer, A controlled distribution copolymer comprising 5 to 100 parts by mass of a compatibilizing agent and comprising at least one conjugated diene and at least one alkenylarene described in US Patent Application Publication No. 2007/0225429 a formulation containing no soft modifier consisting of, per 100 parts by weight of the S-EB / S-S block copolymer and softening agent in the formulation A formulation excluding the formulations acrylic-based soft multilayer resin is added in an amount exceeding 200 parts by weight, with the flexibility and melt bonded by extrusion to the surface of the molded article of the blend base resin A thermoplastic resin composition characterized in that it is used for   The number average molecular weight of the S block in the block copolymer (S-EB / S-S) ranges from 6,500 to 45,000, and the number average molecular weight of the EB / S block ranges from 40,000 to 275. The thermoplastic resin blend according to claim 1, wherein the total amount of styrene in the block copolymer (S-EB / S-S) is 35 to 70% by mass.   The thermoplastic resin blend according to claim 1 or 2, wherein the compatibilizing agent is a polyurethane block copolymer, and / or an acid-modified polyolefin, and / or an acid-modified styrene elastomer.   In the thermoplastic resin blend according to any one of claims 1 to 3, further, with respect to 100 parts by mass in total of the S-EB / S-S block copolymer and the softener in the blend, A thermoplastic resin composition, wherein an acrylic soft multilayer structure resin is added and mixed in an amount of 200 parts by mass or less.   In the thermoplastic resin blend according to any one of claims 1 to 4, further to a total of 100 parts by weight of the S-EB / S-S block copolymer and the softener in the blend, A thermoplastic resin composition, wherein acrylic modified polytetrafluoroethylene is added in an amount of 30 parts by mass or less. The thermoplastic resin composition is melted on the surface of the base resin by extruding the melt of the thermoplastic resin composition according to any one of claims 1 to 5 onto the surface of the base resin molded body. A composite material characterized by bonding.   The composite material according to claim 6, wherein the base resin is at least one polar resin selected from polycarbonate, styrene-based resin, polyvinyl chloride, modified polyphenylene ether, acrylic resin, polyamide, and polyester. A method for producing a composite material according to claim 6 or 7,
Using a two-layer extruder, while extruding the base resin from one extruder, extruding the thermoplastic resin composition from the other extruder, the base resin extruded from the one extruder, and the above A method for producing a composite material, comprising melt-bonding the thermoplastic resin compound extruded from the other extruder.

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