JP2000178429A - Damping thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a damping thermoplastic resin composition having an excellent damping property and having excellent mechanical strength, heat resistance and moldability. SOLUTION: This damping thermoplastic resin composition comprises (A) 70-96 wt.% of a thermoplastic resin comprising (a-1) 40-100 wt.% of an aromatic polycarbonate resin and (a-2) 60-0 wt.% of one or more kinds of thermoplastic resins selected from a styrenic resin, a polyester resin, etc., the total amount of the components (a-1) and (a-2) being 100 wt.%, (B) 3-20 wt.% of a damping block copolymer having a number-average mol.wt. of 30,000-300,000 and comprising (b-1) a block comprising a vinylaromatic compound component and having a number-average mol.wt. of 2,500-40,000 and (b-2) a block comprising a conjugated dienic compound component and having a number-average mol.wt. of 10,000-200 000 and a glass transition temperature of -30 to 30 deg.C, and (C) 1-10 wt.% of a polyester-styrenic elastomer-block copolymer, wherein the total amount of the components A, B and C is 100 wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a damping thermoplastic resin composition. More specifically, an aromatic polycarbonate resin, a specific vibration-damping block copolymer, a polyester-styrene-based elastomer block copolymer,
The present invention relates to a vibration damping thermoplastic resin composition having excellent mechanical properties, heat resistance, moldability, and vibration damping performance.

[0002]

2. Description of the Related Art Aromatic polycarbonate resins have excellent impact strength and heat resistance and are used in many applications such as mechanical parts, automobile parts, electric and electronic parts. In recent years, with the increase in the speed of OA equipment, not only the rigidity or heat resistance of various mechanical parts has been improved, but also the demand for vibration suppression from vibration sources generated by the drive system has been increasing. It is required to provide vibration damping.

In general, as a method for imparting vibration damping properties to a thermoplastic resin, for example, a method for imparting damping properties to a styrene resin such as an ABS resin is disclosed in JP-A-3-45646.
Japanese Patent Application Laid-Open Publication No. HEI 10-115,086 discloses a method of blending a block copolymer composed of a block composed of a vinyl aromatic compound component and a block composed of an isoprene and / or butadiene component. However, in aromatic polycarbonate resin,
Even if such a block copolymer is blended, it is inferior in mechanical properties due to poor mutual compatibility, and a practically sufficient one cannot be obtained.

In Japanese Patent Application Laid-Open No. 8-12832, a block copolymer composed of a thermoplastic polyester resin, a resin such as an ABS resin, and a block composed of a vinyl aromatic compound component and a block composed of an isoprene and / or butadiene component is disclosed. It is described that a resin composition having an excellent balance between damping properties and mechanical properties can be obtained by blending the coalesced particles. However, even if a polycarbonate resin is used in place of the thermoplastic polyester resin based on the description, there is still a problem that the resulting composition has low mechanical strength due to poor compatibility.

As means for solving these problems, JP-A-5-202287 discloses a resin comprising a thermoplastic resin such as an aromatic polycarbonate resin, a polyester resin or a polyamide resin and a block copolymer imparting vibration damping properties. A method has been proposed in which a modified polymer in which a functional group reactive with a thermoplastic resin such as a carboxyl or epoxy group is bonded to the composition. However, in such a case, the reactivity between the modified polymer and the aromatic polycarbonate resin is poorer than that of the polyester resin or the polyamide resin, so that the effect of improving the mechanical properties is slight, and is still sufficiently practical. It cannot be said.

On the other hand, as an elastomer having good compatibility with an aromatic polycarbonate resin and imparting vibration damping properties, a method of blending a polyester elastomer with an aromatic polycarbonate resin is known from Japanese Patent Application Laid-Open No. Hei 6-23904. . However, in such a case, since the compatibility is too high, there is a disadvantage that the heat resistance, which is one of the important properties of the aromatic polycarbonate, is significantly reduced.

That is, at present, a resin composition containing an aromatic polycarbonate resin that sufficiently satisfies vibration damping properties, mechanical properties, heat resistance, and the like has not yet been obtained.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a vibration-damping thermoplastic resin composition which is excellent in vibration-damping property and excellent in mechanical strength, heat resistance and moldability. The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a resin composition comprising an aromatic polycarbonate resin and a specific aromatic vinyl-conjugated diene block copolymer that imparts vibration damping properties is made of polyester-styrene. The present inventors have found that a resin composition containing a series elastomer block copolymer is excellent in mechanical properties, heat resistance, molding workability and vibration damping performance, and have completed the present invention.

[0009]

The present invention relates to (a-1) an aromatic polycarbonate resin of 40 to 100% by weight and (a)
-2) polystyrene resin, copolymer containing components consisting of vinyl cyanide compound and aromatic vinyl compound, polyester resin, polyolefin resin, polyarylate resin, polyamide resin, polyphenylene ether resin,
Polysulfone resin, polyphenylene sulfide resin,
One or more thermoplastic resins selected from polyalkyl methacrylate resins, polyether sulfone resins, phenoxy resins, polyether ether ketone resins, polyvinyl chloride resins, polyacetal resins, and polyimide resins in an amount of 60 to 0% by weight. 70-96% by weight of a thermoplastic resin (A component) comprising 100% by weight in total, (b-1)
A number average molecular weight of 2,50
A block having a number average molecular weight of 10,000 to 2 comprising a block of 0 to 40,000 and (b-2) a conjugated diene compound component;
It is composed of blocks having a glass transition temperature of -30 ° C to 30 ° C and a number average molecular weight of 30,000.
3 to 20% by weight of a vibration-damping block copolymer (component B) of 100 to 300,000, and 1 to 1 of a polyester-styrene elastomer block copolymer (component C).
The present invention relates to a vibration-damping thermoplastic resin composition comprising 0% by weight and a total of 100% by weight of components A, B and C.

Hereinafter, the present invention will be described specifically. The aromatic polycarbonate resin (hereinafter, may be simply referred to as (a-1)) used as (a-1) in the component A used in the present invention is a solution method of dihydric phenol and a carbonate precursor. Alternatively, it is an aromatic polycarbonate resin produced by reacting with a melting method. Representative examples of dihydric phenols include 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], bis (4-hydroxyphenyl) methane, and 2,2-bis (4
-Hydroxy-3,5-dimethylphenyl) propane,
2,2- (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) sulfone,
1,1-bis (4-hydroxyphenyl) ethane, 1,
1-bis (4-hydroxyphenyl) cyclohexane,
1,1-bis (4-hydroxyphenyl) -3,3,5
-Trimethylcyclohexane, α, α'-bis (4-hydroxydiphenyl) -m-diisopropylbenzene and the like. Preferred dihydric phenols are those based on bis (4-hydroxyphenyl) alkanes, especially bisphenol A.

Examples of the carbonate precursor include carbonyl halide, carbonyl ester and haloformate, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and a mixture thereof. In producing the polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more. In addition, suitable molecular weight regulators, branching agents, catalysts for accelerating the reaction, and the like can also be used. The molecular weight of the aromatic polycarbonate resin is not specified.
If it exceeds 50,000, the moldability decreases, so that the viscosity average molecular weight is 10,000 to 50,000.
000, preferably 15,000 to 30,000
Are particularly preferred. Further, two or more aromatic polycarbonate resins may be mixed. The viscosity average molecular weight in the present invention is determined by inserting the specific viscosity (η _sp ) obtained from a solution obtained by dissolving 0.7 g of an aromatic polycarbonate resin in 100 ml of methylene chloride at 20 ° C. into the following equation. η _sp /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity) [η] = 1.23 × 10 ^-4 M ^0.83 c = 0.7

Next, the basic means for producing an aromatic polycarbonate resin will be briefly described. In the solution method using phosgene as a carbonate precursor, the reaction is usually performed in the presence of an acid binder and an organic solvent. As the acid binder, for example, a hydroxide of an alkali metal such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. For promoting the reaction, a catalyst such as a tertiary amine or a quaternary ammonium salt can be used. Examples of the molecular weight regulator include alkyl-substituted phenols such as phenol and p-tert-butylphenol and 4- (2 It is desirable to use a terminal terminator such as an aralkyl-substituted phenol such as (-phenylisopropyl) phenol. The reaction temperature is usually 0 to 40 ° C, the reaction time is preferably several minutes to 5 hours, and the pH during the reaction is preferably maintained at 10 or more. It is not necessary that all of the resulting molecular chain ends have a structure derived from the terminator.

In the transesterification reaction (melting method) using a carbonic acid diester as a carbonate precursor, a predetermined ratio of a dihydric phenol component and, if necessary, a branching agent and the like are agitated while heating with a carbonic acid diester under an inert gas atmosphere. This is carried out by a method of distilling off alcohols or phenols produced. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be formed, etc.
The range is from 0 to 300 ° C. The reaction is completed while distilling off alcohol or phenols generated under reduced pressure from the beginning. Also, to promote the reaction,
It is also possible to use catalysts used in transesterification reactions known at present such as alkali metal compounds and nitrogen-containing basic compounds. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate,
Examples include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and the like. Of these, diphenyl carbonate is particularly preferred. Adding diphenyl carbonate, methyl (2-phenyloxycarbonyloxy) benzenecarboxylate, or the like as a terminal terminator at an early stage of the reaction or at an intermediate stage of the reaction;
It is also preferable to add various conventionally known catalyst deactivators immediately before the end of the reaction.

Furthermore, in the component A of the present invention, (a-2)
It is also possible to use The component (a-2) used in the component A refers to a copolymer containing a component consisting of a polystyrene resin, a vinyl cyanide compound and an aromatic vinyl compound, a polyester resin, a polyolefin resin, a polyarylate resin, a polyamide resin, and a polyphenylene ether. One or two selected from a resin, a polysulfone resin, a polyphenylene sulfide resin, a polyalkyl methacrylate resin, a polyether sulfone resin, a phenoxy resin, a polyether ether ketone resin, a polyvinyl chloride resin, a polyacetal resin, and a polyimide resin
It refers to at least one kind of thermoplastic resin (hereinafter sometimes simply referred to as (a-2)). Among them, from the viewpoint of the compatibility of the entire resin composition composed of the components A to C, a copolymer containing a component composed of a vinyl cyanide compound and an aromatic vinyl compound, and a polyester resin achieve the object of the present invention. Above.

The copolymer containing a component comprising a vinyl cyanide compound and an aromatic vinyl compound used as (a-2) in the present invention is defined as a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. Other examples include copolymers obtained by copolymerizing at least one selected from other vinyl monomers copolymerizable with these and, if necessary, rubbery polymers.

Examples of the vinyl cyanide compound used in (a-2) include acrylonitrile, methacrylonitrile and the like, and acrylonitrile is particularly preferable.

The aromatic vinyl compound used in (a-2) includes styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, and p-tert-butylstyrene. And styrene derivatives such as vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene. Styrene and α-methylstyrene are preferably used, and styrene is particularly preferable. These may be used alone or in combination of two or more.

Other vinyl monomers copolymerizable with the vinyl cyanide compound and the aromatic vinyl compound include aryl esters of acrylic acid such as phenyl acrylate and benzyl acrylate, methyl acrylate, ethyl acrylate, propyl acrylate and butyl. Acrylate, amyl acrylate, hexyl acrylate, 2
-Ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate, alkyl esters of acrylic acid such as dodecyl acrylate, phenyl methacrylate, aryl methacrylate such as benzyl methacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, Epoxy group-containing methacrylic esters such as 2-ethylhexyl methacrylate, octyl methacrylate, cyclohexyl methacrylate, dodecyl methacrylate and other methacrylic acid alkyl esters, glycidyl methacrylate and the like, maleimide, N-methylmaleimide, N-
Maleimide monomers such as phenylmaleimide; and α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid, and anhydrides thereof.

Examples of the rubbery polymer copolymerizable with the vinyl cyanide compound and the aromatic vinyl compound include random copolymers and block copolymers of polybutadiene, polyisoprene, styrene / butadiene, and acrylonitrile / butadiene copolymer. Copolymers of alkyl acrylate or alkyl methacrylate and butadiene, diene copolymers such as butadiene / isoprene copolymer, random copolymers of ethylene / propylene and block copolymers, random copolymers of ethylene / butene Copolymers of ethylene and α-olefins such as polymers and block copolymers, ethylene-methyl methacrylate copolymers, copolymers of ethylene and unsaturated carboxylic acid esters such as ethylene-butyl acrylate copolymer, Ethylene and vinyl acetate Copolymers of ethylene and aliphatic vinyl, ethylene / propylene / non-conjugated diene terpolymers such as ethylene / propylene / hexadiene copolymer, acrylic rubbers such as polybutyl acrylate, and polyorganosiloxane rubber components And a polyalkyl (meth) acrylate rubber component, and a composite rubber (hereinafter referred to as IPN type rubber) having a structure entangled with each other so as not to be separated.

Examples of the copolymer containing such a component comprising a vinyl cyanide compound and an aromatic vinyl compound include:
For example, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / acrylonitrile / butadiene / styrene copolymer (MABS resin), acrylonitrile / acryl rubber / styrene copolymer (AAS resin), acrylonitrile / ethylene propylene rubber / styrene copolymer (AES resin), acrylonitrile / acryl-butadiene rubber / styrene copolymer, and resin such as acrylonitrile / styrene / IPN type rubber copolymer, or these. And mixtures thereof.

Among them, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), acrylonitrile / acryl rubber / styrene copolymer (AAS resin),
1 selected from the group consisting of acrylonitrile, ethylene propylene rubber, and styrene copolymer (AES resin)
It is preferable to use species or a mixture of two or more species,
Among them, AS resin and ABS resin are most preferable.

The AS resin used in the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Such vinyl cyanide compounds include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound, those described above can be similarly used, but styrene and α-methylstyrene can be preferably used.
The ratio of each component in the AS resin was 10
When the amount is 0% by weight, the content of the vinyl cyanide compound is 5 to 50%.
%, Preferably 15 to 35% by weight, 95 to 50% by weight of aromatic vinyl compound, preferably 85 to 65% by weight
It is. Further, these vinyl compounds may be used in combination with other copolymerizable vinyl compounds described above, and the content thereof is preferably 15% by weight or less in the AS resin component. An initiator used in the reaction,
As the chain transfer agent and the like, various conventionally known ones can be used as necessary.

The AS resin may be produced by any of bulk polymerization, suspension polymerization and emulsion polymerization, but is preferably produced by bulk polymerization. The method of copolymerization may be either one-stage copolymerization or multi-stage copolymerization. The reduced viscosity of the AS resin is as follows.
0.2 to 1.0 dl / g, preferably 0.3 to 1.0 dl / g.
0.5 dl / g. Reduced viscosity is 0.25 AS resin
g was precisely weighed, and a solution dissolved in 50 ml of dimethylformamide over 2 hours was measured using an Ubbelohde viscometer.
It was measured in an environment of ° C. The viscometer used has a solvent flow time of 20 to 100 seconds. The reduced viscosity is determined by the following equation from the number of seconds for the solvent to flow (t ₀ ) and the number of seconds for the solution to flow (t). Reduced viscosity (η _SP / C) = {(t / t ₀ ) -1} /0.5 When the reduced viscosity is 0.2 to 1.0 dl / g, both impact strength and fluidity are good. It is possible to keep.

The ABS resin used in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound on a diene rubber component, and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound. It is a mixture of coalescence. As the diene rubber component forming the ABS resin, for example, a rubber having a glass transition temperature of −30 ° C. or less such as polybutadiene, polyisoprene, and styrene-butadiene copolymer is used, and the ratio is 100% by weight of the ABS resin component. It is preferably 5 to 80% by weight, more preferably 8 to 50% by weight, particularly preferably 10 to 80% by weight.
３０30% by weight. Examples of the vinyl cyanide compound to be grafted to the diene rubber component include those described above, and acrylonitrile is particularly preferably used. As the aromatic vinyl compound to be grafted to the diene rubber component, those described above can be similarly used, but styrene and α-methylstyrene are particularly preferably used. The proportion of the component grafted to the diene rubber component is 95 to 100% by weight of the ABS resin component.
It is preferably 20% by weight, particularly preferably 50 to 90% by weight. Further, it is preferable that the vinyl cyanide compound is 5 to 50% by weight and the aromatic vinyl compound is 95 to 50% by weight based on 100% by weight of the total amount of the vinyl cyanide compound and the aromatic vinyl compound. Further, methyl (meth) acrylate, ethyl acrylate, maleic anhydride, N-substituted maleimide, and the like can be mixed and used for a part of the components grafted to the diene rubber component. 15% by weight
The following are preferred. Further, as the initiator, chain transfer agent, emulsifier and the like used in the reaction, various conventionally known ones can be used as necessary.

In the ABS resin of the present invention, the rubber particle diameter is preferably from 0.1 to 5.0 μm, more preferably from 0.2 to 3.0 μm, particularly preferably from 0.3 to 1.5 μm.
m. As the distribution of the rubber particle diameter, any of a single distribution and a distribution having a plurality of peaks of two or more peaks can be used, and the rubber particles form a single phase in the morphology. The rubber particles may have a salami structure by containing an occluded phase around the rubber particles, but preferably have a high proportion of rubber particles forming a single phase.

It is well known that an ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound which are not grafted to a diene rubber component. It may contain a free polymer component generated. The reduced viscosity of such a copolymer comprising a free vinyl cyanide compound and an aromatic vinyl compound is as follows:
The reduced viscosity (3) determined by the method described in the description of the S resin
0 ° C) is 0.2 to 1.0 dl / g, more preferably 0.1 to 1.0 dl / g.
It is 3 to 0.7 dl / g.

The ratio of the grafted vinyl cyanide compound and aromatic vinyl compound to the diene rubber component is preferably from 20 to 200%, more preferably from 20 to 70%, expressed as a graft ratio (% by weight). belongs to.

Such ABS resin is used for bulk polymerization, suspension polymerization,
Although it may be manufactured by any method of emulsion polymerization,
In particular, those obtained by bulk polymerization are preferred. Further, the copolymerization method may be one-stage copolymerization or multi-stage copolymerization. Also, a blend of a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component with the ABS resin obtained by such a production method can be preferably used.

The AAS resin used in the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound onto an acrylic rubber component, or the thermoplastic graft copolymer, and a vinyl cyanide. A mixture of a compound and a copolymer of an aromatic vinyl compound.
The acrylic rubber in the present invention is one containing an alkyl acrylate unit having 2 to 10 carbon atoms, and further containing styrene, methyl methacrylate, and butadiene as other copolymerizable components as necessary. Is also good. Preferred examples of the alkyl acrylate having 2 to 10 carbon atoms include 2-ethylhexyl acrylate and n-butyl acrylate, and the alkyl acrylate is preferably contained at 50% by weight or more in 100% by weight of the acrylate rubber. Further, such an acrylate rubber is at least partially cross-linked, and examples of such a cross-linking agent include ethylene glycol diacrylate, butylene glycol diacrylate, ethylene glycol dimethacrylate, allyl methacrylate, and polypropylene glycol diacrylate. The crosslinking agent is preferably used in an amount of 0.01 to 3% by weight based on the acrylate rubber. The ratio of the vinyl cyanide compound and the aromatic vinyl compound is 100% by weight of the total amount.
5 to 50% by weight of a vinyl cyanide compound and 95 to 50% by weight of an aromatic vinyl compound, particularly 15 to 35% by weight of a vinyl cyanide compound and 85 to 65% by weight of an aromatic vinyl compound. Are preferred.

The AES resin used in the present invention is an ethylene-propylene rubber component or ethylene-propylene-
Thermoplastic graft copolymer obtained by graft-polymerizing a vinyl cyanide compound and an aromatic vinyl compound to a diene rubber component,
Alternatively, it is a mixture of the thermoplastic graft copolymer and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound.

The polyester resin used as (a-2) in the present invention is a polymer or a copolymer obtained by a condensation reaction containing an aromatic dicarboxylic acid and a diol or an ester derivative thereof as main components.

The aromatic dicarboxylic acids mentioned here include terephthalic acid, isophthalic acid, orthophthalic acid, 1,5-
Naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-
Biphenyl ether dicarboxylic acid, 4,4'-biphenylmethane dicarboxylic acid, 4,4'-biphenyl sulfone dicarboxylic acid, 4,4'-biphenyl isopropylidene dicarboxylic acid, 1,2-bis (phenoxy) ethane-
4,4′-dicarboxylic acid, 2,5-anthracene dicarboxylic acid, 2,6-anthracene dicarboxylic acid, 4,4 ′
Aromatic dicarboxylic acids such as -p-terphenylenedicarboxylic acid and 2,5-pyridinedicarboxylic acid are preferably used, and terephthalic acid and 2,6-naphthalenedicarboxylic acid are particularly preferably used.

The aromatic dicarboxylic acids may be used as a mixture of two or more kinds. If the amount is small, it is also possible to use a mixture of one or more aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid and dodecane diacid, and alicyclic dicarboxylic acids such as cyclohexane dicarboxylic acid together with the dicarboxylic acid. .

The diol which is a component of the aromatic polyester of the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-
Examples thereof include aliphatic diols such as propanediol, diethylene glycol and triethylene glycol, alicyclic diols such as 1,4-cyclohexanedimethanol, and mixtures thereof.

Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene -1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, and the like,
Copolymerized polyesters such as polyethylene isophthalate / terephthalate, polybutylene terephthalate / isophthalate and the like can be mentioned. Of these, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, which are well balanced in mechanical properties and the like, can be preferably used.

According to a method for producing such an aromatic polyester resin, a dicarboxylic acid component and the diol component are polymerized while heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony and the like according to a conventional method.
It is performed by discharging water or lower alcohol by-product to the outside of the system.

With respect to the molecular weight of the aromatic polyester resin, the intrinsic viscosity measured at 25 ° C. using o-chlorophenol as a solvent is 0.4 to 1.2, preferably 0.65.
１．１1.15.

In the above component A, (a-1) and (a-
The ratio of (a) is (a-
1) is 40 to 100% by weight and (a-2) is 60 to 0% by weight. When (a-1) is less than 40% by weight, compatibility of heat resistance, impact resistance and the like becomes insufficient.

The block having a number average molecular weight of 2,500 to 40,000 (hereinafter simply referred to as (b-1)) comprising the (b-1) vinyl aromatic compound component of the vibration-damping block copolymer used as the B component of the present invention. ) Sometimes abbreviated as a block)
Are mainly vinyl aromatic compounds, and specific examples thereof include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, and 4-methylstyrene.
Propylstyrene, 4-cyclohexylstyrene, 4-
Dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned, but styrene is most preferred. When the molecular weight of the (b-1) block is smaller than 2,500 or 4
If it exceeds 000, the compatibility with other components becomes poor, and a composition having both sufficient vibration damping properties and mechanical properties cannot be obtained.

The proportion of the block (b-1) in the vibration-damping block copolymer as the component B is from 5% by weight to 5% by weight.
It is preferably in the range of 0% by weight. If this proportion is less than 5% by weight, the mechanical strength decreases, and conversely, 50% by weight.
When it exceeds, the vibration damping property becomes insufficient.

On the other hand, the vibration-damping block copolymer used as the component B of the present invention comprises a (b-2) conjugated diene compound component and has a number average molecular weight of 10,000 to 200,000.
A conjugated diene-based compound forming a block having a glass transition temperature in a range of −30 ° C. to 30 ° C. (hereinafter may be simply referred to as a block (b-2)) is isoprene, butadiene or isoprene-butadiene. Is preferred. When both isoprene and butadiene are used, the form of the copolymer may be any of random, block, and tapered.

The glass transition temperature of such a damping block copolymer is measured at a heating rate of 10 ° C./min by DSC measurement. If the above temperature is lower than -30 ° C, the vibration damping performance is not sufficient, and if it is higher than 30 ° C, the impact resistance at around room temperature decreases, which is not preferable.

The above glass transition temperature is -30 ° C. to 30 ° C.
In order to obtain the above, 1,2-
It is necessary that the content of the bond and the 3,4-linkage of the (b-2) block is 30% by weight or more (100% by weight).
But it doesn't matter). The number average molecular weight of the (b-2) block of the vibration-damping block copolymer as the B component is 10,10.
It must be in the range of 000 to 200,000. If the molecular weight is lower than 10,000, the elastic properties are impaired and vibration damping properties are not sufficiently imparted. Also, 200,00
If it is larger than 0, the processability (fluidity) deteriorates, which is not preferable.

In the present invention, the number average molecular weight of the vibration-damping block copolymer of the component B is from 30,000 to 30.
It must be in the range of 0000. Molecular weight 3
If it is lower than 000, the mechanical properties deteriorate, and
If it exceeds 00, the compatibility becomes poor, and the mechanical properties such as impact strength also deteriorate. The preferred range is 80,000-
250,000. Here, when the (b-1) block in the B component of the present invention is abbreviated as (b-2) block, the block form of the block copolymer of the B component is-(-) n or (-). A block type represented by n is preferably used. Here, n is an integer of 1 or more, preferably an integer of 1 or more and 10 or less. Of these, those of the form ---- are preferably used.

Further, in the block (b-2), part or all of the carbon-carbon double bonds in the block may be hydrogenated in order to improve heat resistance. In order to enhance the performance, those not hydrogenated are preferable.

The vibration-damping block copolymer as the component B of the present invention can be obtained by the following method. Regarding the polymerization of the entire block copolymer, a conjugated diene compound as a component of the (b-2) block and a vinyl aromatic compound as a component of the (b-1) block are prepared by using an alkyl lithium such as butyl lithium as an initiator. Can be obtained by, for example, a method of sequentially polymerizing the respective monomers, or a method of separately performing a polymerization reaction for each monomer and bonding the obtained polymer with a bifunctional coupling agent or the like. Further, a method of polymerizing a conjugated diene compound which is a component of the block (b-2) using a dilithium compound as an initiator, and then polymerizing a monomer of a vinyl aromatic compound may, for example, be mentioned.

Examples of the alkyl lithium include an alkyl compound having an alkyl group having 1 to 10 carbon atoms, preferably methyl lithium, ethyl lithium, pentyl lithium and butyl lithium. As the coupling agent, dichloromethane, dibromomethane, dichloroethane, dibromoethane, dibromobenzene and the like are used. Examples of the dilithium compound include naphthalenedilithium. The amount of the initiator used is determined by the molecular weight of the target B component, but is based on 100 parts by weight of all monomers used for polymerization.
The range is approximately 0.01 to 0.2 parts by weight, and the range is 0.04 to 0.8 parts by weight when a coupling agent is used.

The (b-2) block used in the component B has a glass transition temperature of -30 ° C. to 30 ° C., and thus has a 1,2-bond and 3,4-bond content of 30.
In order to control the content by weight or more, a Lewis base is used as a cocatalyst when the conjugated diene component of the block (b-2) is polymerized. Examples of Lewis bases include ethers such as dimethyl ether, diethyl ether and tetrahydrofuran, glycol ethers such as ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, and amine compounds such as triethylamine, N, N, N ', N'-tetramethylethylenediamine. And the like. The amount of these Lewis bases used is in the range of about 0.1 to 1000 times the number of moles of lithium in the polymerization initiator.

Further, in the polymerization, it is preferable to use a solvent in order to facilitate the control of the reaction. As a solvent inert to the polymerization initiator, in particular, an aliphatic or alicyclic group having 6 to 12 carbon atoms, Aromatic hydrocarbons can be preferably used. For example, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene and the like can be mentioned.

The polyester-styrene elastomer block copolymer (C component) used in the present invention is a block copolymer having a polyester block (P) and an aromatic vinyl copolymer block (Q), For example, 1
Diblock copolymer in which one polyester block (P) and one aromatic vinyl copolymer block (Q) are bonded, and one on each side of one diester block with one polyester block (P) in between A triblock copolymer to which the aromatic vinyl copolymer block (Q) is bonded, and one polyester block on each side of the one aromatic vinyl copolymer block (Q). P) is a triblock copolymer, and a polyblock is a polyester block (P) and an aromatic vinyl copolymer block (Q) alternately bonded in a total of four or more. Although it is composed of one or more kinds of polymers, etc., depending on the production method and conditions, the components derived from the unreacted polyester block (P) and the aromatic vinyl copolymer block (Q It may contain components derived.

The polyester block (P) of the polyester-styrene elastomer block copolymer (component (C)) of the present invention may be any polymer block derived from a thermoplastic polyester polymer. For example, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate resin, polybutylene naphthalate resin, poly-
Examples include polymer blocks derived from polyester polymers such as 1,4-cyclohexane dimethylene terephthalate resin, polycaprolactone resin, p-hydroxybenzoic acid polyester resin, and polyarylate resin. Among them, the polyester block (P) in the polyester-styrene-based elastomer block copolymer (component C) is at least one of a polyethylene terephthalate-based resin and a polybutylene terephthalate-based resin in view of compatibility with the aromatic polycarbonate resin. The polymer block is preferably a polymer block derived from a polybutylene terephthalate resin.

The polyester block (P) in the polyester-styrene-based elastomer block copolymer (component (C)) of the present invention may have a basic structure as required if it is at most 30 mol% based on all structural units. It may have a dicarboxylic acid other than the dicarboxylic acid unit and / or another diol unit other than the diol unit constituting the basic structure. That is, the polybutylene terephthalate resin refers to a resin in which a unit exceeding 70 mol% based on all structural units is composed of a polybutylene terephthalate unit.

Examples of dicarboxylic acid units which may be contained in the polyester block (P) in the polyester-styrene elastomer block copolymer (component (C)) include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as bis (p-carboxyphenyl) methane, 1,5-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, sodium 5-sulfoisophthalate, adipic acid, sebacic acid, and azelaic acid Acids, aliphatic dicarboxylic acids such as dodecanedioic acid, and 1,
Examples thereof include alicyclic dicarboxylic acids such as 3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and dicarboxylic acid units derived from ester-forming derivatives thereof. Polyester-styrene elastomer block copolymer of the present invention (component C)
The polyester block (P) in the above may have only one kind of the above-mentioned dicarboxylic acid units, or may have two or more kinds.

Examples of the diol unit which can be contained in the polyester block (P) in the polyester-styrene elastomer block copolymer (component C) of the present invention include ethylene glycol, propylene glycol, and the like.
1,4-butanediol, neopentyl glycol, 2
An aliphatic diol having 2 to 10 carbon atoms such as -methylpropanediol and 1,5-pentanediol, alicyclic diols such as cyclohexanedimethanol and cyclohexanediol, diethylene glycol, polyethylene glycol, poly-1,3-propylene glycol, Examples thereof include diol units derived from polyalkylene glycol having a molecular weight of 6,000 or less, such as polytetramethylene glycol. The polyester block (P) in the polyester-styrene-based elastomer block copolymer (C component) of the present invention has one of the diol units described above.
It may have one or more species.

Further, the polyester block (P) in the polyester-styrene-based elastomer block copolymer (component C) of the present invention has one unit based on all the structural units.
If it is less than mol%, for example, glycerin, trimethylolpropane, pentaerythritol, trimellitic acid,
It may have a structural unit derived from a trifunctional or higher functional monomer such as pyromellitic acid.

The polyester block (P) in the polyester-styrene elastomer block copolymer (component C) of the present invention was measured at 25 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio = 1/1). Is preferably derived from a polyester polymer having an intrinsic viscosity in the range of 0.3 to 1.5.

The aromatic vinyl copolymer block (Q) in the polyester-styrene elastomer block copolymer (component C) of the present invention is a polymer block (q1) mainly composed of an aromatic vinyl compound unit or an aromatic vinyl compound block. A polymer block (qa) composed of any of a polymer block (q1) mainly composed of vinyl compound units and a hydrogenated polybutadiene block (q2) having a 1,2-bond content of less than 30% and a hydrogenated polybutadiene block (q2); At least one selected from the group consisting of an isoprene block (q3), a hydrogenated polybutadiene block (q4) having a 1,2-bond content of 30 to 80%, and a hydrogenated isoprene / butadiene copolymer block (q5) Vinyl block copolymer (qα) consisting of a polymer block (qb) consisting of Those derived from at least one of mainly of fine aromatic vinyl compound unit polymer block (qc) and polyisobutylene blocks (qd) consisting the aromatic vinyl block copolymer (Q [beta]).

The polymer block (qa) and the polymer block (qb) which can constitute the aromatic vinyl copolymer block (Q) in the polyester-styrene elastomer block copolymer (component C) of the present invention. Examples of the block structure of the aromatic vinyl-based block (Qα) derived from the aromatic vinyl-based block copolymer (qα) include those represented by the following general formulas (1) to (4). be able to. (Ab) _e (1) (ba) _f (2) a- (ba ') _g (3) b- (ab') _h (4) (in the above formula, a and a 'Is a polymer block (q
a) wherein b and b ′ are polymer blocks (q
b), and e, f, g and h each independently represent an integer of 1 or more. )

The number of repetitions e, f, g in the aromatic vinyl-based block (Qα) represented by the above general formulas (1) to (4)
And h can be arbitrarily determined, but usually 1
It is preferably an integer in the range of 5 to 5. As the aromatic vinyl-based block (Qα), among the aromatic vinyl-based blocks represented by the above general formulas (1) to (4), a formula in which e = 1 in the above general formula (1) is used. :
An aromatic vinyl block represented by ab or an addition-polymerized triblock represented by the formula: aba ′ in which g = 1 in the above general formula (3) is more preferable.

In addition, the aromatic vinyl polymer block (qc) and the polyisobutylene which can constitute the aromatic vinyl copolymer block (Q) in the polyester-styrene elastomer block copolymer (component C) of the present invention. Examples of the block structure of the aromatic vinyl block (Qβ) derived from the aromatic vinyl block copolymer (qβ) composed of the block (qd) are represented by the following general formula (5) or (6). Can be listed. c- (dc ′) _j (5) d- (cd ′) _k (6) (wherein c and c ′ each represent an aromatic vinyl polymer block (qc), and d and d 'Represents a polyisobutylene block (qd), and j and k each independently represent an integer of 1 or more.)

J and k in the aromatic vinyl block (Qβ) represented by the above general formula (5) or (6) can be arbitrarily determined, but are usually integers in the range of 1 to 5. Preferably, there is. Further, among the aromatic vinyl-based blocks (Qβ) represented by the general formula (5) or (6), the aromatic vinyl block (Qβ) is represented by the formula cdc ′ in which j = 1 in the general formula (5). More preferably, it is an aromatic vinyl-based triblock represented by the formula dcd ′ wherein k = 1 in the general formula (6).

The polymer block (q1) constituting the aromatic vinyl block (Qα) and the aromatic vinyl polymer block (q) constituting the aromatic vinyl block (Qβ)
In c), the aromatic vinyl compound forming the aromatic vinyl compound unit includes styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene,
Vinyl naphthalene and vinyl anthracene can be exemplified. Among them, from the viewpoint of compatibility with the damping block copolymer (component B), the aromatic vinyl-based block (Q
The aromatic vinyl compound forming the aromatic vinyl compound unit of the polymer block (q1) constituting the α) and the aromatic vinyl polymer block (qc) constituting the aromatic vinyl block (Qβ) is styrene, α It is preferable to be composed of one or two selected from -methylstyrene, and among them, those composed of styrene are particularly preferred.

The hydrogenated polybutadiene block (q2), which can be a constituent block of the polymer block (qa) in the aromatic vinyl-based block (Qα), has less than 30% of 1,2-bonds in the polybutadiene block. And more preferably 25% or less. The hydrogenated polybutadiene block (q2) is a polybutadiene block in which part or all, preferably 90% or more, of the unsaturated bonds have been converted to saturated bonds by hydrogenation. Before hydrogenation, the polybutadiene constituting the hydrogenated polybutadiene block (q2) preferably has a vinylethylene group (1,2-bonded butadiene unit) of less than 30 mol%, more preferably 25 mol% or less.
And the remainder is a 2-butene-1,4-diyl group (1,4
-Butadiene units of linkage).

The hydrogenated polyisoprene block (q3), which can be a constituent block of the polymer block (qb) in the aromatic vinyl-based block (Qα), is not a polyisoprene mainly composed of monomer units derived from isoprene. A polymer block in which part or all of the saturated bonds are hydrogenated to form unsaturated bonds. In the hydrogenated polyisoprene block (q3), before hydrogenation, the unit derived from isoprene is 2-methyl-2-butene-
1,4-diyl group (1,4-bonded isoprene unit),
An isopropenylethylene group (3,4-bonded isoprene unit) and a 1-methyl-1-vinylethylene group (1,2
-Isoprene unit of a bond).

The hydrogenated polybutadiene block (q4) which can be a constituent block of the polymer block (qb) in the aromatic vinyl-based block (Qα) has a 1,2-bond amount in the polybutadiene block of preferably 30 to 30.
The polybutadiene block is 80%, more preferably 35 to 60%, and further has a part or all of the unsaturated bonds that have become saturated by hydrogenation. In the polybutadiene constituting the hydrogenated polybutadiene block (q4), preferably 30 to 80 mol%, more preferably 35 to 60 mol% thereof is a vinylethylene group (1,2-bonded butadiene unit) before hydrogenation, Preferably 70 to 20 mol%, more preferably 65 to 40 mol%
Is a 2-butene-1,4-diyl group (butadiene unit having a 1,4-bond).

The hydrogenated isoprene / butadiene copolymer block (q) which can be a constituent block of the polymer block (qb) in the aromatic vinyl block (Qα)
5) is an isoprene / butadiene copolymer mainly composed of a unit derived from isoprene and a unit derived from butadiene, and a part or all of the unsaturated bonds are saturated by hydrogenation. It is a copolymer block. In the hydrogenated isoprene / butadiene copolymer block (q5), before hydrogenation,
The units derived from isoprene include a 2-methyl-2-butene-1,4-diyl group, an isopropenylethylene group and 1
At least one group selected from the group consisting of -methyl-1-vinylethylene group, and the unit derived from butadiene is a vinylethylene group and / or a 2-butene-1,4-diyl group. The ratio of those groups in the isoprene / butadiene copolymer block before addition is not particularly limited. In the hydrogenated isoprene / butadiene copolymer block (q5), the unit derived from butadiene and the unit derived from isoprene may be in any of random, block, and tapered block configurations. .

Then, the aromatic vinyl block (Qα)
Hydrogenated polybutadiene block (q2), hydrogenated polyisoprene block (q3), hydrogenated polybutadiene block (q4) and hydrogenated isoprene /
In the butadiene copolymer block (q5), as described above, some or all of the carbon-carbon double bonds may be completely hydrogenated. In the entire system block (Qα),
50 mol% or more, particularly 80 mol%, of carbon-carbon double bonds in butadiene units and / or isoprene units
It is preferable that the above is hydrogenated from the viewpoint that the heat-aging resistance and the weather resistance of the polyester-styrene-based elastomer block copolymer (component C) are improved.

The polyisobutylene block (qd) in the aromatic vinyl block (Qβ) of the polyester-styrene elastomer block copolymer (component C) of the present invention is a polymer block mainly composed of isobutylene units.

In the polyester-styrene-based elastomer block copolymer of the present invention, {the total content of the polymer block (qa)} in the aromatic vinyl-based block (Qα): {the total content of the polymer block (qb) ｛And the total content of the polymer block (qc) in the aromatic vinyl-based block (Qβ)｝: ｛the polymer block (q
d) is preferably in the range of 1: 9 to 9: 1 (weight ratio), and particularly preferably in the range of 2: 8 to 7: 3 (weight ratio).

The polymer block (qa) in the aromatic vinyl block (Qα) and the polymer block (q) in the aromatic vinyl block (Qβ) of the polyester-styrene elastomer block copolymer of the present invention.
c) has a number average molecular weight of 2,500 to 5 respectively.
It is preferably in the range of 000. The polymer block (q) in the aromatic vinyl block (Qα)
The number average molecular weight of b) and the polyisobutylene block (qd) in the aromatic vinyl-based block (Qβ) is preferably in the range of 10,000 to 10,000. Further, even if the polyester-styrene-based elastomer block copolymer of the present invention has one or more kinds of aromatic vinyl-based blocks (Qα), and / or
Alternatively, it may have one or more aromatic vinyl-based blocks (Qβ).

The block copolymer having the polyester block (P) and the aromatic vinyl copolymer block (Q) contained in the polyester-styrene elastomer block copolymer (component C) of the present invention has a number average molecular weight. Is preferably in the range of 13,000 to 300,000, and more preferably in the range of 20,000 to 200,000. In the present invention, the number average molecular weight is GP
A value calculated based on standard polystyrene by C measurement. The ratio between the polyester block (P) and the aromatic vinyl copolymer block (Q) was 9: 1 by weight.
１ ： 1: 9, preferably 8: 2 to 2: 8. If the weight ratio is out of the range of 9: 1 to 1: 9, the compatibilizing effect becomes insufficient, which is not preferable.

The method for producing the polyester-styrene-based elastomer block copolymer (component C) of the present invention is not particularly limited. For example, a polyester-based resin and a functional group capable of reacting with the polyester-based resin are contained in the molecule. The aromatic vinyl-based polymer of the present invention is kneaded under melting conditions, followed by solid-phase polymerization, and the resulting polyester-based reaction product is used to obtain a polyester block (P) and an aromatic vinyl-based copolymer block ( The basic method is a production method for extracting and recovering a block copolymer having Q). However,
A block copolymer having a polyester block (P) and an aromatic vinyl-based copolymer block (Q), and a polyester-based reaction product itself obtained by the solid-phase polymerization;
It is also possible to use it in a state containing each block component which is not formed into a block copolymer, and such use is industrially more preferable because the step of extraction and recovery can be omitted.

In the above production method, the melt kneading of the polyester resin and the aromatic vinyl polymer can be carried out using a melt kneading apparatus such as a single screw extruder, a twin screw extruder, a kneader, and a Banbury mixer. it can. Melt kneading conditions can be appropriately selected according to the type of polyester resin or aromatic vinyl polymer to be used, the type of equipment, and the like. Usually, the temperature is 180 to 300 ° C and 3 to 15 ° C.
It is good to do for about a minute. In addition, solid state polymerization after melt kneading,
After solidifying and granulating the resin obtained by melt-kneading the polyester-based resin and the aromatic vinyl-based polymer, the resin is transferred to an appropriate solid-state polymerization reactor, and subjected to a pretreatment of 120%.
Drying, crystallization, and the like can be performed at a temperature of about 180 ° C., followed by solid phase polymerization. The solid-state polymerization reaction is usually carried out 5 to 6 times higher than the melting point of the polyester resin.
The heat treatment may be performed under an inert gas stream or under vacuum while maintaining the temperature at about 0 ° C. lower. Solid phase polymerization may be performed in either a batch mode or a continuous mode, and by appropriately adjusting the residence time and the processing time in the solid phase polymerization reaction device,
The desired degree of polymerization and reaction rate can be obtained.

In the above, extraction and recovery of a block copolymer having a polyester block (P) and an aromatic vinyl-based copolymer block (Q) from a polyester-based reaction product obtained by solid-phase polymerization can be performed, for example, using a polyester-based reaction product. The reaction product was dissolved in a mixed solvent of hexafluoroisopropanol / chloroform, and the solution was poured into tetrahydrofuran for precipitation. The precipitate was recovered and dissolved in chloroform, and insolubles were removed from the chloroform solution by filtration or the like. Thereafter, the chloroform solution can be concentrated, dried and solidified to recover a block copolymer having a polyester block (P) and an aromatic vinyl copolymer block (Q) as a solid content.

The aromatic vinyl polymer having a functional group capable of reacting with the polyester resin used for producing the polyester-styrene elastomer block copolymer (component (C)) of the present invention is the above-mentioned aromatic vinyl polymer. An aromatic vinyl polymer having a structure in which a functional group is added to the copolymer block (Q) is preferably used. The functional group in that case is not particularly limited as long as it is a functional group capable of reacting with the polyester resin, for example, a hydroxyl group, a carboxyl group, an ester group, an amide group, an amino group, an epoxy group,
A thiol group, a thioester group, a cyclic imino ether group such as a 2-oxazoline group, a succinic anhydride-2-yl group,
Examples thereof include groups having an acid anhydride structure such as a succinic anhydride-2,3-diyl group. Particularly preferred for an aromatic polycarbonate resin are a hydroxyl group, a carboxyl group, an epoxy group, and a 2-yl succinic anhydride group. In an aromatic vinyl-based polymer having a functional group capable of reacting with a polyester-based resin, the functional group is located at any position in the molecular main chain or molecular side chain of the aromatic vinyl-based polymer or at a molecular terminal. However, it is preferably located at the molecular end. In addition, the content of the functional group is preferably 0.5 or more per molecule on average, and 0.7 to
More preferably, the number is one.

The component C of the present invention may contain an aromatic vinyl-conjugated diene block copolymer as a by-product during the production. Therefore, the amounts of the aromatic polyester resin and the aromatic vinyl-conjugated diene block copolymer derived from the component C are not included in the amounts of the components (a-2) and B in the component A of the present invention. In addition, such a by-product is
In particular, when a small amount of a styrene-based elastomer is reacted with a large amount of polyester, when a large amount of a styrene-based elastomer is reacted with a small amount of polyester, the polymerization time is short, or when the polymerization temperature is low, it is easily formed.

The proportions of the components A, B and C of the present invention are as follows:
70 to 96% by weight of the component, 3 to 20% by weight of the component B, and 1 to 10% by weight of the component C. Preferably, component A is 77-92% by weight, component B is 5-15% by weight, and C
The components are 3-8% by weight.

When the component A is less than 70% by weight, mechanical properties such as impact strength, heat resistance, and flame retardancy are required when flame retardancy is required. Makes it difficult to balance vibration damping and mechanical properties.
When the amount of the component B is less than 3% by weight, the vibration damping property is not sufficiently imparted. When the amount exceeds 20% by weight, the mechanical properties deteriorate, which is not preferable. When the amount of the component C is less than 1% by weight, the improvement of the compatibility is insufficient. When the amount is more than 10% by weight, the effect as a compatibilizing agent is saturated and the amount of other components is reduced, which is preferable. Absent.

Further, in the present invention, the components A to C
It is also possible to add various inorganic fillers for the purpose of improving rigidity and strength to the resin composition comprising the components,
Even in such a case, a sufficiently high vibration damping property is exhibited. Here, as the inorganic filler, glass fiber (chopped strand), glass short fiber (milled fiber), glass bead, glass balloon, carbon fiber, metal-coated carbon fiber, carbon short fiber, heat-resistant organic fiber, metal fiber,
Metal fibers, calcium carbonate, talc, mica, kaolin, glass flakes, wollastonite, clay, titanium oxide, potassium titanate whiskers, aluminum borate whiskers, etc., particularly preferably,
Glass fiber, short glass fiber, talc and mica. The addition amount of the inorganic filler is 1 to 1 with respect to 100 parts by weight of the damping thermoplastic resin composition comprising the components A to C of the present invention.
00 parts by weight, preferably 10 to 80 parts by weight.

The vibration-damping thermoplastic resin composition of the present invention comprises:
Flame retardants and the like may be blended as long as the object of the present invention is not impaired. As the flame retardant to be added, first, a red phosphorus-based flame retardant can be used. As the red phosphorus flame retardant to be used, red phosphorus in which the surface of red phosphorus is microencapsulated with a thermosetting resin and / or an inorganic material can be used in addition to general red phosphorus. Further, in the use of such microencapsulated red phosphorus, a master pellet is preferably used in order to improve safety and workability. Examples of inorganic materials used for such microencapsulation include magnesium hydroxide, aluminum hydroxide, titanium hydroxide, tin hydroxide, cerium hydroxide, and the like. Examples of thermosetting resins include phenol / formalin and urea / formalin And melamine-formalin resins. Further, red phosphorus or the like obtained by forming a coating using a thermosetting resin on a coating coated with such an inorganic material and performing a double coating treatment can also be preferably used. Also, the red phosphorus used may be an electroless plated one, and as the electroless plating film, nickel, cobalt, copper, iron,
A metal plating film selected from manganese, zinc or an alloy thereof can be used. In addition, red phosphorus coated with the above-mentioned inorganic material and thermosetting resin may be used for the electroless plated red phosphorus. The amount of the inorganic material, the thermosetting resin and the component used for microencapsulation such as electroless plating is preferably 20% by weight or less in 100% by weight of the red phosphorus-based flame retardant.
More preferably, it is 5 to 15% by weight. If the content exceeds 20% by weight, adverse effects such as a decrease in flame retardancy and a decrease in mechanical properties are more unfavorable than effects of suppressing phosphine and ensuring safety. The average particle size of the red phosphorus flame retardant is 1 to 100 μm, preferably 1 to 40 μm. Commercial products of such microencapsulated red phosphorus flame retardants include NOVA EXCEL 140, NOVA EXCEL F-5 (trade name, manufactured by Rin Kagaku Kogyo Co., Ltd.), and Hishiguard TP-10 (manufactured by Nippon Chemical Industry Co., Ltd.). : Trade name), Hostafram RP614 (Clariant Japan K.K.)
(Trade name).

Examples of the brominated flame retardant include halogenated flame retardants represented by brominated bisphenol, brominated polystyrene, carbonate oligomers of brominated bisphenol A, copolymers of brominated bisphenol A and bisphenol A, and copolymerized oligomers. And one or more phosphate ester-based flame retardants represented by the following general formula (1).

[0082]

Embedded image

(Where X in the above formula is hydroquinone,
Derived from resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide Wherein j, k, l, m are each independently 0 or 1, n is an integer of 0 to 5,
Alternatively, in the case of a blend of phosphate esters having different n numbers, the average value is 0 to 5, and R ₁ , R ₂ , R ₃ , and R ₄ are each independently substituted or substituted with one or more halogen atoms. Phenol, cresol, xylenol, isopropylphenol, butylphenol, p-
It is derived from cumylphenol. )

Among them, X in the above formula preferably includes those derived from hydroquinone, resorcinol and bisphenol A, j, k, l and m are each 1 and n is 0-3. Is an integer or an average value of 0 to 3 in the case of a blend of n different phosphate esters, and R ₁ , R ₂ , R ₃ , and R ₄ each independently represent one or more halogen atoms. It is derived from substituted or unsubstituted phenol, cresol, xylenol.

Furthermore, particularly preferably, X is derived from resorcinol, j, k, l, m are each 1, n is 0 or 1, and R ₁ , R ₂ , R ₃ ,
And R ₄ are each independently derived from phenol or xylenol.

Among such phosphate ester flame retardants,
Triphenyl phosphate as the monophosphate compound and resorcinol bis (dixylenyl phosphate) as the condensed phosphate ester can be preferably used because of their good flame retardancy and good fluidity during molding.

Examples of additives other than the flame retardant include impact modifiers such as an acryl-butadiene impact modifier, and a structure in which a polyorganosiloxane component and a poly (meth) alkyl acrylate component are entangled with each other so that they cannot be separated. Examples of the composite rubber having a polymer include a polymer obtained by grafting an alkyl (meth) acrylate and an optionally copolymerizable vinyl polymer. A specific example of the former is HIA15 (trade name) manufactured by Kureha Chemical Co., Ltd., and a specific example of the latter is Metablen S2001 manufactured by Mitsubishi Rayon Co., Ltd.
(Product name). Other flame-retardant aids such as antimony trioxide and sodium antimonate; anti-drip agents such as polytetrafluoroethylene having fibril-forming ability; and heat stabilizers such as hindered phenolic, amine-based, phosphorus-based, and sulfur-based. It is possible to add various additives such as various stabilizers, ultraviolet absorbers, release agents, lubricants, antistatic agents, colorants and the like.

The composition thus obtained can be easily molded by a known method such as injection molding, injection compression molding, high-speed injection molding, rapid heating mold molding, extrusion molding, compression molding or rotational molding. .

[0089]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples.

[Examples 1 to 8, Comparative Examples 1 to 7] Among the components shown in Tables 1 to 3, components other than the filler of glass fiber, short glass fiber or talc were uniformly mixed in a V-type blender. After mixing, a 30 mmφ vent-type twin-screw extruder [Nippon Steel Works TE.
X-30XSST], and melt-extruded into a pellet at a cylinder temperature of 260 ° C. and a discharge rate of 20 kg / hour using a vacuum pump under a vacuum of 40 torr. For the sample containing the above filler, the filler was mixed with the mixture from the first inlet through the second inlet of the side feed portion in the middle of the cylinder using a measuring device [CWF manufactured by Kubota Corporation]. Melt extrusion was performed under the same conditions as described above, with the filler at the two inlets being set at a predetermined ratio, to obtain pellets. The obtained pellet is heated at 110 ° C.
For 5 hours in a hot-air circulation type dryer, and a test piece for evaluation was prepared at 260 ° C. cylinder temperature and 70 ° C. mold temperature by an injection molding machine [FANUC T-150D]. Evaluation was performed by the method.

(I) Mechanical properties and flame retardancy of the damping thermoplastic resin composition Rigidity: Flexural modulus was measured in accordance with ASTM D-790. Impact resistance: Izod reverse notched impact was measured according to ASTM D-256. That is, a 3.2 mm thick test piece was used to impact a weight from the notch side, and the impact value was measured (evaluated by Izod test method E). Heat resistance: 18.6 according to ASTM D-648
The deflection temperature under load was measured with a load of kgf / cm ² . Flammability: According to UL Standard 94, a vertical / horizontal combustion test was performed with a thickness of 1.6 mm.

(II) Vibration Suppression (Loss Coefficient) A strip-shaped test piece having a length of 150 mm, a width of 20 mm, and a thickness of 3 mm was injection-molded under the same conditions as the above-mentioned test piece, and a complex elastic modulus measuring device (Bruell & Co., Ltd.) The loss coefficient at 30 ° C. was measured by a central vibration method using a 3560 type multi-analyzer system manufactured by Care and a loss coefficient measurement software MS1018 manufactured by Matsushita Intertechno.

The symbols for resins, carbon fibers, flame retardants and the like in Tables 1 to 3 are as follows. (A component) (a-1) PC: aromatic polycarbonate resin [L-1225, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 22,500] (a-2) AS: acrylonitrile-styrene copolymer [Mitsui Chemicals, Inc. ABS: acrylonitrile-butadiene-styrene copolymer [Santak UT-61 manufactured by Mitsui Chemicals, Inc.] PET: polyethylene terephthalate resin [Teijin Co., Ltd.]
TR-8580, intrinsic viscosity 0.80]

(Component B) Vibration-damping copolymer: Styrene-isoprene block copolymer [Hybler 5127 (VS-
1)]

(Component C) C-1: Polyester-styrene-based elastomer block copolymer polybutylene terephthalate resin shown below (“Hauser S1000F” manufactured by Kuraray Co., Ltd .: intrinsic viscosity [η] = 0.85) 70 weight Parts and hydrogenated SBIS-OH
ポ リ ス チ レ ン Polystyrene block having a hydroxyl group at one end (number average molecular weight 6,000) / 1 hydrogenated copolymer block of 1,3-butadiene and isoprene (number average molecular weight 28,000
0) / polystyrene block (number average molecular weight 6,000)
0), hydroxyl group content =
0.8 styrene / 1 molecule, styrene content before hydrogenation = 30
% By weight, molar ratio of 1,3-butadiene / isoprene = 1
/ 1, number-average molecular weight = 40,000 重量 30 parts by weight were premixed, and a twin-screw extruder (“TEX44” manufactured by Japan Steel Works, Ltd.) was used.
C ") and melt-kneaded at 250 ° C. to produce pellets. The pellets were transferred to a solid-state polymerization apparatus,
For about 4 hours. Thereafter, the pressure inside the solid-state polymerization apparatus was reduced to 0.2 mmHg, and the temperature was raised to 200 ° C. to start the polymerization reaction. After about 14 hours, nitrogen gas was introduced into the reactor to return to normal pressure, and a desired polyester-styrene-based elastomer block copolymer (C-1) was obtained as a reaction product.

The polyester-styrene elastomer block copolymer (C-1) obtained as described above contains a block copolymer in which a polybutylene terephthalate block and a hydrogenated SBIS block are bonded, as follows. Confirmed by

That is, the obtained polyester-styrene elastomer block copolymer (C-1) was dissolved in a mixed solvent of hexafluoroisopropanol / chloroform (1/1), and the resulting solution was poured into tetrahydrofuran to precipitate. I got something. Further, after heating and refluxing in chloroform, the mixture was filtered off, and the chloroform solution was concentrated to dryness to form a block in which a polybutylene terephthalate block and a hydrogenated SBIS block were bonded from the polyester-styrene elastomer block copolymer (C-1). The copolymer component is separated and the ¹ H-N
By the MR measurement, a peak derived from the chemical structure of polybutylene terephthalate (peak at 8.1, 4.1, 2.2 ppm) and a peak derived from the chemical structure of hydrogenated SBIS-OH (7.0, 6.6, 0.7-2.0 ppm), and the chemical shift of the peak of the methylene proton adjacent to the hydroxyl group at the molecular end observed in the hydrogenated SBIS-OH used was shifted. Also, GPC
In the measurement, it showed a single molecular weight distribution, and its number average molecular weight was almost equal to the sum of the number average molecular weight of polybutylene terephthalate used as a raw material and the number average molecular weight of hydrogenated SBIS-OH. It is.

The ratio of the block copolymer component in which the polybutylene terephthalate block and the hydrogenated SBIS block were combined in the polyester-styrene elastomer block copolymer (C-1) was 52% by weight.

C-2: SB used in the following polyester-styrene elastomer block copolymer C-1
A diblock consisting of hydrogenated SI-OH instead of IS-OH and a polystyrene block having a hydroxyl group at the end of the polystyrene block (number average molecular weight 10,000) / hydrogenated polyisoprene block (number average molecular weight 20,000) Polymer, hydroxyl group content = 0.8 / molecule,
The styrene content in the block copolymer before hydrogenation = 33% by weight and the number average molecular weight = 30,000 °
In the same manner as in -1, a solid-phase polymerization reaction product containing a polyester-aromatic vinyl-based block copolymer was obtained. The obtained solid-phase polymerization reaction product is dissolved in a mixed solvent of hexafluoroisopropanol / chloroform (1/1),
The solution was poured into tetrahydrofuran to obtain a precipitate. After further heating and refluxing in chloroform, the mixture was filtered off, and the chloroform solution was concentrated to dryness to obtain the desired polyester-styrene elastomer block copolymer (C-2). Further, it was confirmed that this was a block copolymer by the same method as in C-1.

(Components other than Component C) W-1: Polyester mixture shown below Polybutylene terephthalate (“Hauser S1000F” manufactured by Kuraray Co., Ltd .: intrinsic viscosity [η] = 0.85) 70 parts by weight and hydrogenated SBIS @ polystyrene block (number average molecular weight 6,000) / 1 hydrogenated copolymer block of 1,3-butadiene and isoprene (number average molecular weight 28,000)
/ Polystyrene block (number average molecular weight 6,000), triblock copolymer, styrene content before hydrogenation = 30% by weight, 1,3-butadiene / isoprene molar ratio = 1/1, number average molecular weight = 40,000｝ 30
The parts by weight were preliminarily mixed and melt-kneaded at 250 ° C. using a twin-screw extruder (“TEX44C” manufactured by Japan Steel Works, Ltd.) to obtain a mixture of polyester and SBIS (W-1).

W-2: Instead of the hydrogenated SBIS used in the polyester mixture W-1 shown below, hydrogenated SI ｛polystyrene block (number average molecular weight 10,000) / hydrogenated polyisoprene block (number average Molecular weight 2
000), except that the styrene content in the block copolymer before hydrogenation was 33% by weight and the number average molecular weight was 30,000 °.
In the same manner as in Example 1, a mixture (W-2) of the target polyester and SI was obtained.

W-3: Polyester-polystyrene block copolymer shown below Polybutylene terephthalate resin (“Hauser S1000F” manufactured by Kuraray Co., Ltd .: intrinsic viscosity [η] = 0.85) 7
0 parts by weight and polystyrene having a hydroxyl group at one end (number average molecular weight 15,000, hydroxyl group content = 0.8 / 1)
30 parts by weight of a molecule) are charged into a separable kolben and 240
A dehydration reaction was performed at 12 ° C. for 12 hours under a nitrogen stream to obtain a reaction product. The obtained reaction product was dissolved in a mixed solvent of hexafluoroisopropanol / chloroform (1/1), and the solution was poured into tetrahydrofuran to form a precipitate, and the precipitate was collected. The collected precipitate was heated and refluxed in chloroform, filtered, and the chloroform solution was concentrated and dried to obtain a target polyester-polystyrene block copolymer (W-3).

The following points confirmed that the polyester-polystyrene block copolymer (W-3) obtained above was a block copolymer in which a polybutylene terephthalate block and a polystyrene block were bonded.

That is, the peak (8.1, 4.1, 2.2 ppm peak) derived from the chemical structure of polybutylene terephthalate was determined by ¹ H-NMR measurement of the obtained polyester-polystyrene block copolymer (W-3). ) And the peaks (7.0, 6.6 ppm) derived from the chemical structure of the hydroxyl group-containing polystyrene, and the peak chemistry of the methylene proton adjacent to the molecular terminal hydroxyl group observed in the hydroxyl group-containing polystyrene used. The shift was moving. GPC measurement also showed a single molecular weight distribution, and the number average molecular weight was almost equal to the sum of the number average molecular weight of polybutylene terephthalate used as a raw material and the number average molecular weight of hydroxyl group-containing polystyrene. That is.

(Other Components) Filler-1: Glass fiber [3PE93 manufactured by Nitto Boseki Co., Ltd.]
7, fiber diameter 13 μm, epoxy bundle] Filler-2: short glass fiber [Nitto Boseki Co., Ltd. PFE-
301, fiber diameter 9 μm, average fiber length 40 μm] Filler-3: talc [HST-0.
8, average particle size of 2.8 μm] FR-1: Red phosphorus-based flame retardant [NOVA EXCEL 140 manufactured by Rin Kagaku Kogyo Co., Ltd., Red phosphorus-based flame retardant microencapsulated with phenol / formalin-based resin, containing red phosphorus FR-2: halogen-based flame retardant [Fireguard FG-7000, Teijin Chemicals Ltd., carbonate oligomer of tetrabromobisphenol A] FR-3: phosphorus-based flame retardant [Daichi Chemical Industry Co., Ltd. ) TPP,
Triphenyl phosphate] Additive-1: Phosphate stabilizer (trimethyl phosphate) Additive-2: Phosphite stabilizer [Nippon Ciba Geigy Co., Ltd. Irgafos 168]

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

As is clear from these tables, for example, from the comparison between Example 1 and Comparative Example 1 or Example 4 and Comparative Example 6, the addition of the polyester-styrene-based elastomer block copolymer (component C) was confirmed. It can be seen from the result that a good impact value is achieved while maintaining the vibration damping property. In Comparative Example 3, since the added amount of the damping block copolymer (component B) was small, no damping performance was exhibited. Also, a polyester-styrene elastomer block copolymer (component C)
When the polyester-based block component (P) and the aromatic vinyl-based block component (Q), which are the constituent blocks of the above, do not react and bond with each other and do not form a block copolymer,
As can be seen from the comparison between Examples 2 and 3 and Comparative Examples 3, 4 and 5, it can be seen that the effect of improving compatibility was not exhibited and the impact strength was insufficient.

Also, from the comparison between Example 8 and Comparative Example 7, it can be seen that when the polyester-styrene-based elastomer block copolymer (component C) is not blended, the impact resistance becomes insufficient.

[0111]

The vibration-damping thermoplastic resin composition of the present invention comprises:
Since it has excellent vibration damping properties and excellent mechanical strength, flame retardancy, and moldability, it can be used for materials that require vibration damping properties.
In particular, it is effective for countermeasures against vibration by a drive system such as a mechanical component in the field of OA equipment and electric and electronic equipment, and the industrial effect achieved is outstanding.

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (reference) C08L 59/04 C08L 59/04 67/02 67/02 67/03 67/03 71/02 71/02 71/08 71 / 08 77/02 77/02 79/08 79/08 Z 81/02 81/02 81/06 81/06 F16F 15/02 F16F 15/02 Q F term (reference) 3J048 AB01 AC01 BD03 DA10 EA07 4J002 BB00X BC03X BC06X BD04X BG04X BN06X BN12X BN14X BN15X BP013 BP034 CB00X CF04X CF16X CG00W CH07X CH08X CH09X CL00X CM04X CN01X CN03X DA016 DA066 DE136 DE186 DE236 DJ006 DJ036 DJ046 DJ056 DK006 DL006 FA016 FA016 FA016

Claims (2)

[Claims] (1) 40 to 100% by weight of an aromatic polycarbonate resin and (a-2) a polystyrene resin,
Copolymer containing components consisting of vinyl cyanide compound and aromatic vinyl compound, polyester resin, polyolefin resin, polyarylate resin, polyamide resin, polyphenylene ether resin, polysulfone resin, polyphenylene sulfide resin, polyalkyl methacrylate resin, polyether Sulfone resin, phenoxy resin,
Thermoplastic resin composed of a total of 100% by weight of 60 to 0% by weight of one or more thermoplastic resins selected from polyetheretherketone resin, polyvinyl chloride resin, polyacetal resin, and polyimide resin (component A)
70-96% by weight, (b-1) a block composed of a vinyl aromatic compound component having a number average molecular weight of 2,500-40,000, and (b-2) a conjugated diene compound component composed of a block number 10,000. A block having a glass transition temperature in the range of −30 ° C. to 30 ° C. and a number average molecular weight of 30,000 to 300,000 (component B). Vibration-damping thermoplastic resin composition comprising 20% by weight and 1 to 10% by weight of a polyester-styrene elastomer block copolymer (component (C)) and a total of 100% by weight of components A, B and C object. 2. The vibration damper according to claim 1, wherein 1 to 100 parts by weight of an inorganic filler is further blended with respect to 100 parts by weight of the damping thermoplastic resin composition comprising the A component, the B component and the C component. Thermoplastic resin composition.