WO2015198883A1 - 滑り止め材 - Google Patents
滑り止め材 Download PDFInfo
- Publication number
- WO2015198883A1 WO2015198883A1 PCT/JP2015/066857 JP2015066857W WO2015198883A1 WO 2015198883 A1 WO2015198883 A1 WO 2015198883A1 JP 2015066857 W JP2015066857 W JP 2015066857W WO 2015198883 A1 WO2015198883 A1 WO 2015198883A1
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- thermoplastic elastomer
- molecular weight
- propylene
- slip material
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
- C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
- C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
Definitions
- the present invention relates to an anti-slip material comprising a thermoplastic elastomer composition, and more specifically, a thermoplastic elastomer having high mechanical strength and anti-slip property as an anti-slip material, and at the same time excellent in oil resistance and cleanability, and less in oil bleed.
- the present invention relates to an anti-slip material comprising the composition.
- thermoplastic elastomers have been used as anti-slip materials used for automobile interior parts, industrial machine parts, building materials, grips, and the like (Patent Documents 1 to 4).
- Thermoplastic elastomers are easy to recycle because they are not cross-linked, and do not generate toxic gases such as sulfide gas even when incinerated during disposal. From the viewpoint of energy saving, resource saving, and global environmental protection. It is advantageous.
- thermoplastic elastomer when a softening agent is added to the thermoplastic elastomer in order to give flexibility, bleeding of the softening agent component (oil bleed) may be a problem.
- oil bleed when this thermoplastic elastomer is used for automobile interior parts, oil resistance is required, and depending on the type of automobile interior parts, it is also required that liquids adhering to the parts can be easily cleaned (cleanability). It is done.
- an anti-slip material comprising a thermoplastic elastomer composition containing (a) a thermoplastic elastomer, (b) a softener, and (c) a propylene-based resin.
- a thermoplastic elastomer composition containing (a) a thermoplastic elastomer, (b) a softener, and (c) a propylene-based resin.
- the anti-slip material of the present invention has high mechanical strength and anti-slip properties, it can exhibit high durability and grip strength as an anti-slip material. At the same time, the anti-slip material of the present invention is excellent in oil resistance and cleanability when a liquid or the like adheres, has less oil bleed, and can suppress stickiness.
- the anti-slip material of the present invention comprises (a) a thermoplastic elastomer, (b) a softening agent, and (c) a thermoplastic elastomer composition containing a propylene-based resin.
- the thermoplastic elastomer (a) has a polymer block (A) made of a vinyl aromatic compound in the molecule, and a block copolymer having a polymer block (B) made of a conjugated diene compound in the molecule. It is comprised from the hydrogenated block copolymer obtained by hydrogenating.
- aromatic vinyl compound constituting the polymer block (A) examples include styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, and t-butylstyrene. 2,4-dimethylstyrene, 2,4,6-trimethylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene and the like.
- An aromatic vinyl compound may be used independently and may use 2 or more types together. Among these, it is preferable that a polymer block (A) is comprised from the structural unit derived from styrene.
- the polymer block (A) may contain a small amount of a structural unit derived from another copolymerizable monomer together with a structural unit derived from an aromatic vinyl compound.
- the proportion of structural units derived from other copolymerizable monomers is preferably 10% by weight or less, more preferably 5% by weight or less based on the weight of the polymer block (A). preferable.
- copolymerizable monomers examples include ionic polymerizable monomers such as 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether. These other copolymerizable monomers can be used alone or in combination of two or more.
- the polymer block (A) has a structural unit derived from another copolymerizable monomer such as an aromatic vinyl compound in addition to the structural unit derived from the aromatic vinyl compound, the bonding form thereof is random, tapered. Any form such as a shape may be used.
- Examples of the conjugated diene compound constituting the polymer block (B) include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, and the like. Can be mentioned. Among these, 1,3-butadiene, isoprene or a mixture thereof is preferable. A conjugated diene compound may be used independently and may use 2 or more types together.
- the microstructure of the conjugated diene block in the thermoplastic elastomer (a) is not particularly limited.
- the 1,4 bond amount is preferably 40% to 80%.
- the 1,4 bond amount is desirably 70% or more.
- the polymer block (B) may contain a small amount of a structural unit derived from another copolymerizable monomer together with a structural unit derived from a conjugated diene compound.
- the proportion of structural units derived from other copolymerizable monomers is preferably 30% by weight or less based on the weight of the polymer block (B), more preferably 10% by weight or less. preferable.
- Examples of other copolymerizable monomers include styrene, ⁇ -methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,3-dimethylstyrene, diphenylethylene, 1-vinylnaphthalene, Examples include monomers capable of anion polymerization such as aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene.
- aromatic vinyl compounds such as 4-propylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene.
- copolymerizable monomers can be used alone or in combination of two or more.
- the polymer block (B) has a structural unit derived from another copolymerizable monomer such as an aromatic vinyl compound in addition to the structural unit derived from the conjugated diene compound, the bonding form thereof is random, tapered, etc. Either of these may be used.
- the diene portion of the conjugated diene compound is usually 70% or more hydrogenated, preferably 90% or more hydrogenated.
- a hydrogenation rate of 70% or more is preferable because of excellent mechanical strength and weather resistance.
- the hydrogenated block copolymers preferably used in the present invention include styrene-ethylene / propylene / styrene type triblock copolymers, styrene / ethylene / butylene / styrene type triblock copolymers obtained by hydrogenation of 90% or more.
- Block copolymers styrene-ethylene / ethylene / propylene / styrene type triblock copolymers, etc., among others, styrene / ethylene / butylene / styrene type triblock copolymers, styrene / ethylene / ethylene / propylene / Styrenic triblock copolymers are preferred.
- the hydrogenation rate of the diene moiety in the polymer block (B) is determined by measuring the content of unsaturated double bonds in the polymer block (B) before and after hydrogenation by measuring iodine value, infrared spectrophotometer (IR), nuclear magnetic resonance ( 1 H-NMR), etc., and can be determined from the measured values.
- the content of the polymer block (A) in the thermoplastic elastomer (a) is preferably 5 to 70% by weight, more preferably 15 to 50% by weight, based on the total weight of the thermoplastic elastomer (a). It is preferable for the content of the polymer block (A) to be within this range since sufficient tensile strength can be imparted to the thermoplastic elastomer composition.
- the content of the polymer block (B) in the thermoplastic elastomer (a) is preferably 30 to 90% by weight, more preferably 50 to 80% by weight, based on the total weight of the thermoplastic elastomer (a). It is preferable for the content of the polymer block (B) to be within this range since sufficient rubber elasticity can be imparted to the thermoplastic elastomer composition.
- the weight average molecular weight Mw of the thermoplastic elastomer (a) is preferably 150,000 to 500,000, more preferably 200,000 to 400,000.
- the weight average molecular weight Mw of the thermoplastic elastomer (a) is 150,000 or more, it has sufficient mechanical strength, and at the same time, it is difficult to cause stress deformation in a high temperature environment (40 to 80 ° C.). Good compression set.
- the weight average molecular weight Mw of the thermoplastic elastomer (a) is 500,000 or less, the moldability is good.
- the number average molecular weight Mn and the weight average molecular weight Mw in the present invention can be measured by gel permeation chromatography and calculated by polystyrene conversion.
- thermoplastic elastomer (a) examples include TAIPOL manufactured by TSRC Corporation, and Septon manufactured by Kuraray Co., Ltd.
- softening agent (b) examples include process oils such as paraffinic, naphthenic, and aromatic oils, liquid paraffin, and the like. Among these, from the viewpoint of compatibility with the thermoplastic elastomer (a) and prevention of yellowing. Paraffinic and naphthenic oils are preferred, and paraffinic oils are more preferred. These may be used alone or in combination of two or more.
- the weight average molecular weight Mw of the softening agent (b) is preferably 700 or more, and more preferably 750 or more.
- the weight average molecular weight Mw of the softening agent (b) is preferably 1500 or less, and more preferably 1400 or less. If the weight average molecular weight Mw of the softener (b) is 700 or more, the anti-slip material has very little oil bleed, and has better fogging properties. If the weight average molecular weight Mw is 1500 or less, molding processing is performed. Good properties.
- the above-mentioned softener (b) is not particularly limited in its production, and can be produced by, for example, a conventionally known method.
- Representative commercial products of the softener (b) include, for example, Diana Process Oil PW series (paraffinic oil) manufactured by Idemitsu Kosan Co., Ltd., Diana Process Oil NR series (naphthenic oil) manufactured by Idemitsu Kosan Co., Ltd. NIBKO OIL PRODUCTS Co., Ltd. NOBEL process oil AB series (aromatic oil) and the like.
- Component (b) is blended in an amount of 150 to 200 parts by weight, preferably 170 to 190 parts by weight per 100 parts by weight of component (a).
- amount of component (b) is 150 parts by weight or more, flexibility and anti-slip properties are good, and when it is 200 parts by weight or less, mechanical strength and wear resistance are good.
- propylene-based resin (c) examples include polypropylene or a copolymer composed of propylene, and a homo-type polypropylene, a block type of propylene and a small amount of other ⁇ -olefin, or a random type of co-polymer. One or more selected from coalescence are used.
- the propylene-based resin (c) in the present invention is preferably a random type copolymer of propylene and other small amount of ⁇ -olefin from the viewpoint of oil resistance and low volatility.
- the propylene-based resin (c) is usually 100 to 90% by weight, preferably 99 to 92% by weight of structural units obtained from propylene, based on the total weight of the propylene-based resin (c), and is obtained from ⁇ -olefin. It is preferable that the structural unit is contained in a proportion of usually 0 to 10% by weight, preferably 1 to 8% by weight.
- ⁇ -olefins examples include ethylene and ⁇ -olefins having 4 to 20 carbon atoms such as ethylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 4-methyl-1-pentene. Can be mentioned. Two or more ⁇ -olefins can be used in combination. When the structural unit of ⁇ -olefin is within the above range, good rigidity can be maintained. Preferably, ethylene is used as the ⁇ -olefin from the viewpoint of imparting good mechanical properties. A propylene / ethylene random copolymer having an ethylene content of preferably 1 to 5% by weight, more preferably 2 to 4% by weight is desirable.
- the structural unit obtained from propylene in the propylene-based resin (c) and the structural unit obtained from ⁇ -olefin are measured using a nuclear magnetic resonance method ( 13 C-NMR) and obtained from the measured values. be able to.
- the MFR of the propylene resin (c) is usually 3 to 40 g / 10 minutes, preferably 4 to 38 g / 10 minutes, more preferably 5 to 35 g / 10 minutes. When the MFR is outside the above range, a problem occurs in formability.
- the MFR can be measured in accordance with JIS K7210 (230 ° C., 2.16 kg load).
- the propylene-based resin (c) has a molecular weight distribution Mw / Mn (weight average molecular weight / number average molecular weight) of 3.0 or less, preferably 2.9 or less, more preferably 2.85 or less, and usually 1 or more. Preferably, it is 1.01 or more.
- Mw / Mn weight average molecular weight / number average molecular weight
- the molecular weight distribution Mw / Mn can be controlled by adjusting polymerization conditions (polymerization temperature, polymerization pressure) during production, using a metallocene catalyst as a catalyst, and changing the type.
- the propylene-based resin (c) is not particularly limited in its production, and can be produced by, for example, a conventionally known method.
- a typical commercial item of the said propylene-type resin (c) the Nippon Polypro Co., Ltd. Wintech series is mentioned, for example.
- Component (c) is added in an amount of 25 to 50 parts by weight, preferably 30 to 45 parts by weight, per 100 parts by weight of component (a).
- amount of component (c) is 25 parts by weight or more, moldability and cleanability are good, and when it is 50 parts by weight or less, slip resistance is good.
- the anti-slip material of the present invention may further contain an additive (d) in addition to the components (a), (b) and (c) as necessary.
- Examples of the additive (d) include an antioxidant, a heat stabilizer, a light stabilizer, an ultraviolet absorber, an inorganic filler, a crystal nucleating agent, a foaming agent, a colorant, an antiblocking agent, a lubricant, and an antistatic agent.
- antioxidants examples include 2,6-ditert-butyl-p-cresol, 2,6-ditert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4′-dihydroxydiphenyl, Tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, tetrakis [methylene-3- (3,5-ditert-butyl-4-hydroxyphenyl) propionate] methane, 3,9-bis ⁇ 2- [3- (3-tert-Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl ⁇ -2,4,8,10-tetraoxaspiro-5,5-undecane
- Phenolic antioxidants such as phosphite antioxidants, thioether antioxidants and the like. Of these, phenolic antioxidants and phosphite antioxidants are preferred.
- the blending amount of the antioxidant is preferably 0.01 to 1 part by weight, more preferably 0.1 to 0.5 part by weight with respect to 100 parts by weight of the component (a).
- polyethylene, styrene resin, or inorganic fillers such as calcium carbonate, talc, carbon black, titanium oxide, silica, clay, barium sulfate, and magnesium carbonate are used for the purpose of improving and increasing the weather resistance depending on the application. Can be mixed.
- inorganic or organic fibrous materials such as glass fibers and carbon fibers can be mixed.
- thermoplastic elastomer composition used in the present invention can be crosslinked in the presence of a peroxide and a crosslinking aid.
- the peroxide include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di ( tert-butylperoxy) hexyne-3,1,3-bis (tert-butylperoxyisopropyl) benzene, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, n-butyl -4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butylperoxybenzoate, tert-but
- crosslinking aid for example, polyfunctionality such as divinylbenzene, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate
- Multifunctional vinyl monomers such as methacrylate monomers, vinyl butyrate or vinyl stearate can be formulated.
- the A-type durometer hardness is preferably adjusted to be 10 to 80 degrees from the viewpoint of cleanability and anti-slip properties, and preferably 10 to 50 degrees. It is more preferable to adjust, and even more preferable to adjust so as to be 20 to 50 degrees.
- the measuring method of A type durometer hardness is mentioned later.
- thermoplastic elastomer composition in the present invention a conventional resin composition or a rubber composition can be used.
- the set temperature of the processing machine can be arbitrarily selected from 150 ° C. to 300 ° C., and the manufacturing method is not limited.
- the anti-slip material of the present invention can be obtained by subjecting the thermoplastic elastomer composition to a conventionally known method such as hot pressing, injection molding, extrusion molding, or calendar molding. Furthermore, you may use the shaping
- the thermoplastic elastomer composition according to the present invention and a hard resin such as a propylene-based resin can be integrally formed by composite injection molding using two kinds of materials such as two-color molding and insert molding, or multilayer extrusion molding.
- the shape of the anti-slip material thus obtained is arbitrary, and examples thereof include a circle and a polygon.
- Test method 1. Hardness Using an injection molded sheet (thickness: 6 mm) produced using an injection molding machine according to the formulation shown in Table 1, A type durometer hardness (spring type) was measured by a method in accordance with JIS K6253. After contacting the hardness tester with the test piece, the value after 3 seconds was read.
- Breaking strength and breaking elongation The breaking strength and breaking elongation of an injection molded sheet produced using an injection molding machine according to the formulation shown in Table 1 were measured. The measurement was based on JIS K6251 and a dumbbell shape No. 3 was punched out (TD direction) from an injection molded sheet produced using the above-described injection molding machine, and used as a test piece. These test pieces were subjected to a tensile strength test (tensile speed: 500 mm / min) using a tensile testing machine (Autograph AG-500NI manufactured by Shimadzu Corporation) in accordance with JIS K7311. The stress at that time was measured as the breaking strength.
- Static friction coefficient The static friction coefficient of an injection molded sheet produced using an injection molding machine according to the formulation shown in Table 1 was measured. The measurement is based on JIS K7125, and if the coefficient of static friction is 3 or more, the slip resistance is good.
- Oil resistance test was performed on an injection molded sheet produced using an injection molding machine in accordance with the formulation shown in Table 1. From an injection molded sheet produced using an injection molding machine, a circular sheet having a diameter of 120 mm and 2 mm was punched out to obtain a test piece. A cylindrical enclosure having an inner diameter of 41 mm was placed on these test pieces, and a 150 g weight was placed on the enclosure. On the test piece in this enclosure, 1.5 g of liquid paraffin (manufactured by Nacalai Tesque, product code: 26132-35, specific gravity: 0.82-0.845) was dropped, and then heated at 80 ° C. for 24 hours. . After heating, the dimensional change rate of the thickness of the test piece before and after the test was measured. If the dimensional change rate of the thickness of the test piece before and after the test is 24.0% or less, the oil resistance is good.
- Oil Bleed An oil bleed test was performed on an injection molded sheet produced using an injection molding machine according to the formulation shown in Table 1. A rectangular sheet of 50 mm ⁇ 100 mm and thickness 2 mm was punched out from an injection molded sheet produced using an injection molding machine to obtain a test piece. These test pieces were sandwiched between paper (New Sun Ace R100 manufactured by Huayang Paper Industry Co., Ltd., size: 70 mm ⁇ 120 mm) and heated for 1 week in a thermostatic bath set at 100 ° C. (Davier specs gear oven, GPH-200). did. After heating, it was confirmed that the oil soaked into the paper.
- paper New Sun Ace R100 manufactured by Huayang Paper Industry Co., Ltd., size: 70 mm ⁇ 120 mm
- thermoplastic elastomer When used for automobile interior parts, the softening agent component volatilizes due to long-term use, which may cause a problem such as fogging phenomenon that causes fogging of the window glass.
- a fogging test was performed on an injection molded sheet produced using an injection molding machine according to the formulation shown in Table 1. The test was based on ISO 6452 and DIN 75201, and a circular sheet having a diameter of 80 mm and a thickness of 2 mm was punched out from an injection-molded sheet produced using the above-described injection molding machine to obtain a test piece.
- test pieces were put into a tall beaker placed in an oil bath set at 80 ° C., and volatile components were adhered to a glass plate set at 20 ° C. for 3 hours. Based on the light transmittance of the glass plate in a state where no test piece was put in, the light transmission ratio of the glass plate to which the volatile component adhered was measured. Glossiness is measured using True GLOSS GM-26PRO manufactured by Murakami Color Research Laboratory Co., Ltd., and optical conditions are in accordance with ISO 2813, ASTM D523, and JIS Z8741, with a measurement angle of 60 ° and a measurement area. Was 14 mm ⁇ 22 mm, and the measurement aperture was 26 mm ⁇ 40 mm.
- the anti-slip material made of the thermoplastic elastomer composition of the present invention in Examples 1 to 4 has high breaking strength and excellent mechanical strength. Moreover, the coefficient of static friction was high, it had sufficient anti-slip properties, and good results were shown in the evaluation of oil resistance, oil bleed and cleanability. Furthermore, when the weight average molecular weight Mw of the softening agent (b) is within a predetermined range, good results were obtained in the evaluation of fogging properties. On the other hand, Comparative Examples 1 to 5 did not show good results in the above evaluation because they did not contain the predetermined propylene resin (c) in the present invention. In Comparative Example 6 consisting only of propylene-based resin, good results are not shown in the above evaluation, and the object of the present invention cannot be achieved.
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Abstract
Description
すなわち、本発明には、以下の好適な実施態様が含まれる。
〔1〕(a)分子中にビニル芳香族化合物からなる重合体ブロック(A)を有し、かつ、分子中に共役ジエン化合物からなる重合体ブロック(B)を有するブロック共重合体を水素添加して得られる水素添加ブロック共重合体から構成される熱可塑性エラストマー100重量部、
(b)軟化剤150~200重量部、および
(c)分子量分布Mw/Mn(重量平均分子量/数平均分子量)が3.0以下であるプロピレン系樹脂25~50重量部
を含有する熱可塑性エラストマー組成物からなる滑り止め材。
〔2〕軟化剤(b)は、700~1500の重量平均分子量Mwを有する、上記〔1〕に記載の滑り止め材。
〔3〕軟化剤(b)は、パラフィン系オイルである、上記〔1〕または〔2〕に記載の滑り止め材。
〔4〕プロピレン系樹脂(c)は、プロピレン/エチレンランダム共重合体である、上記〔1〕~〔3〕のいずれかに記載の滑り止め材。
本発明の滑り止め材は、(a)熱可塑性エラストマー、(b)軟化剤、および(c)プロピレン系樹脂を含有する熱可塑性エラストマー組成物からなる。
上記熱可塑性エラストマー(a)は、分子中にビニル芳香族化合物からなる重合体ブロック(A)を有し、かつ、分子中に共役ジエン化合物からなる重合体ブロック(B)を有するブロック共重合体を水素添加して得られる水素添加ブロック共重合体から構成される。
成分(a)
・(a-1)TSRC Corporation製TAIPOL6151、Mw:260000
・(a-2)(株)クラレ製セプトン4055、Mw:280000
・(b-1)出光興産(株)製ダイアナプロセスオイルPW-380、パラフィン系オイル、Mw:1300
・(b-2)出光興産(株)製ダイアナプロセスオイルPW-90、パラフィン系オイル、Mw:790
・(b-3)出光興産(株)製ダイアナプロセスオイルPW-32、パラフィン系オイル、Mw:510
・(c-1)日本ポリプロ(株)製BC-1、MFR(230℃、2.16kg荷重):30、Mw/Mn:15.7
・(c-2)日本ポリプロ(株)製ウィンテックWFX4T、MFR(230℃、2.16kg荷重):7.0、Mw/Mn:2.8
・(c-3)(株)プライムポリマー製F327、MFR(230℃、2.16kg):30、Mw/Mn:4.6
・(c-4)日本ポリプロ(株)製ノバテックLDPE LJ8041、MFR(230℃、2.16kg荷重):23、密度:0.918g/cm3、Mw/Mn:8.4
フェノール系酸化防止剤、(株)ADEKA製アデカスタブAO-80
1.硬度
表1に示す配合に従って射出成形機を用いて作製した射出成形シート(厚み:6mm)を用いて、JIS K6253準拠の方法によるAタイプデューロメータ硬さ(スプリング式)を測定した。硬度計を試験片に接触させた後、3秒後の数値を読み取った。
表1に示す配合に従って射出成形機を用いて作製した射出成形シートの破断強度、破断伸びを測定した。測定はJIS K6251に準拠し、前述の射出成形機を用いて作製した射出成形シートからダンベル形状3号形を打ち抜き(TD方向)、試験片とした。これらの試験片について、JIS K7311に準拠し、引張試験機((株)島津製作所製オートグラフAG-500NI)を用いて引張強度試験(引張速度:500mm/分)を行い、破断時の伸び、およびその際の応力を破断強度として測定した。
表1に示す配合に従って射出成形機を用いて作製した射出成形シートの静摩擦係数を測定した。測定はJIS K7125に準拠し、静摩擦係数が3以上の数値であれば、防滑性が良好である。
表1に示す配合に従って射出成形機を用いて作製した射出成形シートの耐油性試験を行った。射出成形機を用いて作製した射出成形シートから、直径120mm、2mmの円形シートを打ち抜き、試験片とした。これらの試験片の上に、内径41mmの円筒状の囲いをのせ、さらに囲いの上に150gの重りをのせた。この囲い中の試験片上に、流動パラフィン(ナカライテスク(株)製、商品コード:26132-35、比重:0.82~0.845)1.5gを滴下した後、80℃で24時間加熱した。加熱後、試験前後の試験片の厚みの寸法変化率を測定した。
試験前後の試験片の厚みの寸法変化率が24.0%以下であれば、耐油性が良好である。
表1に示す配合に従って射出成形機を用いて作製した射出成形シートのオイルブリード試験を行った。射出成形機を用いて作製した射出成形シートから、50mm×100mm、厚み2mmの長方形シートを打ち抜き、試験片とした。これらの試験片を、紙(華陽紙業(株)製新サンエースR100、サイズ:70mm×120mm)で挟み、100℃に設定した恒温槽(ダバイエスペック製ギアオーブン、GPH-200)において1週間加熱した。加熱後、紙へのオイルの染み込みを確認した。
オイルブリードの評価は、オイルの染み込みが全く認められない場合およびわずかに求められるが目立たない場合を○、やや著しい場合を△、かなり著しい場合を×とした。
表1に示す配合に従って射出成形機を用いて作製した射出成形シートの清掃性評価を行った。射出成形機を用いて作製した射出成形シートから、50mm×100mm、厚み2mmの長方形シートを打ち抜き、試験片とした。これらの試験片の表面に、(株)石原製の珪砂5号を2g付着させ、藤原産業(株)製SK11竹ブラシ曲柄ナイロン毛No.17ですべて払い落とす際の回数を評価した。
ブラシで払い落とす回数が15回以下であれば、清掃性が良好である。
熱可塑性エラストマーを自動車内装部品に使用する場合、長期間の使用によって軟化剤成分が揮発し、窓ガラスの曇りが生じるフォギング現象といった問題が生じることがある。フォギング現象に対する耐性を評価するため、表1に示す配合に従って射出成形機を用いて作製した射出成形シートのフォギング性試験を行った。試験はISO 6452、DIN 75201に準拠し、前述の射出成形機を用いて作製した射出成形シートから、直径80mm、厚み2mmの円形シートを打ち抜き、試験片とした。これらの試験片を、80℃に設定したオイルバスに入れたトールビーカー中に投入し、20℃に設定したガラス板に揮発成分を3時間付着させた。試験片を投入しない状態でのガラス板の光透過性を基準とし、揮発成分が付着したガラス板の光透過性の透過比率を測定した。なお、光沢度測定は、(株)村上色彩技術研究所製のTrue GLOSS GM-26PROを用いて行い、光学条件は、ISO 2813、ASTM D523、JIS Z8741に準じ、測定角度を60°、測定面積を14mm×22mm、測定開口を26mm×40mmとした。
Claims (4)
- (a)分子中にビニル芳香族化合物からなる重合体ブロック(A)を有し、かつ、分子中に共役ジエン化合物からなる重合体ブロック(B)を有するブロック共重合体を水素添加して得られる水素添加ブロック共重合体から構成される熱可塑性エラストマー100重量部、
(b)軟化剤150~200重量部、および
(c)分子量分布Mw/Mn(重量平均分子量/数平均分子量)が3.0以下であるプロピレン系樹脂25~50重量部
を含有する熱可塑性エラストマー組成物からなる滑り止め材。
- 軟化剤(b)は、700~1500の重量平均分子量Mwを有する、請求項1に記載の滑り止め材。
- 軟化剤(b)は、パラフィン系オイルである、請求項1または2に記載の滑り止め材。
- プロピレン系樹脂(c)は、プロピレン/エチレンランダム共重合体である、請求項1~3のいずれかに記載の滑り止め材。
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