JP2002060634A - Vibration-damping thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a vibration-damping thermoplastic resin composition which shows a suppressed temperature dependence of the vibration-damping effect and is excellent in mechanical strength, thermal resistance and moldability. SOLUTION: The vibration-damping thermoplastic resin composition comprises 10-99 wt.% of component A, 1-20 wt.% of component B and 0-70 wt.% of component C in a total of 100 wt.% of the components A, B and C, wherein the component B comprises two or more block copolymers with different glass transition temperatures of the block-2, wherein component (A) is a thermoplastic resin; component (B) is a block copolymer comprising a block (block-(1)) formed by polymerizing an aromatic vinyl compound and a block (block-(2)) formed by polymerizing a conjugated diene compound and having the glass transition temperature thereof measured by DSC ranging from -30 deg.C to 30 deg.C; and component (C) is a reinforcing filler.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a damping thermoplastic resin composition. More specifically, a thermoplastic resin, particularly a thermoplastic resin mainly composed of a polycarbonate resin, comprising two or more kinds of specific block copolymers having different glass transition temperatures, and more preferably further comprising a reinforcing filler. It is. Further, the present invention relates to a damping thermoplastic resin composition having excellent mechanical properties, heat resistance, moldability, and damping performance in a wide temperature range.

[0002]

2. Description of the Related Art In recent years, for example, in the field of OA equipment, the processing speed of OA equipment has been remarkably increased.
With the increase in speed, various mechanical parts are required not only to improve rigidity or heat resistance, which is conventionally required, but also to attenuate vibrations newly generated from the drive system, so-called vibration damping properties. Conventionally, various thermoplastic resin compositions have been used in this field. A typical example thereof is a polycarbonate resin composition. Polycarbonate resin has excellent impact strength and heat resistance. As described above, there are fields in which various thermoplastic resin compositions including a polycarbonate resin composition are required to have good vibration damping properties.

In general, the following proposals have already been made as a method for imparting vibration damping properties to a composition such as a polycarbonate resin composition. JP-A-5-2022
No. 87, a functional group having reactivity with a thermoplastic resin such as a carboxyl or epoxy group is further bonded to a resin composition comprising a thermoplastic resin such as a polycarbonate resin and a block copolymer for imparting vibration damping properties. A method for incorporating a modified polymer is described. JP 9
Japanese Patent Publication No. -40840 describes a method of blending a vibration damping elastomer and a fibrous filler with a thermoplastic resin such as a polycarbonate resin. However, these formulations do not yet provide sufficient damping properties.

For example, when a damping elastomer and a filler are used in combination, there is a problem that the temperature dependency of the damping effect is large. That is, the resin composition had sufficient damping properties at around room temperature, but had a property of decreasing the damping properties in a higher temperature region. Parts requiring vibration damping, such as an optical chassis of an optical printer, are usually used in a wide temperature range. This is because heat generated by the drive system and other heat sources are present around the component, and the surrounding temperature rises. Therefore, there is a need for a damping thermoplastic resin composition having a small temperature dependency of the damping effect.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a vibration-damping thermoplastic resin composition which suppresses the temperature dependence of the vibration-damping effect and is excellent in mechanical strength, heat resistance and moldability. is there. The present inventors have conducted intensive studies to achieve the above object, and as a result, a thermoplastic resin, particularly a thermoplastic resin mainly composed of a polycarbonate resin, and a block in which an aromatic vinyl compound is polymerized, and a conjugated diene compound Is a block copolymer consisting of blocks having a glass transition temperature measured by DSC in the range of -30 ° C to 30 ° C, wherein the block copolymers have different glass transition temperatures.
The present inventors have found that a vibration-damping thermoplastic resin composition containing at least one kind of block copolymer can achieve the above object, and have completed the present invention.

[0006]

According to the present invention, 10 to 99% by weight of A component, 1 to 20% by weight of B component and 0% of C component in a total of 100% by weight of the following components A, B and C: A vibration-damping thermoplastic resin composition comprising about 70% by weight and a B component comprising two or more block copolymers having different glass transition temperatures of the blocks. (A component) a thermoplastic resin (B component) a block (block) formed by polymerization of an aromatic vinyl compound, and a conjugated diene compound formed by polymerization, and its glass transition temperature measured by DSC is -3.
The present invention relates to a block copolymer (component C) reinforced filler composed of blocks (blocks) in the range of 0 ° C to 30 ° C.

Further, according to the present invention, in the method of measuring a loss coefficient defined in the text, the difference (Δη) between the maximum value (ηmax.) And the minimum value (ηmin.) Of the loss coefficient at 10 ° C. to 50 ° C. 0.04 or less, and ηmin. Is 0.03
The present invention provides a vibration-damping thermoplastic resin composition as described above. More preferably, the vibration-damping thermoplastic satisfies that the deflection temperature under load at a load of 1.813 MPa measured according to ASTM D648 is 100 ° C. or more, and the flexural modulus measured according to ASTM D790 is 2,000 MPa or more. The present invention provides a resin composition. Hereinafter, the present invention will be described specifically.

As the component A of the present invention, various thermoplastic resins can be used. Particularly, a thermoplastic resin mainly composed of a polycarbonate resin can be preferably mentioned. This is because a thermoplastic resin mainly composed of a polycarbonate resin is widely used as a material in a field where vibration damping properties are required in the future, such as a chassis of OA equipment.

The preferred A component is a polycarbonate resin (a-1 component), a polycarbonate resin and B
A resin composed of a thermoplastic resin (component (a-2)) other than the component block copolymer and containing at least 50% by weight of a polycarbonate resin in 100% by weight of the component A. a-2
The thermoplastic resin as a component is appropriately added according to the purpose.

The polycarbonate resin (component (a-1)) used in the present invention is usually obtained by reacting a dihydric phenol with a carbonate precursor by an interfacial polycondensation method or a melt transesterification method. It is obtained by polymerizing a polymer by a solid phase transesterification method or by polymerizing a polymer by a ring opening polymerization method of a cyclic carbonate compound.

Representative examples of the dihydric phenol used here include hydroquinone, resorcinol, 4,4
4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, bis {(4-hydroxy-3,5-
Dimethyl) phenyl @ methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4
-Hydroxyphenyl) propane (commonly known as bisphenol A), 2,2-bis {(4-hydroxy-3-methyl)
Phenyl {propane, 2,2-bis {(4-hydroxy-3,5-dimethyl) phenyl} propane, 2,2-bis {(3-isopropyl-4-hydroxy) phenyl}
Propane, 2,2-bis {(4-hydroxy-3-phenyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4
-Bis (4-hydroxyphenyl) -2-methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4 -Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-
Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis {(4-hydroxy-3-methyl) phenyl} fluorene, α , Α'-bis (4-hydroxyphenyl) -o-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m
-Diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,
3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane, 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxydiphenylsulfoxide, 4,4′-dihydroxydiphenylsulfide,
4,4'-dihydroxydiphenyl ketone, 4,4'-
Examples thereof include dihydroxydiphenyl ether and 4,4′-dihydroxydiphenyl ester, and these can be used alone or as a mixture of two or more.

Among them, bisphenol A, 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane,
2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
A homopolymer obtained from at least one bisphenol selected from the group consisting of -hydroxyphenyl) -3,3,5-trimethylcyclohexane and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, or Copolymers are preferred.

In particular, (1) a homopolymer of bisphenol A, and (2) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, bisphenol A, 2,2-bis {( 4-hydroxy-3-
Methyl) phenyl} propane or α, α′-bis (4
A copolymer with (-hydroxyphenyl) -m-diisopropylbenzene is preferably used.

In the case of the above (1), it is preferable that the heat resistance and the mechanical properties are more excellent. On the other hand, in the case of (2),
This is preferable in that the vibration damping characteristics are improved. That is, by further increasing the damping property of the base polycarbonate resin, the damping property of the damping thermoplastic resin composition of the present invention can be further increased.

As the carbonate precursor, carbonyl halide, carbonate ester or haloformate is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and the like.

In producing the polycarbonate resin by reacting the dihydric phenol with the carbonate precursor by an interfacial polycondensation method or a melt transesterification method, if necessary, a catalyst, a terminal stopper and a dihydric phenol are oxidized. For example, an antioxidant or the like may be used to prevent the oxidation.
Further, the polycarbonate resin may be a branched polycarbonate resin obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound, or a polyester carbonate resin obtained by copolymerizing an aromatic or aliphatic bifunctional carboxylic acid,
Further, a mixture of two or more of the obtained polycarbonate resins may be used.

Examples of the trifunctional or higher polyfunctional aromatic compound include phloroglucin, phloroglucid, and 4,6-
Dimethyl-2,4,6-tris (4-hydroxydiphenyl) heptene-2,2,4,6-trimethyl-2,4
6-tris (4-hydroxyphenyl) heptane, 1,
3,5-tris (4-hydroxyphenyl) benzene,
1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) ) -4-Methylphenol, 4
-{4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene} -α, α-dimethylbenzylphenol and other trisphenols, tetra (4-hydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) )
Examples thereof include ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and acid chlorides thereof, among which 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-
Tris (3,5-dimethyl-4-hydroxyphenyl)
Ethane is preferred, and 1,1,1-tris (4-hydroxyphenyl) ethane is particularly preferred.

When a polyfunctional compound which produces such a branched polycarbonate resin is contained, the proportion is preferably from 0.001 to 1 mol%, more preferably from 0.005 to 0.5 mol%, particularly preferably from the total amount of the aromatic polycarbonate. 0.01
~ 0.3 mol%. In particular, in the case of the melt transesterification method, a branched structure may be generated as a side reaction. The amount of such a branched structure is also 3, and 0.001 to 1 mol%, preferably 0.005 mol%, of the total amount of the aromatic polycarbonate.
It is preferably from 0.5 to 0.5 mol%, particularly preferably from 0.01 to 0.3 mol%. The ratio is ¹
It can be calculated by 1 H-NMR measurement.

The reaction by the interfacial polycondensation method is usually a reaction between dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. Examples of the acid binder include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide and amine compounds such as pyridine.
As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. Further, for promoting the reaction, for example, a catalyst such as tertiary amine such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, a quaternary ammonium compound, and a quaternary phosphonium compound may be used. it can. At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

In such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such a terminal stopper. Monofunctional phenols are commonly used as molecular terminators for molecular weight control, and such monofunctional phenols are generally phenols or lower alkyl substituted phenols,
Monofunctional phenols represented by the following general formula (1) can be shown.

[0021]

Embedded image

(Where A is a hydrogen atom or a carbon number of 1 to 9)
Wherein r is an integer of 1 to 5, preferably 1 to 3. Specific examples of the above monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol. Further, the terminal stoppers may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and is produced by mixing the dihydric phenol with the carbonate ester while heating in the presence of an inert gas. It is performed by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, but is usually in the range of 120 to 350 ° C. In the late stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The distillation of alcohol or phenol generated by reducing the pressure to about 3.3 Pa is facilitated. Reaction time is usually 1-4
About an hour.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms. Specifically, diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like can be mentioned, with diphenyl carbonate being preferred.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include sodium hydroxide, potassium hydroxide, alkali metal compounds such as sodium salt and potassium salt of dihydric phenol, and water. Alkaline earth metal compounds such as calcium oxide, barium hydroxide and magnesium hydroxide; nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine; alkoxides of alkali metals and alkaline earth metals Manganese, organic acid salts of alkali metals and alkaline earth metals, zinc compounds, boron compounds, aluminum compounds, silicon compounds, germanium compounds, organic tin compounds, lead compounds, osmium compounds, antimony compounds Compounds, titanium compounds, usually the esterification reaction, such as zirconium compounds, there can be used a catalyst used in the transesterification reaction. The catalyst may be used alone or in combination of two or more. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × with ^respect to 1 mol of the starting dihydric phenol.
It is selected in the range of 10 ⁻³ equivalents, more preferably 1 × 10 ^{−7 to} 5 × 10 ⁻⁴ equivalents.

In the polymerization reaction, in order to reduce the number of phenolic terminal groups, for example, bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, bis (nitrophenyl) carbonate is used later or after completion of the polycondensation reaction. , Bis (phenylphenyl)
Carbonate, chlorophenylphenyl carbonate,
Compounds such as bromophenyl phenyl carbonate, nitro phenyl phenyl carbonate, phenyl phenyl carbonate, methoxy carbonyl phenyl phenyl carbonate and ethoxy carbonyl phenyl phenyl carbonate can be added. Among them, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate and 2-ethoxycarbonylphenylphenyl carbonate are preferred,
Particularly, 2-methoxycarbonylphenylphenyl carbonate is preferably used.

It is preferable to use a deactivator for neutralizing the activity of the catalyst in such a polymerization reaction. Specific examples of the deactivator include, for example, benzenesulfonic acid, p-toluenesulfonic acid, methylbenzenebenzenesulfonate, ethylbenzenebenzenesulfonate, butylbenzenesulfonate, octylbenzenesulfonate, phenylbenzenesulfonate, and p-toluenesulfone. Sulfonates such as methyl acrylate, ethyl p-toluenesulfonate, butyl p-toluenesulfonate, octyl p-toluenesulfonate, and phenyl p-toluenesulfonate; further, trifluoromethanesulfonic acid, naphthalenesulfonic acid, and sulfonated polystyrene , Methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyl dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid-2-
Phenyl-2-butyl, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, tetrabutylphosphonium benzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, dodecylbenzenesulfonate Acid tetrahexyl phosphonium salt, dodecyl benzene sulfonic acid tetraoctyl phosphonium salt, decyl ammonium butyl sulfate, decyl ammonium decyl sulfate, dodecyl ammonium methyl sulfate, dodecyl ammonium ethyl sulfate, dodecyl methyl ammonium methyl sulfate, dodecyl dimethyl ammonium tetradecyl sulfate, tetradecyl Dimethyl ammonium Chill sulfate, tetramethylammonium hexyl sulfate, decyltrimethylammonium hexadecyl sulfate, tetrabutylammonium dodecylbenzyl sulfate, tetraethylammonium dodecylbenzyl sulfate, there may be mentioned compounds such as tetramethylammonium dodecylbenzyl sulfate, and the like. Two or more of these compounds can be used in combination.

Among the deactivators, those of the phosphonium salt or ammonium salt type are preferred. The amount of such a catalyst is preferably 0.5 to 50 mol based on 1 mol of the remaining catalyst, and 0.01 to 500 ppm, more preferably 0 to 500 ppm, based on the polycarbonate resin after polymerization. 0.01 to 300 ppm, particularly preferably 0.01 to 100 ppm.

Although the molecular weight of the polycarbonate resin is not specified, if the molecular weight is less than 10,000, the strength or the like is reduced, and if the molecular weight exceeds 50,000, the moldability decreases. 10,000
~ 50,000, preferably 14,000 to 3
000 is more preferable, and 1 is more preferable.
4,000 to 24,000. Also, two or more polycarbonate resins may be mixed. In this case, it is of course possible to mix with a polycarbonate resin having a viscosity average molecular weight outside the above range.

Particularly, a mixture with a polycarbonate resin having a viscosity average molecular weight of more than 50,000 has properties derived from its high entropy elasticity (properties to improve melting properties such as anti-drip properties, drawdown properties and jetting properties). It is preferable because it exerts its effect. This is because, in the future, products requiring vibration damping properties are required to have any of these characteristics. More preferably, it is a mixture with a polycarbonate resin having a viscosity average molecular weight of 80,000 or more, and further preferably, a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more. That is, GPC
(Gel permeation chromatography) or the like having a molecular weight distribution of two peaks or more can be preferably used.

The viscosity-average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C. η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of falling methylene chloride, t is the number of seconds of falling of the sample solution] The obtained specific viscosity is inserted by the following equation to obtain the viscosity average molecular weight M.
Ask for. 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

Various thermoplastic resins can be used as the component a-2 of the present invention. Examples of such a thermoplastic resin include polyethylene resin, polypropylene resin, polystyrene resin, HIPS resin, MS resin, AB
S resin, AS resin, AES resin, ASA resin, SMA resin, poly-4-methylpentene-1, phenoxy resin,
Acrylic resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, aliphatic polyester resin, polyamide resin, cyclic polyolefin resin, hydrogenated polystyrene resin, polyarylate resin (amorphous polyarylate, liquid crystal polyarylate), poly Ether ether ketone, polyetherimide, polysulfone, polyethersulfone, polyphenylene sulfide and the like can be mentioned. Further, various thermoplastic elastomers can also be used.

Among them, from the viewpoint of compatibility with the polycarbonate resin, ABS resin, AS resin, AES resin, AS resin, polyphenylene ether resin, aromatic polyester resin, aliphatic polyester resin, polyarylate resin, polyester-based heat Plastic elastomers and polyurethane-based thermoplastic elastomers are preferred.

On the other hand, from the viewpoint of the damping properties of the resin, acrylic resins (particularly polymethyl methacrylate) and cyclic polyolefin resins can be preferably mentioned as resins having relatively good damping properties. Examples of the acrylic resin include Delpet 80N and SR-8500 manufactured by Asahi Kasei Corporation.

The thermoplastic resin of the component a-2 can be appropriately selected depending on the purpose. The thermoplastic resin of the component a-2 can be used in combination of two or more components.

A typical example of the component a-2 will be further described below. The AS resin of the present invention is a thermoplastic copolymer obtained by copolymerizing a vinyl cyanide compound and an aromatic vinyl compound. Such vinyl cyanide compounds include:
Acrylonitrile and methacrylonitrile can be mentioned, and acrylonitrile is particularly preferable. As the aromatic vinyl compound, those described above can be used, and styrene and α-methylstyrene are preferable. As the ratio of each component in the AS resin, when the whole is 100% by weight, the vinyl cyanide compound is 5 to 50% by weight, preferably 15 to 35% by weight, and the aromatic vinyl compound is 95 to 50% by weight.
%, Preferably 85-65% by weight. 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. As the initiator, chain transfer agent, and the like used in the reaction, conventionally known various ones can be used as needed.

The AS resin may be produced by any of bulk polymerization, suspension polymerization and emulsion polymerization, but is preferably produced by bulk polymerization. As the method of copolymerization, either one-step copolymerization or multi-step copolymerization can be selected. The reduced viscosity of the AS resin is 0.2 to 1.0 dl / g, preferably 0.3 to 1.0 dl / g.
0.5 dl / g. Reduced viscosity is AS resin 0.2
5 g was precisely weighed and dissolved in 50 ml of dimethylformamide for 2 hours.
It was measured in an environment of 0 ° 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 of the solvent flowing down (t ₀ ) and the number of seconds of the solution flowing down (t). Reduced viscosity (η _sp / C) = [(t / t ₀ ) −1] /0.5 When the reduced viscosity is less than 0.2 dl / g, the impact is reduced,
If it exceeds 1.0 dl / g, the fluidity becomes poor.

The ABS resin usable in the present invention includes 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 polymers. Examples of diene monomers include butadiene and isoprene. Examples of the form of the diene rubber component serving as a base for graft polymerization include polybutadiene, polyisoprene, and a styrene-butadiene copolymer. The ratio of the component obtained by polymerizing the diene monomer in the ABS resin is ABS ABS
It is preferably from 5 to 80% by weight, more preferably from 8 to 50% by weight, particularly preferably from 1 to 100% by weight in 100% by weight of the resin component.
0 to 30% by weight.

As the vinyl cyanide compound to be grafted to the diene rubber component, the above-mentioned compounds can be mentioned, and acrylonitrile is particularly preferably used. Examples of the aromatic vinyl compound to be grafted to the diene rubber component include those described above, and styrene and α-methylstyrene are particularly preferable. The proportion of the component grafted to the diene rubber component is 100% for the ABS resin component.
It is preferably from 95 to 20% by weight, particularly preferably from 50 to 90% by weight. Furthermore, 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. What is not more than weight% is 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.

The rubber particle diameter of the ABS resin is 0.1 to 5.0.
μm is preferred, and more preferably 0.2 to 3.0 μm,
Particularly preferably, it is 0.3 to 1.5 μm. The distribution of the rubber particle diameter may be a single distribution or a distribution having two or more peaks, and the morphology is such that the rubber particles form a single phase. Alternatively, the rubber particles may have a salami structure by containing an occlude phase around the rubber particles.

It is well known that the ABS resin contains a vinyl cyanide compound and an aromatic vinyl compound which are not grafted to the diene rubber component. It may contain a free polymer component generated. The reduced viscosity of the copolymer comprising the free vinyl cyanide compound and the aromatic vinyl compound is such that the reduced viscosity (30 ° C.) determined by the method described above is 0.2 to
1.0 dl / g, more preferably 0.3 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). Things.

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. Further, a blend of an ABS resin obtained by such a production method and a vinyl compound polymer obtained by separately copolymerizing an aromatic vinyl compound and a vinyl cyanide component can also be preferably used.

The ASA resin of the present invention refers to a thermoplastic graft copolymer obtained by graft-polymerizing an acrylic rubber component with a vinyl cyanide compound and an aromatic vinyl compound, or the thermoplastic graft copolymer and a vinyl cyanide compound. It refers to a mixture with an aromatic vinyl compound copolymer. The acrylic rubber referred to 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. The alkyl acrylate having 2 to 10 carbon atoms is preferably 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 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. Further, the ratio of the vinyl cyanide compound and the aromatic vinyl compound is 5 to 50% by weight of the vinyl cyanide compound and 95 to 50% by weight of the aromatic vinyl compound with respect to the total amount of 100% by weight. Those having 15 to 35% by weight of a vinyl compound and 85 to 65% by weight of an aromatic vinyl compound are preferred.

The AES resin of the present invention is a thermoplastic graft copolymer obtained by graft-polymerizing an ethylene-propylene rubber component or an ethylene-propylene-diene rubber component with a vinyl cyanide compound and an aromatic vinyl compound, or the thermoplastic graft copolymer. It is a mixture of a polymer and a copolymer of a vinyl cyanide compound and an aromatic vinyl compound.

The aromatic polyester resin of 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.

[0048] Two or more aromatic dicarboxylic acids may be used as a mixture. In addition, if it is a small amount, 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 usable in the present invention includes ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, 2-methyl-1,3-propanediol, diethylene glycol. , Aliphatic diols such as triethylene glycol, 1,
Alicyclic diols such as 4-cyclohexanedimethanol and the like, 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. Among these, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate, which have well-balanced 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, etc.
It is performed by discharging water or lower alcohol by-product to the outside of the system.

Regarding the molecular weight of the aromatic polyester resin, the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is preferably from 0.4 to 1.2, more preferably from 0.65 to 1.15. .

The component B of the present invention is obtained by polymerizing a block (block) obtained by polymerizing an aromatic vinyl compound and a conjugated diene compound, and has a glass transition temperature measured by DSC of -30.degree. Is a block copolymer composed of blocks (blocks) in the range of (1).

Here, as the aromatic vinyl compound, styrene, α-methylstyrene, o-methylstyrene, p-
Methylstyrene and the like can be mentioned. The molecular weight of the block is not limited, but preferably has a number average molecular weight in the range of 2,500 to 40,000. More preferably, the number average molecular weight is 5,000 to 30,
000. Within such a range, mechanical properties and moldability can be sufficiently satisfied.

The proportion of such a block in the B component is preferably in the range of 5 to 50% by weight based on 100% by weight of the B component. More preferably, it is 10 to 40% by weight, further preferably 15 to 35% by weight. 5 to 50% by weight
In the range, good compatibility with the component A is achieved, so that the mechanical properties are good. On the other hand, since the amount of the block is sufficiently secured, the vibration damping property is also good. That is, both mechanical characteristics and vibration damping properties can be achieved. Incidentally, methyl methacrylate as long as the effects of the present invention are not impaired,
It is also possible to copolymerize other vinyl monomers such as ethyl acrylate, methyl vinyl ketone, acrylonitrile.

Examples of the conjugated diene compound include butadiene and isoprene. More preferred are polyisoprene, polybutadiene, and a copolymer of isoprene and butadiene. In the case of a copolymer, the form is a random copolymer,
Either a block copolymer or a tapered copolymer can be selected.

Although the molecular weight of the block in the component B is not limited, the number average molecular weight is 10,000-2.
Those in the range of 00,000 are preferred. More preferably, the number average molecular weight is 15,000 to 150,000. In such a range, it is possible to obtain a sufficient vibration damping property. Also, the moldability is good.

The proportion of the block in the B component in the B component is preferably in the range of 95 to 50% by weight in 100% by weight of the B component. More preferably, it is 90 to 60% by weight, still more preferably 85 to 65% by weight. 95-5
When the content is in the range of 0% by weight, both good vibration damping property and mechanical properties can be achieved.

In the component B of the present invention, the block has a glass transition temperature of −30 ° C. or more measured by DSC.
It is in the range of 30 ° C. Here, the DSC measurement was performed at a heating rate of 10
° C / min. It is measured at.

In order to set the glass transition temperature of the block in the component B to -30 ° C. to 30 ° C., for example, the content of 1,2-bond and 3,4-bond in the block is adjusted to 30% by weight in 100% by weight of the block. % (The upper limit can be 100% by weight).

The number average molecular weight of the vibration-damping block copolymer of component B is preferably in the range of 30,000 to 300,000. In such a range, since the polymer has a sufficient molecular weight as a whole, it has excellent mechanical properties. On the other hand, since the melt viscosity is in an appropriate range, the moldability is good,
Further, the dispersion of the B component is also good. Good dispersion has a good effect on vibration damping. The more preferable number average molecular weight of the component B is from 80,000 to 250,000.

As the block form of the block copolymer of the component B, a block form represented by the formula (-) n or (-) n is preferably used. Here, represents a block in the B component of the present invention, represents a block, and n is an integer of 1 or more, preferably 1
It is an integer of 10 or more and 10 or less. Of these, those of the form-are preferably used.

Further, in the above-mentioned block, part or all of carbon-carbon double bonds in the block may be hydrogenated for improving heat resistance.

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 method of sequentially polymerizing a conjugated diene-based compound as a block component and an aromatic vinyl compound as a block component sequentially with an alkyl lithium such as butyl lithium as an initiator, or The polymer can be obtained by a method in which a polymerization reaction is carried out separately for each body, and the obtained polymer is bound with a bifunctional coupling agent or the like. Further, a conjugated diene compound which is a component of a block is polymerized using a dilithium compound as an initiator,
Next, a method of polymerizing an aromatic vinyl compound and the like can 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 preferably about 0.01 to 0.2 part by weight, and 0.04 to 0.8 part by weight when a coupling agent is used.

The block used for the component B is -30.
C. to 30.degree. C., so that its 1,2- and 3,4-bond content is 30% by weight.
To achieve the above, a Lewis base is used as a cocatalyst when polymerizing the conjugated diene component of such a block. 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; amine compounds such as triethylamine and N, N, N ', N'-tetramethylethylenediamine. And the like. The amount of these Lewis bases used is preferably 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, and particularly as an inert solvent for the polymerization initiator, 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.

Further, the component B of the present invention is characterized by comprising two or more block copolymers having different glass transition temperatures of the blocks. It is considered that by including two or more components having different glass transition temperatures, an effect of attenuating the vibration in a wide temperature range can be obtained. Further, by including two or more different components, it becomes possible to attenuate the vibration of the frequency that could not be attenuated in a certain B component by another component,
It is considered that the properties of the component B are fully utilized.

In a preferred embodiment, the component B includes a component having a glass transition temperature of the block of less than 0 ° C. (component B-1) and a component having a glass transition temperature of the block of 0 ° C. or higher (component B-2). And the weight ratio is B-1
Component / B-2 component = 9/1 to 1/9. In such a case, it is possible to improve the temperature dependency of the vibration damping property. More preferably, B-1 component / B-2 component = 9/1 to 1
3/7 (weight ratio), and more preferably B-1 component /
B-2 component = 9/1 to 5/5 (weight ratio). In addition, B
The -1 component and the B-2 component can each be used in combination of two or more components.

In a further preferred embodiment, the difference between the glass transition temperature of the block of component B-1 and the glass transition temperature of the block of component B-2 is 10 ° C. or more, and their weight ratio is B-1. Component / B-2 component = 9/1 to 1 /
9 can be mentioned. In such a case, it is possible to further improve the temperature dependency of the vibration damping property. Even when the glass transition temperature difference between the blocks of the B-1 component and the B-2 component is 10 ° C. or more, the ratio of B-1 component / B-2 component is preferably 9/1 to 3/7 (weight ratio). Preferably B-1 component / B-2 component = 9/1 to 5/5 (weight ratio)
It is.

On the other hand, the difference between the glass transition temperatures of the B-1 component and the B-2 component blocks may be too large to cause a region where the effect is reduced in the temperature dependence of vibration damping. ℃ is more preferable,
More preferably, it is within 30 ° C.

As the C component of the present invention, various reinforcing fillers can be used. For example, glass fiber (chopped strand), glass short fiber (milled fiber), glass bead, glass balloon, glass flake, metal-coated glass flake, ultra-thin glass flake, carbon fiber, metal-coated carbon fiber, carbon short fiber, ultra-fine carbon Fiber, heat-resistant organic fiber, heat-resistant organic powder, metal fiber, metal fiber, calcium carbonate, calcium carbonate whisker, talc, ultrafine talc, mica, kaolin, wollastonite, clay, montmorillonite, saponite, bentonite, activated clay, sepiolite, Imogolite, sericite, calcined clay, zeolite, zeeklite, diatomaceous earth, calcined diatomaceous earth, shirasu, cordierite, eucryptite, spodumene, titanium oxide (including ultrafine titanium oxide), titanium oxide whisker, zinc oxide ( Comprising particulate zinc oxide), zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, can be mentioned silica. Particularly preferred are glass fiber, short glass fiber, talc, mica, graphite, carbon fiber, heat-resistant organic powder and short carbon fiber. The mixing ratio of the reinforcing filler can be 70% by weight or less when the total of the A component, the B component, and the C component is 100% by weight. Preferably it is 5-55% by weight.

Plate-like fillers such as talc, mica, and glass flakes having a large shape have a large synergistic effect with the B component. In addition, in the case of short glass fiber (milled fiber), short carbon fiber and heat-resistant organic powder, it has an effect of shifting the loss factor to a higher temperature region than talc or mica which is a plate-like filler by the action of the B component. ing.

The reinforcing filler may have been subjected to various surface treatments. For example, surface treatment agents include fatty acids, resin acids, maleic acid, organic acid compounds such as sorbic acid, ester compounds of organic acid compounds and monohydric or polyhydric alcohols, epoxy resins, phenoxy resins, phenol-formalin resins, phenols -Urea resin, melamine-formalin resin, polyamide resin, sulfonic acid surfactant, organic titanate coupling agent, organic aluminate coupling agent, phosphate coupling agent, organic silane coupling agent, polybutadiene, Examples thereof include diene-based polymers such as polyisoprene, and a lubricant component described later. On the other hand, almost the same effect as the above-mentioned surface treatment can be obtained by post-addition without surface treatment in advance.

It is possible to further enhance the vibration damping property by surface treatment. However, in such a case, the formulation differs depending on the size and shape of the reinforcing filler, etc., which will be described below.

It is preferable that the reinforcing filler is formulated to enhance the adhesion. For example, silane coupling agent treatment (especially epoxy silane compound or amino silane compound, etc.)
Examples of the treatment include an epoxy resin. In the case of post-addition, for example, the silane coupling agent is
0.01 to 0.2 parts by weight per 100 parts by weight of the total of the component C, or an epoxy resin (for example, bisphenol A)
Type epoxy resin YD-7020 manufactured by Toto Kasei Co., Ltd.
) And a phenoxy resin (for example, YP-50 manufactured by Toto Kasei Co., Ltd.) and the like.
Addition of 0.01 to 5 parts by weight, alone or in combination, with respect to parts by weight improves the vibration damping property. Further, even when the surface treatment is performed in advance, it is preferable that the ratio of the surface treatment agent satisfies the above ratio.

The reason is considered as follows. As the adhesion to the reinforcing filler increases, the resin between the reinforcing fillers is restricted. Therefore, the deformation given as vibration from the outside becomes a deformation in a state in which the resin is restrained to some extent, and it is possible to give a larger strain to the resin. It is considered that such deformation is easily converted to heat, and the damping of vibration becomes larger.

On the other hand, for a fine filler such as mica or talc having a particle size of 10 μm or less, a formulation for reducing the adhesion to the resin is also effective for improving the vibration damping property.
In this case, in consideration of the affinity with the thermoplastic resin of the component A, in particular, a thermoplastic resin mainly composed of a polycarbonate resin, it is preferable to perform the surface treatment with various lubricant components. As the lubricant component, for example, mineral oil, synthetic oil, higher fatty acid ester, higher fatty acid amide, silicone oil, silicon powder, paraffin wax, polyolefin wax, polyalkylene glycol, fluorinated fatty acid ester, trifluorochloroethylene, polyhexafluoropropylene And fluorine oil such as glycol. The surface treatment can be performed by a stirring mixer such as a super mixer or a mechanochemical device. For example, for a fine filler having a particle size of 10 μm or less,
It can be obtained by mixing the above lubricant components directly or, preferably, in a state of being dissolved or dispersed in various kinds of water or organic solvents.

On the other hand, in the case of post-addition, it is preferable to use a lubricant component modified with various functional groups so as to easily coat the reinforcing filler selectively. Examples of the functional group include a carboxyl group, a carboxylic anhydride group, an epoxy group, and an oxazoline group.

As such a lubricant component modified with a functional group, preferably, an olefin wax modified with an acid such as maleic anhydride can be mentioned. Specifically, for example, Diacarna PA30 manufactured by Mitsubishi Chemical Corporation And P
A30M and the like.

As the ratio of the lubricant component, it is preferable to add 0.05 to 3 parts by weight based on 100 parts by weight of the total of components A to C. The same applies to the case where the lubricant component is surface-treated in advance.

In the case of a fine reinforcing filler having a particle size of 10 μm or less, the reason why an advantageous effect can be obtained even with a low adhesion to the reinforcing filler is considered as follows. It is considered that heat is also generated by slipping at the interface between the reinforcing filler surface and the resin. Therefore, it is considered that the deformation of the vibration is converted into heat and the vibration is attenuated. When a fine reinforcing filler is contained, the interface between the surface of the reinforcing filler and the resin increases, and as a result, it is considered that the attenuation of vibration is improved.

The composition ratio of the components A, B and C of the present invention will be described. The component B of the present invention is preferably 1 to 20% by weight, more preferably 3 to 1% by weight, based on 100% by weight of the total of the components A, B and C.
8% by weight. When the proportion of the component B is less than 1% by weight, the vibration damping effect tends to be insufficient. If the content exceeds 20% by weight, the rigidity is reduced and the loss coefficient is improved even if a filler is added, but the difference in the loss coefficient depending on the measured temperature may become larger. On the other hand, the A component of the present invention is an A component, a B component,
10 to 99% by weight based on a total of 100% by weight of component C and component C
It is. Preferably it is 37 to 92% by weight.

The mixing ratio of the B-1 component and the B-2 component is as follows: B-1 component / B-2 component = 9/1 to 1/9 by weight ratio.
And more preferably 9/1 to 3/7. However, the ratio of the B-1 component and the B-2 component in the B component varies depending on the type and amount of the C component, and thus the optimum value can be appropriately determined according to the purpose. For example, B
When the amount of the components and the types and ratios of the B-1 component and the B-2 component are fixed, the peak value of the loss coefficient is improved by the type or the composition ratio of the C component, or the peak value is in a high temperature range. Such effects as shifting occur.

The composition ratio of the component C is from 0 to 70% by weight based on a total of 100% by weight of the components A, B and C.
More preferably, the content is 5 to 55% by weight. If the content of the component C is 70% by weight or more, sufficient vibration damping properties cannot be exhibited. On the other hand, the C component is more preferably contained because it has an effect of improving the vibration damping property and improving the high-temperature vibration damping property.

As described above, according to the present invention, there is provided a vibration damping thermoplastic resin composition which suppresses the temperature dependency of the vibration damping effect and is excellent in mechanical strength, heat resistance and moldability. More specifically, according to the present invention, the maximum value (ηmax.) And the minimum value (ηmin.) Of the loss coefficient at 10 ° C. to 50 ° C. in the method for measuring the loss coefficient defined below.
Is not more than 0.04 and ηmin. Is 0.0
A vibration-damping thermoplastic resin composition having 3 or more is provided.

The method of measuring the loss coefficient referred to here is a method in which an impedance head is attached to one end of a strip-shaped test piece and is obtained by a mechanical impedance method. Also,
The normal circle method was used to calculate the loss factor. As a specific measuring device, MS101 manufactured by Matsushita Intertechno Co., Ltd.
Eight vibration suppression performance evaluation systems.

Further, as a preferred embodiment of the present invention, in the method for measuring a loss coefficient as defined above, the temperature is preferably from 10 ° C. to 50 ° C.
The difference (Δη) between the maximum value (ηmax.) And the minimum value (ηmin.) Of the loss coefficient at 0 ° C. is 0.04 or less and ηm
in. Is 0.03 or more, and the deflection temperature under load at 1.813 MPa measured in accordance with ASTM D648 is 100 ° C. or more, and the flexural modulus measured in accordance with ASTM D790 is 2,000 MPa or more. A composition is provided. Such a resin composition has a very low temperature dependency of the vibration damping effect, and is also a resin composition having excellent heat resistance and rigidity. The resin composition is used in a chassis such as an optical printer and a chassis of another optical medium driving device. It is a resin composition that is extremely suitable for fields requiring heat resistance and rigidity as well as vibration effects.

Further, as a preferred embodiment of the present invention, the method for measuring a loss coefficient as defined above is performed at a temperature of 10 ° C. to 5 ° C.
The difference (Δη) between the maximum value (ηmax.) And the minimum value (ηmin.) Of the loss coefficient at 0 ° C. is 0.04 or less and ηm
in. Is 0.03 or more, and the deflection temperature under load at 1.813 MPa measured according to ASTM D648 is 100 ° C. or more, and the flexural modulus measured according to ASTM D790 is 2,000 MPa or more. A vibration-damping thermoplastic resin composition comprising a B component and a C component is provided. (A component) a thermoplastic resin mainly composed of a polycarbonate resin (B component) a glass (block) formed by polymerization of an aromatic vinyl compound and a conjugated diene compound, and a glass transition temperature measured by DSC thereof But -3
Block copolymer comprising a block (block) in the range of 0 ° C to 30 ° C (Component C) Reinforcing filler

The vibration damping thermoplastic resin composition of the present invention comprises:
As long as the object of the present invention is not impaired, it may contain a flame retardant or the like. Flame retardants include red phosphorus flame retardants, phosphate flame retardants, phosphazene flame retardants, silicone flame retardants, halogen flame retardants, inorganic phosphates, metal hydroxides, metal sulfides, and alkali organic sulfonates. (Earth) metal salts, inorganic (earth) metal salts of inorganic sulfonates,
An alkali (earth) metal salt of an organic carboxylate, an alkali (earth) metal salt of an inorganic carboxylate, and the like can be given.

As the red phosphorus flame retardant, 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 material 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 plated coating, use a metal plated coating selected from nickel, cobalt, copper, iron, manganese, zinc or an alloy thereof. be able to. Further, red phosphorus coated with the above-mentioned inorganic material and thermosetting resin can be used for the electroless-plated red phosphorus. The amount of the component used for microencapsulation such as the inorganic material, the thermosetting resin, and the electroless plating is as follows.
The content is desirably 20% by weight or less, more preferably 5 to 15% by weight in 00% 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-based flame retardants include Nova Excel 140 and Nova Excel F-5 (trade name, manufactured by Rin Kagaku Kogyo KK). With respect to the red phosphorus-based flame retardant, a metal oxide such as zinc oxide can be used in combination to suppress the phosphine odor.

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 (2).

[0093]

Embedded image

(Where Y in the above formula is hydroquinone,
Bivalent such as resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) sulfide Those derived from phenol, j,
k, l, m is 0 or 1 each independently, n is an integer of 0 to 5, or when n number of different mixtures of phosphoric acid ester is an average value of 0 to 5, R ¹ , R ² ,
R ³ and R ⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, and p-cumylphenol substituted or unsubstituted with one or more halogen atoms. )

Among these organic phosphate ester flame retardants, triphenyl phosphate is used as a monophosphate compound, and resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are used as condensed phosphate esters. It has good properties and can be used preferably.

Examples of the phosphate-based flame retardant include compounds represented by the following general formula (3).

[0097]

Embedded image

(Wherein R ⁵ and R ⁶ each have 1 to 2 carbon atoms)
0 alkyl group, aryl group having 6 to 20 carbon atoms or alkylaryl group, aralkyl group having 7 to 30 carbon atoms, cycloalkyl group having 4 to 20 carbon atoms, and 2- (4-oxyphenyl having 15 to 25 carbon atoms) ) Represents a propyl-substituted aryl group. The cycloalkyl group and the aryl group can be selected from those not substituted with an alkyl group and those substituted with an alkyl group. R ⁵ and R ⁶ are preferably each a phenyl group, a 2-methylphenyl group, a 2,6-xylyl group,
Examples include a tert-butylphenyl group, a 2-naphthyl group, and a 4- (2-phenylisopropyl) phenyl group.

Further, a compound represented by the following general formula (4) can also be used as a phosphate-based flame retardant.

[0100]

Embedded image

(In the formula (4), R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R
¹³ , R ¹⁴ and R ¹⁵ each represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms, an aryl group or an aralkyl group having 6 to 20 carbon atoms, and R ¹¹ represents It represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ¹² represents a hydrogen atom or a methyl group. As the aromatic cyclic phosphate compound represented by the formula (4), for example, 6-oxo-6-phenoxy-12
H-dibenzo (d, g) (1,3,2) -dioxaphosphine, 2,10-dimethyl-6-oxo-6-phenoxy-12H-dibenzo (d, g) (1,3,2) -Dioxaphosphosine, 6-oxo-6- (2,6-dimethylphenoxy) -12H-dibenzo (d, g) (1,
3,2) -dioxaphosphine and the like can be preferably used.

The phosphazene flame retardants of the present invention include:
Phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers can be mentioned.

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 the polymer include a polymer in which an alkyl (meth) acrylate and an optionally copolymerizable vinyl polymer are grafted. 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.

Further, as long as the effects of the present invention are not impaired, a nucleating agent (eg, sodium stearate, ethylene-sodium acrylate copolymer, etc.), a stabilizer (eg, phosphate, phosphite, phosphonite, etc.), an antioxidant Agents (eg, hindered phenol compounds), light stabilizers, release agents, anti-drip agents (eg, fibrillated polytetrafluoroethylene), coloring agents (eg, inorganic pigments, organic pigments, organic dyes, carbon black), It is also possible to blend various additives that are generally blended in trace amounts, such as a foaming agent and an antistatic agent.

As a stabilizer, a phosphite-based stabilizer can be preferably exemplified. Preferable examples of the phosphite-based stabilizer include phosphite compounds having an aryl group in which two or more alkyl groups are substituted. For example,
Tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris ( 2,6-di-tert-butylphenyl)
Examples thereof include phosphite and tris (2,6-di-tert-butylphenyl) phosphite, and particularly preferred is tris (2,4-di-tert-butylphenyl) phosphite.

Further, a phosphite compound having an aryl group in which part of the aryl group has a cyclic structure can also be used. For example, 2,2'-methylenebis (4,6-di-te
rt-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2-te
rt-butyl-4-methylphenyl) phosphite,
2,2′-methylenebis (4-methyl-6-tert-
Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-ethylidenebis
(4-methyl-6-tert-butylphenyl) (2-
tert-butyl-4-methylphenyl) phosphite and the like.

Other examples of the phosphorus-based heat stabilizer other than those described above include the following. As the phosphite compound, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) Pentaerythritol diphosphite, phenylbisphenol A
Pentaerythritol diphosphite, dicyclohexylpentaerythritol diphosphite and the like are preferable, and distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2, 6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, 4,4′-
Isopropylidene diphenol ditridecyl phosphite.

Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, and dibutyl phosphate. Dioctyl phosphate,
Diisopropyl phosphate and the like,
Preferred are triphenyl phosphate and trimethyl phosphate.

As the phosphonite compound, tetrakis (2,4-di-tert-butylphenyl) -4,4 ′
-Biphenylenediphosphonite, tetrakis (2,4-
Di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,4-di-ter
t-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite,
Tetrakis (2,6-di-tert-butylphenyl)
-4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3 '
-Biphenylenediphosphonite, bis (2,4-di-t
tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl)- 3-phenyl-
Phenylphosphonite, bis (2,6-di-tert-
Butylphenyl) -4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)-
3-phenyl-phenylphosphonite and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite are preferred,
Tetrakis (2,4-di-tert-butylphenyl)
-Biphenylenediphosphonite, bis (2,4-di-t
(tert-butylphenyl) -phenyl-phenylphosphonite is more preferred. Such a phosphonite compound can be preferably used in combination with the phosphite compound having an aryl group in which two or more alkyl groups are substituted.

The vibration damping thermoplastic resin composition of the present invention can contain various stabilizers. Examples of the antioxidant include a phenol-based antioxidant and a sulfur-based antioxidant. Various phenolic antioxidants can be used.

Specific examples of the phenolic antioxidant include, for example, n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, 2-tert-butyl-6- (3'-ter
t-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy] -1,
1, -dimethylethyl {-2,4,8,10-tetraoxaspiro [5,5] undecane, and tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) Propionate] methane and the like, and n-octadecyl-β
More preferred is-(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate.

Specific examples of the sulfur-based antioxidant of the present invention include dilauryl-3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, and dimyristyl-3,3'-. Thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra (β
-Laurylthiopropionate) ester, bis [2-
Methyl-4- (3-laurylthiopropionyloxy)
-5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole,
2-mercapto-6-methylbenzimidazole, 1,
1'-thiobis (2-naphthol) and the like can be mentioned. More preferably, pentaerythritol tetra (β-laurylthiopropionate) ester can be mentioned.

The vibration damping thermoplastic resin composition of the present invention can contain an ultraviolet absorber. As an ultraviolet absorber,
For example, benzophenone represented by 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane UV absorbers.

As the ultraviolet absorber, for example, 2-
(2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole,
-(2'-hydroxy-3 ', 5'-bis (α, α'-
Dimethylbenzyl) phenylbenzotriazole, 2,
2 ′ methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl-5- (2H -Benzotriazol-2-yl) -4
And benzotriazole-based ultraviolet absorbers represented by condensates with -hydroxyphenylpropionate-polyethylene glycol.

Further, as an ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxy-phenol, 2- (4,
6-bis- (2,4-dimethylphenyl-1,3,5-
Examples thereof include hydroxyphenyltriazine compounds such as triazin-2-yl) -5-hexyloxy-phenol.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-
2,4-diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethylpiperidyl) imino]} and hindered amine light stabilizers represented by polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane and the like. Such light stabilizers exhibit better performance in terms of weather resistance and the like when used in combination with the above-mentioned ultraviolet absorbers and various antioxidants.

The composition ratio of the phosphorus-based stabilizer such as the phosphite compound, the phenol-based antioxidant, the sulfur-based antioxidant and the like is 0 parts by weight based on 100 parts by weight of the total of the A component, the B component and the C component. 0.0001 to 1 part by weight. More preferably, the amount is 0.0005 to 0.5 part by weight based on 100 parts by weight of the total of the components A to C. More preferably, it is 0.001 to 0.2 parts by weight.

On the other hand, the composition ratio of the ultraviolet absorber and the light stabilizer is 0.01 to 5 parts by weight, more preferably 0.02 to 1 part by weight, based on 100 parts by weight of the total of the components A to C. .

The flame retardant resin composition of the present invention can contain a release agent, and preferably contains a release agent.
Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc .; those modified with a functional group-containing compound such as acid modification can also be used), silicone compound (silicone oil) , A silicone resin, etc. Those which are modified with a functional group-containing compound such as acid modification can be used), a fluorine compound (such as a fluorine oil represented by polyfluoroalkyl ether), a paraffin wax,
Beeswax and the like can be mentioned.

Preferred release agents include saturated fatty acid esters, for example, glycerin fatty acid esters such as monoglyceride, diglyceride, and triglyceride of stearic acid, and polyglycerin fatty acid esters such as decaglycerin decastearate and decaglycerin tetrastearate. And lower fatty acid esters such as stearic acid stearate, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate. The release agent is preferably used in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the total of the components A to C.

For producing the vibration-damping thermoplastic resin composition of the present invention, any method is employed. For example, there is a method in which all of the A component and the B component, and optionally, the C component and the other components are premixed, then melt-kneaded and pelletized. Examples of the premixing means include a V-type blender, a Henschel mixer, a mechanochemical device, and an extruder. In some cases, granulation can be performed using an extruder or a briquetting machine. Examples of the melt kneader include a vent type twin-screw ruder. Pelletization can be performed by various devices such as a pelletizer.

In addition, there is a method in which the component A and the component B, and optionally the component C and other components are independently supplied to a melt kneader typified by a vented twin-screw ruder. Other examples include a method of premixing the components A, B and C and a part of the other components, and then supplying the mixture to the melt kneader independently of the remaining components. In addition, when there is a liquid component to be blended, a so-called liquid injection device or liquid addition device can be used for supply to the melt kneader.

The vibration-damping thermoplastic resin composition thus obtained can be prepared by a known method such as injection molding, injection compression molding, high-speed injection molding, rapid heating mold molding, extrusion molding, compression molding, blow molding, or rotational molding. It can be easily formed by the method.

The vibration-damping thermoplastic resin composition of the present invention is one in which the temperature dependence of the vibration-damping effect is suppressed to a low level. That is, it has sufficient vibration damping properties in a wide usage environment of the product. Further, it has excellent mechanical strength, heat resistance, and moldability. Therefore, the damping thermoplastic resin composition of the present invention,
It is suitable for various electronic / electric devices, mechanical products, household electric products, vehicle parts, and the like. In particular, in electronic and electrical equipment, the present invention is suitable for a precision chassis represented by a chassis of an optical printer or a chassis of an optical medium driving device, a housing of a motor, and the like. In mechanical products, it is suitable for a housing of a power tool or a motor. Also, as household appliances,
It is suitable for a chassis or a housing of a VTR device or a video camera, a speaker box, and a chassis or a housing of a vacuum cleaner or a refuse treatment machine using various large motors. Furthermore, as parts for vehicles,
Fender panel, door panel, side protector,
Suitable for exterior parts such as spoilers and various pillars, and interior parts such as instrument panels, console boxes, speaker boxes, door linings, ceiling linings, various pillar linings, sheet aggregates, rear trays, and rear shelves. is there.

[0125]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. [Examples 1 to 13 and Comparative Examples 1 to 12] Among the components described in Tables 1 to 10, after other components other than the A component, the B component and the C component were uniformly mixed with a V-type blender, Using a measuring device [CWF manufactured by Kubota Co., Ltd.], a 30 mmφ vented twin-screw extruder [TEX-30XSS, Japan Steel Works, Ltd.]
T] from the first input port, and use a vacuum pump to set 0.1.
Under a vacuum of 5 kPa, a cylinder temperature of 260 ° C.
Screw rotation speed 150rpm and discharge amount 20kg
/ Hr and extruded into pellets. For the sample containing the above-mentioned reinforcing filler, the C component was mixed with the mixture from the first input port using a measuring instrument [CWF manufactured by Kubota Corporation] through the second input port of the side feed portion in the middle of the cylinder. Melt extrusion was performed under the same conditions as above, with the filler at the second inlet being set at a predetermined ratio, to obtain pellets.
The obtained pellets were dried at 110 ° C. for 5 hours with a hot-air circulation type dryer, and an injection molding machine [FANUC T-15
0D], cylinder temperature 260 ° C, mold temperature 70 ° C
A test piece for evaluation was prepared in the above section, and evaluation was performed by the following evaluation method.

(I) Mechanical properties and flame retardancy of the damping thermoplastic resin composition Rigidity: Flexural modulus was measured in accordance with ASTM D790. Heat resistance: 1.813 according to ASTM D648
The deflection temperature under load was measured under a load of MPa. Flammability: The composition containing a flame retardant was subjected to a vertical burning test with a thickness of 1.6 mm in accordance with UL Standard 94. (II) Damping properties (loss coefficient) Length (effective length) 120 mm, width 13 mm, thickness 2 mm
(Only Example 13 and Comparative Examples 11 and 12 have a thickness of 1.2 m.
The impedance head was attached to one end of the strip-shaped test piece of m), and the loss coefficient was calculated by the method described in the text. The system used was an MS1018 complex elastic modulus measurement device (using a 3560 type multi-analyzer system manufactured by Brüel & Care Corp., manufactured by Matsushita Intertechno Co., Ltd.). (Η-252R), the measurement temperature is 10 ° C. to 50
The test specimen was left for 1 hour under each temperature environment.

(A-1 component) PC-1: polycarbonate resin powder [L-1225WP, manufactured by Teijin Chemicals Ltd., viscosity average molecular weight 22.5]
PC-2: Polycarbonate resin powder Among the aromatic dihydroxy components, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [bisphenol TMC] was 45 mol%,
4 ′-(m-phenylenediisopropylidene) diphenol [bisphenol M] is 55 mol%, and pt
using tert-butylphenol as a terminator,
Aromatic polycarbonate having a viscosity average molecular weight of 15,000 obtained by a solution method using phosgene (a-2 component) ABS: acrylonitrile-butadiene-styrene copolymer [Santac UT manufactured by A & L Japan Co., Ltd.]
61] AS: Acrylonitrile-styrene copolymer [Light Tack A 980 PCU manufactured by Nippon A & L Co., Ltd.] PO: Amorphous polyolefin resin [ZEONEX E48R manufactured by Nippon Zeon Co., Ltd.]

(Component B) Vibration-damping block copolymer-1 (Component B-1): Styrene-hydrogenated isoprene block copolymer [Hybler 7125 (HVS-3) manufactured by Kuraray Co., Ltd.]
Glass transition temperature of block −19 ° C.] Vibration-damping block copolymer-2 (Component B-2) Styrene-isoprene block copolymer [Hibler 5127 (VS-1) manufactured by Kuraray Co., Ltd .:
Glass transition temperature of block 8 ° C]

(Component C) Reinforcing filler GF-1: Short glass fiber (milled fiber) [PFE-301 manufactured by Nitto Boseki Co., Ltd., fiber diameter 9 μm, average fiber length 40 μm] GF-2: glass fiber [NEC Glass Co., Ltd. T-5
11, fiber diameter 13 μm, cut length 3 mm] GF-3: short glass fiber (milled fiber) [MF 06JB1-20 manufactured by Asahi Glass Fiber Co., Ltd., fiber diameter 10 μm, average fiber length 70 μm] TALC: talc [Co., Ltd.] Victorylite talc R, average particle size 8.5 μm, manufactured by Katsumitsu Mining Co., Ltd.] MICA: Mica [B-82, manufactured by Yamaguchi Mica Co., Ltd., average particle size 100 μm]
(By laser method) Graphite [Nippon Sheet Glass Co., Ltd. Scale-like graphite 200]
85, average particle diameter 35 μm] GFL: glass flake [Nippon Sheet Glass Co., Ltd., Freka REFG-101 average particle diameter 600 μm, average thickness 5 μm]

(Other components) FR-1: Halogen flame retardant [Fireguard FG-7000, Teijin Chemicals Ltd., carbonate oligomer of tetrabromobisphenol A] FR-2: Red phosphorus flame retardant [Nova Excel 140] (Rin Kagaku Kogyo KK)] FR-3: Organophosphorus flame retardant [FP made by Asahi Denka Kogyo KK]
-500] FR-4: Fibrillated PTFE [Daikin Industries, Ltd.
Additive-1: Phosphate-based stabilizer [Trimethyl phosphate (TMP) manufactured by Daihachi Chemical Co., Ltd.] Additive-2: Release agent SL-Manufactured by Riken Vitamin Co., Ltd.
900] Additive-3: a polycarbonate resin having a dihydroxy component of bisphenol A (viscosity average molecular weight 15,000
0) and Carbon Black 970 manufactured by Mitsubishi Chemical Corporation
#: Melt mixed at a weight ratio of 60:40 Additive-4: Acid-modified olefin wax [Diacarna PA30M manufactured by Mitsubishi Chemical Corporation] Additive-5: Epoxy resin [YD manufactured by Toto Kasei Co., Ltd.] −
7020] Additive-6: silane coupling agent [Shin-Etsu Chemical Co., Ltd.
KBM-403 manufactured by K.K.) Additive-7: zinc oxide [No.3 zinc white (granular product) manufactured by Mitsui Kinzoku Mining Co., Ltd.]

[0131]

[Table 1]

[0132]

[Table 2]

[0133]

[Table 3]

[0134]

[Table 4]

[0135]

[Table 5]

[0136]

[Table 6]

[0137]

[Table 7]

[0138]

[Table 8]

[0139]

[Table 9]

[0140]

[Table 10]

From the above, it can be seen that the thermoplastic resin composition of the present invention has a good absolute value of the vibration damping property and its property is little changed in a wide temperature range. In the sample of Example 7, a speaker box-shaped molded product was manufactured. In the sample of Example 12, a molded product of the OA equipment chassis was manufactured, and a molded product having good dimensional accuracy was obtained.

[0142]

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) // F16F 15/08 F16F 15/08 D

Claims (9)

[Claims] 1. A total of 100% by weight of the following component A, component B and component C, 10 to 99% by weight of component A, component 1
A vibration-damping thermoplastic resin composition comprising from 20 to 20% by weight, and from 0 to 70% by weight of a C component, and wherein the B component contains two or more block copolymers having different glass transition temperatures of the blocks. (A component) a thermoplastic resin (B component) a block (block) formed by polymerization of an aromatic vinyl compound, and a conjugated diene compound formed by polymerization, and its glass transition temperature measured by DSC is -3.
Block copolymer comprising a block (block) in the range of 0 ° C to 30 ° C (Component C) Reinforcing filler 2. The vibration-damping thermoplastic resin composition according to claim 1, wherein the component A is a thermoplastic resin mainly composed of a polycarbonate resin. 3. The component B comprises a component having a block whose glass transition temperature is lower than 0 ° C. (component B-1) and a component having a block whose glass transition temperature is 0 ° C. or higher (component B-2). Weight ratio B-1 component / B-2 component = 9
The vibration damping thermoplastic resin composition according to claim 1, wherein the ratio is from 1/1 to 1/9. 4. The vibration-damping thermoplastic resin composition according to claim 3, wherein the difference between the glass transition temperature of the block of the B-1 component and the glass transition temperature of the block of the B-2 component is 10 ° C. or more. 5. A total of 1 of A component, B component and C component
37% to 92% by weight of component A and 3-1 of component B in 00% by weight
2% by weight and 5 to 55% by weight of component C.
5. The vibration-damping thermoplastic resin composition according to any one of items 4 to 4. 6. The B-1 component / B-2 component = 9/1 to 3 /
The vibration-damping thermoplastic resin composition according to claim 3, which is 7. 7. A method of measuring a loss coefficient defined in the text, wherein a difference (Δη) between a maximum value (ηmax.) And a minimum value (ηmin.) Of the loss coefficient at 10 ° C. to 50 ° C. is 0.04 or less. And ηmin. Is 0.03 or more. 8. The deflection temperature at a load of 1.813 MPa measured according to ASTM D648 is 100.
The vibration-damping thermoplastic resin composition according to claim 7, which has a flexural modulus of at least 2,000 MPa measured according to ASTM D790. 9. The vibration-damping thermoplastic resin composition according to claim 8, comprising the following components A, B and C. (A component) a thermoplastic resin mainly composed of a polycarbonate resin (B component) a glass (block) formed by polymerization of an aromatic vinyl compound and a conjugated diene compound, and a glass transition temperature measured by DSC thereof But -3
Block copolymer comprising a block (block) in the range of 0 ° C to 30 ° C (Component C) Reinforcing filler