JP4444602B2 - Composite molded body - Google Patents

Description

  The present invention relates to a thermoplastic resin composition for composite molding of a thermoplastic elastomer composition and a polyacetal resin containing a urethane-based thermoplastic elastomer, a molded body thereof, and a composite molding of the molded body and a molded body of a polyacetal resin. In particular, a thermoplastic resin composition for composite molding with a polyacetal resin with a urethane-based thermoplastic elastomer using a thermoplastic elastomer composition that is rich in flexibility and excellent in compatibility with a urethane-based thermoplastic elastomer, The present invention relates to the molded body and a composite molded body using the molded body.

  In recent years, thermoplastic elastomers, which are soft materials with rubber elasticity and do not require a vulcanization process, can be molded and processed like thermoplastic resins, and can be recycled. Automotive elastomers, home appliance parts, wire coatings, medical use Widely used in the fields of parts, footwear, sundries, etc.

Among thermoplastic elastomers, polystyrene-based thermoplastic elastomers such as styrene-butadiene block polymer (SBS) and styrene-isoprene block polymer (SIS), which are block copolymers of aromatic vinyl compound-conjugated diene compound, are flexible. The thermoplastic elastomer composition that is rich and has good rubber elasticity at normal temperature and has excellent processability is widely used as a substitute for vulcanized rubber.
In addition, an elastomer composition obtained by hydrogenating an intramolecular double bond of a block copolymer of styrene and a conjugated diene in these elastomers is further improved as an elastomer having improved heat aging resistance (thermal stability) and weather resistance. Widely used.

However, thermoplastic elastomer compositions using these hydrogenated block copolymers still have problems with rubber-like properties such as oil resistance, heat-press deformation rate (compression set) and rubber elasticity at high temperatures. In order to improve this point, a crosslinked product obtained by crosslinking a composition containing a hydrogenated derivative of the block copolymer has been proposed (see, for example, Patent Documents 1 to 5).
The crosslinked composition of the hydrogenated block copolymer disclosed in the above-mentioned patent document has a problem that compression set is still insufficient at a high temperature, particularly at 100 ° C., and mechanical strength tends to decrease. At present, the performance level required for vulcanized rubber applications has not been reached. In extrusion molding, the shape retention is deteriorated due to low melt tension at high temperature, and there are many problems on the molding surface such as a longer molding cycle in injection molding.

In addition, attempts have been made to blend these thermoplastic elastomers with resins having polar groups such as polyamide polymers, polyester polymers, or polyurethane polymers. For example, hydrogenated SBS block copolymers, olefin elastomers, and diene resins. A melt blend of a thermoplastic polymer selected from an elastomer, a urethane-based elastomer, and a plasticized polyvinyl chloride and a polyester-based thermoplastic elastomer or a polyether block amide has been proposed (see, for example, Patent Documents 6 to 7). .
However, these compositions have the disadvantages that the property balance between compression set and hardness is poor, and the bending fatigue property and wear resistance are poor due to insufficient compatibility.

  In order to solve such a problem, a modified polystyrene resin containing an epoxy group, an acid anhydride group, or an oxazoline group and / or a composition containing a hydrogenated derivative of a block copolymer and a polyester resin. By adding a modified polyolefin-based resin, a composition improved in compatibility and excellent in flexibility, heat resistance and chemical resistance (for example, see Patent Document 8) is disclosed, and hydrogenation of a block copolymer is disclosed. A hydrogenated derivative containing a derivative and a carboxylic acid group or a derivative group thereof, and a composition comprising a polyolefin resin and a thermoplastic polyester (for example, see Patent Documents 9 to 10) are disclosed.

  Also disclosed are compositions comprising a hydrogenated derivative of a block copolymer, a hydrogenated derivative containing a carboxylic acid group or a derivative group thereof, and a thermoplastic polyurethane (see, for example, Patent Documents 11 to 14).

  However, none of the compositions is yet sufficiently compatible with the thermoplastic elastomer, the tensile properties at high temperatures, particularly at 100 ° C. or more, deteriorate, and the property balance between compression set and hardness is poor. Had. Depending on the alloy ratio with the thermoplastic elastomer, surface layer peeling and flow marks may occur in injection molding, and moldability may deteriorate due to occurrence of grease and rough skin in extrusion molding.Further, low molecular weight components may bleed. Also had.

In addition, the inventors have prepared a composition comprising a hydrogenated derivative of a block copolymer and an epoxy group, or a hydrogenated derivative containing the derivative group, and a thermoplastic polyurethane (see, for example, Patent Document 15), a block copolymer. A composition comprising a polymer hydrogenated compound and a compound containing an epoxy group-containing compound, a carboxyl group-containing compound, etc., for flexibility, heat distortion resistance, molding processability, particularly oil resistance, and mechanical properties at high temperatures. An excellent thermoplastic elastomer composition (see, for example, Patent Document 16), and further, a thermoplastic elastomer composition having excellent abrasion resistance comprising two types of polyurethane resins and a rubber-like elastic composition (see, for example, Patent Document 17). .) Has been developed.
However, none of the above-described inventions have examined a composition excellent in composite moldability with a polyacetal resin.
JP 59-6236 A JP-A 63-57662 Japanese Patent Publication No. 3-49927 Japanese Patent Publication No. 3-11291 Japanese Patent Publication No. 6-13628 JP-A-1-139241 Japanese Patent Laid-Open No. 3-100045 JP-A-5-214209 Japanese Patent Publication No. 5-75016 Japanese Patent Laid-Open No. 1-230660 JP-A-3-234745 JP-A-3-234755 Japanese Patent Laid-Open No. 5-171003 Japanese Patent Laid-Open No. 7-126474 Japanese Patent Laid-Open No. 2-97554 JP-A-10-310617 JP 2002-146180 A

  In view of the above problems, the object of the present invention is from a thermoplastic elastomer composition and a urethane-based thermoplastic elastomer that are rich in flexibility, excellent in heat distortion resistance, molding processability, and compatibility with a urethane-based thermoplastic elastomer. A thermoplastic resin composition for composite molding with a polyacetal resin, a molded body from the thermoplastic resin composition, and a heat-bonding property between the molded body of the thermoplastic resin composition and a molded body of a polyacetal resin The object is to provide a composite molded body.

  As a result of intensive studies to achieve the above object, the present inventors have determined that the hydrogenation ratio of the styrene-based thermoplastic elastomer, preferably the high hydrogenation rate hydrogenated block copolymer and the low hydrogenation block copolymer. Heat obtained by heat-treating a rubber softener, organic peroxide, liquid polybutadiene and, if necessary, various monomers, etc. into an elastomer mixture of a specific proportion of two different types of hydrogenated block copolymers It has been found that a composition containing a thermoplastic elastomer composition and a urethane-based thermoplastic elastomer, and if necessary, a composition containing a petroleum resin can be a thermoplastic resin composition for composite molding with a polyacetal resin having excellent compatibility. The present invention has been completed.

That is, according to the first invention of the present invention, (A) (a) at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. At least two of a hydrogenated block copolymer obtained by hydrogenating a conjugated diene block of a block copolymer and / or a polymer block A mainly composed of an aromatic vinyl compound, and a conjugated diene With respect to 100 parts by weight of an elastomer composed of a block copolymer composed of at least one of polymer blocks B mainly composed of a compound,
(B) 5 to 300 parts by weight of a rubber softener,
(C) Molten composition containing 0.01 to 3 parts by weight of an organic peroxide and (d) 1 to 80 parts by weight of a (co) polymer having a functional group and a repeating unit derived from a diene 100 parts by weight of a thermoplastic elastomer composition obtained by kneading,
(B) A thermoplastic resin composition comprising 10 to 1500 parts by weight of a urethane-based thermoplastic elastomer is provided.

  Further, according to the second invention of the present invention, in the first invention, (a) comprises (a-1) at least two polymer blocks A mainly composed of an aromatic vinyl compound and a conjugated diene compound. 5 to 95% by weight of a hydrogenated block copolymer obtained by hydrogenating 90% or more of a conjugated diene block of a block copolymer consisting of at least one of polymer blocks B mainly composed of (a-2) Hydrogenated less than 90% of a conjugated diene block of a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound There is provided a thermoplastic resin composition characterized in that it is a mixture comprising 95 to 5% by weight of a hydrogenated block copolymer obtained as described above.

  According to the third invention of the present invention, in the second invention, (a-1) the number average molecular weight in terms of polystyrene of the hydrogenated block copolymer is in the range of 30,000 to 500,000, (A-2) A polystyrene-reduced number average molecular weight of the hydrogenated block copolymer is in the range of 10,000 to 500,000, and a thermoplastic resin composition is provided.

  According to the fourth invention of the present invention, in any one of the first to third inventions, (A) the thermoplastic elastomer composition further comprises (e) 100 parts by weight of component (e). A thermoplastic resin composition comprising 1 to 20 parts by weight of an unsaturated glycidyl compound or a derivative thereof is provided.

  According to the fifth invention of the present invention, in any one of the first to fourth inventions, (A) the thermoplastic elastomer composition further comprises (f) 100 parts by weight of component (a). A thermoplastic resin composition containing 1 to 20 parts by weight of an unsaturated carboxylic acid or a derivative thereof is provided.

  According to the sixth invention of the present invention, in any one of the first to fifth inventions, (A) the thermoplastic elastomer composition further comprises (g) 100 parts by weight of the component (a). A thermoplastic resin composition characterized by containing 0.02 to 10 parts by weight of an ester-based crosslinking aid is provided.

  According to a seventh invention of the present invention, in any one of the first to sixth inventions, (A) the thermoplastic elastomer composition further comprises (h) 100 parts by weight of the component (h). A thermoplastic resin composition comprising 1 to 200 parts by weight of a peroxide-decomposable olefin resin is provided.

  According to an eighth invention of the present invention, in any one of the first to seventh inventions, (A) the thermoplastic elastomer composition further comprises (i) 100 parts by weight of component (a). A thermoplastic resin composition comprising 1 to 200 parts by weight of an olefin copolymer rubber is provided.

  According to the ninth invention of the present invention, in any one of the first to eighth inventions, (A) the thermoplastic elastomer composition further comprises (j) 100 parts by weight of component (a). A thermoplastic resin composition comprising 1 to 200 parts by weight of an inorganic filler is provided.

  According to a tenth aspect of the present invention, in any one of the first to ninth aspects, the thermoplastic resin composition further comprises (C) 100 parts by weight of the thermoplastic elastomer composition (C). A thermoplastic resin composition comprising 10 to 500 parts by weight of a petroleum resin is provided.

  According to an eleventh aspect of the present invention, there is provided the thermoplastic resin composition according to any one of the first to tenth aspects, which is a thermoplastic resin composition for composite molding with a polyacetal resin. The

  According to the twelfth aspect of the present invention, there is provided a molded body comprising the thermoplastic resin composition according to any one of the first to eleventh aspects.

  According to the thirteenth aspect of the present invention, a composite obtained by heat-sealing a molded body made of the thermoplastic resin composition of any of the first to 10th aspects and a molded body made of a polyacetal resin. A shaped body is provided.

  The thermoplastic resin composition for compound molding with the polyacetal resin of the present invention is polar with the thermoplastic elastomer composition (A) excellent in heat distortion resistance, molding processability, bleed resistance, and compatibility with the urethane-based thermoplastic elastomer. Since it is a thermoplastic resin composition for composite molding with a polyacetal resin composed of urethane-based thermoplastic elastomer (TPU) (B), petroleum resin (C), etc., which is a resin having a group, it is rich in flexibility and heat distortion resistance In addition, it is excellent in moldability and bleed resistance, and is excellent in heat fusion with a polyacetal resin (POM).

The components, production methods, and uses constituting the present invention will be described in detail below.
1. Component of thermoplastic resin composition for composite molding with polyacetal resin (A) Component of thermoplastic elastomer composition (a) Elastomer (a) Elastomer component used in the thermoplastic elastomer composition of the present invention is a styrene-based component A block copolymer and / or a hydrogenated block copolymer thereof.
The block copolymer component is a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. For example, an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA, or the like can be given.
The block copolymer contains 5 to 60% by weight, preferably 20 to 50% by weight of an aromatic vinyl compound.

The polymer block A mainly composed of an aromatic vinyl compound is preferably composed only of an aromatic vinyl compound, or is a copolymer of an aromatic vinyl compound of 50% by weight or more, preferably 70% by weight or more and a conjugated diene compound. It is a polymer block.
The polymer block B mainly composed of a conjugated diene compound is preferably composed of only a conjugated diene compound, or is a copolymer of 50% by weight or more, preferably 70% by weight or more of an aromatic vinyl compound with a conjugated diene compound. It is a coalesced block.

  The number average molecular weight of the block copolymer is preferably in the range of 5,000 to 1,500,000, more preferably 10,000 to 550,000, still more preferably 100,000 to 400,000. Distribution is 10 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.

  Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of aromatic vinyl compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  Specific examples of the block copolymer include styrene-butadiene-styrene copolymer (SBS) and styrene-isoprene-styrene copolymer (SIS).

  Many methods for producing these block copolymers have been proposed. As typical methods, for example, a lithium catalyst or a Ziegler-type catalyst is prepared by the method described in Japanese Patent Publication No. 40-23798. It can be obtained by block polymerization in an inert medium.

  The hydrogenated block copolymer used in the present invention is an elastomer comprising a mixture of the following (a-1) high hydrogenation rate hydrogenated block copolymer and (a-2) low hydrogenation rate hydrogenated block copolymer. Is preferred.

(A-1) Hydrogenated block copolymer (a-1) High hydrogenation rate hydrogenated block copolymer component is mainly composed of at least two polymer blocks A mainly composed of an aromatic vinyl compound and a conjugated diene compound. The hydrogenated high hydride in which 90% or more of the aliphatic double bond portion derived from the conjugated diene in the conjugated diene block of the block copolymer comprising at least one of the polymer blocks B is hydrogenated. For example, the hydrogenation rate of a conjugated diene block of an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA, etc. A hydrogenated block copolymer obtained by hydrogenation of 90% or more can be exemplified.

  The polymer block A mainly composed of an aromatic vinyl compound is preferably composed of an aromatic vinyl compound alone, or a conjugated diene hydrogenated with 50% by weight or more, preferably 70% by weight or more of the aromatic vinyl compound. It is a copolymer block with a compound.

The polymer block B mainly composed of a hydrogenated conjugated diene compound is preferably composed of only a hydrogenated conjugated diene compound or 50% by weight or more, preferably 70%, of a hydrogenated conjugated diene compound. It is a copolymer block of at least% by weight and an aromatic vinyl compound.
The block copolymer contains 5 to 60% by weight, preferably 20 to 50% by weight of an aromatic vinyl compound.

  As the aromatic vinyl compound constituting the block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. preferable. In addition, as the conjugated diene compound, for example, one or two or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene and These combinations are preferred.

  Further, in the polymer block A mainly composed of these aromatic vinyl compounds and the polymer block B mainly composed of conjugated diene compounds, the distribution of units derived from the conjugated diene compound or aromatic vinyl compound in the molecular chain is random, It may be tapered (in which the monomer component increases or decreases along the molecular chain), partially in a block form, or any combination thereof. When there are two or more polymer blocks A mainly composed of aromatic vinyl compounds or polymer blocks B mainly composed of conjugated diene compounds, each polymer block has a different structure even if each has the same structure. There may be.

  These block copolymers can be obtained by block polymerization in an inert medium using a lithium catalyst or a Ziegler type catalyst by a known method, for example, the method described in JP-B-40-23798. The hydrogenated block copolymer can be obtained by hydrogenating the above block copolymer by a known method. Hydrogenation mainly hydrogenates an aliphatic double bond derived from a conjugated diene of a conjugated diene block, and its hydrogenation rate is preferably 90% or more. If the hydrogenation rate is less than 90%, flexibility and transparency tend to be slightly deteriorated.

  The polymer structure B in the hydrogenated component (a-1) and mainly composed of a conjugated diene compound has an arbitrary microstructure. For example, in a polybutadiene block, the 1,2-microstructure is Preferably it is 20 to 50 weight%, Most preferably, it is 25 to 45 weight%. In the polyisoprene block, it is preferable that 70 to 100% by weight of isoprene has a 1,4-microstructure.

(A-1) The polystyrene-equivalent number average molecular weight (Mn) of the hydrogenated block copolymer is 30,000 to 500,000, preferably 100,000 to 400,000, more preferably 150,000 to 350,000. 000, more preferably in the range of 200,000-350,000, and the molecular weight distribution (ratio of weight average molecular weight (Mw) to number average molecular weight (Mn) (Mw / Mn)) is preferably 5 or less, more preferably Is 2 or less. The molecular structure of the block copolymer may be linear, branched, radial, or any combination thereof.
When the number average molecular weight (Mn) is less than the lower limit, the heat resistance, scratch resistance and oil resistance are lowered. On the other hand, when the upper limit is exceeded, fluidity is deteriorated, and appearance defects such as short shots and flow marks occur in the molded product in injection molding. In extrusion molding, the occurrence of rough skin, eye grease, etc. becomes prominent. In addition, the molecular weight in this invention is the value calculated | required on the basis of the polystyrene whose molecular weight is known by GPC. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on GPC conditions such as a reference sample, apparatus, and data processing method.

  Specific examples of the hydrogenated block copolymer of component (a-1) include styrene-ethylene-butene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), and styrene-ethylene. -An ethylene-propylene-styrene copolymer (SEEPS) etc. can be mentioned.

(A-2) Low hydrogenation rate hydrogenated block copolymer (a) The low hydrogenation rate hydrogenated block copolymer component used in the elastomer is a polymer block mainly composed of an aromatic vinyl compound. Less than 90% of the aliphatic double bond portion derived from the conjugated diene of the conjugated diene block of the block copolymer comprising at least two of A and at least one of the polymer blocks B mainly composed of the conjugated diene compound Low hydrogenation rate hydride. For example, the hydrogen content of the conjugated diene block of the block copolymer of aromatic vinyl compound-conjugated diene compound having a structure such as ABA, BABA, ABBABA, etc. A hydrogenated block copolymer obtained by hydrogenation of less than 90% can be mentioned. Here, the polymer block A is preferably 40% by weight or less.

  The polymer block A mainly composed of an aromatic vinyl compound may be a polymer composed only of an aromatic vinyl compound or a copolymer of an aromatic vinyl compound and less than 50% by weight of a conjugated diene compound. The polymer block B mainly composed of a conjugated diene compound may be a polymer composed solely of a conjugated diene compound or a copolymer of a conjugated diene compound and less than 50% by weight of an aromatic vinyl compound.

  As the aromatic vinyl compound constituting the component (a-2), for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc., among which styrene Is preferred. Further, as the conjugated diene compound, for example, one or more kinds are selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, etc., among which butadiene, isoprene, and these The combination of is preferable.

  The microstructure in the polymer block B mainly composed of a conjugated diene compound can be selected arbitrarily. In the butadiene block, the 1,2-microstructure has a lower limit of 1% or more, preferably 5% or more, more preferably 10% or more, and an upper limit of 95% or less, preferably 80% or less, more preferably 75% or less. is there.

  The hydrogenation rate of the aliphatic double bond based on the conjugated diene of the conjugated diene block in the hydrogenated copolymer of component (a-2) is less than 90%, preferably less than 80%, more preferably 75. %, Particularly preferably less than 60%. The lower limit is preferably 3% or more, more preferably 5% or more, still more preferably 7 or more, and particularly preferably 9% or more. Further, the 1,2-vinyl bond after hydrogenation is preferably 0.5 to 12%, more preferably less than 10%, still more preferably 5% or less, and still more preferably 3% or less. When the hydrogenation rate exceeds 90%, the crosslinking efficiency tends to decrease and the heat resistance and oil resistance tend to decrease.

  The number average molecular weight in terms of polystyrene of the (a-2) hydrogenated block copolymer having the above structure is 10,000 to 500,000, preferably 10,000 to 200,000, more preferably 10,000 to It is in the range of 150,000. The molecular weight distribution (ratio (Mw / Mn) of weight average molecular weight (Mw) to number average molecular weight (Mn)) is preferably 10 or less, more preferably 5 or less, and more preferably 2 or less. The molecular structure of the hydrogenated block copolymer may be linear, branched, radial, or any combination thereof.

  When the number average molecular weight (Mn) is less than the lower limit, the mechanical properties, heat resistance, scratch resistance, and oil resistance of the molded product are lowered. On the other hand, when the upper limit is exceeded, fluidity is deteriorated, and appearance defects such as short shots and flow marks occur in the molded product in injection molding. In extrusion molding, the occurrence of rough skin, eye grease, etc. becomes prominent. In addition, the molecular weight in this invention is the value calculated | required on the basis of the polystyrene whose molecular weight is known by GPC. Therefore, the value is a relative value, not an absolute value, and may vary by about ± 30% depending on GPC conditions such as a reference sample, apparatus, and data processing method.

  Specific examples of the (a-2) hydrogenated block polymer component having a hydrogenation rate of less than 90% include partially hydrogenated styrene-butadiene-styrene copolymer having 1,2-bonds selectively hydrogenated in the butadiene block. Examples include coalescence (SBBS). Moreover, a partially hydrogenated styrene-isoprene-styrene copolymer, a partially hydrogenated styrene-isoprene / butadiene-styrene copolymer, and the like can be given. In the present invention, the hydrogenated product of the aromatic vinyl compound-conjugated diene compound block copolymer may be used alone or in combination of two or more.

  (A) The blending ratio of (a-1) and (a-2) in the elastomer component is preferably 5 to 95% by weight of component (a), more preferably 50 to 85% by weight. -2) is preferably 95 to 5% by weight, more preferably 50 to 15% by weight. When the component (a-1) is less than 5% by weight (the component (a-2) exceeds 95% by weight), the heat resistance and mechanical properties of the resulting thermoplastic elastomer composition are slightly lowered. In addition, the thermoplastic resin composition has a slight decrease in heat resistance, a slight decrease in flexibility and mechanical properties, and a slight decrease in moldability. On the other hand, when the component (a-1) exceeds 95% by weight (the component (a-2) is less than 5% by weight), the heat resistance of the resulting thermoplastic elastomer composition slightly decreases. Further, the fluidity is slightly insufficient, and the moldability of the resulting thermoplastic elastomer composition is slightly deteriorated. In the thermoplastic resin composition, mechanical properties and moldability are slightly deteriorated due to a decrease in compatibility.

(B) Rubber softener The (b) rubber softener component used in the thermoplastic elastomer composition of the present invention may be a non-aromatic rubber softener component or an aromatic rubber softener component. Although ester plasticizers can also be used, non-aromatic mineral oils and ester plasticizers are particularly preferred.
Non-aromatic mineral oil softeners include paraffin softeners in which the number of carbon atoms in the paraffin chain accounts for 50% or more of the total number of carbon atoms.

  Among the ester plasticizers, cyclic plasticizers include, for example, phthalic anhydride ester and trimellitic ester, N-cyclohexyl-p-toluenesulfonamide, dibenzyl sebacate, diethylene glycol dibenzoate, di-t -Octylphenyl ether, dipropanediol dibenzoate, N-ethyl-p-toluenesulfonamide, isopropylidene diphenoxypropanol, alkylated naphthalene, polyethylene glycol dibenzoate, o, p-toluenesulfonamide, trimethylpentanediol dibenzoate and And trimethylpentanediol, monoisobutyrate, monobenzoate and the like. In these, a phthalic anhydride ester and trimellitic acid ester are preferable.

  Representative examples of the phthalic anhydride ester include, for example, butyl octyl phthalate, butyl 2-ethylhexyl phthalate, butyl n-octyl phthalate, dibutyl phthalate, diethyl phthalate, diisodecyl phthalate, dimethyl phthalate, dioctyl phthalate, di (2 -Ethylhexyl) phthalate, diisooctyl phthalate, diisononyl phthalate (DINP), di-tridecyl phthalate, n-hexyl n-decyl phthalate, n-octyl n-decyl phthalate, alkyl benzyl phthalate, bis (4-methyl) -1,2-pentyl) phthalate, butyl benzyl phthalate, butyl cyclohexyl phthalate, di (2-butoxyethyl) phthalate, cyclohexyl isodecyl phthalate, disi Rohexyl phthalate, diethyl isophthalate, di-n-heptyl phthalate, dihexyl phthalate, di (2-methoxyethyl) phthalate, dimethyl isophthalate, dinonyl phthalate, dioctyl phthalate, dicapryl phthalate, di (2-ethylhexyl) isophthalate, Mixed dioctyl phthalate, diphenyl phthalate, 2- (ethylhexyl) isobutyl phthalate, butyl phthalyl butyl glycolate, ethyl (and methyl) phthalyl ethyl glycolate, polypropylene glycol bis (amyl) phthalate, hexyl isodecyl phthalate, isodecyl -Tridecyl phthalate, isooctyl, isodecyl phthalate, etc. are mentioned.

  Representative examples of trimellitic acid esters include, for example, triisooctyl trimellitate, tri-n-octyl / n-decyl trimellitate, trioctyl trimellitate, tri (2-ethylhexyl) trimellitate (TOTM) , Tri-n-hexyl / n-decyl trimellitate, tri-n-hexyl trimellitate, triisodecyl trimellitate, triisononyl trimellitate and the like.

  Acyclic plasticizers include phosphate ester, adipic acid ester, azelaic acid ester, citric acid ester, acetyl citrate ester, myristic acid ester, ricinoleic acid ester, acetyl ricinoleic acid ester, sebacic acid ester, stearic acid ester , Epoxidized esters, further 1,4-butanediol dicaprylate, butoxyethyl pelargonate di [(butoxyethoxy) ethoxy] methane, dibutyl tartrate, diethylene glycol dipelargonate, diisooctyl diglycolate, isodecyl Nonanoate, tetraethylene glycol di (2-ethyl-butyrate), triethylene glycol di (2-ethyl-hexanoate), triethylene glycol dipelargonate and branched 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, ester of aliphatic dihydric alcohol, 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (TXIB), Examples include acrylic polymers.

  Representative examples of phosphate esters include, for example, cresyl diphenyl phosphate, tricresyl phosphate, dibutyl phenyl phosphate, diphenyl octyl phosphate, methyl diphenyl phosphate, tributyl phosphate, triphenyl phosphate, tri (2-butoxyethyl) phosphate , Tri (2-chloroethyl) phosphate, tri (2-chloropropyl) phosphate and trioctyl phosphate.

  Representative examples of adipic acid esters include di [2- (2-butoxyethoxy) ethyl] adipate, di (2-ethylhexyl) adipate, diisononyl adipate (DINA), diisodecyl adipate, dioctyl adipate (diisooctyl) Adipate), n-hexyl n-decyl adipate, n-octyl n-decyl adipate and di-n-heptyl adipate.

  Representative examples of sebacic acid esters include, for example, dibutyl sebacate, di (2-ethylhexyl) sebacate, dibutoxyethyl sebacate, diisooctyl sebacate and diisopropyl sebacate.

  Representative examples of azelaic acid esters include, for example, di (2-ethylhexyl) azelaate, dicyclohexylazelaate, diisobutylazelaate and diisooctylazelaate.

  As the acrylic polymer plasticizer, a reaction product obtained by reacting a mixture of (i) a radical polymerizable monomer and (ii) a modifying compound in the presence or absence of a polymerization initiator. A polymer composed of a product is exemplified. This polymer is preferably (ii) a polymer in which the bonding mode of the modifying compound to the polymer is an ester bond, (i) using (meth) acrylic acid as a radical polymerizable monomer, and (ii) ) A polymer using an aliphatic or alicyclic alcohol as the modifying compound may be used.

  In the acrylic polymer plasticizer, as the radical polymerizable monomer (i), (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) Alkyl (meth) acrylates such as acrylate; hydroxyl-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; maleic anhydride, maleic acid, mono- and dialkyl esters of maleic acid; styrene, Aromatic vinyl monomers such as α-methylstyrene; vinyl esters such as vinyl acetate and vinyl propionate; alkenes such as ethylene and propylene; dienes such as butadiene and isoprene; (meth) acrylonitrile, (meth) acrylamide, and chloride Vinyl, chloride Vinylidene, allyl chloride and allyl alcohol and the like.

  The modifying compound (ii) includes cycloalkanols such as cyclohexyl alcohol; alkanols such as isopropyl alcohol; halogen-containing alcohols such as fluoroalkyl alcohol; alkylene diols such as ethylene glycol and butanediol; cyclohexanediol and cyclohexyldi Cycloalkylene diols such as methanol; hydroxyl group-containing modifiers such as polyethers having hydroxyl groups at the ends, polymers such as polyester, cyclohexyl carboxylic acid, cyclohexyl dicarboxylic acid, adipic acid, sebacic acid, fluoroalkyldicarboxylic acid, maleic anhydride and Carboxyl group-containing compounds such as fumaric acid; ethyl acetate, butyl acetate, cellosolve acetate, methylpropylene glycol acetate, carbitol acetate Ester group-containing modifiers such as bets and ethyl carbitol acetate, cyclohexene, include alkenes such as cyclopentene and isobutene.

  Examples of acrylic polymers in the combination of (i) and (ii) include (i) (meth) acrylic acid, maleic anhydride, maleic acid or maleic acid monoalkyl ester, and the like of (ii) A polymer in which the modifying compound is introduced into the polymer is obtained by esterification using a compound having a hydroxyl group. Further, by using an ester group-containing monomer such as (i) methyl (meth) acrylate, ethyl acrylate, butyl acrylate and 2-ethylhexyl acrylate and a compound having a hydroxyl group of (ii), a transesterification reaction is performed. A functional polymer is obtained. Furthermore, the formation of an ester bond by the reaction of the hydroxyl group-containing monomer of (i) 2-hydroxyethyl (meth) acrylate or hydroxypropyl (meth) acrylate with the carboxyl group or ester group-containing compound of (ii) A polymer into which a functional group has been introduced is obtained. Furthermore, by using a carboxyl group-containing monomer such as (meth) acrylic acid (i) and an alkene (ii), the carboxyl group is added to an ethylenically unsaturated bond to form an ester bond, which is modified. A polymer into which the compound for quality is introduced is obtained.

  In the acrylic polymer plasticizer that can be used in the present invention, butyl acrylate, ethyl acrylate, hexyl acrylate, mesooxyethyl acrylate, and glycidyl acrylate are preferable as the above (i), and ethyl acrylate is the main component. Is optimal.

The weight average molecular weight (Mw) of the acrylic polymer plasticizer is preferably 500 to 10,000, more preferably 1,000 to 6,000, and still more preferably 1,000 to 3,000. The viscosity is preferably from 100 to 9,000 mPa · s, more preferably from 1,000 to 6,000 mPa · s, still more preferably from 3,000 to 5,000 mPa · s, and the SP value determined from Acetone-Water Tolerance. Is preferably 10.5 to 16.5, more preferably 13 to 16, and still more preferably 14 to 16.
Among these plasticizers that are ester compounds, DINP, DINA, and TOTM are particularly preferable.

  The compounding quantity of a component (b) is 5-300 weight part with respect to 100 weight part of component (a), Preferably it is 20-150 weight part. If the blending amount is less than 5 parts by weight, the flexibility of the resulting thermoplastic elastomer composition is lowered. Moreover, the softness | flexibility of the thermoplastic resin composition which consists of a thermoplastic elastomer composition obtained and a urethane type thermoplastic elastomer falls, and a moldability deteriorates. When it exceeds 300 parts by weight, the softening agent tends to bleed out from the resulting thermoplastic elastomer composition, and peeling, deformation and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes significant. In addition, the thermoplastic resin composition is likely to be bleed, and the heat-fusibility with the polyacetal resin is also lowered.

(C) Organic peroxide The (c) organic peroxide component used in the thermoplastic elastomer composition (A) in the present invention generates radicals and causes the radicals to react in a chain manner. Or, it serves to crosslink the component (i) to be blended as necessary. At the same time, (d) is graft-polymerized, and components (e) to (g) to be blended as necessary are graft-polymerized to component (a) and / or component (i), and urethane in the thermoplastic resin composition It works to improve the compatibility with the elastomer. Furthermore, the component (h) to be blended is decomposed or cross-linked as necessary to control the fluidity of the composition at the time of melt-kneading to improve the dispersion of the rubber component.

  Examples of the component (c) 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, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, n-butyl-4,4-bis (tert-butylperoxy) valerate, benzoyl peroxide, p-chloro Benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, tert-butyl peroxybenzoate, tert- Chill peroxyisopropylcarbonate, diacetyl peroxide, lauroyl peroxide, may be mentioned tert- butyl cumyl peroxide and the like. Of these, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, 2,5-dimethyl-2,5-di, from the viewpoint of odor, colorability, and scorch safety. -(Tert-Butylperoxy) hexyne-3,1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane is particularly preferred.

  The compounding quantity of a component (c) is 0.01-3 weight part with respect to 100 weight part of component (a), Preferably it is 0.05-1.5 weight part. When the blending amount is less than 0.01 parts by weight, crosslinking cannot be sufficiently achieved, and the heat resistance and oil resistance of the resulting thermoplastic elastomer composition are deteriorated. In addition, since the introduction of the functional group becomes insufficient, the moldability deteriorates due to the poor compatibility of the thermoplastic resin composition comprising the thermoplastic elastomer composition and the urethane-based thermoplastic elastomer, resulting in polyacetal. The heat-fusibility with the resin also decreases. On the other hand, even if it exceeds 3 parts by weight, the mechanical properties and moldability of the resulting thermoplastic elastomer deteriorate, and the moldability of the thermoplastic resin composition comprising the thermoplastic elastomer composition and urethane thermoplastic elastomer obtained is poor. Become.

(D) a (co) polymer having a functional group and a repeating unit derived from a diene (d) a repeating unit derived from a diene having a functional group used in the thermoplastic elastomer composition (A) in the present invention When the thermoplastic elastomer composition (A) is melt-kneaded, the (co) polymer component is graft-polymerized mainly in the presence of an organic peroxide to the component (a), and the thermoplastic elastomer composition ( A) The effect of suppressing the bleed out of the low molecular weight substance in A) is exhibited, and at the same time, the compatibility with the urethane-based thermoplastic elastomer is improved in the thermoplastic resin composition.
Examples of the functional group of component (d) in the present invention include a hydroxyl group, an isocyanate group, a carboxy group, an epoxy group, an acryloyl group, an amino group, and a mercapto group, with a hydroxyl group being particularly preferred. Examples of the (co) polymer containing a repeating unit derived from diene include liquid polybutadiene, liquid polyisoprene, liquid styrene-butadiene copolymer, liquid acrylonitrile-butadiene copolymer, and liquid polychloroprene. Is preferred. Moreover, the hydrogenated substance of the said compound can also be used.

The functional group content in component (d) is preferably 0.01 to 30 milliequivalents per gram of component (b), more preferably 0.1 to 5 milliequivalents. The bonding position of the functional group may be either in the molecule or at the molecular end, but the molecular end is preferred. A method for introducing a functional group at the molecular end is described in, for example, “Synthesis and Application of Reactive Polymers”, supervised by Takeshi Endo, (publisher name: CMC, publication year: 1990.7.13, pages 177-178). Has been. Introduction of a functional group into the molecule can be performed, for example, by reacting a peroxide to introduce an epoxy group into an ethylene group and then adding a group that reacts with an epoxy group such as an amino group.
Examples of the (co) polymer having a functional group-containing repeating unit derived from a diene and / or a hydrogenated product thereof include, for example, polybutadiene having a hydroxyl group at a terminal, trade name: R-45HT (trademark) (Idemitsu Petrochemical Co., Ltd.), as a hydrogenated compound of polybutadiene having a hydroxyl group at the terminal, trade name: Polytail H (trademark) (Mitsubishi Chemical Corporation), among which polybutadiene having a hydroxyl group at the terminal is preferable.

  The terminal hydroxyl group-containing liquid polybutadiene component (d) is a liquid which is transparent at room temperature, and has a main chain microstructure of vinyl 1,2-bond type, trans 1,4-bond type, cis 1,4-bond type. It is a polymer. Here, the vinyl 1,2-bond is preferably 30% by weight or less, and if the vinyl 1,2-bond exceeds 30% by weight, the low temperature characteristics of the resulting thermoplastic elastomer composition are lowered, which is preferable. Absent.

Here, the terminal hydroxyl group content (JIS K 1557) is preferably 0.05 to 3.0 mol / kg, more preferably 0.1 to 1.5 mol / kg.
The number average molecular weight of the liquid polybutadiene is preferably 1,000 to 5,000, more preferably 2,000 to 4,000. When the number average molecular weight is less than 1,000, the heat-resistant deformation property of the resulting thermoplastic elastomer composition is lowered, and when it exceeds 5,000, the compatibility of the obtained thermoplastic elastomer composition is lowered.

The amount of component (d) is preferably 1 to 80 parts by weight, particularly preferably 3 to 50 parts by weight, per 100 parts by weight of component (a). If the blending amount exceeds 80 parts by weight, the softening agent tends to bleed out from the resulting thermoplastic elastomer composition (A), and peeling, deformation and flow marks are likely to occur in the molded product. Also in the thermoplastic resin composition, the softening agent bleed-out, peeling or deformation, and flow marks are likely to occur in the molded product, and the heat-fusibility with the polyacetal resin is also lowered.
When the amount is less than 1 part by weight, the thermoplastic elastomer composition is not improved in flexibility and moldability. In the thermoplastic resin composition, peeling or deformation and a flow mark are likely to occur in a molded product due to a decrease in compatibility.

(E) Unsaturated glycidyl compound or derivative thereof In the thermoplastic elastomer composition (A) of the present invention, (e) an unsaturated glycidyl compound or a derivative component thereof can be blended as necessary. Component (e) is used as a modifier, and preferably a glycidyl compound having an unsaturated group and a glycidyl group copolymerizable with an olefin in the molecule is used, particularly preferably glycidyl methacrylate (GMA). Is used. With the modifier, (a) the soft component of the hydrogenated block copolymer in the elastomer component, the copolymer rubber component, and further components such as a peroxide-crosslinked olefin resin blended as necessary are modified, Compatibility with the urethane-based thermoplastic elastomer in the thermoplastic resin composition is improved.

  When blended, the amount of component (e) is preferably 1 to 20 parts by weight, particularly preferably 1 to 10 parts by weight, per 100 parts by weight of component (a). When the blending amount exceeds 20 parts by weight, not only the heat distortion resistance and mechanical properties of the resulting thermoplastic elastomer composition are deteriorated, but the effect of improving the compatibility with the urethane-based thermoplastic elastomer is not recognized.

(F) Unsaturated carboxylic acid or derivative thereof In the thermoplastic elastomer composition (A) in the present invention, (f) an unsaturated carboxylic acid or derivative component thereof can be blended as necessary. Component (f) is used as a modifier, and preferably includes acrylic acid, methacrylic acid, maleic acid, dicarboxylic acid or derivatives thereof such as acids, halides, amides, imides, anhydrides, ester derivatives and the like. Can be mentioned. Particularly preferably, maleic anhydride (MAH) is used. By the modifier, the peroxide-decomposable olefin resin of component (a) and component (h) blended as necessary, preferably polypropylene or the like, or component (i) blended as necessary, is modified with urethane. Improves compatibility with thermoplastic elastomer.

  When blended, the amount of component (f) is preferably 1 to 20 parts by weight, more preferably 1 to 10 parts by weight with respect to 100 parts by weight of component (a). When the blending amount exceeds 20 parts by weight, severe yellowing occurs in the thermoplastic elastomer composition, and not only the heat distortion resistance and mechanical properties deteriorate, but also when the urethane thermoplastic elastomer is blended, The effect of improving the compatibility is not recognized.

(G) Ester-based crosslinking aid In the thermoplastic elastomer composition of the present invention, an (g) ester-based crosslinking aid component can be used as necessary. Component (g) can be blended in the crosslinking treatment with the above-mentioned (c) organic peroxide of the thermoplastic elastomer composition of the present invention, whereby a uniform and efficient crosslinking reaction can be performed. . Also, by blending in a large amount, softeners for non-aromatic rubbers, especially low molecular weight paraffinic oils, etc., are appropriately cross-linked to suppress bleed out from the thermoplastic elastomer composition and thermoplastic resin composition. be able to.

  Specific examples of the component (g) include, for example, triallyl cyanurate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, and polyethylene glycol having 9 to 14 repetitions of ethylene glycol. Polyfunctional methacrylate compounds such as dimethacrylate, trimethylolpropane trimethacrylate, allyl methacrylate, 2-methyl-1,8-octanediol dimethacrylate, 1,9-nonanediol dimethacrylate, polyethylene glycol diacrylate, 1,6 -Hexanediol diacrylate, trimellirol propane tetraacrylate, sometimes pentaerythritol polyacrylate, neopentyling Call diacrylate, polyfunctional acrylate compounds such as propylene glycol diacrylate, can be mentioned polyfunctional vinyl compounds such as vinyl butyrate or vinyl stearate. These may be used alone or in combination of two or more. Of these crosslinking aids, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolpropane tetraacrylate, and dipentaerythritol polyacrylate are particularly preferable.

  When blended, the amount of component (g) is preferably 0.02 to 10 parts by weight, more preferably 0.1 to 3 parts by weight, per 100 parts by weight of component (a). If it exceeds 10 parts by weight, the degree of cross-linking decreases due to self-polymerization and the effect cannot be obtained.

(H) Peroxide-decomposable olefin-based resin In the thermoplastic elastomer composition of the present invention, (h) a peroxide-decomposable olefin-based resin component can be blended as necessary. Ingredient (h) improves the rubber dispersion of the resulting thermoplastic elastomer composition and thermoplastic resin composition, improves the appearance of the molded product, and has an effect of adjusting the hardness and shrinkage rate. . The component is an olefin polymer or copolymer that is thermally decomposed by heat treatment in the presence of peroxide to reduce the molecular weight and increase fluidity at the time of melting, such as isotactic polypropylene and propylene. And other α-olefins such as ethylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

  The melting point by DSC measurement of the homo part of the olefin copolymer is preferably in the range of Tm of 150 to 167 ° C. and ΔHm of 25 to 83 mJ / mg. The crystallinity can be estimated from Tm and ΔHm of DSC measurement. When Tm and ΔHm are outside the above ranges, the oil resistance of the resulting thermoplastic elastomer composition and the rubber elasticity at 100 ° C. or higher are not improved.

  The melt flow rate (MFR, ASTM D-1238, L condition, 230 ° C.) of component (h) is preferably 0.1 to 200 dg / min, more preferably 0.5 to 100 dg / min. If the MFR is less than 0.1 dg / min, the moldability of the resulting thermoplastic elastomer composition deteriorates, and if it exceeds 200 dg / min, the rubber elasticity of the obtained thermoplastic elastomer composition deteriorates.

  When blended, the amount of component (h) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of component (a). If it exceeds 200 parts by weight, the moldability of the thermoplastic resin composition obtained from the thermoplastic elastomer composition and the urethane elastomer is deteriorated, and peeling, deformation and flow marks are likely to occur in the molded product, and the thermoplastic elastomer composition The hardness of the thermoplastic resin composition composed of the product and the urethane-based elastomer becomes so high that the flexibility is lost and a rubber-like product cannot be obtained.

(I) Olefin-based copolymer rubber The thermoplastic elastomer composition in the present invention may contain (i) an olefin-based copolymer rubber component, if necessary. Component (i) includes an elastomer obtained by copolymerizing an α-olefin such as ethylene, propylene, 1-butene, 1-pentene, or an olefin copolymer rubber obtained by copolymerizing these with a non-conjugated diene. It is done.
Component (i) has the effect of improving the flexibility and tactile feel of the resulting thermoplastic elastomer composition and the thermoplastic resin composition comprising the urethane-based thermoplastic elastomer.

  Examples of non-conjugated dienes include dicyclopentadiene, 1,4-hexadiene, dicyclooctadiene, methylene norbornene, and 5-ethylidene-2-norbornene.

  Specific examples of such olefin copolymer rubber include ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene copolymer rubber, ethylene-1-butene copolymer rubber, and ethylene-1. -Butene-nonconjugated diene copolymer rubber, ethylene-propylene-1-butene copolymer rubber, and the like.

  When blended, the amount of component (i) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight with respect to 100 parts by weight of component (a). When it exceeds 200 parts by weight, the mechanical strength of the resulting thermoplastic elastomer composition is significantly reduced.

(J) Inorganic filler (j) An inorganic filler component can be mix | blended with the thermoplastic elastomer composition (A) in this invention as needed. In addition to the effect of improving some physical properties such as compression set of molded articles obtained from the thermoplastic elastomer composition and the thermoplastic resin composition, the component (j) has an economic advantage due to the increase in the amount. As the component (j), wollastonite, chlorite, calcium carbonate, talc, silica, diatomaceous earth, barium sulfate, magnesium carbonate, magnesium hydroxide, mica, clay, titanium oxide, carbon black, glass fiber, hollow glass balloon, Examples thereof include carbon fiber, calcium titanate fiber, natural silicic acid, and synthetic silicic acid (white carbon). Of these, calcium carbonate, wollastonite, chlorite and talc are particularly preferred.

  When blended, the amount of component (j) is preferably 1 to 200 parts by weight, more preferably 1 to 100 parts by weight, per 100 parts by weight of component (a). When the amount exceeds 200 parts by weight, the mechanical strength of the resulting thermoplastic resin composition is remarkably lowered, the hardness is increased, the flexibility is lost, and a rubber-like product cannot be obtained.

(K) Other components In addition to the above-described components, the thermoplastic elastomer composition in the present invention may further include various anti-blocking agents, sealability improvers, thermal stabilizers, antioxidants, if necessary. It is also possible to contain a light stabilizer, an ultraviolet absorber, a lubricant, a crystal nucleating agent, a colorant and the like. Here, examples of the antioxidant include 2,6-di-tert-p-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4 , 4-dihydroxydiphenyl, tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and the like, phenolic antioxidants, phosphite antioxidants, thioether antioxidants, and the like. Of these, phenolic antioxidants and phosphite antioxidants are particularly preferred. The antioxidant is preferably 0 to 3.0 parts by weight, particularly preferably 0.1 to 1.0 parts by weight based on 100 parts by weight of the total of the components (a) to (i).

  In addition to the above components, the thermoplastic elastomer composition in the present invention may further include an ester group, a carboxyl group, a carbonyl group, an acid anhydride group, an amino group, a hydroxyl group, a glycidyl group, and an oxazolyl group, as necessary. It is also possible to contain a compound having one or more polar groups selected from the group consisting of: For example, saponified ethylene-vinyl acetate copolymer (saponified EVA), maleic anhydride-modified polyethylene, maleic anhydride-modified polypropylene, ethylene-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate (HEMA) and the like can be mentioned. When the saponified ethylene-vinyl acetate copolymer (saponified EVA) and 2-hydroxyethyl methacrylate (HEMA) are contained, the blending amount is preferably 0.1 to 100 parts by weight with respect to 100 parts by weight of the component (a). More preferably, it is 0.1-50 weight part.

(B) Urethane-based thermoplastic elastomer The (B) urethane-based thermoplastic elastomer component used in the thermoplastic resin composition for composite molding with the polyacetal resin of the present invention is generally prepared from a polyol, a diisocyanate, and a chain extender. . Examples of the polyol include polyester polyol, polyester ether polyol, polycarbonate polyol, and polyether polyol.

  Here, examples of the polyester polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or their acid esters or acid anhydrides, ethylene glycol, 1,3-propylene glycol, 1 , 2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1 , 3-octanediol, 1,9-nonanediol, etc. Details, polyester polyols obtained by dehydration condensation reaction of a mixture thereof; polylactone diols obtained by ring-opening polymerization of lactones monomer such as ε- caprolactone.

  Examples of the polycarbonate polyol include ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6. -One or more polyhydric alcohols such as hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol and diethylene carbonate, Polycarbonate polyols obtained by reacting with dimethyl carbonate, diethyl carbonate and the like can be mentioned. Further, it may be a copolymer of polycaprolactone polyol (PCL) and polyhexamethylene carbonate (PHL).

  Further, examples of the polyester ether polyol include aliphatic dicarboxylic acids such as succinic acid, adipic acid, sebacic acid, and azelaic acid, and aromatic dicarboxylic acids such as phthalic acid, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid. Alicyclic dicarboxylic acids such as hexahydrophthalic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid, or their acid esters or anhydrides and glycols such as diethylene glycol or propylene oxide adducts, etc. Or the compound obtained by dehydration condensation reaction with these mixtures is mentioned.

Furthermore, examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like obtained by polymerizing cyclic ethers such as ethylene oxide, propylene oxide, and tetrahydrofuran, and copolyethers thereof.
Of the various polyols described above, polyether polyols are preferred from the viewpoint of hydrolysis resistance.

  Examples of the isocyanate include tolylene diisocyanate (TDI), 4,4′-diphenylmethane diisocyanate (MDI), 1,5-naphthylene diisocyanate (NDI), tolidine diisocyanate, 1,6-hexamethylene diisocyanate (HDI). ), Isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), hydrogenated XDI, triisocyanate, tetramethylxylene diisocyanate (TMXDI), 1,6,11-undecane triisocyanate, 1,8-diisocyanate methyloctane, lysine ester Triisocyanate, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, dicyclohexylmethane diisocyanate (hydrogenated MDI; H DI), and the like. Of these, 4,4'-diphenylmethane diisocyanate (MDI) is preferably used.

  As the chain extender, a low molecular weight polyol is used. For example, ethylene glycol, 1,3-propylene glycol, 1,2-propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5 -Pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, 1,4-cyclohexanedimethanol, Aliphatic polyols such as glycerin and aromatic glycols such as 1,4-dimethylolbenzene, bisphenol A, bisphenol A ethylene oxide or propylene oxide adducts.

The urethane-based thermoplastic elastomer does not include a dissolving grade having a chloroform insoluble residue ratio of 40% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less, and is preferably Shore A95 or less. .
Here, the chloroform-insoluble residual ratio was obtained by extracting 0.2 g of a 3 mm square pellet sample using 20 ml of chloroform at room temperature (23 ° C.) for 24 hours, followed by filtration and drying. It is calculated by the following formula from the object weight.
Chloroform insoluble residue ratio (% by weight) = [insoluble matter weight (g) / sample weight (g)] × 100

  Specific examples of commercially available products include C80A10 (manufactured by Takeda Birdish), C80A50 (manufactured by Takeda Birdish), and T- as an ester (adipate) polyurethane copolymer. 5000V (manufactured by DIC Bayer Polymer), TR-3080 (manufactured by DIC Bayer Polymer), 1180A50 (manufactured by Takeda Birdish), T-8180 (manufactured by DIC Bayer Polymer) Desmopan DesKU2-88586 (manufactured by DIC Bayer Polymer Co., Ltd.) and the like as ether-ester polyurethane copolymers such as T-8283 (manufactured by DIC Bayer Polymer Co., Ltd.), and these may be used alone or in combination. It may be used Te.

  The compounding quantity of a component (B) is 10-1500 weight part with respect to 100 weight part of component (A), Preferably it is 20-1200 weight part. When the amount is less than 10 parts by weight, the effect of addition is not recognized, and when it exceeds 1500 parts by weight, the flexibility of the resulting thermoplastic resin composition is lowered. By blending a thermoplastic elastomer composition, the oil resistance, abrasion resistance, and high temperature properties such as tensile properties at high temperatures of the resulting thermoplastic resin composition for composite molding with the polyacetal resin are dramatically improved. Can do.

(C) Petroleum resin In the thermoplastic resin composition for composite molding with the polyacetal resin of the present invention, (C) a petroleum resin component can be added as necessary. The component (C) functions to specifically improve the heat-fusibility with the polyacetal resin.
Component (C) is obtained by copolymerizing resinous materials obtained in various processes in the petroleum refining industry and petrochemical industry, or unsaturated hydrocarbons obtained in those processes, particularly in the naphtha decomposition process. is a petroleum resin, for example, C ₅ aliphatic petroleum resin whose main raw material fractions, aromatic petroleum resin to the C ₉ fraction main raw material by-produced in the steam cracking of petroleum, both And C ₅ C ₉ copolymer resins, alicyclic petroleum resins mainly composed of cyclopentadiene compounds, copolymerized petroleum resins thereof, and hydrogenated petroleum resins that are hydrogenated products thereof. It is done. Hydrogenated petroleum resins are obtained by hydrogenating the above petroleum resins by known methods, such as hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymer petroleum resins, and hydrogenated fats. Examples include cyclic petroleum resins and hydrogenated terpene resins.
Among these, hydrogenated petroleum resins are preferable among the petroleum resins used in the present invention, and those obtained by hydrogenating petroleum resins obtained by copolymerizing cyclopentadiene compounds and aromatic vinyl compounds such as styrene are particularly preferable.

  When blended, the amount of component (C) is 10 to 500 parts by weight, preferably 50 to 300 parts by weight, per 100 parts by weight of component (A). If the amount is less than 10 parts by weight, the effect of addition is not recognized. If the amount exceeds 500 parts by weight, the flexibility and moldability of the resulting thermoplastic resin composition are lowered. By blending the petroleum resin, the heat-fusibility between the polyacetal resin and the thermoplastic resin composition for composite molding with the obtained polyacetal resin can be dramatically improved.

2. Production of thermoplastic elastomer composition and thermoplastic resin composition for composite molding with polyacetal resin (1) Production of thermoplastic elastomer composition The thermoplastic elastomer composition in the present invention comprises the above components (a) to (d), Or it can manufacture by adding component (e)-(k) etc. as needed, adding each component simultaneously or in arbitrary orders, and melt-kneading.
The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be continuously performed by using a suitable L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of melt kneading is preferably 160 to 220 ° C.

  The thermoplastic elastomer composition used in the present invention has good compatibility with a urethane-based elastomer, and the flexibility, extrusion moldability, injection moldability, etc. of the resin having a polar group are reduced in heat resistance, oil resistance and A thermoplastic resin composition can be formed without bleed of low molecular weight.

(2) Manufacture of a thermoplastic resin composition for composite molding with a polyacetal resin The thermoplastic resin composition for composite molding with a polyacetal resin of the present invention comprises the above components (A), (B), or components as necessary. (C), (D), and the antioxidant used in the above thermoplastic elastomer composition may be added, and the components may be added simultaneously or in any order, and melt kneaded.
The method of melt kneading is not particularly limited, and generally known methods can be used. For example, a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, or various kneaders can be used. For example, the above operation can be continuously performed by using a suitable L / D twin screw extruder, Banbury mixer, pressure kneader, or the like. Here, the temperature of melt kneading is preferably 170 to 200 ° C.

3. Composite molded body The thermoplastic resin composition for composite molding with the polyacetal resin used in the present invention is excellent in flexibility, heat distortion resistance, molding processability, oil resistance, abrasion resistance, etc., and with the polyacetal resin (POM). Since it is excellent in heat-fusibility, a composite molded body can be easily molded by heat-sealing a molded body from the thermoplastic resin composition and a POM molded body.

The POM used in the composite molded article of the present invention includes an acetal homopolymer and an acetal copolymer. An acetal homopolymer is a polymer composed of repeating oxymethylene units (CH ₂ O) and is obtained by homopolymerizing formaldehyde and trioxane. An acetal copolymer is a polymer having a structure in which oxyalkylene units are randomly inserted into a chain composed of oxymethylene units. The insertion rate of oxyalkylene units in the polyacetal copolymer is preferably 0.05 to 50 mol, more preferably 0.1 to 20 mol, per 100 mol of oxymethylene units. Examples of oxyalkylene units include oxyethylene units, oxypropylene units, oxytrimethylene units, oxytetramethylene units, oxybutylene units, oxyphenylethylene units, and the like. Among these oxyethylene units, a component suitable for enhancing the performance of the polyacetal composition is a combination of oxymethylene units and oxytetramethylene units.
Further, in the copolymerization with other units other than the oxymethylene group, any of a copolymer, a terpolymer, and a block copolymer may be used, and it may have a branched or crosslinked structure as well as a linear shape. The terminal is not particularly limited, and the degree of polymerization, branching, and degree of crosslinking are not particularly limited as long as they have melt molding processability. Furthermore, a modified polyacetal copolymer having a functional group such as a nitrile group, a carboxyl group, a carboxylic acid ester group, or an amide group in the side chain may be used. Moreover, the structure derived from cyclic ether or cyclic formal may be included.

  Specific examples of the molded body from the thermoplastic resin composition include electric wires and electrical parts such as connectors, switch covers, plugs, gaskets, grommets, cable jacket curl cords, electric wire insulation coatings, and the like. Examples of parts include pressure-resistant hoses, diaphragms, gaskets, packing, casters, grommets, roller coupling grips, hoses and the like. Examples of medical equipment / food-related parts include syringe tips, drug stoppers, grommets, and sampling. Examples of automobile parts include CVJ boots, rack and opinion boots, shock absorber dust boots, vacuum connectors, air ducts, tubes, run channels, grommets, handle covers, and the like. Ah bag outer cover steering, mud guard and the like, as a building material, for example, window frame seals, expansion joints, sponge seals, handrail cover, stair slip and the like. Other applications include, for example, grip materials such as pen grips, bicycle grips, toothbrush grips, toy parts, mats, goggles, dust / gas masks, and shoe soles.

  Examples of particularly preferable specific products of the composite molded body include a shift knob grip, a door grip, and an electric saw grip.

  The present invention will be specifically described by the following examples and comparative examples, but the present invention is not limited to these examples. In addition, the measuring method and sample of the physical property used by this invention are shown below.

(Test method)
(1) Measurement of hydrogenation rate of conjugated diene block part: A sample is collected in an NMR sample tube (5 mmφ), deuterated chloroform is added and dissolved sufficiently, and a nuclear magnetic resonance apparatus (NMR) JSX GSX The ¹ H-NMR measurement was performed using a −400 type at normal temperature, 400 MHz, and 3029 integrations.
(2) Specific gravity: According to JIS K7112, the test piece was measured using a 1 mm thick press sheet.
(3) Hardness: Measured with durometer hardness / type A in accordance with JIS K 6253. A 6.3 mm thick press sheet was used as the test piece.
(4) Tensile strength: In accordance with JIS K 6251, the test piece was a 1 mm thick press sheet punched into a No. 3 dumbbell type test piece. The tensile speed was 500 mm / min. (Measured at room temperature and 120 ° C)
(5) 100% stress: In accordance with JIS K 6251, a 1 mm thick press sheet was punched into a No. 3 dumbbell-shaped test piece. The tensile speed was 500 mm / min.
(6) Elongation at break: In accordance with JIS K 6251, the test piece was a 1 mm thick press sheet punched into a No. 3 dumbbell type test piece. The tensile speed was 500 mm / min.
(7) Volume change rate: In accordance with JIS K 6258, a 1 mm thick press sheet was punched into a No. 3 dumbbell-shaped test piece. Using IRM # 903 oil, the weight change at 120 ° C. for 72 hours was measured.
(8) Injection moldability: Using an injection molding machine with a clamping pressure of 120 tons, a molding temperature of 220 ° C., a mold temperature of 40 ° C., an injection speed of 55 mm / second, an injection pressure of 600 kg / cm ² , and a holding pressure of 400 kg / cm ^2. A sheet of 13.5 × 13.5 × 2 mm was formed with an injection time of 6 seconds and a cooling time of 45 seconds. The presence or absence of delamination, surface layer peeling, deformation, and the presence of a flow mark that significantly deteriorated the appearance was judged by visual observation, and evaluated according to the following criteria.
○: Good ×: Poor (9) Extrudability: A 50 mm × 1 mm sheet was extruded, the drawdown property, surface appearance and shape were observed, and evaluated according to the following criteria.
○: Good ×: Poor (10) Bleed resistance: Extruded sheet that is bent and fixed with a clip is allowed to stand at room temperature and 110 ° C. for 168 hours and visually observed for low molecular weight bleed and blooming. Evaluation based on the criteria.
○: Good ×: Bad

(11) Thermal fusion property: Using the test piece 1 shown in FIGS.
1 to 3, a polyacetal resin (POM) resin plate 3 having a length of 150 mm, a width of 25 mm, and a thickness of 4 mm was prepared by injection molding under the following injection conditions. The resin used for the resin plate preparation is as follows. (The injection conditions of the resin plate conformed to the recommended injection conditions of the resin manufacturer used.)
Injection molding machine: FS-120 manufactured by Nissei Plastic Industrial Co., Ltd.
Molding temperature: 200-260 ° C
Mold temperature: 20-50 ° C
Injection speed: 40 to 90 mm / sec Injection pressure: 1000 to 1700 kg / cm ²
Holding pressure: 400 to 600 kg / cm ²
Injection time: 4-10 seconds Cooling time: 30-60 seconds

  The paper 4 is pasted on a part of the POM resin plate 3 obtained as described above with a double-sided tape and inserted into a mold, and then the thermoplastic resin composition is injected under the following conditions to obtain the POM resin plate 3 and The test piece which the thermoplastic resin composition board 2 heat-bonded in the location of A was created.

Injection molding machine: FS-120 manufactured by Nissei Plastic Industrial Co., Ltd.
Molding temperature: 200 ° C or 240 ° C
Injection temperature: 40 ° C
Injection speed: 55 mm / sec Injection pressure: 1400 kg / cm ²
Holding pressure: 0 kg / cm ²
Injection time: 6 seconds Cooling time: 45 seconds

  Next, 180 degree peeling strength was measured about the obtained test piece by bend | folding the thermoplastic resin composition board 2 as shown in FIG. 3, and pulling the both ends of 2 and 3 in the direction of the arrow, respectively.

(Samples used in Examples and Comparative Examples)
(1) Component of thermoplastic resin composition for composite molding with polyacetal resin (A) Component of thermoplastic elastomer composition (a-1) High hydrogenation rate hydrogenated block copolymer: Septon 4077 (SEPS; Kuraray Co., Ltd.) (Made by company), styrene content: 30% by weight, number average molecular weight: 260,000, weight average molecular weight: 320,000, molecular weight distribution: 1.23, hydrogenation rate: 90% or more (a-2) low hydrogenation Hydrogenated block copolymer: Tuftec P Series JT90C (SBBS; manufactured by Asahi Kasei Co., Ltd.), styrene content: 30% by weight, number average molecular weight; 91,000, weight average molecular weight; 110,000, molecular weight distribution; 11. Hydrogenation rate of butadiene block: 75.1%, (hydrogenation rate of 1,2-butadiene 92.7%, hydrogenation rate of 1,4-butadiene 61. %)
(A-3) Maleic anhydride-modified styrene block copolymer (modified SEBS): Tuftec M1913 (manufactured by Asahi Kasei Corporation) Specific gravity: 0.92, hardness: 84A, tensile strength: 22 MPa, elongation: 600%
(B) Rubber softener: PW90 (trademark; manufactured by Idemitsu Petrochemical Co., Ltd.), number average molecular weight 980
(C) Organic peroxide (Peroxide): Perhexa TMH (1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane; manufactured by NOF Corporation)
(D) a (co) polymer having a functional group and a repeating unit derived from a diene: terminal hydroxyl group-containing liquid polybutadiene R-45HT (manufactured by Idemitsu Petrochemical Co., Ltd.), a hydroxyl group (0.83 mol / kg) as a functional group ) And a copolymerization reactive unsaturated double bond (1,4 bond: 80%), number average molecular weight 2800
(E) Unsaturated glycidyl compound: glycidyl methacrylate (GMA) (manufactured by NOF Corporation)
(F) Unsaturated carboxylic acid: maleic anhydride (MAH) (manufactured by NOF Corporation)
(G) Ester-based crosslinking assistant: TMPT (Trimethylol Propane Trimethacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.) Molecular weight: 338,
(H) Peroxide-decomposable olefin resin (PP): PP-BC8 (polypropylene; manufactured by Nippon Polychem Co., Ltd.), crystallinity: Tm 166 ° C., ΔHm; 82 mJ / mg, MFR: 1.8 g / 10 min ( i) Ethylene-butene copolymer rubber (EBR): Esprene N0441 (manufactured by Sumitomo Chemical Co., Ltd.)
(J) Calcium carbonate (CaCO ₃ ): NS400 (manufactured by Sankyo Seimitsu Co., Ltd.)
(K) Hindered phenol / phosphite / lactone composite antioxidant: HP2215 (manufactured by Ciba Specialty Chemicals)
(B) Polyurethane thermoplastic elastomer (TPU): Pandex T-5000V (manufactured by DIC Bayer Ltd.), specific gravity: 1.19, hardness: 81A
The following components were used as comparative components for component (B).
Comparative component (1): Polyester thermoplastic elastomer (COPE): Hytrel 4057 (manufactured by Toray DuPont) Specific gravity: 1.15, Hardness: 40D
Comparative component (2): Polyamide thermoplastic elastomer (COPA): Pebax 5533SN01 (manufactured by Atofina Japan) Specific gravity: 1.01, hardness: 55D
(C) Petroleum resin: Imabe P-140 (manufactured by Idemitsu Petrochemical Co., Ltd.), specific gravity: 1.03, softening point: 140 ° C.
(2) Resin for composite molded body: Polyacetal resin (POM): Duracon M-90 (manufactured by Polyplastics Co., Ltd.) Specific gravity: 1.41, flexural modulus: 2650 MPa

(Thermoplastic elastomer composition production examples 1 to 10)
Using each component in the amount shown in Table 1, the mixture was charged into a twin screw extruder having an L / D of 47, melt kneaded at a kneading temperature of 180 ° C. and a screw rotation speed of 350 rpm, and then a thermoplastic elastomer composition (E- 1 to E-10) were obtained and pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The physical properties are shown in Table 1.

In Table 1, E-1 to E-4 are thermoplastic elastomer compositions used in the present invention. Excellent values were shown for tensile strength, 100% stress, and elongation at break.
On the other hand, E-5 and E-6 are those in which the amount of component (b) is out of the scope of the present invention. If the amount of the component (b) is too small, the resulting thermoplastic elastomer composition will be too hard, and if the amount of the component (b) is too large, the mechanical properties will decrease, and the softening agent will be removed from the resulting thermoplastic elastomer composition. It is easy to bleed out, and peeling, deformation, and flow marks are likely to occur in the molded product. Furthermore, the gas generated during processing becomes significant.
E-7 and E-8 are those in which the amount of component (c) is out of the scope of the present invention. When there are too few components (c), bridge | crosslinking cannot fully be achieved but the manufacturability and pellet shape of the thermoplastic elastomer composition obtained will deteriorate. Even if there is too much component (c), mechanical characteristics will fall and the moldability and pellet shape of the thermoplastic elastomer composition obtained will worsen.
E-9 and E-10 are those in which the amount of component (d) is out of the scope of the present invention. When there are too few components (d), the manufacturability of the thermoplastic elastomer composition obtained will deteriorate. When there are too many components (d), a softening agent will bleed out easily from the thermoplastic elastomer composition obtained, and peeling, a deformation | transformation, and a flow mark will arise easily in a molded article. Furthermore, the gas generated during processing becomes significant.

(Examples 1-4)
A twin-screw extruder having an L / D of 47, blending the thermoplastic elastomer compositions (E-1 to E-4) of Table 1, urethane-based thermoplastic elastomers (TPU) and petroleum resins in the proportions shown in Table 2. The mixture was melt kneaded at a kneading temperature of 220 ° C. and a screw rotation speed of 350 rpm to obtain a thermoplastic resin composition for composite molding with a polyacetal resin, which was pelletized. Next, the obtained pellet was injection-molded to prepare a test piece, which was used for each test. The evaluation results are shown in Table 2. Example 1 is a reference example.

(Comparative Examples 1-2)
The case of TPU alone and the case of petroleum resin alone were evaluated in the same manner as in the examples. The results are shown in Table 2.

(Comparative Examples 3 to 8)
A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 2 except that E-5 to E-10 were used as the thermoplastic elastomer composition. The results are shown in Table 2.

(Comparative Examples 9 to 10)
A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that a polyester-based thermoplastic elastomer and a polyamide-based thermoplastic elastomer were used as the component (B). The results are shown in Table 2.

(Comparative Examples 11-12)
A thermoplastic resin composition was obtained and evaluated in the same manner as in Example 1 except that E-11 to E-12 were used as the thermoplastic elastomer composition. The results are shown in Table 2.

As is apparent from Table 2, Examples 1 to 4 are thermoplastic resin compositions for composite molding of the thermoplastic elastomer composition of the present invention and a polyacetal resin of TPU and petroleum resin. The thermoplastic resin composition for composite molding with the polyacetal resin obtained in the present invention is excellent in compatibility with TPU and petroleum resin, compared with the case of TPU alone (Comparative Example 1) and petroleum resin alone (Comparative Example 2). , Excellent balance of flexibility, mechanical properties, oil resistance, moldability, bleed resistance, and heat fusion with POM.
On the other hand, when the thermoplastic elastomer composition (E-5) having a component (b) content of less than the lower limit is used, the flexibility of the thermoplastic resin composition is lowered and the moldability is deteriorated. When the thermoplastic elastomer composition (E-6) in which the blending amount of the component (b) exceeds the upper limit is used, bleeding tends to occur in the thermoplastic resin composition, and the heat-fusibility with the polyacetal resin also decreases (comparison). Examples 3, 4).
When the thermoplastic elastomer composition (E-7) having a component (c) content less than the lower limit is used, crosslinking cannot be sufficiently achieved, and the introduction of functional groups becomes insufficient, resulting in a thermoplastic elastomer composition. The moldability deteriorates due to the deterioration of the compatibility of the thermoplastic resin composition comprising the product and the urethane-based thermoplastic elastomer, and the heat-fusibility with the polyacetal resin also decreases. When the thermoplastic elastomer composition (E-8) in which the blending amount of the component (c) exceeds the upper limit is used, the moldability of the thermoplastic resin composition comprising the thermoplastic elastomer composition and urethane thermoplastic elastomer obtained is poor. (Comparative Examples 5 and 6)
In the thermoplastic resin composition using the thermoplastic elastomer composition (E-9) in which the blending amount of the component (d) is less than the lower limit, peeling, deformation and flow marks are likely to occur in the molded product due to a decrease in compatibility. . When the thermoplastic elastomer composition (E-10) in which the blending of the component (d) exceeds the upper limit is used, bleed-out, peeling, deformation and flow mark of the softening agent are generated in the molded product even in the obtained thermoplastic resin composition. It becomes easy and the heat-fusibility with a polyacetal resin also falls (Comparative Examples 7 and 8).
Moreover, the thermoplastic resin composition which uses the polyester-type thermoplastic elastomer and the polyamide-type thermoplastic elastomer instead of the urethane-type thermoplastic elastomer is inferior in heat-fusibility with the polyacetal resin (Comparative Examples 9 and 10).
Furthermore, when the thermoplastic elastomer composition (E-11, E-120) using acid-modified SEBS was used, the heat-fusibility with the polyacetal resin was inferior (Comparative Examples 11 and 12).

  The present invention relates to a thermoplastic elastomer composition excellent in heat distortion resistance, molding processability, bleed resistance, and compatibility with a urethane-based thermoplastic elastomer (TPU) and a urethane-based thermoplastic elastomer (TPU). Because it is a thermoplastic resin composition for composite molding with petroleum resin and polyacetal resin, it has high flexibility, excellent heat resistance deformation, molding processability, bleed resistance, and heat fusion with polyacetal resin (POM). Because of its excellent properties, it can be used in the fields of electric wires / electric parts, industrial machine parts, medical equipment / food-related parts, automobile parts, building materials and the like.

It is a front view of the test piece for measuring peeling strength. It is sectional drawing of the test piece for measuring peeling strength. It is a figure explaining the measuring method for measuring peeling strength.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Test piece 2 Thermoplastic elastomer composition board 3 Polyacetal resin board 4 Paper A Thermal fusion part

Claims (9)

A composite molded article obtained by heat-sealing a molded article comprising the following thermoplastic resin composition and a molded article comprising a polyacetal resin.
Thermoplastic resin composition:
(A) (a) A conjugated diene block of a block copolymer comprising at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound At least two of a hydrogenated block copolymer and / or polymer block A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. With respect to 100 parts by weight of an elastomer comprising a block copolymer comprising
(B) 5 to 300 parts by weight of a rubber softener,
(C) organic peroxide 0.01 to 3 parts by weight, and (d) having a hydroxyl group include repeating units derived from diene (co) polymer composition containing 1 to 80 parts by weight 100 parts by weight of a thermoplastic elastomer composition obtained by melt-kneading;
(B) 10 to 1500 parts by weight of a urethane-based thermoplastic elastomer;
(C) A thermoplastic resin composition comprising 10 to 500 parts by weight of a petroleum resin.   (A) is a block copolymer comprising (a-1) at least two polymer blocks A mainly composed of an aromatic vinyl compound and at least one polymer block B mainly composed of a conjugated diene compound. 5% to 95% by weight of a hydrogenated block copolymer obtained by hydrogenating 90% or more of the conjugated diene block, and (a-2) at least two polymer blocks A mainly composed of an aromatic vinyl compound; A mixture comprising 95 to 5% by weight of a hydrogenated block copolymer obtained by hydrogenating less than 90% of a conjugated diene block of a block copolymer comprising at least one polymer block B mainly comprising a diene compound. The composite molded article according to claim 1, wherein the composite molded article is provided.   (A-1) The number average molecular weight in terms of polystyrene of the hydrogenated block copolymer is in the range of 30,000 to 500,000, and the number average molecular weight in terms of polystyrene of (a-2) hydrogenated block copolymer is It is the range of 10,000-500,000, The composite molded object of Claim 2 characterized by the above-mentioned.   The thermoplastic elastomer composition (A) further comprises (e) 1 to 20 parts by weight of an unsaturated glycidyl compound with respect to 100 parts by weight of the component (a). 2. The composite molded article according to item 1.   The thermoplastic elastomer composition (A) further contains (f) 1 to 20 parts by weight of an unsaturated carboxylic acid with respect to 100 parts by weight of the component (a). 2. The composite molded article according to item 1.   The thermoplastic elastomer composition (A) further contains (g) 0.02 to 10 parts by weight of an ester-based crosslinking aid with respect to 100 parts by weight of the component (a). The composite molded body according to any one of 5.   2. The thermoplastic elastomer composition (A) further contains 1 to 200 parts by weight of (h) a peroxide-decomposable olefin resin with respect to 100 parts by weight of the component (a). The composite molded body according to any one of -6.   The thermoplastic elastomer composition (A) further contains 1 to 200 parts by weight of (i) an olefin copolymer rubber with respect to 100 parts by weight of the component (a). The composite molded body according to any one of the above.   The thermoplastic elastomer composition (A) further contains 1 to 200 parts by weight of an inorganic filler (j) with respect to 100 parts by weight of the component (a). The composite molded article according to item 1.

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