JP2000143934A5 - - Google Patents

Description

[0001]
[Technical field to which the invention belongs]
The present invention is addition polymerized block copolymer, modified polyolefin resin, relates to a thermoplastic elastomer composition comprising a polyurethane elastomer and paraffinic oils. Since the thermoplastic elastomer composition of the present invention has excellent adhesiveness to a polar resin and has good rubber properties, oil resistance, and moldability, it can be molded by itself or together. By molding by a method such as extrusion or multi-layer molding, it can be widely used for various purposes such as automobile interior parts, home appliance parts, sporting goods, miscellaneous goods, and stationery.

Generally, as a method for producing these laminates, a method of adhering the same or different materials with an adhesive, or a method of co-extruding or adhering by multi-layer molding without using an adhesive can be mentioned. it can. However, sufficient adhesive strength may not be obtained depending on the type of materials to be laminated or a combination thereof. In order to bond materials that are not adhesive to each other by co-extrusion without using an adhesive, a material that is adhesive to both materials is used as an intermediate adhesive layer, but sufficient adhesion is performed. There is a problem that the strength may not be obtained, or the adhesive strength is inferior in durability and water resistance. Various techniques aimed at solving these problems have been conventionally proposed, and a resin composition in which a polyurethane elastomer is blended with an addition polymerization block copolymer is known (Japanese Patent Laid-Open No. 6-1078998). , Japanese Patent Application Laid-Open No. 8-72204, etc.). However, this resin composition, for compatibility of the addition polymerized block copolymer and a poly urethane elastomer is poor, the mechanical strength is low, especially the surface of the release and adhesion in laminates obtained by multi-layer injection molding Problems such as force variation are likely to occur.

In the above-mentioned polybutadiene block which can be a block constituting the polymer block (B) mainly composed of a conjugated diene compound, 70 to 20 mol% of the butadiene unit, particularly 65 to 40 mol%, is 2- before the hydrogenation. butene-1,4-diyl group -; a _{(-CH 2 -CH = CH-CH} 2 1,4- bond butadiene unit), 30 to 80 mol%, in particular 35 to 60 mol% ethylene vinyl group [ -CH (CH = CH ₂ ) -CH _2- ; 1,2-bonded butadiene unit] is preferable.
If the amount of 1,4-bond in the polybutadiene block deviates from the above-mentioned range of 70 to 20 mol%, the rubber physical characteristics may be deteriorated.

Addition polymerized block copolymer (I), from the viewpoint of heat resistance and weather resistance of the thermoplastic elastomer composition becomes excellent, unsaturated double in mainly Na Ru polymer block (B) from the conjugated diene compound It is preferred that some or all of the heavy bonds are hydrogenated. Preferably the hydrogenation ratio is 50 mol% or more of that time primarily name Ru polymer block of a conjugated diene compound (B), more preferably 60 mol% or more, 80 mol% or more More preferred.
The addition polymerized block copolymer (I) mainly composed of an aromatic vinyl compound in polymer block (A), binding forms of mainly made polymer block of a conjugated diene compound (B) is not particularly limited, a straight It may be chain-like, branched, radial, or a bond form in which two or more of them are combined, and a linear bond form is preferable.

The addition polymerization block copolymer (I) has a structure in which a polymer block (A) mainly composed of an aromatic vinyl compound and a polymer block (B) mainly composed of a conjugated diene compound are linearly bonded. If so, a diblock structure represented by AB, a triblock structure represented by ABA or BAB, ABAB or BAB- A tetrablock structure represented by A or a polyblock structure in which five or more A and B are linearly bonded can be adopted. Among them, a diblock structure represented by AB or a triblock structure represented by ABA is preferable from the viewpoints of elasticity, mechanical properties, melt adhesiveness, handleability, and the like. ..

Addition polymerized block copolymer for (I), [mainly of polymer block of an aromatic vinyl compound (A)]: the weight ratio of [mainly of polymer block of a conjugated diene compound (B)] is 1: 9 The ratio of ~ 9: 1 is preferable from the viewpoint of improving the heat resistance and mechanical properties of the thermoplastic elastomer composition and the molded product obtained from the thermoplastic elastomer composition.
Furthermore, addition polymerization-based block copolymer for (I), the molecular weight of predominantly polymer blocks of an aromatic vinyl compound (A) and mainly comprising polymer block of a conjugated diene compound (B) is not particularly limited, hydrogen In the state before addition, the number average molecular weight of the polymer block (A) mainly composed of the aromatic vinyl compound is in the range of 2,500 to 100,000, and that of the polymer block (B) mainly composed of the conjugated diene compound. It is preferable that the number average molecular weight is in the range of 10,000 to 200,000 from the viewpoint that the tensile elongation at break, the tensile strength at break, and the like of the thermoplastic elastomer composition are excellent.

The number-average molecular weight of the addition polymerization-based block copolymer (I), with hydrogenation previous state, in the range of 15,00 0 300,000, mechanical characteristics, terms of moldability Is preferable.
The number average molecular weight referred to in the present specification means a value obtained from a standard polystyrene inspection line by a gel permeation chromatography (GPC) method.
The addition polymerization type block copolymer (I) used in the thermoplastic elastomer composition of the present invention is a block copolymer having the above-mentioned block structure and generally not having a functional group such as a hydroxyl group at the molecular terminal.

Method as a method of introducing a functional group having polarity to the polyolefin resin, for example, in preparing the poly olefin resin, the alpha, copolymerizing or radical addition to β- unsaturated carboxylic acid and / or its derivatives Can be mentioned.
alpha, as the beta-unsaturated carboxylic acid and / or its derivatives, acrylic acid, alpha such as methacrylic acid, beta-unsaturated monocarboxylic acid; maleic acid, Lee itaconic acid, such as phthalic acid alpha, beta-unsaturated dicarboxylic acid; glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, alpha, such as hydroxyethyl methacrylate, beta-unsaturated monocarboxylic acid ester; maleic acid, anhydrous itaconic acid, alpha, such as phthalic anhydride, beta-unsaturated dicarboxylic acid anhydrides such may be mentioned, among this, maleic anhydride, anhydrous itaconic acid, alpha, such as phthalic anhydride, beta-unsaturated dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, hydroxyethyl acrylate, hydroxypropyl Α, β-Unsaturated monocarboxylic acid esters such as ethyl methacrylate are preferable.
The polar functional group is preferably introduced at a ratio of 0.01 to 10 mol% with respect to the polyolefin resin.

The polyurethane elastomer (III) used in the thermoplastic elastomer composition of the present invention is a thermoplastic polyurethane elastomer obtained by the reaction of a polymer diol, an organic diisocyanate and a chain extender.
The polymer diol constituting the polyurethane elastomer (III) has a number average molecular weight of 1,000 to 6,000, which means that the thermoplastic elastomer composition containing the polyurethane elastomer (III) has mechanical properties, heat resistance, and cold resistance. It is preferable from the viewpoint of improving properties, elastic recovery, and the like.
Here, the number average molecular weight of the polymer diol used in the present specification is a number average molecular weight calculated on the basis of the measurement the hydroxyl value in accordance with JIS K-1557.

More specifically, examples of the polyesterdiol include aliphatic dicarboxylic acids having 5 to 12 carbon atoms and terephthalic acids such as glutaric acid, adipic acid, pimelli acid, suberic acid, azelaic acid, sebacic acid, and dodecanedioic acid. , Isophthalic acid, orthophthalic acid and other aromatic dicarboxylic acids and their ester-forming derivatives, and, for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 3 One or two aliphatic diols having 2 to 10 carbon atoms such as −methyl-1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, and 2-methyl-1,8-octanediol. Examples thereof include polyesterdiol, polycaprolactone diol, and polyvalerolactone diol obtained by subjecting the above to a polycondensation reaction.

Further, as the chain extender used in the production of the polyurethane elastomer (III), any of the chain extenders conventionally used in the production of the polyurethane elastomer can be used, and the type thereof is not particularly limited. Among them, as the chain extender, aliphatic diols, on one or more kinds of alicyclic diols and aromatic diols are preferably used. Specific examples of the chain extender preferably used include ethylene glycol, diethylene glycol, 1,4-butanediol, 1,5-pentanediol, 2-methyl-1,3-propanediol, 1,6-hexanediol, and neopentyl. Examples thereof include diols such as glycol, 1,9-nonanediol, cyclohexanediol, and 1,4-bis (β-hydroxyethoxy) benzene. Among the above, an aliphatic diol having 2 to 6 carbon atoms is more preferably used as the chain extender, and 1,4-butanediol is particularly preferably used.

In the thermoplastic elastomer composition of the present invention, as the polyurethane elastomer (III), the polyurethane elastomer having a number average molecular weight is 2,000 or more poly (3-methyl-1,5-pentane adipate) diol and a soft segment, i.e. with adipic acid It can be obtained by using a polyester diol having a number average molecular weight of 2000 or more obtained by polycondensation with 3-methyl-1,5-pentanediol and a polyurethane elastomer obtained by reacting the above-mentioned chain extender and organic diisocyanate. It is preferable because the thermoplastic elastomer composition has excellent adhesiveness to the polar resin.

In the present invention, as the paraffin oil (IV), a paraffin oil having a kinematic viscosity at 40 ° C. of 20 to 800 centimeter stokes (CST), a fluidity of 40 to 0 ° C. and a flash point of 200 to 400 ° C. is used. Paraffinic oils having a kinematic viscosity at 40 ° C. of 50 to 600 cts, a fluidity of -30 to 0 ° C. and a flash point of 250 to 350 ° C. are more preferably used.
Generally, an oil used as a process oil or the like is a mixture of a component having an aromatic ring such as a benzene ring and a naphthen ring, a paraffin component (chain hydrocarbon), and the like, and the number of carbon atoms constituting the paraffin chain is the oil. Oil that occupies 50% by weight or more of the total carbon number of the oil is called "paraffin oil".

The paraffin oil (IV) used in the thermoplastic elastomer composition of the present invention, any can be used as long as it is referred to as paraffin oleate yl, content of the component having an aromatic ring is 5 Those having a weight of% or less are preferably used.

The thermoplastic elastomer composition of the present invention may contain other thermoplastic resins such as an olefin resin, a styrene resin, a polyphenylene ether resin, and polyethylene glycol in addition to the above-mentioned components, if necessary.
In particular, it is preferable to include an olefin resin in the thermoplastic elastomer composition of the present invention because the moldability, mechanical strength, etc. of the thermoplastic elastomer composition can be improved . The o olefin resins, e.g., polyethylene, polypropylene, polybutene resins, one or more, such as block copolymer or random copolymer with other α- olefins such as propylene and ethylene and 1-butene Can be used. The amount of the olefin resin blended in the thermoplastic elastomer composition of the present invention is 100 parts by weight of the addition polymerization block copolymer (I) so as not to impair the flexibility of the thermoplastic elastomer composition. It is preferably 200 parts by weight or less.

Furthermore, the thermoplastic elastomer composition of the present invention may contain an inorganic filler, if necessary. The inorganic filler is useful for increasing the hardness of the thermoplastic elastomer composition of the present invention and improving the economic efficiency as a bulking agent. As the inorganic filler, for example, one or more of calcium carbonate, talc, clay, synthetic silicon, titanium oxide, carbon black, barium sulfate and the like can be used. The blending amount of the inorganic filler is preferably in a range in which the flexibility of the thermoplastic elastomer composition is not impaired, and is generally preferably 100 parts by weight or less with respect to 100 parts by weight of the addition polymerization block copolymer (I). ..

In addition to the above-mentioned components, the thermoplastic elastomer composition of the present invention also contains, if necessary, a lubricant, a light stabilizer, a pigment, a flame retardant, an antistatic agent, a silicone oil, an antiblocking agent, an ultraviolet absorber, and an antioxidant. It may contain one kind or two or more kinds of agents and the like.
Preparation of the thermoplastic elastomer composition of the present invention is not particularly limited, be prepared by any method as long as the method can uniformly mix the ingredients described above for use in had us in the thermoplastic elastomer composition of the present invention Also, the melt-kneading method is usually used.
The melt-kneading can be performed using, for example, a melt-kneading device such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer, and usually melt-kneads at about 180 ° C. to 270 ° C. for about 3 to 15 minutes. Thereby, the thermoplastic elastomer composition of the present invention can be obtained.

(1) Production of thermoplastic elastomer composition (pellets):
Among the materials used in the following examples and comparative examples, a polymer material other than paraffin-based oil is dry-blended, and paraffin-based oil is added to and impregnated to form a mixture, or paraffin-based oil is used. A mixture is prepared without addition, the mixture is supplied to a twin-screw extruder (“BT-30” manufactured by Plastic Industrial Research Institute) , melt-kneaded at a cylinder temperature of 220 ° C. and a screw rotation speed of 150 rpm, and then extruded into a strand shape. , To produce a thermoplastic elastomer composition.

(3) Measurement of 100% modulus, tensile strength at break and elongation at break:
The pellets of the thermoplastic elastomer composition produced in the above (1), an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. "IS-80"; measured at 80 ton injection molding machine) using a cylinder temperature of 220 ° C. And injection molding was performed under the condition of mold temperature of 40 ° C. to form a No. 3 dumbbell test piece, and the dumbbell test piece was used for JIS-K6301 using an autograph (manufactured by Shimadzu Seisakusho Co., Ltd.). Similarly, 100% modulus, tensile breaking strength and tensile breaking elongation were measured under the condition of 500 mm / min.

(4) Measurement of permanent tensile elongation:
The pellets of the thermoplastic elastomer composition produced in the above (1), an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. "IS-80"; measured at 80 ton injection molding machine) using a cylinder temperature of 220 ° C. And injection molding was performed under the condition of mold temperature of 40 ° C. to form a No. 3 dumbbell test piece, and using the dumbbell test piece, using an autograph (manufactured by Shimadzu Seisakusho Co., Ltd.), 100 mm / min. Stretched under conditions. When the tensile elongation reached 100%, the elongation was stopped and held in that state for 10 minutes. Then, the test piece was released and left for another 10 minutes, and then the permanent tensile elongation was measured.

(5) Measurement of compression set:
The pellets of the thermoplastic elastomer composition produced in the above (1), an injection molding machine (manufactured by Nissei Plastic Industrial Co., Ltd. "IS-80"; measured at 80 ton injection molding machine) using a cylinder temperature of 220 ° C. And injection molding was performed under the condition of a mold temperature of 40 ° C. to produce a straight columnar molded product having a diameter of 29.0 mm and a thickness of 12.7 mm, and according to JIS-K6301 at a temperature of 70 ° C. and compression deformation. The compression set was measured after being left for 22 hours under the condition of 25% volume.

○ Addition polymerization block copolymer (I)
Addition polymerization block copolymer (I-1): "Septon 4055" manufactured by Kuraray Co., Ltd.
Addition polymerization block copolymer (I-2): "Septon 4044" manufactured by Kuraray Co., Ltd.
○ Modified polyolefin resin (II)
Modified Polyolefin Resin (II-1): "T7761P" manufactured by Nippon Synthetic Rubber Co., Ltd. (maleic anhydride-modified EPR)
Modified Polyolefin Resin (II-2): "ADMER QF500" manufactured by Mitsui Chemicals, Inc. (maleic anhydride-modified PP)
Modified Polyolefin Resin (II-3): "ADMER NF500" manufactured by Mitsui Chemicals, Inc. (maleic anhydride-modified LLDPE)
○ Polyurethane elastomer (III): “Chramiron U 8165” manufactured by Kuraray Co., Ltd. [ Polyester polyurethane elastomer having poly (3-methyl-1,5-pentaneadipate) diol as a soft segment]
○ Paraffin oil (IV): "PW-380" manufactured by Idemitsu Kosan Co., Ltd.