JP4395591B2 - Thermoplastic resin composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a thermoplastic resin composition for bonding a polyacetal resin and a molded body using the same, and in particular, a urethane that is rich in flexibility, excellent in heat distortion resistance, molding processability, and heat fusion with a polyacetal resin. The present invention relates to a thermoplastic resin composition (alloyed product) for bonding a polyacetal resin comprising a thermoplastic elastomer, a thermoplastic elastomer composition, and a petroleum resin, and a molded body using the same.

  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).

  Moreover, the crosslinked composition of the hydrogenated block copolymer disclosed in the above patent document has a problem that the compression set is still insufficient at a high temperature, particularly at 100 ° C., and the mechanical strength tends to decrease. The current level of performance has not reached the performance level required for vulcanized rubber applications. 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.

  Furthermore, 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 dienes. There has been proposed a melt blend of a thermoplastic polymer selected from elastomers, urethane elastomers and plasticized polyvinyl chloride and polyester thermoplastic elastomers or polyether block amides (see Patent Documents 6 to 7).

  However, the composition has a defect that the characteristic balance between compression set and hardness is poor, and the bending fatigue characteristic and wear resistance are poor due to insufficient compatibility.

  In order to solve this problem, a modified polystyrene resin and / or a modified polyolefin containing an epoxy group, an acid anhydride group, or an oxazoline group in a composition containing a hydrogenated derivative of a block copolymer and a polyester resin A composition (see, for example, Patent Document 8) that improves compatibility and is excellent in flexibility, heat resistance, and chemical resistance is disclosed by adding a resin, and further, hydrogen of a block copolymer is disclosed. A composition comprising an additive derivative and a hydrogenated derivative containing a carboxylic acid group or a derivative group thereof, and a polyolefin resin and a thermoplastic polyester (see, for example, Patent Documents 9 to 10) is disclosed.

  Also disclosed is a composition 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). A composition (for example, see Patent Document 15) comprising a hydrogenated derivative of a polymer and an epoxy group, or a hydrogenated derivative containing the derivative group, and a thermoplastic polyurethane is disclosed.

  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 drawbacks. Depending on the alloy ratio with the thermoplastic elastomer, surface layer peeling and flow marks may occur during injection molding, and moldability may deteriorate due to the occurrence of grease and rough skin during extrusion molding, and low molecular weight components may bleed. Also had the disadvantage of.

On the other hand, polyacetal resin has excellent mechanical properties, fatigue resistance, friction / wear resistance, chemical resistance, slidability, and moldability, so it can be used for automobile parts, electrical / electronic equipment parts, and other precision products. Widely used in fields such as machine parts, building materials / piping members, daily life / makeup parts, and medical parts. However, with the expansion and diversification of applications, characteristics that are contradictory to polyacetal that cannot be achieved with polyacetal resin alone, such as soft tactile sensation, grip / slip effect with other materials, and damper effect are required. .
Furthermore, insert molding and two-color molding are effective in obtaining resins with different characteristics and processing conditions as a single molded body, and further reducing the processing process and eliminating the need for an adhesive, so no organic solvent is required. It is a processing method that is excellent in economic safety and environmental safety including work environment.
However, although polyacetal resin is modified by alloying or terminal alteration, and integral molding by insert molding or two-color molding has been attempted (for example, see Patent Documents 16 and 17), by modifying polyacetal, In many cases, the inherent properties of the polyacetal resin are lost.
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 2003-001761 A JP 2003-268193 A

  In view of the above problems, an object of the present invention is to provide a thermoplastic resin composition for bonding a polyacetal resin which is rich in flexibility, excellent in heat distortion resistance and moldability, and particularly excellent in adhesiveness with a polyacetal resin and the like. It is in providing the used molded object.

  As a result of intensive studies to achieve the above object, the present inventors have conducted hydrogenation obtained by hydrogenating 50% or more of a conjugated diene block of a block copolymer of an aromatic vinyl compound and a conjugated diene compound. Hydrogenated block copolymer and / or block copolymer of conjugated diene compound, organic peroxide, carboxylated liquid polybutadiene, and, if necessary, rubber softener, ester crosslinking aid, polar resin Of thermoplastic elastomer composition, polyurethane-based thermoplastic elastomer, and petroleum resin obtained by blending an organic peroxide with an inert isobutylene block copolymer and heat treatment. As a result, it was found that a thermoplastic resin composition excellent in adhesiveness with a polyacetal resin was obtained, and the present invention was 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. With respect to 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating 50% or more of a conjugated diene block of a block copolymer consisting of one and / or a hydrogenated product of a conjugated diene compound block copolymer,
(B) Thermoplastic elastomer composition containing 0.01 to 3 parts by weight of organic peroxide and (c) 1 to 80 parts by weight of carboxylated liquid polybutadiene: 5 to 60% by weight,
(B) Urethane-based thermoplastic elastomer: 95 to 40% by weight, and (C) Petroleum resin: 1 to 40 parts by weight per 100 parts by weight in total of components (A) and (B) A characteristic thermoplastic resin composition for bonding a polyacetal resin is provided.

  According to the second invention of the present invention, in the first invention, a polyacetal resin characterized in that the vinyl 1,2-bond in the microstructure of the polybutadiene of component (c) is 30% by weight or less. An adhesive thermoplastic resin composition is provided.

  According to a third invention of the present invention, in the first or second invention, the polyacetal is characterized in that the cis 1,4-bond in the microstructure of the polybutadiene of component (c) is 40% by weight or more. A thermoplastic resin composition for bonding a resin is provided.

  According to the fourth aspect of the present invention, in any one of the first to third aspects, the hydrogenated block copolymer of the component (a) has a polystyrene-equivalent number average molecular weight of 50,000 to 400,000. A thermoplastic resin composition for bonding a polyacetal-based resin is provided.

  According to a fifth invention of the present invention, in any one of the first to fourth inventions, (A) the thermoplastic elastomer composition, (d) 100 parts by weight of component (a) (d) rubber softener A thermoplastic resin composition for bonding a polyacetal resin is further provided, which further contains 1 to 350 parts by weight.

  According to a sixth invention of the present invention, in any one of the first to fifth inventions, in (A) the thermoplastic elastomer composition, (e) an ester-based crosslinking aid with respect to 100 parts by weight of the component (a). There is further provided a thermoplastic resin composition for bonding a polyacetal resin, which further contains 0.02 to 10 parts by weight of an agent.

  According to a seventh invention of the present invention, in any one of the first to sixth inventions, in (A) the thermoplastic elastomer composition, (f) an isobutylene polymer with respect to 100 parts by weight of the component (a). There is provided a thermoplastic resin composition for bonding a polyacetal resin, further comprising 1 to 500 parts by weight of an isobutylene block copolymer composed of a block and an aromatic vinyl polymer block.

  According to an eighth aspect of the present invention, the molding is characterized in that the thermoplastic resin composition for bonding a polyacetal resin according to any one of the first to seventh aspects and a polyacetal resin are heat-sealed. The body is provided.

  According to a ninth aspect of the present invention, there is provided the molded product according to the eighth aspect, wherein the thermal fusion with the polyacetal resin is thermal fusion by insert molding and / or two-color molding. Is done.

  According to the tenth invention of the present invention, in the eighth and ninth inventions, the polyacetal resin is any one of a homopolymer, a copolymer, or a modified polyacetal resin containing a third component. The body is provided.

  According to an eleventh aspect of the present invention, in any one of the eighth to tenth aspects, the polyacetal resin has a melt index (MI) measured at 190 ° C. and a load of 2160 g of 1 to 50 g / min. There is provided a molded body characterized in that the molded body is obtained by injection molding.

  The thermoplastic resin composition of the present invention is rich in flexibility, excellent in heat distortion resistance and molding processability, excellent in adhesion to a polyacetal resin, and suitably used as a thermoplastic resin composition for bonding a polyacetal resin. Can do.

  The present invention includes (a) hydrogenated block copolymer and / or hydrogenated conjugated diene compound block copolymer, (b) organic peroxide, (c) carboxylated liquid polybutadiene, d) Rubber softener, (e) Ester-based crosslinking agent, (f) Isobutylene block copolymer, (g) Thermoplastic elastomer composition (A) containing other components, Urethane-based thermoplastic elastomer composition (B), a thermoplastic resin composition for bonding a polyacetal resin containing a petroleum resin (C), and a molded body using the same. The components, production methods, and uses constituting the present invention will be described in detail below.

1. Component of composition (A) Thermoplastic elastomer composition (a) Hydrogenated block copolymer and / or hydrogenated conjugated diene compound block copolymer Water used for (A) thermoplastic elastomer composition of the present invention The hydrogenated product (a) of the additive block copolymer and / or the conjugated diene compound block copolymer exhibits rubber elasticity and mechanical properties.

  The hydrogenated block copolymer 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. It is a polymer obtained by hydrogenating 50% or more of an aliphatic double bond portion derived from a conjugated diene in a conjugated diene block. For example, hydrogenating a conjugated diene block of an aromatic vinyl compound-conjugated diene compound block copolymer having a structure such as ABA, BABA, ABBABA, etc. Examples thereof include a hydrogenated block copolymer obtained by hydrogenation at a rate of 50% or more.

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.
The content of the aromatic vinyl compound in the hydrogenated block copolymer is preferably 5 to 60% by weight, more preferably 20 to 50% by weight.

  As the aromatic vinyl compound constituting the hydrogenated block copolymer, for example, one or more kinds can be selected from styrene, α-methylstyrene, vinyltoluene, p-tert-butylstyrene, etc. Styrene is preferred. 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.

The number average molecular weight (Mn) in terms of polystyrene of the hydrogenated block copolymer is preferably 50,000 to 400,000, more preferably 60,000 to 350,000. When the number average molecular weight (Mn) is less than the lower limit, the mechanical properties and scratch resistance of the resulting thermoplastic resin composition are lowered. On the other hand, when the upper limit value is exceeded, the moldability deteriorates.
Here, the number average molecular weight is a value obtained by GPC on the basis of polystyrene having a known molecular weight. 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.

  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 is to hydrogenate aliphatic double bonds mainly derived from conjugated dienes of a conjugated diene block, and the hydrogenation rate needs to be 50% or more. When the hydrogenation rate is less than 50%, the flexibility tends to deteriorate.

  Specific examples of the hydrogenated block copolymer include styrene-ethylene / butene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), and styrene / ethylene / ethylene / propylene / styrene copolymer. Polymer (SEEPS), partially hydrogenated styrene-butadiene-styrene copolymer (SBBS), partially hydrogenated styrene-isoprene-styrene copolymer, partially hydrogenated styrene-isoprene / butadiene-styrene copolymer, etc. Can do. 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.

Examples of the hydrogenated conjugated diene compound block copolymer include a block copolymer (CEBC) having a crystalline ethylene block and an amorphous ethylene-butene block obtained by hydrogenating a block copolymer of butadiene. Etc. In the present invention, the hydrogenated product of the conjugated diene compound block copolymer may be used alone or in combination of two or more.
Moreover, the weight average molecular weight of the hydrogenated product of the conjugated diene block copolymer is 350,000 or less, preferably 30,000 to 250,000. If the weight average molecular weight exceeds 350,000, the moldability deteriorates.

(B) Organic peroxide (A) The organic peroxide used in the thermoplastic elastomer composition in the present invention generates radicals and causes the radicals to react in a chain manner to crosslink component (a). It works to dampen. At the same time, the component (c) carboxylated liquid polybutadiene is graft-polymerized, and the crosslinking and grafting reaction is promoted by the action of the component (e) to be blended as necessary, and the phase with the urethane elastomer in the thermoplastic resin composition. It works to improve tolerance.

  Examples of the component (b) include dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane, and 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 (b) is 0.01-3 weight part with respect to 100 weight part of component (a), Preferably it is 0.05-1.5 weight part. If 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 resin composition are deteriorated. Moreover, since the introduction of the functional group becomes insufficient, the moldability deteriorates due to the compatibility deterioration of the thermoplastic resin composition obtained, and the heat-fusibility with the polyacetal resin also decreases. On the other hand, even if it exceeds 3 parts by weight, the moldability of the resulting thermoplastic resin composition and the thermal fusing property with the polyacetal resin are deteriorated.

(C) Carboxylated liquid polybutadiene (c) Carboxylated liquid polybutadiene used in the thermoplastic elastomer composition of the present invention is mainly graft-polymerized in the presence of an organic peroxide on component (a) and contains a polar group. It fulfills the function of improving compatibility with the resin.
In particular, it is preferable to melt and knead the thermoplastic elastomer composition (A) in advance from the viewpoint of the efficiency of graft polymerization to the component (a).
The maleic anhydride, terminal hydroxyl group-containing liquid polybutadiene, and the like as in the prior art have problems such as gas generation and mixing of bubbles into the molded product depending on severe molding conditions, and the present invention uses the component (c) for the problem. It was solved by that.
Component (c) is a liquid polymer that is transparent at room temperature and has a main chain microstructure of polybutadiene of vinyl 1,2-bond type, trans 1,4-bond type, and cis 1,4-bond type. . 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 flexibility and moldability of the resulting thermoplastic resin composition deteriorate. Therefore, it is not preferable. Further, the cis 1,4-bond is preferably 40% by weight or more. When the cis 1,4-bond is less than 40% by weight, the thermoplastic resin composition obtained has flexibility, heat resistance and moldability. Since it gets worse, it is not preferable.

  (C) Carboxylated liquid polybutadiene is obtained by reacting liquid polybutadiene with a carboxyl group-introducing compound, and the ratio of 1,3-butadiene and carboxyl group-introducing compound constituting the liquid polybutadiene is 1,3-butadiene 80 ~ It is preferably 98% by weight and 2 to 20% by weight of the carboxyl group-introducing compound.

  The liquid polybutadiene used for the reaction preferably has a molecular weight of 500 to 10,000 as a number average, and desirably has a wide molecular weight distribution. Moreover, it is more preferable that liquid polybutadiene has an iodine value measured according to DIN53241 and iodine of 30 to 500 g / 100 g of substance. Further, the liquid polybutadiene preferably has a molecular structure of 70 to 90% cis-double bonds, 10 to 30% trans-double bonds, and 0 to 3% vinyl double bonds.

  As the carboxyl group-introducing compound, an ethylenically unsaturated dicarboxy compound such as an ethylenically unsaturated dicarboxylic acid, an anhydride or a monoester thereof can be used. Specific compounds include maleic acid, fumaric acid, itaconic acid, 3,6-tetrahydrophthalic acid, itaconic anhydride, 1,2-dimethylmaleic anhydride, maleic acid monomethyl ester or maleic acid monoethyl ester. Can be mentioned. Of these, maleic anhydride is preferred for reasons of economy and reactivity.

  Production of a polybutadiene / maleic anhydride-addition product comprising polybutadiene and maleic anhydride can be carried out by a known method.

  The acid value of maleated liquid polybutadiene according to DIN ISO 3682 is preferably 50 to 120 (mgKOH / g), more preferably 70 to 90 (mgKOH / g). When the acid value is less than 50 (mgKOH / g), the compatibility of the obtained thermoplastic elastomer composition with the polar group-containing resin is lowered, and when it exceeds 120 (mgKOH / g), the obtained thermoplastic elastomer composition is obtained. And the heat-resistant deformation property of a thermoplastic resin composition falls.

  Further, the maleation rate of the maleated liquid polybutadiene has a balance with the viscosity, but is preferably 6 to 20%, more preferably 6 to 15%, still more preferably 7 to 10%.

  Further, the viscosity (20 ° C.) of maleated liquid polybutadiene measured by DIN 53214 is preferably 3 to 16 Pa · s, more preferably 5 to 13 Pa · s, and further preferably 6 to 9 Pa · s.

Further, the maleated liquid polybutadiene has a vinyl-double bond of 30% or less, and those having a cis-double bond in the above range are more flexible than liquid polybutadiene having a cis-double bond less than the lower limit. And has a high maleation rate (acid value) as described above. Therefore, the obtained thermoplastic resin composition is rich in flexibility, easy to adjust the flexibility, and excellent in compatibility because it is sufficiently polar.
Liquid polybutadiene having a cis-double bond less than the above lower limit rapidly increases in viscosity as the maleation rate increases, but those having a cis-double bond in the above range have a small increase in viscosity. Since the viscosity is low as in the above range, the reactivity increases and the graft ratio to the component (a) increases. In addition, since the amount of gas generated during the molding process of the thermoplastic resin composition obtained is small, the working environment is good and bubbles are not generated inside the molded product.

  Examples of commercially available maleated liquid polybutadiene include POLYVEST OC 800S (registered trademark) and 1200S manufactured by Degussa.

  The compounding quantity of a component (c) is 1-80 weight part with respect to 100 weight part of component (a), Preferably it is 5-60 weight part. If the blending amount exceeds 80 parts by weight, the resulting thermoplastic resin composition will have noticeable stickiness due to bleed, thermal deformation resistance will be reduced, gas will be generated during molding, and drawdown will become prominent. Or releasability deteriorates. If the blending amount is less than 1 part by weight, in the thermoplastic resin composition, peeling, deformation, and flow marks are likely to occur in the molded product due to a decrease in compatibility, and the heat-fusibility with the polyacetal resin is lowered.

(D) Rubber Softener (A) In the thermoplastic elastomer composition used in the present invention, (d) a rubber softener can be used as necessary. The component (d) may be a non-aromatic rubber softener component or an aromatic rubber softener component, and an ester plasticizer may be used. In particular, a non-aromatic mineral oil or ester may be used. A plasticizer is preferred.

  As the non-aromatic mineral oil softener, paraffin-based softeners in which the number of carbon atoms in the paraffin chain occupies 50% or more of the total carbon number, particularly non-aromatic mineral oil or liquid or low molecular weight synthetic softening An agent can be mentioned. The mineral oil softener used for rubber is a mixture of the aromatic ring, naphthene ring, and paraffin chain, and the paraffin chain carbon number accounts for 50% or more of the total carbon number. A naphthene ring having 30 to 40% carbon atoms is distinguished by being called a naphthene type, and those having 30% or more aromatic carbon number being called aromatic.

  The mineral oil rubber softeners used as the non-aromatic rubber softeners of the present invention are classified into paraffinic and naphthenic ones. As the non-aromatic rubber softener of the present invention, paraffin-based ones are preferable, and paraffin-based ones having less aromatic ring components are particularly suitable. Examples of the liquid or low molecular weight synthetic softener include polybutene, hydrogenated polybutene, and low molecular weight polyisobutylene.

These non-aromatic rubber softeners have a dynamic viscosity at 37.8 ° C. of 20 to 50,000 cSt, preferably 20 to 1,000 cSt, and a dynamic viscosity at 100 ° C. of 5 to 1,500 cSt. Preferably, it is 5 to 100 cSt, the pour point is -10 to -25 ° C, and the flash point (COC) is 170 to 350 ° C. Furthermore, a thing with a weight average molecular weight of 100-2,000 is preferable.
Among these, aliphatic paraffin oils such as PW-90 and PW-380 manufactured by Idemitsu Kosan Co., Ltd. can be mentioned as non-aromatic rubber softeners that are generally available.

  Among the ester plasticizers, examples of the cyclic plasticizer include phthalic anhydride ester and trimellitic acid ester, N-cyclohexyl-p-toluenesulfonamide, dibenzyl sebacate, diethylene glycol dibenzoate, di- t-octylphenyl ether, dipropanediol dibenzoate, N-ethyl-p-toluenesulfonamide, isopropylidenediphenoxypropanol, alkylated naphthalene, polyethylene glycol dibenzoate, o, p-toluenesulfonamide, trimethylpentanediol dibenzoate 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.

  When blended, the amount of component (d) is preferably 1 to 350 parts by weight, more preferably 20 to 150 parts by weight, based on 100 parts by weight of component (a). When the blending amount exceeds 350 parts by weight, it is obtained. In the thermoplastic resin composition, bleeding tends to occur, and the heat-fusibility with the polyacetal resin also decreases.

(E) Ester-based crosslinking aid In the (A) thermoplastic elastomer composition used in the present invention, (e) an ester-based crosslinking aid can be used as necessary. The component (e) can be preferably blended in the crosslinking treatment with the above-mentioned (b) organic peroxide of the thermoplastic elastomer composition of the present invention, thereby performing a uniform and efficient crosslinking reaction. Can do.

  Specific examples of the component (e) 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, dipentaerythritol 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 (e) 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.

(F) Isobutylene-based block copolymer In the (A) thermoplastic elastomer composition used in the present invention, (f) an isobutylene-based block copolymer can be used as necessary. Component (f) is an isobutylene block copolymer composed of an isobutylene polymer block and an aromatic vinyl polymer block. The urethane thermoplastic elastomer and petroleum resin used in the thermoplastic resin composition of the present invention Excellent compatibility with. Component (f) is a thermoplastic elastomer that is inert to organic peroxides. By adding component (f), molding processing is carried out without reducing compatibility with urethane-based thermoplastic elastomers and petroleum resins. And flexibility can be improved.

  The isobutylene block copolymer used in the present invention may be any having any structure as long as it has a unit mainly composed of isobutylene and a unit mainly composed of an aromatic vinyl compound. However, from the balance of physical properties and ease of synthesis, a triblock body having a structure of (units mainly composed of aromatic vinyl compounds-units composed mainly of isobutylene-units composed mainly of aromatic vinyl compounds) A diblock body having a structure of a unit mainly composed of isobutylene-a unit mainly composed of an aromatic vinyl compound), or a mixture thereof can be used. There is no particular limitation on the ratio of the unit mainly composed of isobutylene of the block copolymer and the unit mainly composed of the aromatic vinyl compound, but from the balance of physical properties, the monomer 95 to 20 composed mainly of isobutylene. 5 to 80 parts by weight of a monomer mainly comprising an aromatic vinyl compound and 90 to 60 parts by weight of a monomer mainly comprising isobutylene and an aromatic vinyl compound The main monomer is preferably 10 to 40 parts by weight.

  The number average molecular weight of the isobutylene block copolymer is not particularly limited, but is preferably 30,000 to 500,000, particularly preferably 50,000 to 400,000. When the number average molecular weight is less than 30,000, the mechanical properties are lowered, and when it exceeds 500,000, the moldability is deteriorated.

  Examples of the aromatic vinyl compound used in the aromatic vinyl polymer block include styrene, α-methylstyrene, β-methylstyrene, p-methylstyrene, t-butylstyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, and indene. Etc. Among the above compounds, styrene, α-methylstyrene, p-methylstyrene, and indene are preferable from the balance of cost, physical properties, and productivity, and two or more of them may be selected.

  Specific examples of the isobutylene block copolymer include 103T (weight average molecular weight = 100,000) or 073T (weight average molecular weight = 65,000) manufactured by Kaneka Chemical Co., Ltd.

  When blended, the amount of component (f) is preferably 1 to 500 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of component (a). If the blending amount exceeds 500 parts by weight, the stickiness of the resulting thermoplastic resin composition becomes remarkable, the heat distortion resistance is lowered, the drawdown becomes remarkable, and the releasability is deteriorated.

(G) Other components (A) In the thermoplastic elastomer composition used in the present invention, various antioxidants such as phosphorus-based, phenol-based, and sulfur-based antioxidants, antioxidants, Various weathering agents such as light stabilizers and UV absorbers, copper damage prevention agents, modified silicone oils, silicone oils, waxes, acid amides, fatty acids, fatty acid metal salts, and various other lubricants, aromatic phosphate metal salts, gelols Various additives such as various nucleating agents, various plasticizers such as glycerin fatty acid ester, and various colorants can be used. In order to prevent troubles such as bleeding out on the surface of the molded product, (A) a material having high compatibility with the thermoplastic elastomer composition is preferable.

  The blending amount of the component (A) in the polyacetal resin-adhesive thermoplastic resin composition of the present invention is 5 to 60% by weight, preferably 100% by weight of the sum of the component (A) and the component (B), preferably 10 to 40% by weight. When the blending amount is less than 5% by weight, the effect of addition is not recognized. When the blending amount exceeds 60% by weight, the mechanical properties, heat resistance, dimensional stability, and moldability of the resulting thermoplastic resin composition deteriorate.

(B) Urethane-based thermoplastic elastomer (B) The urethane-based thermoplastic elastomer used in the thermoplastic resin composition for bonding a 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.

  (B) Specific examples of commercially available urethane-based thermoplastic elastomers include C80A10 (manufactured by Takeda Birdish), C80A50 (manufactured by Takeda Birdish), and ester (adipate) as ester (lactone) polyurethane copolymers. T-5000V (manufactured by DIC Bayer Polymer Co., Ltd.), TR-3080 (manufactured by DIC Bayer Polymer Co., Ltd.), and 1180A50 (manufactured by Takeda Birdish Co., Ltd.), T- Desmopan DesKU2-88586 (manufactured by DIC Bayer Polymer Co., Ltd.) and the like as ether-ester polyurethane copolymers, such as 8180 (manufactured by DIC Bayer Polymer Co., Ltd.), T-8283 (manufactured by DIC Bayer Polymer Co., Ltd.), etc. , They may be used singly or may be used in combination.

  The blending amount of the component (B) in the thermoplastic resin composition for bonding a polyacetal resin of the present invention is 95 to 40% by weight, where the total of the component (A) and the component (B) is 100% by weight, preferably 90 to 60% by weight. When the blending amount is less than 40% by weight, the effect of addition is not recognized, and when it exceeds 95% by weight, the flexibility of the obtained thermoplastic resin composition is lowered.

(C) Petroleum resin (C) Petroleum resin used in the thermoplastic resin composition for bonding a polyacetal resin of the present invention functions to specifically improve the heat-fusibility with a 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.

  The blending amount of the component (C) in the polyacetal resin-adhesive thermoplastic resin composition of the present invention is 1 to 40 parts by weight with respect to 100 parts by weight in total of the component (A) and the component (B), preferably Is 5 to 30 parts by weight. If the amount is less than 1 part by weight, the effect of addition is not recognized, and if it exceeds 40 parts by weight, the tackiness and moldability of the resulting thermoplastic resin composition are reduced.

2. Production of Thermoplastic Resin Composition The thermoplastic resin composition for bonding a polyacetal resin of the present invention is obtained by melting and kneading components (B), (C), and constituent components (a) to (c) of (A) in a lump. However, it is preferable from the viewpoint of compatibility that the components (a) to (c) of the component (A) are melt-kneaded and then further melt-kneaded with the components (B) and (C).
When the thermoplastic elastomer composition (A) used in the present invention is previously melt-kneaded, the above components (a) to (c) or components (d) to (g) and the like are added as necessary, and the respective components are added. Are melt-kneaded at the same time or in any order. 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 (A) used in the present invention has good compatibility with the urethane elastomer, and the flexibility, extrusion moldability, injection moldability, etc. of the resin having a polar group are reduced in heat resistance, oil resistance It is possible to form a thermoplastic resin composition without lowering the properties and bleeding of low molecular weight substances.

  After melt kneading the component (A) in advance, the melt kneading with the components (B) and (C) may be carried out by adding the antioxidant used in the thermoplastic elastomer composition as necessary. Can be produced by melting and kneading them simultaneously or in any order. The melt kneading in this case can be performed in the same manner as in the case of the component (A), but the temperature of the melt kneading is preferably 160 to 250 ° C.

3. The molded article using the thermoplastic resin composition The thermoplastic resin composition for bonding a polyacetal resin of the present invention is excellent in flexibility, heat distortion resistance, molding processability, oil resistance, abrasion resistance, and the like. In order to be excellent in adhesiveness to POM), the molded product from the thermoplastic resin composition and the molded product of POM are heat-sealed, or the thermoplastic resin composition is applied to a mold inserted with the POM molded product. A molded body can be easily obtained by injection, insert-molding a film of the thermoplastic resin composition into a POM molded body, or two-color molding.

The polyacetal resin is a polymer compound having an oxymethylene group (—OCH ₂ —) as a main structural unit, such as a polyacetal homopolymer or polyoxymethylene (for example, trade name “Delrin”, Asahi Kasei Kogyo Co., Ltd., USA) And a polyacetal copolymer containing an oxymethylene unit and a comonomer unit (for example, a product name “Duracon” manufactured by Polyplastics Co., Ltd.). In the copolymer, the comonomer unit includes an oxyalkylene unit (for example, an oxyethylene group (—OCH ₂ CH ₂ —), an oxypropylene group, an oxytetramethylene group having about 2 to 6 carbon atoms (preferably about 2 to 4 carbon atoms). Group). The content of the comonomer unit is a small amount, for example, 0.01 to 20 mol%, preferably 0.03 to 15 mol% (for example, 0.05 to 10 mol%), more preferably based on the whole polyacetal resin. It can select from the range of about 0.1-10 mol%.
The polyacetal copolymer may be a copolymer composed of two components, a terpolymer composed of three components, or the like. The polyacetal copolymer may be a random copolymer, a block copolymer (eg, Japanese Patent Publication No. 2-24307, manufactured by Asahi Kasei Kogyo Co., Ltd., trade names “Tenac LA”, “Tenac LM”, etc.), a graft copolymer, and the like. . Moreover, the polyacetal resin may have a branched structure as well as a linear structure, and may have a crosslinked structure. Furthermore, the terminal of the polyacetal resin may be stabilized by, for example, esterification with a carboxylic acid such as acetic acid or propionic acid or an anhydride thereof, urethanization with an isocyanate compound, or etherification. The polymerization degree, branching degree, and crosslinking degree of the polyacetal are not particularly limited as long as it can be melt-molded. Furthermore, it is preferable that injection molding can be performed, and a melt index (MI) measured at 190 ° C. and a load of 2160 g is preferably 1 to 50 g / min. When MI is too small, the processability is inferior, and when it is too large, the mechanical properties expected of polyacetal are inferior.

  As the heat-sealed molded product of the thermoplastic resin composition of the present invention and POM, a molded product obtained by insert molding and / or two-color molding is preferable, and in particular, electric wire / electric parts, industrial machine parts, medical equipment. It can be used for parts, food-related parts, automobile parts, building materials, etc.

  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.

1. Test method (1) Specific gravity: In accordance with JIS K 7112, the test piece was measured using a gel or solid sample.
(2) 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.
(3) 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 100 ° C)
(4) 100% elongation stress: In accordance with JIS K 6251, a 1 mm thick press sheet was punched into a No. 3 dumbbell type test piece and used. The tensile speed was 500 mm / min.
(5) 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. (6) 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 speed. A 13.5 × 13.5 × 2 mm sheet was formed with a pressure / pressure of 400 kg / cm ² , 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 (7) Extrudability: A sheet of 50 mm × 1 mm was extruded, the drawdown property, surface appearance and shape were observed, and evaluated according to the following criteria.
○: Good ×: Bad (8) Bleed resistance: The extruded sheet, which 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 ×: Poor (9) POM Adhesiveness: Composite molded body (width 25 mm × length 100 mm × thickness 5 mm) having an adherend (polyacetal (POM): Duracon M90S, manufactured by Polyplastics Co., Ltd.) as a core material Using a strip-shaped test piece, a 180 degree peel test (tensile speed of 200 mm / min) is performed to measure the peel strength (kN / 25 mm) at the fusion interface of the core material (POM) / skin material (thermoplastic resin composition). did.
(10) Hydrogenation rate of the conjugated diene block portion: A sample is taken in an NMR sample tube (5 mmφ), deuterated chloroform is added and dissolved sufficiently, and a nuclear magnetic resonance apparatus (NMR) JSX GSX-400 Using a mold, ¹ H-NMR measurement was performed at normal temperature, 400 MHz, and 3029 integrations to obtain a hydrogenation rate.

2. Samples used in Examples and Comparative Examples (1) Hydrogenated block copolymer (a-1): Septon 4077 (SEEPS; manufactured by Kuraray Co., Ltd.), 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 (2) Partially hydrogenated block copolymer (a-2): Tuftec P series JT90C (SBBS; manufactured by Asahi Kasei Corporation) ), Styrene content: 30% by weight, number average molecular weight: 99,000, weight average molecular weight; 110,000, molecular weight distribution; 1.11, hydrogenation rate of butadiene block: 75.1%, (1,2- (Butadiene hydrogenation rate 92.7%, 1,4-butadiene hydrogenation rate 61.0%)
(3) Organic peroxide (b): Perhexa 25B (2,5-dimethyl-2,5-di- (tert-butylperoxy) hexane; manufactured by NOF Corporation)
(4) Carboxylated liquid polybutadiene (c): POLYVEST OC 800S (manufactured by Degussa), viscosity (20 ° C.): 6000-9000 (mPa · s), acid value: 70-90 (KOH / g)
(5) Rubber softener (d): PW90 (trademark; manufactured by Idemitsu Petrochemical Co., Ltd.), number average molecular weight 980
(6) Ester-based crosslinking aid (e): TMPT (Trimethylol Propane Trimethacrylate; manufactured by Shin-Nakamura Chemical Co., Ltd.) Molecular weight: 338,
(7) SIBS (styrene-isobutylene-styrene block copolymer obtained by living cationic polymerization) (f): SIBSTER 103T (SIBS; manufactured by Kaneka Chemical Co., Ltd.), styrene content: 31% by weight, number average molecular weight : 96,000, weight average molecular weight: 105,000, molecular weight distribution: 1.09, hardness: 57A, unsaturated bond: 0%
(8) Hindered phenol / phosphite / lactone composite antioxidant (g): HP2215 (manufactured by Ciba Specialty Chemicals)
(9) Urethane thermoplastic elastomer (TPU) (B): Pandex T-8180 (manufactured by DIC Bayer Polymer Co., Ltd.)
(10) Petroleum resin (C): Imabe P-140 (manufactured by Idemitsu Petrochemical Co., Ltd.): Specific gravity: 1.03, Average molecular weight: 930, Softening point: 140 ° C.
(11) Polyacetal (POM): Duracon M90S (manufactured by Polyplastics Co., Ltd.)

(Examples 1-4, Comparative Examples 1-8)
Using each component in the amount shown in Table 1, the mixture was put 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, pelletized, and shown in Table 1 ( The thermoplastic elastomer compositions A-1) to (A-8) were obtained.
Next, the thermoplastic elastomer compositions (A-1) to (A-8), the urethane-based thermoplastic elastomer (TPU), and the petroleum resin are blended in the proportions shown in Table 2, and a twin screw extruder having an L / D of 47. The mixture was melt-kneaded at a kneading temperature of 200 ° C. and a screw rotation speed of 350 rpm, and 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. Moreover, evaluation in the case of only TPU and petroleum resin was performed as Comparative Example 5, and evaluation in the case of TPU alone was performed as Comparative Example 6. The results are shown in Table 2.

  As is apparent from Tables 1 and 2, the thermoplastic elastomer composition (A) having the composition ratio of the present invention is used, and the thermoplastic resin composition in which TPU and petroleum resin are blended at the composition ratio of the present invention is good. It showed properties and was excellent in adhesiveness with POM (Examples 1 to 4).

On the other hand, in Comparative Examples 1 and 2, the amount of component (b) in the thermoplastic elastomer composition (A) is out of the scope of the present invention. If the component (b) is less than the lower limit, the compatibility of the resulting thermoplastic resin composition with TPU, the heat-fusibility with POM is lowered, and the molding processability such as surface layer peeling is deteriorated. When the upper limit is exceeded, the appearance of the product deteriorates and the mechanical properties, gloss unevenness, pinholes and the like of the resulting thermoplastic resin composition deteriorate.
In Comparative Examples 3 and 4, the amount of component (c) in the thermoplastic elastomer composition (A) is out of the scope of the present invention. When the component (c) is less than the lower limit, the compatibility with TPU is lowered, and the fusion property with POM is lowered. When the component (c) exceeds the upper limit, the mechanical properties are lowered, and the stickiness of the product is deteriorated.
Comparative Example 5 is an alloy of component (B) and component (C). In the absence of component (A), defects in molding processability were observed.
In Comparative Example 6, only the component (B) was contained, and the component (A) and the component (C) were not included.
In Comparative Example 7, the component (C) was less than the lower limit, and the fusibility with POM was deteriorated.
In Comparative Example 8, the component (C) exceeded the upper limit and the tackiness was deteriorated.

  The thermoplastic resin composition of the present invention is excellent in heat distortion resistance, molding processability and bleed resistance, and is excellent in heat fusion with a polyacetal resin. The thermoplastic resin composition is rich in flexibility, excellent in heat distortion resistance, molding processability and bleed resistance, and in the fields of electric wires / electric parts, industrial machine parts, medical equipment / food-related parts, automobile parts, building materials, etc. Can be used for

Claims (9)

(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 With respect to 100 parts by weight of a hydrogenated block copolymer obtained by hydrogenating 50% or more of
(B) 0.01 to 3 parts by weight of an organic peroxide, and (c) a thermoplastic elastomer composition containing 1 to 80 parts by weight of maleated liquid polybutadiene obtained by reacting liquid polybutadiene with maleic anhydride : 5-60% by weight,
(B) Urethane-based thermoplastic elastomer: 95 to 40% by weight, and (C) Petroleum resin: Polyacetal system containing 1 to 40 parts by weight with respect to 100 parts by weight in total of component (A) and component (B) A thermoplastic resin composition for resin bonding,
The polyacetal resin-adhesive thermoplastic resin composition, wherein the polybutadiene of the component (c) satisfies all of the following (i) to (iii):
(I) The vinyl 1,2-bond in the microstructure of the polybutadiene of component (c) is 30% by weight or less, and the cis 1,4-bond in the microstructure of the polybutadiene of component (c) is 40% by weight or more. It is .
(Ii) The acid value according to DIN ISO 3682 of the polybutadiene of component (c) is 70 to 90 (mgKOH / g).
(Iii) The viscosity (20 ° C.) measured by DIN 53214 of the polybutadiene of the component (c) is 6 to 9 Pa · s.   The thermoplastic resin composition for bonding a polyacetal resin according to claim 1, wherein the number average molecular weight in terms of polystyrene of the hydrogenated block copolymer of component (a) is in the range of 50,000 to 400,000. object.   3. The polyacetal system according to claim 1, wherein (A) the thermoplastic elastomer composition further comprises 1 to 350 parts by weight of (d) a rubber softening agent for 100 parts by weight of component (a). A thermoplastic resin composition for resin bonding.   The thermoplastic elastomer composition (A) further comprises 0.02 to 10 parts by weight of (e) an ester-based crosslinking aid with respect to 100 parts by weight of the component (a). The thermoplastic resin composition for bonding a polyacetal resin according to claim 1.   (A) In the thermoplastic elastomer composition, 1 to 500 parts by weight of an isobutylene block copolymer composed of (f) an isobutylene polymer block and an aromatic vinyl polymer block with respect to 100 parts by weight of the component (a) The thermoplastic resin composition for bonding a polyacetal resin according to any one of claims 1 to 4, further comprising:   A molded article obtained by heat-sealing the polyacetal resin-adhesive thermoplastic resin composition according to any one of claims 1 to 5 and a polyacetal resin.   The molded article according to claim 6, wherein the thermal fusion with the polyacetal resin is thermal fusion by insert molding and / or two-color molding.   The molded article according to claim 6 or 7, wherein the polyacetal resin is any one of a homopolymer, a copolymer, and a modified polyacetal resin containing a third component.   The polyacetal resin has a melt index (MI) of 1 to 50 g / min measured at 190 ° C. and a load of 2160 g, and the molded product is obtained by injection molding. The molded product according to Item.