JPH07126474A - Thermoplastic elastomer composition having excellent adhesiveness - Google Patents

Abstract

PURPOSE:To provide a thermoplastic elastomer composition composed of each specific hydrogenated block copolymer, modified block copolymer and thermoplastic polyurethane elastomer, etc., capable of firmly bonding to a resin, having excellent moldability, thermal stability in molding, appearance of molded article and oil resistance and useful for interior trim of automobile, etc. CONSTITUTION:The objective composition is composed of (A) a hydrogenated block copolymer having a number-average molecular weight of 30,000-300,000 and obtained by hydrogenating a block copolymer composed of (i) a polymer block composed mainly of at least one vinyl aromatic compound and (ii) a polymer block composed mainly of at least one conjugated diene compound, (B) a modified block copolymer obtained by bonding carboxylic acid group, etc., to a hydrogenated block copolymer having a number-average molecular weight of 30,000-100,000 and produced by the hydrogenation of a block copolymer composed of the component (i) and the component (ii), (C) a thermoplastic polyurethane elastomer, (D) a hindered phenol of the formula I, etc., and (E) a phosphite compound of the formula II, etc.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention has a strong adhesive property with resin.
The present invention also relates to a thermoplastic elastomer composition which is excellent in molding processability and thermal stability during molding, molding appearance, oil resistance, mechanical strength, and rubber properties.

[0002]

2. Description of the Related Art Conventionally, by adhering dissimilar materials to form a laminate, the advantages of both materials are imparted, or by disposing different materials with the same material to form a laminate. There are attempts to produce laminates that compensate for the shortcomings of these materials. In particular, in recent years, in order to improve the cheap feeling and the uncomfortable feeling of plastic, an attempt has been made to laminate rubber on the plastic. The laminated rubber is soft to the touch, has a good feel, has a high-class feel, and has excellent soundproofing and vibration-proofing properties. Therefore, it can be said that it is suitable for automobile interior parts and home electric appliance parts. As a thermoplastic resin which is a material of such a laminate, polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, nylon, polycarbonate, polystyrene, impact resistance Polystyrene, polyacetal, polyvinyl chloride, polyvinylidene chloride,
PMMA resin, AS resin, ABS resin or the like, or a mixture of two or more kinds of these is used. As a form of these laminates, they are used as sheets, films, or molded articles having complicated shapes.

For these laminates, generally, a method of adhering the same or different materials with an adhesive, a method of forming a laminate by a multi-layer extrusion method or a multi-layer injection molding method without using an adhesive, etc. are generally used. It is being appreciated. Examples of the multi-layer molding method described here include a multi-layer extrusion molding method and a multi-layer blow molding method in which a thermoplastic resin layer and a thermoplastic elastomer layer are simultaneously extruded by a plurality of extruders, and both layers are heat-sealed in a molten state. A layer that constitutes one side, such as a molding method (for example, a thermoplastic resin layer)
Is molded in advance, and the melt of the layer (for example, thermoplastic elastomer layer) constituting the other is supplied and heat-sealed to obtain a laminate easily by a molding method such as multi-layer injection molding. Obtainable.

However, depending on the kind of materials to be laminated or a combination thereof, a sufficient adhesive effect may not be obtained, and in particular, when a laminate is obtained by a multi-layer extrusion method or a multi-layer injection molding method without using an adhesive. , It is not possible to use materials that do not heat-bond to each other. for that reason,
In the case of obtaining a laminate of materials which are not heat-fusible to each other by the multi-layer extrusion method, a method of using a material having heat-fusible property for both materials as an adhesive layer is used.
Vinyl acetate copolymers, ionomer resins, styrene-butadiene block copolymers and the like are used. However, these resins also have problems in that a sufficient adhesive effect may not always be obtained depending on the type of material to be extruded in multiple layers, and the durability of adhesive strength, water resistance, etc. are poor. Furthermore, it is difficult to use an adhesive layer in the case of an injection-molded product having a complicated shape, and under the present circumstances, the multi-layer injection molding method can be performed only in the case of a limited combination having adhesiveness.

In order to solve these problems, as a further advanced technique, the one obtained by adding a thermoplastic polymer having a polar group to an acid-modified hydrogenated block copolymer described in JP-B-62-13911 is used. Techniques for doing so are disclosed. The laminate described in the publication is a resin having polarity, glass,
Shows excellent adhesion to metals and the like, which is an effective method, but may have poor fluidity depending on the combination of compositions,
There is a problem that it is difficult to obtain a molded product having a complicated shape.

Further, JP-A-63-254156 discloses a composition in which a thermoplastic polyurethane is blended with an acid-modified hydrogenated block copolymer. However, although the composition described in this publication is a useful composition which exhibits excellent properties such as mechanical strength and adhesiveness with other resins, it is inferior in moldability and further improvement is desired. Furthermore, JP-A-64
No. 33201 discloses a composition comprising a thermoplastic polyurethane having a specific viscosity and a non-hydrogenated block copolymer or a hydrogenated block copolymer. However, since the composition described in this publication has a poor affinity between the thermoplastic polyurethane and the non-hydrogenated or hydrogenated block copolymer, the mechanical strength is low, and there is a problem that peeling occurs in the molded product, and further improvement is required. Is desired.

Further, JP-A-3-234755 discloses a composition of a hydrogenated block copolymer, an acid-modified hydrogenated block copolymer, and a thermoplastic polyurethane elastomer. The composition described in this publication enhances the affinity between the hydrogenated block copolymer and the thermoplastic polyurethane elastomer, and the mechanical strength is significantly improved. But,
These are inferior in thermal stability at the time of molding unless a proper heat stabilizer is selected, and the range of the temperature at which the adhesive strength with different materials is obtained and the temperature at which the thermoplastic polyurethane elastomer starts thermal decomposition is very narrow. However, there is a problem that molding is difficult.

[0008]

DISCLOSURE OF THE INVENTION The present invention is directed to injection molding,
It provides a thermoplastic elastomer having excellent molding processability such as extrusion molding and appearance, high adhesiveness with a polar resin, and excellent mechanical strength and rubber properties. The present invention provides a thermoplastic elastomer composition suitable for use.

[0009]

The present invention provides (a) a polymer block A containing at least one vinyl aromatic compound as a main component and a polymer block B containing at least one conjugated diene compound as a main component. 100 parts by weight of a hydrogenated block copolymer having a number average molecular weight of 30,000 to 300,000 obtained by hydrogenating a block copolymer consisting of (b) a polymer block A mainly composed of at least one vinyl aromatic compound And a hydrogenated block copolymer having a number average molecular weight of 30,000 to 100,000, which is obtained by hydrogenating a block copolymer consisting of at least one conjugated diene compound-based polymer block B,
10 to 200 parts by weight of a modified block copolymer to which a molecular unit containing a carboxylic acid group or a derivative group thereof is bound,
(C) Thermoplastic polyurethane elastomer 10-250
A thermoplastic elastomer composition, characterized in that it comprises 0.01 part by weight of (d) 0.01 to 4 parts by weight of hindered phenol and 0.01 to 4 parts by weight of (e) phosphite compound.

The hindered phenol (d) is at least one of the compounds of the following general formulas (1) to (3), and the phosphite compound is the following general formulas (4) to (3).
It is preferable that the thermoplastic elastomer composition according to claim 1 is at least one kind of the compound of (6).

[0011]

[Chemical 3]

(Wherein R _{1 to} R ₈ are a hydrogen atom, a halogen, or an alkyl group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, or these groups are an alkyl group, an aryl group. Groups, alkoxy groups, aryloxy groups, heterocyclic groups, halogens, etc. may be substituted, and these may be the same or different, provided that the two substituents in the ortho position with respect to the OH group. At least one of them is the above-mentioned substituent containing at least one carbon atom, and x, x ′,
y represents an integer of 1 to 20 and n represents an integer of 2 to 6, respectively, and Z represents an atom of any of C, Si, S, Sn, and Zn. )

[0013]

[Chemical 4]

(Wherein R _{1 to} R ₁₀ are alkyl groups having 1 to 20 carbon atoms, alkoxy groups, halogen-substituted alkyl groups,
Aryl-substituted alkyl group, halogen-substituted alkoxy group,
Aryl-substituted alkoxy group or the like, and _R'1, R'
₂ is an alkylene group having 1 to 20 carbon atoms, an arylene group, a halogen-substituted alkylene group, a halogen-substituted arylene group,
It represents an aryl-substituted alkylene group, an alkyl-substituted arylene group or the like, which may be the same or different. Further, x, x ', y, y'represent an integer of 1 to 20, n is an integer of 1 to 10, and l and m are integers of 0 to 3, respectively, and always satisfy l + m = 3. ) Hereinafter, the present invention will be described in detail.

The hydrogenated block copolymer used as the component (a) in the present invention is at least 1, preferably 2 units.
A block copolymer obtained by hydrogenating a block copolymer consisting of at least one vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B. Yes, for example, AB
-A, B-A-B-A, A-B-A-B-A, B-A-
B-A-B, (A -B) 4 -Si, (B-A-B) 4 -
It has a structure such as Si, (A-B) _4- Sn, (B-A-B) _4- Sn.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing these conjugated diene compounds have a distribution of the vinyl aromatic compound or the conjugated diene compound in each polymer block. It may be random or tapered (in which the monomer component increases or decreases along the molecular chain), partially block-like or any combination thereof, and when each of the polymer blocks B is two or more, The polymer blocks may have the same structure or different structures. As used herein, the expression "based on" means that the monomer units in question are at least 50% by weight of the polymer block, preferably at least 70%.
Means to occupy the above.

Examples of the vinyl aromatic compound constituting the block copolymer of the present invention include styrene, α-methylstyrene, p-vinyltoluene, p-tertiary butylstyrene (hereinafter the third is abbreviated as t-). ) And the like, one kind or two or more kinds can be selected, and styrene is preferable among them.
Examples of the conjugated diene compound include butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-
One type or two or more types can be selected from 1,3-butadiene and the like, and among them, butadiene, isoprene and a combination thereof are preferable. The polymer block B mainly composed of the conjugated diene compound before hydrogenation can have a microstructure in the block arbitrarily selected. For example, in the case of a polybutadiene block, a 1,2-vinyl bond structure is used. Is 20 to 50% by weight, preferably 25 to 45% by weight, and in the polyisoprene block, 1,4-bond is 80% by weight or more, preferably 90% by weight or more.

The number average molecular weight of the hydrogenated block copolymer used as the component (a) of the present invention is 30,000 to 300,000,
More preferably, it is 80,000 to 200,000. By using the hydrogenated block copolymer having a number average molecular weight in the range of 30,000 to 300,000, it is possible to obtain a composition having an excellent balance of molding processability and physical properties such as mechanical strength and compression set. Further, the molecular weight distribution of the hydrogenated block copolymer [ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn) (Mw / M
n)] is 5 or less, preferably 2 or less, more preferably 1.5 or less. If the molecular weight distribution exceeds 5, the mechanical strength and heat resistance of the elastomer composition are not sufficient, which is not preferable.

The number average molecular weight and molecular weight distribution of these hydrogenated block copolymers can be easily determined by gel permeation chromatography using standard polystyrene. These block copolymers are not limited as long as they have the above-mentioned structure, and the production method thereof is not limited. For example, according to the method described in Japanese Examined Patent Publication No. 40-23798, a lithium catalyst is used. A vinyl aromatic compound-conjugated diene compound block copolymer can be synthesized in an active solvent. Further, as a method for producing a hydrogenated vinyl aromatic compound-conjugated diene compound block copolymer that exhibits more preferable performance,
For example, Japanese Patent Publication No. 42-8704 and Japanese Patent Publication No. 43-6.
Although the method described in Japanese Patent No. 636 may be used, the use of a titanium-based hydrogenation catalyst is recommended, especially in applications requiring high weather resistance and heat aging resistance.
No. 20147, JP-A-61-33132 or JP-A-62-207303. The aliphatic double bond derived from the conjugated diene compound at that time is
It is selected such that at least 80%, preferably 90% or more, is hydrogenated, while less than 20%, preferably less than 10% of the vinyl aromatic compound is hydrogenated. The hydrogenation rate of the hydrogenated block copolymer can be easily known by infrared spectroscopic analysis or nuclear magnetic resonance analysis.

Next, the acid-modified hydrogenated block copolymer used as the component (b) of the present invention will be described. The hydrogenated block copolymer which is the basis of the acid-modified hydrogenated block copolymer used as the component (b) of the present invention is at least 1
Hydrogenated block copolymer consisting of one, preferably two or more vinyl aromatic compound-based polymer block A and at least one conjugated diene compound-based polymer block B It is a block copolymer, and is, for example, ABA, BABAA, ABA.
-B-A, B-A-B-A-B, (A-B) _4- Si,
(B-A-B) ₄ -Si, (A-B) _4- Sn, (B-
AB) _4- Sn or the like.

Further, the polymer block A mainly containing these vinyl aromatic compounds and the polymer block B mainly containing these conjugated diene compounds have a distribution of the vinyl aromatic compound or the conjugated diene compound in each polymer block. They may be random, tapered, partially block-shaped or any combination thereof, and when there are two or more polymer blocks B, each polymer block may have the same structure or different. It may be a structure.

The vinyl aromatic compound constituting the block copolymer of the present invention is, for example, one or more of styrene, α-methylstyrene, p-vinyltoluene, pt-butylstyrene and the like. Can be selected, and styrene is particularly preferable. As the conjugated diene compound, for example, one kind or two or more kinds can be selected from butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and the like, and among them, butadiene, isoprene and these Combinations are preferred. The polymer block B mainly composed of the conjugated diene compound before hydrogenation can have a microstructure in the block arbitrarily selected. For example, in the case of a polybutadiene block, a 1,2-vinyl bond structure is used. Is 2
0 to 50% by weight, preferably 25 to 45% by weight,
In the polyisoprene block, 1,4-bonds are 80
It is at least wt%, preferably at least 90 wt%.

The modified hydrogenated block copolymer used as the component (b) of the present invention has a number average molecular weight of 30,000 to 100,000, more preferably 35,000 to 70,000. By using the modified hydrogenated block copolymer having a number average molecular weight in the range of 30,000 to 100,000, a composition having an excellent balance of physical properties such as moldability and mechanical strength can be obtained. The component (b) of the present invention is a hydrogenated block copolymer to which a molecular unit containing a carboxylic acid group or a derivative group thereof is bonded. Examples of such a compound containing a carboxylic acid group or a derivative group thereof include maleic acid, halogenated maleic acid, itaconic acid, cis-4-cyclohexene-1,
2-dicarboxylic acid, endo-cis-bicyclo (2,2,2
1) -5-heptene-2,3-dicarboxylic acid, etc., anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, crotonic acid, etc., and esters of these monocarboxylic acids, for example, methacrylic acid Derivatives such as methyl, glycidyl methacrylate and amide can be mentioned. Of these, maleic anhydride is particularly preferable.

The addition amount of the compound containing a carboxylic acid group or its derivative group is 0.1 to 20 parts by weight,
Desirably 0.1 to 10 parts by weight, more preferably 0.1
~ 5 parts by weight. By using the component (b) in which the carboxylic acid group or its derivative group is introduced into the hydrogenated block copolymer, the compatibility between the component (a) and the component (c) of the present invention is remarkably improved, and the composition of the present invention is improved. The adhesive strength with a resin having a polar group is improved, and the mechanical properties are also improved, but if the addition amount of the carboxylic acid group or its derivative group is too large, the fluidity of the composition decreases and the molding process The problem that the sex deteriorates occurs. On the other hand, when the addition amount of the carboxylic acid group or its derivative group is too small, the effect of improving the compatibility between the component (a) and the component (c) of the present invention becomes insufficient. Therefore, the above-mentioned addition amount is desirable.

The amount of the component (b) used in the present invention is in the range of 10 to 200 parts by weight per 100 parts by weight of the component (a) of the present invention. If the amount of the component (b) used is less than 10 parts by weight, the effect of improving the compatibility is insufficient and a composition having an excellent appearance cannot be obtained. Further, even if a large amount is used in excess of 200 parts by weight, the compatibility effect reaches a ceiling, and the fluidity is markedly deteriorated, and the composition is not excellent in appearance as well. Therefore, the above range is suitable. A more desirable range is 20 to 100 parts by weight.

The thermoplastic polyurethane elastomer used as the component (c) of the present invention is obtained by addition-polymerizing a long-chain glycol and a short-chain glycol having active hydrogen at both ends using a diisocyanate compound. There are no particular restrictions on the compound used, but typical long-chain glycols are polyesters, polyethers, polycarbonates and the like. In the polyester system, dehydration condensation products of adipic acid and various glycols such as poly (ethylene adipate), poly (diethylene adipate), and poly (1,4-
Butylene adipate), poly (1,6-hexane adipate) and the like, and polycaprolactone and the like can also be used.
As the polyether type, polyethylene glycol, polypropylene glycol, poly (propylene glycol /
Ethylene glycol) and the like, and examples of the polycarbonate type include poly (1,6-hexamethylene glycol carbonate) and the like.

Polyolefin glycols are also useful, and polybutadiene diol, polyisoprene diol, and hydrogenated products thereof can be preferably used. Aliphatic glycols, aromatic glycols and the like are typical as short-chain glycols, and if specific compound names are shown, aliphatic glycols include ethylene glycol, 1,3-propylene glycol, 1,4 -Butane glycol, 1,5-pentane glycol, 1,6-
Hexane glycol and the like can be exemplified, and examples of the aromatic glycol system include bisphenol A, hydroquinone diethylol ether, bisphenol A / ethylene glycol and the like.

The diisocyanate includes aromatic, alicyclic and aliphatic diisocyanates such as tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate and hexamethylene diisocyanate. ,
Examples include isophorone diisocyanate, and xylylene diisocyanate and hydrogenated products of 4,4′-diphenylmethane diisocyanate.

The thermoplastic polyurethane elastomer used as the component (c) of the present invention has the following synthesis conditions.
It is classified into a complete thermoplastic type and an incomplete thermoplastic type. These are determined by the molar ratio of the OH group of the bifunctional long-chain glycol and the short-chain glycol of the raw material and the NCO group of the diisocyanate, and were synthesized by about 0.95 ≦ NCO / OH ≦ 1. And the incomplete thermoplastic type was synthesized with about 1 <NCO / OH <1.1. Either of these can be used as the component (c) of the present invention.

The amount of component (c) used in the present invention is 10 to 250 parts by weight per 100 parts by weight of component (a). 10
If the amount used is less than parts by weight, the adhesiveness with the resin having a polar group will be insufficient, and conversely, if the amount used exceeds 250 parts by weight, the effect of the adhesiveness will reach the ceiling and rather the compression set will be reduced. That the physical properties such as decrease occurs, further water absorption becomes large, and the cost of the composition increases,
The desired composition cannot be obtained. A more desirable amount used is in the range of 40 to 200 parts by weight.

The hindered phenol in the present invention refers to a compound represented by the following general formula (7).

[0032]

[Chemical 5]

Here, R _{1 to} R ₅ are hydrogen atom, halogen, or an alkyl group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, or the above groups are an alkyl group or an aryl group. , An alkoxy group,
It may be substituted with an aryloxy group, a heterocyclic group, halogen or the like, and among these substituents, ether, ester, urethane, amide, carbonyl, phosphate ester, nitrate ester, thioether are included. , Sulfoxide, sulfone, thiocarbonyl, sulfamide, secondary amine, tertiary amine and the like, and further sulfate, phosphate, nitrate, ammonium salt and the like can be contained. Further, these groups may be the same or different from each other. However, at least one of the two substituents in the ortho position to the OH group is the above-mentioned substituent containing at least one carbon atom. Specific compound names are:
2-methylphenol, 2,6-di-t-butyl-p-
Cresol, 2-methyl-6-isopropylphenol, 2-t-butyl-4-methylphenol, 2-amylphenol, 2-nonylphenol, 2-dodecylphenol, 2,6-diphenyl-4-octadecyloxyphenol, 4 , 4'-thiobis (6-t-butyl-m
-Cresol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), bis [3,3-bis (4- Hydroxy-3-t-butylphenyl) butanoic acid] glycol ester, 2,2′-ethylidene bis (4,6-di-t-butylphenol),
2,2'-ethylidene bis (4-s-butyl-6-t-
Butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane,
Bis [2-t-butyl-4-methyl-6- (2-hydroxy-3-t-butyl-5-methylbenzyl) phenyl] terephthalate, methylenebis-2- (2,6-di-t-butyl)- Phenol, [2,2-bis (2-hydroxyphenyl)] propane, 2-eicosylphenol, 2,4,6-triicosylphenol, 1,3-
Bis (2-hydroxyphenyl) -2-methyl-2-t
-Butylpropane, stearyl (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, distearyl (3,5-di-t-butyl-4-hydroxybenzyl) phosphonate, triethyleneglycol-bis [ 3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] , 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionic acid amide], 2,4-bis- (n-octylthio) -6- (4- Hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,3
5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], octadecyl-3- (3,5-di-
t-Butyl-4-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-
Butyl-4-hydroxy-hydrocinnamide), 3,
5-di-t-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) benzene, bis (3,5-di-
t-Butyl-4-hydroxybenzylethyl phosphate) calcium, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1,
3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene,
1,3,5-Tris [(3,5-di-t-butyl-4-
Hydroxyphenyl) propionyloxyethyl] isocyanurate, 2-t-butyl-4-methyl-6- (2
-Acryloyloxy-3-t-butyl-5-methylbenzyl) phenol, 3,9-bis [1,1-dimethyl-2-{(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy } Ethyl] -2,4
8,10-tetraoxaspiro [5,5] undecane,
2,4-bis [(octylthio) methyl] -6-methylphenol and the like can be mentioned. Among them, preferred examples of the hindered phenol include at least one compound corresponding to any one of the above general formulas (1) to (3).

Specific examples of these hindered phenols include triethylene glycol-bis [3- (3-t-
Butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-). Butyl-4-hydroxyphenyl) propionate] and the like.

The composition of the present invention has these formulas (1) to (3).
It is preferable to use one or a combination of two or more of the hindered phenols shown in (4) above. Among them, triethylene glycol-bis [3- (3-t-butyl-
5-Methyl-4-hydroxyphenyl) propionate] is most preferred. The amount of component (d) used in the present invention is
0.01 to 100 parts by weight of the hydrogenated block copolymer
It is 4 parts by weight, more preferably 0.05 to 3 parts by weight. If the amount is less than 0.01 parts by weight, the effect of improving the thermal stability at the time of molding becomes insufficient, and even if 4 parts by weight or more is added, the effect of improving the thermal stability reaches a peak, and the cost of the composition is rather lowered. It causes rise.

The phosphite compound in the present invention refers to a compound represented by the following general formula (8) and / or (9).

[0037]

[Chemical 6]

Here, R _{1 to} R ₃ represent an alkyl group having 1 to 30 carbon atoms, an aryl group, an aryl-substituted alkyl group, an alkyl-substituted aryl group, a halogen-substituted alkyl group, a halogen-substituted aryl group, etc., and these are the same. However, they may be different from each other, and may be cyclically bonded to each other. R ′ _{1 to} R ′ ₄ are alkylene groups having 1 to 20 carbon atoms, arylene groups, halogen-substituted alkylene groups, halogen-substituted arylene groups, alkyl-substituted arylene groups, aryl-substituted alkylene groups, alkoxy-substituted alkylene groups, aryloxy-substituted alkylene groups. Represents an alkoxy-substituted arylene group, and these may be the same or different. Moreover, n shows the integer of 1-5. Specific compound names include trimethylphosphite, triethylphosphite, tri (n-propyl) phosphite, triisopropylphosphite, tri (n-butyl) phosphite,
Tri (t-butyl) phosphite, tri (n-pentyl) phosphite, tri (n-hexyl) phosphite, tri (n-heptyl) phosphite, tri (n-octyl) phosphite, tri (n-nonyl) ) Phosphite, tri (n-decyl) phosphite, tri (n-octadecyl) phosphite, triphenylphosphite,
n-octyl-diphenylphosphite, tris (4-
n-nonylphenyl) phosphite, bis (monononylphenyl) dinonylphenylphosphite, tris (4
-Methylphenyl) phosphite, tris (2,4-dimethylphenyl) phosphite, tris (4-chlorophenyl) phosphite, tris (2,4-dichlorophenyl) phosphite, tris (4-t-butylphenyl) phosphite , Tris (2,4-di-t-butylphenyl) phosphite, bis (n-octadecyl) pentaerythritol-di-phosphite, bis (2,4-
Di-t-butylphenyl) pentaerythritol-di-
Examples include phosphite and bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite. Among them, preferred examples of the phosphite-based compound include the above-mentioned general formula (4). To at least one compound corresponding to any one of (6) to (6).

Specific examples of these phosphite compounds include triphenyl phosphite and tris (2,4-di-).
t-butylphenyl) phosphite, bis (n-octadecyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,6-di) -T-butyl-4-methylphenyl) pentaerythritol-di-phosphite and the like.

The composition of the present invention has these general formulas (4) to
It is preferable to use one kind or a combination of two or more kinds of the phosphite compounds shown in (6), and among them, it is most preferable to select from the above specific examples.
The amount of component (e) used in the present invention is 0.01 to 4 parts by weight, and more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the hydrogenated block copolymer. If the amount is less than 0.01 parts by weight, the effect of improving the thermal stability at the time of molding becomes insufficient, and even if 4 parts by weight or more is added, the effect of improving the thermal stability reaches a peak, and the cost of the composition is rather lowered. It causes rise.

The thermal stability of the composition of the present invention exerts an additive effect by using the components (d) and (e) together.
This makes it possible to easily obtain a multi-layer molded product having a good molding appearance and excellent adhesive strength. Hydrocarbon oils can be preferably added to the composition of the present invention. Hydrocarbon oil is a component useful not only for imparting flexibility and processability to the resulting composition but also for improving economic efficiency. The hydrocarbon oil used in the present invention is a generally known diluting oil for rubber classified into paraffinic type and naphthenic type. Of these, paraffinic oils are preferred, and among paraffinic oils, those having an aromatic ring component of 5% or less are most desirable. The amount of the hydrocarbon oil used should be kept within a range that does not impair the physical properties of the resulting thermoplastic elastomer composition, but as a rough guideline, it is 0 to 250 parts by weight based on 100 parts by weight of the hydrogenated block copolymer. The amount is about 30 to 150 parts by weight, and more preferably 30 to 150 parts by weight.

A thermoplastic resin, preferably a polyolefin resin, may be added to the composition of the present invention.
The polyolefin resin is very useful in improving the processability and mechanical strength of the thermoplastic elastomer composition. Examples of those preferably used as the polyolefin resin include homopolymers such as low density polyethylene, linear low density polyethylene, high density polyethylene, polypropylene, and polybutene resin, or ethylene and propylene.
Random or block copolymers obtained by combining two or more kinds of structural units arbitrarily selected from α-olefins such as butene and 1-hexene. still,
The amount of the polyolefin resin used should be kept within a range that does not impair the flexibility of the resulting thermoplastic elastomer and the adhesive strength to the resin having a polar group, but a suitable amount is 100 parts by weight of the hydrogenated block copolymer. For 0
It is 100 parts by weight.

Further, the composition of the present invention contains, in addition to the above-mentioned components, an antiblocking agent, a lubricant, a silicone oil, a pigment, carbon black, an inorganic filler, a light stabilizer, an antistatic agent, a flame retardant, if necessary. It is also possible to contain etc. In general, any method known in the art for blending polymer components may be used to make the elastomeric composition of the present invention. In order to obtain the most homogeneous blend, a method of melt kneading using various kneaders such as a mixing roll, a kneader, a Banbury mixer and an extruder which are commonly used is preferable.

Prior to melt-kneading, these blends are previously dry-blended using a mixer such as a Henschel mixer, a tumbler, and a ribbon blender, and the mixture is melt-kneaded to obtain a homogeneous elastomer composition. . The thermoplastic elastomer composition obtained by the present invention is a resin having a polar group, such as AS resin and AES.
It has high adhesiveness to resins, ABS resins, PET resins, PBT resins, polycarbonate resins, PMMA resins, polyamides, etc., and has excellent moldability, oil resistance, heat resistance, mechanical strength, rubber properties, etc. It can be widely used for various purposes such as a material for processing multilayer molded articles.

[0045]

EXAMPLES The test methods in Examples and Comparative Examples are as follows. (1) Hardness was measured according to JIS K6301, A type. (2) Tensile strength [kgf / cm ² ] and elongation [%] are J
IS K6301, No. 3 dumbbell, the sample was measured using a 2 mm thick press sheet. (3) The compression set [%] is JIS K6301, 70
Measured at 22 ° C for 22 hours. (4) Adhesive strength [kgf / cm] is JIS K685
4, 180 ° peeling method (pull speed 200 mm / min, 23 ° C
Atmosphere). (5) The molded appearance was evaluated by visually observing the molded product and using the following scale.

◯: The entire surface is smooth and smooth. △: Flow marks, silver, etc. occurred on a part of the surface,
Some parts are not smooth. X: Flow marks, silver, etc. are generated on the entire surface, and the surface is rough. The moldings used in the tests (4) and (5) are molding machines used: Nissei Jushi Kogyo Co., Ltd., DC120-9ASE.
(Cylinder temperature: 210 ° C., mold temperature: 30 ° C., injection pressure: 500 kgf / cm ² , injection speed: maximum speed of 99
%). Molded product is 10 cm in length, 7.5 cm in width,
Each of the resin layer and the elastomer layer is a flat plate having a thickness of 2 mm.

The components used in the examples and comparative examples are as follows. Component (a) is disclosed in JP-A-60
It was synthesized by the method described in JP-A-220147. Component (a-1) having a structure of BABA, and having a number average molecular weight of 5000
0, molecular weight distribution 1.10, amount of bound styrene 30% by weight,
A hydrogenated block copolymer of styrene / butadiene block copolymer having a 1,2-vinyl bond content of the polybutadiene portion before hydrogenation of 36% by weight and a hydrogenation ratio of the polybutadiene portion of 99% was synthesized.

Component (a-2) having a structure of BABA, and having a number average molecular weight of 12,000.
0, molecular weight distribution 1.25, bound styrene amount 35% by weight,
A hydrogenated block copolymer of styrene / butadiene block copolymer having a 1,2-vinyl bond content of the polybutadiene portion before hydrogenation of 38% by weight and a hydrogenation ratio of the polybutadiene portion of 99% was synthesized.

Component (a-3) having the structure of ABA, number average molecular weight of 51,000, molecular weight distribution of 1.07, bound styrene amount of 28% by weight, 1,2-vinyl of polybutadiene portion before hydrogenation. The amount of binding is 35
A hydrogenated block copolymer of styrene / butadiene block copolymer having a weight percentage of 99% and a hydrogenation rate of polybutadiene of 99% was synthesized.

Component (a-4) having a structure of ABA, number average molecular weight of 54000, molecular weight distribution of 1.06, bound styrene content of 29% by weight, 1,4-polyisoprene part before hydrogenation. A hydrogenated block copolymer of a styrene / isoprene block copolymer having a bonding amount of 94% by weight, a 3,4-bonding amount of 6% by weight and a polyisoprene portion having a hydrogenation rate of 99% was synthesized.

Component (b) has a structure of BABA, and has a number average molecular weight of 5100.
0, molecular weight distribution 1.08, bound styrene content 30% by weight,
A hydrogenated block copolymer of a styrene / butadiene block copolymer having a 1,2-vinyl bond content of 35% by weight in the polybutadiene portion before hydrogenation and a hydrogenation rate of 99% in the polybutadiene portion is disclosed in JP-A-60-220147. It was synthesized by the method described in the publication, and 1 part by weight of maleic anhydride was added to 100 parts by weight of the hydrogenated block copolymer in an extruder.

Component (c) Pandex T-5000V (manufactured by Dainippon Ink and Chemicals) was used. Component (d) and component (e) The components shown in Table 1 were used.

[0053]

[Table 1]

Here, Irganox 245 (manufactured by Ciba Geigy) as the component (d-1), Irganox 1010 (manufactured by the same company) as the component (d-2), and the component (d-3).
Irganox 1076 (manufactured by the same company) was used as ADEKA STAB PEP-36 (manufactured by Asahi Denka Co., Ltd.) as the component (e-1) and ADEKA STAB 211 as the component (e-2).
2 (manufactured by the same company), ADEKA STAB TP as ingredient (e-3)
P (manufactured by the same company), and the component (f) in the comparative example
SUMILIZER TPL-R (manufactured by Sumitomo Chemical Co., Ltd.) was used.

The respective components (a) to (e) and other additives are uniformly dry blended in accordance with the respective blending amounts, and then melt-kneaded under the condition of 200 ° C. in the same direction twin-screw extruder having a diameter of 45 mm. Pellets of the thermoplastic elastomer composition were obtained, and each of the examples and comparative examples was obtained by the above test method.

[0056]

Examples 1 to 4 Ingredients (b), (c), (d-1) and (e-1) were added to the above-mentioned ingredients (a-1) to (a-4), and paraffin was added thereto. PW3 as a system process oil
Table 2 shows 80 (manufactured by Idemitsu Kosan, kinematic viscosity; 381.6 cst).
The amounts described below were blended. All the test pieces fixed in the mold as the resin to be laminated were made of ABS resin (Styrac ABS120; manufactured by Asahi Kasei Kogyo Co., Ltd.), and the adhesiveness to the polar resin was evaluated. The following Examples 1 to 4 are evaluated,
The results are shown in Table 2.

[0057]

[Table 2]

In each case, a molded product having a good appearance was obtained. Further, it is clear that they are excellent in mechanical strength, compression set and adhesive strength.

[0059]

Examples 5 to 9 and Comparative Examples 1 to 4 Components (b), (c), (d-1), (e-1) and PW380 as a paraffin-based process oil in addition to the above-mentioned component (a-2), As a polyolefin resin, Asahi Kasei Polypropylene M16
00 (manufactured by Asahi Kasei Kogyo, MI = 14) was blended in the amounts described in Table 3. The same resin as described above was used as the resin to be laminated, and each physical property was evaluated. Hereinafter, Examples 5 to 9 and Comparative Example 1
~ 4 were evaluated and shown in Table 3.

[0060]

[Table 3]

[0061]

Examples 10 to 14 and Comparative Examples 5 to 9 Despite being carried out under the molding conditions shown in the above evaluation method (6),
Due to the shape of the gate, shearing heat is generated during injection, and the actual resin temperature may rise considerably. Therefore,
Using the components (d) and (e) shown in Table 1 and the component (f) in Comparative Examples, the molding conditions were changed to 230 ° C. for the purpose of evaluating the thermal stability during molding. And the adhesive strength and appearance of the molded product were evaluated. The same resin was used as the resin to be laminated.
Also, the melt flow rate value (230 ° C, 2.16 kg) when retained in the melt indexer at 230 ° C for 5 minutes
f) was also evaluated, and these results are shown in Table 4.

[0062]

[Table 4]

From the results of Examples 5 to 14 and Comparative Examples 1 to 9 described above, the thermoplastic elastomer composition of the present invention has good molding processability and good molding appearance, and has good thermal stability during processing. It is obvious that it is excellent and has excellent adhesive strength to a resin having polarity and mechanical strength. On the other hand, the compositions of Comparative Examples have problems such as poor molding appearance, low mechanical strength, and lack of effective adhesion to polar resins. In addition, especially the component (d),
Regarding (e), the composition of the comparative example is inferior in thermal stability in a high temperature region around 230 ° C., so that the molding appearance is impaired,
There is also a problem that heat deterioration of the composition occurs due to stagnation in the cylinder of the molding machine, and the adhesive strength is extremely reduced due to this, so that it has effective adhesive strength, and It is clear that the width of the molding processing temperature region in which a molded article having an excellent molded appearance is obtained is very narrow, and thus it is not a preferable composition.

[0064]

INDUSTRIAL APPLICABILITY The thermoplastic elastomer composition of the present invention can be molded by a method similar to that of ordinary thermoplastic resins, and is excellent in molding processability and thermal stability during processing, so that it has a good appearance. Moreover, it is possible to obtain a molded product that exhibits excellent adhesiveness to a resin having polarity. It is also a composition excellent in mechanical properties and rubber properties,
It can be used very effectively in the fields of multi-layer extrusion, multi-layer injection molding and the like. Therefore, it is widely used for automobile interior parts, home electric appliances, sports equipment, sundries, etc., and its industrial significance is extremely large.

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Claims (2)

[Claims] 1. A hydrogen-containing block copolymer comprising (a) a polymer block A containing at least one vinyl aromatic compound as a main component and a polymer block B containing at least one conjugated diene compound as a main component. 100 parts by weight of hydrogenated block copolymer having a number average molecular weight of 30,000 to 300,000,
(B) Number obtained by hydrogenating a block copolymer comprising at least one polymer block A mainly containing a vinyl aromatic compound and at least one polymer block B mainly containing a conjugated diene compound. 10 to 200 parts by weight of a modified block copolymer in which a molecular unit containing a carboxylic acid group or its derivative group is bonded to a hydrogenated block copolymer having an average molecular weight of 30,000 to 100,000, (c) thermoplastic polyurethane elastomer 10 To 250 parts by weight, (d) 0.01 to 4 parts by weight of hindered phenol, and (e) 0.01 to 4 parts by weight of phosphite compound, a thermoplastic elastomer composition. 2. A hindered phenol is at least one of the compounds of the following general formulas (1) to (3), and a phosphite compound is at least one of the compounds of the following general formulas (4) to (6). The thermoplastic elastomer composition according to claim 1, wherein the thermoplastic elastomer composition is present. [Chemical 1] (Here, R _{1 to} R ₈ are a hydrogen atom, a halogen, or an alkyl group having 1 to 30 carbon atoms, an aryl group, an alkoxy group, an aryloxy group, a heterocyclic group, or these groups are an alkyl group, an aryl group, an alkoxy group. Group, aryloxy group, heterocyclic group, halogen, etc. may be substituted, and these may be the same or different, provided that at least two substituents in the ortho position to the OH group are present. One is the above-mentioned substituent containing at least one or more carbon atoms, and x, x ′ and y are each 1 to
20, n is an integer of 2 to 6, respectively, Z is C,
Represents any atom of Si, S, Sn, and Zn. ) [Chemical 2] (Here, R _{1 to} R ₁₀ are alkyl groups having 1 to 20 carbon atoms,
It represents an alkoxy group, a halogen-substituted alkyl group, an aryl-substituted alkyl group, a halogen-substituted alkoxy group, an aryl-substituted alkoxy group, etc., and R ′ ₁ and R ′ _{2 each} have 1 carbon atom.
To alkylene groups, arylene groups, halogen-substituted alkylene groups, halogen-substituted arylene groups, aryl-substituted alkylene groups, alkyl-substituted arylene groups, etc., which may be the same or different. Also, x, x ',
(y and y'represent an integer of 1 to 20, n is an integer of 1 to 10, respectively, and l and m are integers of 0 to 3, respectively, and always satisfy 1 + m = 3).