JP5288760B2 - 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 molded body, and a melt-bonded molded body of the thermoplastic resin compound to the surface of the base resin molded body. The present invention relates to a composite material and a method for producing the 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. are soft to the touch, elastic, vibration-proof and sound-proof. In order to impart properties, damage prevention functions, etc., a resin molded body having flexibility and elasticity is joined.

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, it has been proposed to blend polar elastomers such as polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers as means for improving the melt adhesion of the styrene-based elastomer.

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-mentioned conventional elastomer compounding, a drawdown phenomenon in which the elastomer melt hangs down from the die of the extruder during extrusion molding, or a so-called `` eye phenomenon '' in which the solidified material of the elastomer melt adheres to the die. There is a risk.

The present invention has an object to prevent the conventional drawdown phenomenon and the occurrence of a phenomenon in the eyes. As means for solving the above problems, a styrenic polymer (S) block and a conjugated diene compound polymer (B ) The ratio of the styrene-based elastomer, which is a block copolymer that is made of hydrogen and is hydrogenated, and the softener having a kinematic viscosity at 40 ° C. of 40 cSt or more and 1000 cSt or less is 30:70 to 70:30 mass ratio. 120 to 350 parts by mass of polyurethane-based thermoplastic elastomer, 10 to 150 parts by mass of compatibilizer, 0.1 to 30 parts by mass of acrylic-modified polytetrafluoroethylene , and 0 to 30 parts by mass of acrylic soft multilayer structure resin with respect to 100 parts by mass of the mixture a formulation was added and mixed in an amount of 250 parts by weight, weight average molecular weight of the styrene-based elastomer is 10 , There is provided a thermoplastic blend in the range of 000 (100,000) or more.

Styrene content above Symbol styrenic elastomer is desirably 10 to 35 wt%.

Furthermore, the compatibilizing agent is preferably a polyurethane block copolymer, and / or an acid-modified polyolefin, and / or an acid-modified styrene elastomer.

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In the present invention, there is further provided a composite material obtained by melt-bonding the molded body of the thermoplastic resin compound to the molded body of the base resin.

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 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]
The thermoplastic resin composition of the present invention comprises a styrene polymer (S) block, a conjugated diene compound polymer (B), and a styrene polymer (S) block. The styrene-based elastomer is a gel obtained by adding a softening agent having a good compatibility with the styrene-based elastomer and a kinematic viscosity at 40 ° C. of 40 cSt to 1000 cSt. Smoothening and adjusting the hardness, and further adding a polar resin polyurethane-based thermoplastic elastomer (TPU) to improve the melt adhesion with the base resin, but polyurethane block copolymer and acid Add a compatibilizing agent such as a modified polyolefin or acid-modified styrene elastomer to uniformly dissolve the styrene elastomer and TPU, Ya to prevent the occurrence of phenomena, and roughness of the resulting molded article surface is prevented to provide an excellent appearance. Furthermore, acrylic modified polytetrafluoroethylene (acryl modified PTFE) is added to the thermoplastic resin blend 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 die that the melt of the thermoplastic resin composition hangs down from the die of the extruder during extrusion molding. In addition, it suppresses the occurrence of a phenomenon in which the solidified product of the melt of the thermoplastic resin compound is fixed.
Furthermore, if desired, when an acrylic soft multilayer structure resin is added to the thermoplastic resin composition of the present invention, the viscosity of the melt of the thermoplastic resin composition increases, and the drawdown phenomenon and the phenomenon in the eyes are further suppressed, In addition, weather resistance is improved.

〔effect〕
The thermoplastic resin composition of the present invention exhibits good melt adhesion particularly to a polar base resin, and the thermoplastic resin composition exhibits a drawdown phenomenon and a phenomenon in the eyes during extrusion molding. Does not occur.

The present invention is described in detail below.
[Styrene elastomer]
The styrene-based elastomer used in the present invention is composed of a styrene-based polymer (S) block and a conjugated diene compound polymer (B), and the conjugated diene compound polymer (B) block is partially Or all are hydrogenated.
Examples of the styrene polymer (S) block include styrene, o-methylstyrene, p-methylstyrene, p-tertiarybutylstyrene, 1,3-dimethylstyrene, α-methylstyrene, vinylnaphthalene, and vinylanthracene. It is a polymer block of a styrene monomer such as.
The conjugated diene compound polymer (B) block is a polymer block of a conjugated diene compound such as butadiene, isoprene or 1,3-pentadiene.
The styrene-based elastomer has a mass average molecular weight of 100,000 or more, more preferably 200,000 or more, and a styrene content of 10 to 35% by mass. When the mass average molecular weight of the styrene elastomer is less than 100,000, the resulting thermoplastic resin composition may cause a drawdown phenomenon during extrusion molding, and the styrene content is less than 10% by mass. In some cases, the resulting thermoplastic resin blend is inferior in heat resistance, and when it exceeds 35% by mass, it becomes inferior in rubber elasticity.
Examples of the styrene elastomer used in the present invention include styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (SEPS), and styrene-ethylene-ethylene-propylene. -Styrene block copolymer (SEEPS), styrene-butadiene rubber (SBR), acrylonitrile-butadiene rubber (NBR), pyridine-butadiene rubber, styrene-isoprene rubber (SIR), styrene-ethylene copolymer, polystyrene-polybutadiene- Polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), poly (α-methylstyrene) -polybutadiene-poly (α-methylstyrene) (α-MeSBα-MeS), poly (α-methylstyrene) Len) -polyisoprene-poly (α-methylstyrene), ethylene-propylene copolymer (EP), butadiene-styrene copolymer (EP), styrene-chloroprene rubber (SCR), styrene-butadiene-styrene (SBS) Examples thereof include a copolymer and a styrene-isoprene-styrene (SIS) copolymer.

[Softener]
Examples of the softener used in the thermoplastic resin composition of the present invention include rubber softeners such as paraffinic oil, naphthenic oil, and aromatic oil, and the kinematic viscosity is 40 cSt or more and 1000 cSt or less at 40 ° C. Choose one. More preferably, one having a kinematic viscosity of 50 cSt or more and 600 cSt or less at 40 ° C. is selected. When the kinematic viscosity of the softening agent is less than 40 cSt at 40 ° C., a drawdown phenomenon occurs when the thermoplastic resin composition is molded.

[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, and the long chain polyol includes a polyether polyol or polyester polyol having a molecular weight of 500 to 10,000. Are used, and examples of the polyether polyol include polyalkylene glycol, and examples of the polyester polyol include polyalkylene adipate, polycaprolactone, and polycarbonate.

[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 styrene elastomer include a styrene polymer block and a styrene elastomer that is a hydrogenated conjugated diene compound such as butadiene, isoprene, or 1,3 pentadiene, maleic anhydride or the above dicarboxylic acid, monocarboxylic acid, and the like. There are acids or dicarboxylic acid or monocarboxylic acid esters, amides, imides and the like added thereto.

[Acrylic modified PTFE]
The acrylic-modified PTFE used for 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.

[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 (Japanese Patent No. 334208).
The acrylic soft multilayer structure resin is desirably added in an amount of 250 parts by mass or less with respect to 100 parts by mass in total of the styrene elastomer and the softening agent in the thermoplastic resin blend. When the addition amount exceeds 250 parts by mass, the effect on the draw-down phenomenon and the eye phenomenon reaches its peak, and the fusion strength with the base resin tends to decrease.

[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 (PP) such as a propylene-ethylene block copolymer, 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. As the filler,
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,
Inorganic fillers such as white carbon, carbon black, iron powder, aluminum powder, stone powder, blast furnace slag, fly ash, cement, zirconia powder, linter, linen, sisal,
Organic fillers such as wood flour, palm flour, walnut flour, starch, wheat flour, rice flour, or natural fibers such as cotton, hemp, wool, polyamide fiber, polyester fiber, acrylic fiber, viscose fiber,
Examples thereof include organic filler fibers such as acetate fibers, asbestos fibers, glass fibers, carbon fibers, ceramic fibers, metal fibers, whisker fibers, and the like, and particularly preferable examples include talc and calcium carbonate. By adding the filler, the effect of improving the drawdown 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 the styrene elastomer and the softening agent is set in a range of 30:70 to 70:30 (mass ratio). When more softening agent is mixed than the above range, the fusion strength of the resin compound with respect to the polar base resin is lowered, and at the time of molding, a drawdown phenomenon or a defect in the eyes occurs. However, when a small amount of softening agent is added, it becomes difficult to gel the styrene-based elastomer.
In order to suppress the occurrence of the drawdown phenomenon, 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 120 to 350 parts by mass with respect to 100 parts by mass in total of the styrene-based elastomer 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, while when TPU is added in an amount greater than the above range, the drawdown is reduced. Phenomena and phenomena occur in the eyes and the weather resistance of the resin composition also deteriorates.
The compatibilizer is added in the range of 10 to 150 parts by mass with respect to 100 parts by mass in total of the styrene elastomer and the softener. 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.
The acrylic-modified PTFE is added in the range of 0.1 to 30 parts by mass with respect to 100 parts by mass in total of the styrenic elastomer and the 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.
When the acrylic soft multilayer structure resin is added, it is added in an amount of 250 parts by mass or less with respect to a total of 100 parts by mass of the styrene elastomer and the softening agent. The addition of the acrylic soft multilayer structure resin suppresses the occurrence of a drawdown phenomenon or a phenomenon in the eyes, but if the addition amount exceeds 250 parts by mass, the fusion strength with the polar base resin is lowered and the odor is increased. .

  PP improves the pellet moldability of the resin composition and is added for the purpose of adjusting the hardness. The addition amount is added in an amount of 100 parts by mass or less with respect to 100 parts by mass in total of the styrenic elastomer 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 at the time of molding, but if the addition amount in the resin compound exceeds 20% by mass, the fusion strength decreases.

[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 the styrene elastomer, Septon 4099 (trade name, manufactured by Kuraray Co., Ltd .: styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS)) and Kraton G1657 (trade name, manufactured by Kraton Polymer Co., Ltd .: styrene-ethylene-butylene) A block copolymer (SEBS) was used. The SEEPS has a mass average molecular weight of 422,000 and a styrene content of 30% by mass. The SEBS has a mass average molecular weight of 118,000 and a styrene content of 13% by mass.
As a comparative styrene elastomer, Kraton G1652 (trade name, manufactured by Kraton Polymer Co., Ltd .: styrene-ethylene-butylene block copolymer (SEBS)) was used. The SEBS has a mass average molecular weight of 85,560,000 (<100,000) and a styrene content of 29% 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 Tables 3 and 4 show results of formulation and performance evaluation of Comparative Examples 1 to 11.

The compositions of Examples 1 to 16 in Tables 1 and 2 are within the scope of the present invention, and the fusion strength clears 5 (N / mm ² ) or more, the eyes are few, and the drawdown phenomenon occurs. The appearance of the molded product is also good.

  Comparative Example 1 is a sample using SEBS having a molecular weight of 85,660,000 (<100,000) as a styrene-based elastomer. A drawdown phenomenon occurs compared to each sample of the examples, and the surface of the molded product is slightly rough. And the occurrence of fuzz due to poor melting.

  Comparative Example 2 is a sample using a softener with a kinematic viscosity of 32.3 cSt at 40 ° C. (<40 cSt). Compared with each sample of the Example, a slight drawdown phenomenon was observed, and the surface of the molded product was slightly Generation of irregularities due to rough skin and poor melting.

Comparative Example 3 styrene elastomer: mixing ratio 90:10 weight ratio of the softening agent (<70: 30) as a sample and the addition amount insufficient softening agent, die drool is increased compared to the samples of Examples In addition, the surface of the molded product is slightly rough and melted due to poor melting.

Comparative Example 4 Styrene-based elastomer: ten ninety mass ratio the mixing ratio of the softener (> 30: 70) as a sample was added Excessive amount of softener, fusion strength is 3.5 N / mm ² (< 5N / mm ² ), a low value, a large number of eyes and spots, a drawdown phenomenon, and the appearance of rough skin and melting defects on the surface of the molded product.

Comparative Example 5 was a sample in which the amount of TPU added was less than 120 parts by mass (100 parts by mass) with respect to 100 parts by mass of the total amount of styrene elastomer and softener, and the fusion strength was 4.5 N / It showed a low value of mm ² (<5 N / mm ² ).

  Comparative Example 6 is a sample in which the amount of TPU added is more than 350 parts by mass (400 parts by mass) with respect to 100 parts by mass of the total amount of styrene elastomer and softening agent. The phenomenon is noticeable.

  Comparative Example 7 is a sample with no compatibilizing agent added, has more eyes than the samples of the Examples, causes some rough skin on the surface of the molded product, and generates slight flaws due to poor melting. It can be seen.

  Comparative Example 8 is a sample in which the addition amount of the compatibilizer is added in an amount exceeding 200 parts by mass (200 parts by mass) with respect to 100 parts by mass of the total amount of the styrene elastomer and the softening agent, and the drawdown phenomenon Is slightly seen.

Comparative Example 9 is a sample of additive-free acrylic-modified PTFE, fusion strength is ^{4.9N / mm 2 (<5N /} mm 2) and lower die drool many occurs, also drawdown phenomenon observed significantly .

Comparative Example 10 is a sample in which the amount of acrylic modified PTFE added is more than 20 parts by mass (40 parts by mass) with respect to 100 parts by mass of the total amount of styrene elastomer and softener. The strength is as low as 4.2 N / mm ² (<5 N / mm ² ), and the surface of the molded product is markedly rough and melted due to poor melting.

Comparative Example 11 is a sample in which the addition amount of the acrylic soft multilayer structure resin is added in an amount (300 parts by mass) exceeding 250 parts by mass with respect to 100 parts by mass of the total amount of the styrene elastomer and the softening agent. The fusion strength is as low as 4.8 N / mm ² (<5 N / mm ² ), and the surface of the molded product is somewhat rough and the appearance of irregularities is slightly observed.

  The thermoplastic resin composition of the present invention is particularly excellent in melt adhesiveness with a polar base resin, and has no eye-drawing 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 (6)

A styrene elastomer that is a hydrogenated block copolymer comprising a styrene polymer (S) block and a conjugated diene compound polymer (B) block, and a kinematic viscosity at 40 ° C. of 40 cSt or more and 1000 cSt or less Is 100-mass part of a mixture of 30:70 to 70:30 mass ratio of the softener, and 120 to 350 parts by mass of a polyurethane-based thermoplastic elastomer, 10 to 150 parts by mass of a compatibilizer, and acrylic-modified polytetrafluoro. 0.1 to 30 parts by mass of ethylene, and a mixture obtained by adding and mixing acrylic soft multilayer structure resin in an amount of 0 to 250 parts by mass , and the mass average molecular weight of the styrene elastomer is 100,000 (100,000) or more. A thermoplastic resin composition characterized by being in the range of A thermoplastic resin blend as claimed in claim 1 styrene content above Symbol styrene elastomer is 10 to 35 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. A composite material, wherein a molded body of the thermoplastic resin composition according to any one of claims 1 to 3 is melt bonded to a molded body of a base resin. The composite material according to claim 4 , wherein the base resin is at least one polar resin selected from polycarbonate, styrene resin, polyvinyl chloride, modified polyphenylene ether, acrylic resin, polyamide, and polyester. A method for producing a composite material according to claim 4 or 5 ,
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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