JP2000265075A - Vibration-damping thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which is lightweight and is excellent in dimensional accuracy, stiffness, and heat resistance though it has good vibration-damping properties. SOLUTION: This composition comprises (A) 80-97 wt.% amorphous thermoplastic resin and (B) 3-20 wt.% vibration-damping block copolymer comprising (b-1) 5-50 wt.% blocks formed from a vinylaromatic compound and (b-2) 50-95 wt.% blocks formed from a conjugated diene compound, the sum of ingredients A and B being 100 wt.%, and has (1) a tan δ (according to JIS K 7198, at 40 deg.C and 18 Hz) of 0.015-0.080, (2) a water absorption (according to ASTM D 570, immersion in water at 23 deg.C for 24 hr) of 20 wt.% or lower, and (3) a specific gravity (according to JIS K 7112) of 1.00-1.20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a damping thermoplastic resin composition. More specifically, the thermoplastic resin is made of a specific amorphous thermoplastic resin and a specific damping block copolymer, and has excellent dimensional accuracy, rigidity, heat resistance, light weight, and excellent vibration damping properties. To a thermoplastic resin composition.

[0002]

2. Description of the Related Art In recent years, with the increase in the speed of OA equipment, there has been an increasing demand not only for improving the rigidity or heat resistance of various mechanical parts, but also for providing vibration damping to a vibration source generated by a drive system. The provision of vibration damping properties is also required for thermoplastic resin compositions. For example, in the case of optical disks such as CD-ROMs, high-speed rotation of so-called 30 times speed or more is becoming mainstream, and in this case, a good vibration damping property is required for a turntable directly acting on the rotation of the disk and a chassis for supporting them. Have been. Similarly, in an optical printer, a polygon mirror that rotates at a high speed, an optical box that supports the polygon mirror, and the like are also required to have good vibration damping properties, and the demand is increasing as the printing speed increases.

[0003] However, since the vibration damping property of the thermoplastic resin alone is extremely poor, there is a problem that the vibration damping property is insufficient for the speeding up of these OA devices. Rubbers can be cited as a material having high vibration damping properties, but such materials lack rigidity and require high filling with inorganic fillers and the like, resulting in a high specific gravity, which cannot satisfy the requirements. . For high-speed rotation, it is necessary to be lightweight, and there is also an effect on the vibration surface that the natural frequency becomes higher. Heat resistance is also an important factor in order to cope with a use environment or a high temperature environment due to heat generation of internal mechanism components, but such rubbers do not have sufficient heat resistance.

On the other hand, a liquid crystal polymer such as wholly aromatic polyester is known as a resin having high damping properties other than rubbers. However, such a resin is a crystalline resin and exhibits extremely strong anisotropy. There is a drawback that a molded article is likely to be warped and cannot sufficiently cope with a field requiring high dimensional accuracy. Further, with respect to the dimensional accuracy, an element over time is also important, and it is desired that the water absorption is low.

Further, Japanese Patent Application Laid-Open No. 9-40840 proposes a resin composition having high rigidity and excellent vibration damping properties obtained by blending a vibration damping elastomer and a specific whisker into a thermoplastic resin. The composition did not satisfy all of the above-mentioned requirements for vibration damping, low specific gravity, low warpage of molded articles, etc. at a high level.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a thermoplastic resin composition which is excellent in dimensional accuracy, rigidity, heat resistance and lightweight while having good vibration damping properties. . The present inventor has conducted intensive studies to achieve these objects, and as a result, a specific aromatic vinyl-conjugated diene block copolymer imparting vibration damping properties to an amorphous thermoplastic resin having a specific tan δ. The inventors have found that the blended thermoplastic resin composition can achieve the above object, and have reached the present invention.

[0007]

Means for Solving the Problems The present invention relates to JIS K7
Tan measured at 40 ° C. and 18 Hz according to 198
80 to 97% by weight of an amorphous thermoplastic resin (component A) having δ of 0.010 to 0.040, 5 to 50% by weight of a block (b-1) composed of a vinyl aromatic compound component, and (b) -2) a block 50 or more comprising a conjugated diene compound component and having a glass transition temperature in the range of -30 ° C to 30 ° C;
95% by weight, the sum of (b-1) and (b-2) being 100% by weight, and the tan δ measured at 40 ° C. and 18 Hz according to JIS K7198 is 0.15%.
2 to 2 (component B)
It is a thermoplastic resin composition comprising 100% by weight of a component A and a component B in total of 100% by weight, and has the following properties: (1) JIS K7198: 40 ° C., 18H
tan δ measured in z is 0.015-0.08
0, (2) a water absorption of 0.20% by weight measured by immersion in water at 23 ° C. for 24 hours according to ASTM D570.
Hereinafter, (3) the specific gravity measured according to JIS K7112 is 1.00 to 1.20, and (4) ASTM D 6
The present invention relates to a vibration-damping thermoplastic resin composition satisfying that the deflection temperature under load measured under a load of 18.6 kgf / cm ^{2 according} to No. 48 is 120 to 170 ° C.

[0008] The thermoplastic resin used as the component A of the present invention is amorphous and conforms to JIS K7198.
Tan δ measured at 40 ° C. and 18 Hz is 0.01
0 to 0.040. tan δ is preferably 0.012 to 0.035. If it is less than 0.010, the vibration-damping thermoplastic resin composition of the present invention has insufficient vibration-damping properties, and if it exceeds 0.040, it is not preferable in terms of dimensional accuracy. Typical examples of the resin include an aromatic polycarbonate resin, a polysulfone resin, an amorphous polyarylate resin, and a special polyolefin-based resin containing a cyclic polyolefin such as polynorbornene, which satisfies such conditions.
Among them, aromatic polycarbonate resins are preferred. These may be used singly or as a mixture of two or more kinds, and the same kind of resin may be used alone or as a mixture of two or more kinds.

Hereinafter, the aromatic polycarbonate resin of the present invention will be described. As a typical aromatic polycarbonate resin used as a thermoplastic resin which is the component A of the present invention, 1,1-bis (4-hydroxyphenyl) -3,3 represented by the following formula [1] is used. Examples of the polycarbonate resin include 5-trimethylcyclohexane (hereinafter sometimes abbreviated as bisphenol TMC) in a proportion of at least 20 mol% based on 100 mol% of the total amount of the aromatic dihydroxy component.

[0010]

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That is, the preferred aromatic polycarbonate resin of the present invention comprises the bisphenol TMC in an amount of at least 2 per 100 mol% of the total amount of the aromatic dihydroxy component.
0 mol%, preferably 30 to 80 mol% is used. When the proportion of the bisphenol TMC is 20 mol% or more, the tan δ value is high and the vibration damping property is excellent, and the water absorption is low and higher dimensional stability can be achieved. When bisphenol TMC exceeds 80 mol%, the water absorption tends to increase. Therefore, when the ratio of bisphenol TMC is so high, the terminal is modified with a specific terminal group modifier as described later. It is desirable to denature.

The aromatic polycarbonate resin of the present invention comprises:
Bisphenol TM as an aromatic dihydroxy component
Although it is preferable to use C at a certain ratio, two methods are generally employed to obtain desired characteristics, particularly, a water absorption of 0.2% by weight or less, preferably 0.15% by weight or less. Is done. One of them is the bisphenol TMC
The other means is to introduce a terminal modifier having a specific structure into the terminal group. These two means may be used alone or in combination.

According to the study of the present inventors, it has been found that a copolymerized polycarbonate resin obtained by combining the bisphenol TMC with a specific dihydroxy component is particularly suitable as a vibration damping thermoplastic resin. Was issued. That is, the copolymerized polycarbonate resin includes (a) bisphenol TMC (component a) and (b) 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as bisphenol M) represented by the following formula [2]. At least one fragrance selected from 2,2-bis (3-methyl-4-hydroxyphenyl) propane (hereinafter sometimes abbreviated as bisphenol C) represented by the following formula [3]: A copolymer in which the aromatic dihydroxy component (component b) is at least 80 mol% of the total amount of aromatic dihydroxy components of 100 mol%, and the ratio of component a to component b is 20:80 to 80:20 in molar ratio. Polycarbonate resins are particularly preferred as component A of the present invention.

[0014]

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[0015]

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One preferred embodiment of the copolymerized polycarbonate resin is a combination wherein component a is bisphenol TMC and component b is bisphenol M, in which case bisphenol TMC: bisphenol M
Is a molar ratio in the range of 30:70 to 80:20, particularly preferably in the range of 40:60 to 70:30.

In another preferred embodiment, component a is bisphenol TMC and component b is bisphenol C
Wherein the ratio of bisphenol TMC: bisphenol C is 30: 70-80: 2 in molar ratio.
It is preferably in the range of 0, and more preferably in the range of 40:60 to 70:30.

In these preferred embodiments, the sum of component a and component b is advantageously at least 80 mol%, preferably at least 90 mol%, based on 100 mol% of the total aromatic dihydroxy component, and typically Is the component a
And a copolymerized polycarbonate resin substantially formed by component (b).

On the other hand, in the aromatic polycarbonate resin preferably used as the component A of the present invention, the above-mentioned component a and component b have a total amount of aromatic dihydroxy component of 100%.
It is desirable to account for at least 80 mol%, preferably at least 90 mol%, of the other dihydroxy component (component c).
It may contain 20 mol% or less, preferably 10 mol% or less in 0 mol%.

The component c is usually used as a dihydroxy component of an aromatic polycarbonate.
Any component other than the above component a and component b may be used. For example, hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) Propane, 2,2-bis (4-hydroxyphenyl) butane,
1,1-bis (4-hydroxyphenyl) -1-phenylethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4,4 ′-(p -Phenylenediisopropylidene) diphenol, 9,9-bis (4-hydroxyphenyl) fluorene and 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane.

The aromatic polycarbonate resin used as the thermoplastic resin of the present invention is prepared by a reaction means known per se for producing a normal aromatic polycarbonate resin, for example, by adding a carbonate precursor such as phosgene or carbonate diester to an aromatic dihydroxy component. It is manufactured by a method of reacting. Next, basic means of these manufacturing methods will be briefly described.

In the reaction using, for example, phosgene as the carbonate precursor, the reaction is usually carried out in the presence of an acid binder and a 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 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 may be used. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is several minutes to 5 hours.

The transesterification reaction using a carbonic acid diester as a carbonate precursor is a method in which a predetermined ratio of an aromatic dihydroxy component is stirred with a carbonic acid diester while heating under an inert gas atmosphere to distill off the produced alcohol or phenol. It is performed by The reaction temperature varies depending on the boiling point of the produced alcohol or phenol, and is usually in the range of 120 to 300 ° C. The reaction is completed while distilling off alcohol or phenols generated under reduced pressure from the beginning. In order to promote the reaction, it is possible to use a catalyst usually used in a transesterification reaction such as an alkali metal compound and a nitrogen-containing basic compound. Examples of the carbonic acid diester used in the transesterification reaction include diphenyl carbonate, dinaphthyl carbonate, bis (diphenyl) carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate and the like. Of these, diphenyl carbonate is particularly preferred. It is also preferable to add various catalyst deactivators usually used immediately before the completion of the reaction.

In the polymerization reaction, monofunctional phenols which are generally used as a terminal terminator can be used. Particularly in the case of the reaction using phosgene as a carbonate precursor, monofunctional phenols are generally used as a terminator for controlling the molecular weight, and the obtained aromatic polycarbonate resin is usually used in an amount of 80 mol% of the terminal.
Since the above is blocked by a group based on monofunctional phenols, it is excellent in thermal stability as compared with the other one.

The monofunctional phenol may be any one used as a terminal terminator for an aromatic polycarbonate resin, and is generally a phenol or a lower alkyl-substituted phenol, represented by the following general formula [4]. Monofunctional phenols.

[0026]

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[Wherein, R is a hydrogen atom or a carbon number of 1 to 9;
And n represents 1 to 5,
It preferably represents an integer of 1 to 3. ]

Specific examples of the monofunctional phenols include, for example, phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

These monofunctional phenols are used in at least 5 terminals relative to all terminals of the obtained aromatic polycarbonate resin.
Mole%, preferably at least 10 mol% is desirably introduced at the terminal.

If the molecular weight of the aromatic polycarbonate resin used as the component A of the present invention is too low, the strength is not sufficient, and if it is too high, the melt viscosity becomes high and molding becomes difficult. 000 ~
50,000, preferably 13,000 to 30,000
0. Here, the viscosity average molecular weight (M) is 20 g of polycarbonate resin 0.7 g in 100 ml of methylene chloride.
The specific viscosity (ηsp) obtained from the solution dissolved at ° C. was obtained by inserting it into the following equation. ηsp / C = [η] + 0.45 × [η] ² C [η] = 1.23 × 10 ^-4 M ^0.83 (where [η] is the intrinsic viscosity and C is the polymer concentration of 0.7)

The block formed of the (b-1) vinyl aromatic compound component of the vibration-damping block copolymer used as the B component of the present invention (hereinafter, may be simply referred to as (b-1) block). Are mainly vinyl aromatic compounds, and specific examples thereof include styrene, α-methylstyrene, 1-vinylnaphthalene, 3-methylstyrene, 4-propylstyrene, 4-cyclohexylstyrene, and 4-dodecylstyrene. , 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like, and most preferred is styrene. (B
-1) The molecular weight of the block is from 2,500 to 40,000
Preferably, in such a range, compatibility with the component A is good, and sufficient vibration damping properties and mechanical properties can be achieved at the same time.

The proportion of the block (b-1) in the vibration-damping block copolymer as the component B is in the range of 5 to 50% by weight. If it is less than 5% by weight, the mechanical properties become insufficient, and if it exceeds 50% by weight, the vibration damping properties become insufficient.

On the other hand, a block (hereinafter referred to as "b-2") comprising a conjugated diene compound component of the vibration-damping block copolymer used as the component B of the present invention and having a glass transition temperature in the range of -30.degree. The conjugated diene compound forming (b-2) block) is preferably isoprene, butadiene or a mixture of isoprene-butadiene, and is a copolymer in the case of using both isoprene and butadiene. May be random, block, or tapered.

The glass transition temperature of such a damping block copolymer is measured at a heating rate of 10 ° C./min by DSC measurement. The temperature is lower than -30C;
If the temperature is higher than 30 ° C., the vibration damping performance is not sufficient.

The above glass transition temperature is -30 ° C. to 30 ° C.
In order to obtain the above, 1,2-
The content of bonds and 3,4-bonds must be 30% by weight or more (it may be 100% by weight). Further, the number average molecular weight of the (b-2) block of the vibration-damping block copolymer as the B component is preferably in the range of 10,000 to 200,000. Within such a range, both the vibration damping property and the workability (flowability) can be achieved.

The proportion of the block (b-2) in the vibration-damping block copolymer as the component B is from 50 to 95.
% By weight. If it exceeds 95% by weight, the mechanical properties become insufficient, and if it is less than 50% by weight, the vibration damping properties become insufficient.

The vibration-damping block copolymer which is the component B of the present invention comprises the above-mentioned block (b-1) and block (b-2), and further has a size of 40 according to JIS K7198.
Tan δ measured at 18 ° C. and 18 Hz is 0.15 to 2
It satisfies the condition of When the value of tan δ is 0.15 or less, sufficient vibration damping properties cannot be obtained.

Further, 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 is preferably in the range of 000. Within such a range, better mechanical properties can be obtained in the vibration damping thermoplastic resin composition of the present invention. A more preferred range is from 80,000 to 250,000.

Here, (b-)
1) When the block is abbreviated as (b-2) block, the block form of the block copolymer of the B component is preferably a block form represented by-(-) n or (-) n. Can be 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), some or all of the carbon-carbon double bonds in the block may be hydrogenated to improve 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 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 such initiator used is
It is determined by the molecular weight of the target B component, but 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 therefore 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; amine compounds such as triethylamine and 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 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 ratio of the B component is 1 in total of the A component and the B component.
It is 3 to 20% by weight in 00% by weight. If the amount is less than 3% by weight, a sufficient effect for improving the vibration damping property cannot be obtained, and if the amount exceeds 20% by weight, there arises a problem that mechanical properties such as rigidity deteriorate.

The vibration damping thermoplastic resin composition of the present invention is mainly composed of the components A and B, and further satisfies the following various properties.

The vibration damping thermoplastic resin composition of the present invention comprises
The tan δ measured at 40 ° C. and 18 Hz measured by IS K7198 is 0.015 to 0.080, preferably 0.025 to 0.075, particularly preferably 0.025 to 0.075.
It is required to be 30 to 0.070. 0.01
If it is less than 5, the vibration damping property is insufficient, and if it exceeds 0.080, the dimensional accuracy tends to be insufficient.

The vibration-damping thermoplastic resin composition of the present invention comprises A
It is necessary that the water absorption measured by STM D570 under the conditions of immersion in water at 23 ° C. for 24 hours is 0.20% by weight or less, preferably 0.15% by weight or less. If the water absorption exceeds 0.20% by weight, good dimensional accuracy cannot be achieved. In addition, when the component A of the present invention is an aromatic polycarbonate resin, the lower limit is set at 0.0
A value of 8% by weight can be mentioned.

The vibration-damping thermoplastic resin composition of the present invention comprises J
The specific gravity measured by IS K7112 is 1.00 to
It is required to be 1.20, preferably 1.00 to 1.15. When the specific gravity exceeds 1.20, the required lightness is not satisfied.

Further, the vibration-damping thermoplastic resin composition of the present invention has a weight of 18.6 kgf / cm according to ASTM D648.
^The deflection temperature under load measured under ^two loads is 120 to 170
° C, preferably 125-165 ° C. If the temperature is lower than 120 ° C., the heat resistance is insufficient, and
If the temperature exceeds 70 ° C., a high temperature is required at the time of molding and the component B of the present invention tends to be thermally deteriorated, which is not preferable.

Further, in the present invention, various graphite-based inorganic fillers can be added as a C component for the purpose of improving rigidity and vibration damping properties. As the graphite-based inorganic filler as the C component of the present invention, naturally occurring earth graphite and flaky graphite are used, and amorphous carbon obtained from coal, petroleum, coke or the like is crystallized by heating. Artificial graphite is also used. The average particle size of the graphite of the present invention is not particularly limited, but is preferably from 10 to 600 µm, more preferably from 100 to 400 µm. Component C is added in an amount of 5 to 100 parts by weight of the total of components A and B.
20 parts by weight are suitable. Within such a range, it is possible to achieve better damping properties, rigidity, and low specific gravity at a higher level.

The vibration damping thermoplastic resin composition of the present invention comprises:
If necessary, a phosphorus heat stabilizer can be added. As the phosphorus heat stabilizer, phosphites and phosphates are preferably used. Examples of the phosphite include triphenyl phosphite, trisnonylphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite,
Didecyl monophenyl phosphite, dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-tert-butyl-
4-methylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-tert-
Butylphenyl) octyl phosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-
Examples thereof include triesters, diesters and monoesters of phosphorous acid such as (tert-butylphenyl) -4,4-diphenylenephosphonite. Of these, trisnonylphenyl phosphite, distearylpentaerythritol diphosphite, and bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite are preferred.

On the other hand, examples of the phosphoric acid ester used as a heat stabilizer include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, and diphenylmonoorthoxenyl. Phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, diisopropyl phosphate and the like can be mentioned, and among them, triphenyl phosphate and trimethyl phosphate are preferable.

The phosphorus-based heat stabilizers may be used alone or in combination of two or more. The phosphorus heat stabilizer is suitably used in the range of 0.0001 to 0.05 parts by weight based on 100 parts by weight of the total of the component A and the component B of the present invention.

The vibration damping thermoplastic resin composition of the present invention comprises:
Conventionally known antioxidants can be added for the purpose of preventing oxidation. Examples thereof include phenolic antioxidants, and specifically, for example, triethylene glycol-bis (3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate), 1,6
-Hexanediol-bis (3- (3,5-di-ter
t-butyl-4-hydroxyphenyl) propionate), pentaerythritol-tetrakis (3- (3,3)
5-di-tert-butyl-4-hydroxyphenyl)
Propionate), octadecyl-3- (3,5-di-
tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylene Screw (3,5
-Di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-) (Hydroxybenzyl) isocyanurate, 3,9-bis {1,1-
Dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy]
Ethyl {-2,4,8,10-tetraoxaspiro (5,5) undecane and the like. The preferable range of the addition amount of these antioxidants is 0.0001 to 0.05 with respect to 100 parts by weight in total of the component A and the component B of the present invention.
Parts by weight.

Further, a higher fatty acid ester of a polyhydric alcohol can be added to the damping thermoplastic resin composition of the present invention, if necessary. By adding this higher fatty acid ester, the thermal stability of the thermoplastic resin is improved,
The fluidity of the resin during molding is improved, and the releasability of the substrate from the mold after molding is improved. The higher fatty acid ester is preferably a partial ester or a whole ester of a polyhydric alcohol having 2 to 5 carbon atoms and a saturated fatty acid having 10 to 30 carbon atoms. Examples of the polyhydric alcohol include glycols, glycerol and pentaerythritol.

The higher aliphatic acid ester is a compound of the present invention
0.00 with respect to a total of 100 parts by weight of the component and the component B.
It is suitably added in the range of 5 to 2 parts by weight, preferably in the range of 0.02 to 0.1 part by weight. By setting the content in the range of 0.005 to 2 parts by weight, it is possible to obtain the above-mentioned effects without mold staining.

The thermoplastic resin composition of the present invention further comprises glass fiber, carbon fiber, milled fiber, glass flake, mica, talc, wollastonite, whisker,
Inorganic fillers such as carbon black, silica particles, titanium oxide particles and alumina particles, heat-resistant organic fillers such as aramid fibers, polyarylate fibers, polybenzthiazole fibers and aramid powders, halogen-based flame retardants, phosphate ester compounds, Phosphorus flame retardants such as phosphate oligomers and red phosphorus, silicone flame retardants, anti-drip agents such as fibrillated fluororesins, sliding agents such as silicone compounds, fluorine compounds and polyolefin waxes, as well as light stabilizers and colorants And additives such as an antistatic agent and a flow modifier can be added within a range not to impair the properties of the present invention. Further, other thermoplastic resins may be added in a small proportion as long as the object of the present invention is not impaired.

The vibration-damping thermoplastic resin composition of the present invention comprises a tumbler, a V-blender, a Nauta mixer, a Banbury mixer,
The composition can be produced by mixing with a kneading machine such as a kneading roll and an extruder. More preferably, the composition is produced by melt-kneading with an extruder, particularly a twin-screw extruder.

The vibration-damping thermoplastic resin composition thus obtained is applied to extrusion molding, injection molding, compression molding, blow molding, vacuum molding, etc., and has excellent dimensional accuracy, rigidity and heat resistance.
It is possible to obtain a member such as an OA device which is lightweight and excellent in vibration damping properties.

In this case, production by injection molding is particularly preferable. In such a case, it is possible to produce not only a usual cold runner type molding method but also a hot runner which enables runnerless. In addition, in the injection molding, not only a usual molding method but also various molding methods such as gas assist injection molding, injection compression molding, ultra high speed injection molding, and two-color molding can be used.

[0062]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be further described below with reference to examples. Parts in Examples are parts by weight, and% is% by weight.

[Examples 1 to 8, Comparative Examples 1 to 8] After uniformly mixing the components shown in Tables 1 and 2 with a V-type blender, a 30 mmφ vented twin-screw extruder [Kobe Steel, Ltd.] [HYPER KTX-30XST] using a vacuum pump under a vacuum of 10 mmHg at a cylinder temperature of 260 ° C and pelletized. The obtained pellets were dried at 110 ° C. for 5 hours with a hot air circulation dryer, and an injection molding machine [SG150U manufactured by Sumitomo Heavy Industries, Ltd.)
The following test pieces were prepared at a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. according to the mold described above, and evaluated by the following evaluation methods.

(I) Mechanical Properties of Damping-Resistant Thermoplastic Resin Composition Water absorption: 23 ° C., 2 according to ASTM D570
It was measured under the condition of immersion in water for 4 hours. Specific gravity: Measured according to JIS K7112. Flexural modulus: 23 ° C. according to ASTM D 790
Was measured. Deflection temperature under load: according to ASTM D 648
The measurement was performed under a load of 18.6 kgf / cm ² . Molding shrinkage: 100 mm long x 50 mm wide x 4 m thick
m using a mold for forming a square plate, and molding the formed square plate product at 23 ° C., 50%
After standing at RH for 24 hours, the flow direction of the square plate molded product and the dimension in a direction perpendicular to the flow direction are measured with a three-dimensional measuring device (made by Mitutoyo). I asked.

(II) Vibration-damping Viscoelastic properties (tan δ) of the thermoplastic resin composition: tan δ was measured at 40 ° C. and 18 Hz according to JIS K7198. Loss coefficient (η): 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 for mechanical characteristics, and a complex elastic modulus measuring device ((manufactured by Bruel & Care Co., Ltd.) 30 ° C using 3560 type multi analyzer system (Matsushita Intertechno)
Was measured by the central excitation method. In the embodiment of the present invention, the approximate resonance frequency is such that the primary resonance frequency is in a range of about 150 to 200 Hz, the secondary is 900 to 1200 Hz, and the third is 2600 to 340.
The range is 0 Hz. The higher the value of the loss coefficient is, the better the vibration damping property is, and 0.02 in all the first to third order regions.
It is preferably a value of 5 or more, more preferably 0.1.
030 or more, particularly preferably 0.040 or more.

The symbols of the resin, the damping elastomer and the inorganic filler in Table 1 are as follows. PC1: Of the wholly aromatic hydroxy component, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane [bisphenol TMC] is 45 mol%, and 4,4 ′-(m-phenylenediisopropylate) Reden)
Diphenol [bisphenol M] is 55 mol%, p-tert-butylphenol is used as a terminal stopper, and a viscosity average molecular weight of 1 obtained by a phosgene method.
5,000 aromatic polycarbonate copolymer PC2: All aromatic hydroxy components are 2,2-bis (4-hydroxyphenyl) propane [bisphenol A], and p-tert-butylphenol is used as a terminal stopper Aromatic polycarbonate resin having a viscosity average molecular weight of 15,200 obtained by the phosgene method

PO: Cyclic polyolefin resin [Zeonex E48R, manufactured by Zeon Corporation] PAR: Amorphous polyarylate resin [U-Polymer U-8000, manufactured by Unitika Ltd.]

Damping copolymer: styrene content of 20
% By weight, the glass transition temperature based on the conjugated diene block is 8 ° C, and the temperature is 40 ° C, 18H according to JIS K7198.
Styrene-isoprene block copolymer having a tan δ of 0.60 measured in z [“HIBLER 5127 (VS-1)” manufactured by Kuraray Co., Ltd.] Graphite: natural graphite [Nippon Sheet Glass Co., Ltd. “scale graphite (5098) )]] Carbon black: acetylene black [DENKA BLACK manufactured by Denki Kagaku Kogyo KK] Stabilizer: trimethyl phosphate [T manufactured by Daihachi Chemical Co., Ltd.]
MP]

[0069]

[Table 1]

[0070]

[Table 2]

From these tables, a comparison of the aromatic polycarbonate resin alone (Comparative Examples 1 and 2) shows that the copolymer of bisphenol TMC and bisphenol M, which is the component A of the present invention, used as an example. The aromatic polycarbonate has a higher vibration damping property, a lower specific gravity, a lower water absorption, and a higher flexural modulus than the aromatic polycarbonate composed of bisphenol A alone. As can be seen from this, when comparing Examples 1 to 4 and Comparative Examples 1, 2, and 4, bisphenol TMC and bisphenol M
The tan δ and the loss coefficient are greatly increased by using an aromatic polycarbonate made of a copolymer of (1) and adding a styrene-isoprene block copolymer (component B) and a graphite-based inorganic filler (component C). I understand. In addition, it can be seen that as the amount of these additives increases, the vibration damping property becomes higher. When carbon black and graphite are compared, it can be seen that those containing graphite have better vibration damping properties.

[0072]

The vibration-damping thermoplastic resin composition of the present invention comprises:
It is excellent in dimensional accuracy, rigidity, heat resistance and lightweight, and has excellent vibration damping properties.
It is useful in various fields such as the automobile field and the mechanical parts field, and particularly, high-speed rotating objects whose characteristics are required at a high level, and precision mechanism parts including the same are used.
It is useful in the field of electronic, electric, and information equipment such as OA equipment, and the industrial effects achieved are extremely large.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C08L 53:02) F-term (Reference) 4J002 BK001 BP012 CF161 CG011 CN031 DA026 FD010 FD016 FD060 FD070 4J029 AA09 AB01 AC02 AD10 AE01 BB13B BB16C BD09C HA01 HC01 HC03 HC04A HC05A KB02

Claims (5)

[Claims] 1. 40 ° C., 18 according to JIS K7198
Tan δ measured in Hz is 0.010-0.04
80 to 97% by weight of an amorphous thermoplastic resin (component A) which is 0, 5 to 50% by weight of a block (b-1) composed of a vinyl aromatic compound component, and (b-2) a conjugated diene compound component Consists of a glass transition temperature of -30 ° C to 30 ° C
(B)
-1) and (b-2) are 100% by weight, and tan δ measured at 40 ° C. and 18 Hz according to JIS K7198 is 0.15 to 2 (component B). A thermoplastic resin composition comprising 3 to 20% by weight, wherein the total of the component A and the component B is 100% by weight, and (1) JIS K71
Tan δ measured at 40 ° C. and 18 Hz according to 98
0.015 to 0.080, (2) ASTM D57
0, the water absorption measured under the condition of immersion in water at 23 ° C. for 24 hours is 0.20% by weight or less; (3) JIS K711
2 is 1.00 to 1.20, and (4) 18.6 kgf / c according to ASTM D 648.
The deflection temperature under load measured under m ² load is 120 to 17
A vibration damping thermoplastic resin composition satisfying 0 ° C. 2. A total of 100 parts by weight of the component A and the component B,
The vibration-damping thermoplastic resin composition according to claim 1, comprising 5 to 20 parts by weight of a graphite-based inorganic filler (component (C)). 3. The vibration-damping thermoplastic resin composition according to claim 1, wherein the component A is an aromatic polycarbonate resin. 4. Component A is (a) 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (component a), and (b) 4,4 ′-(m-phenylenediene). At least one aromatic dihydroxy component (component b) selected from isopropylidene) diphenol and 2,2-bis (3-methyl-4-hydroxyphenyl) propane based on 100 mol% of the total amount of the aromatic dihydroxy component; The vibration-damping thermoplastic resin composition according to any one of claims 1 to 3, wherein the molar ratio is at least 80 mol%, and the ratio between the component a and the component b is 20:80 to 80:20. 5. The vibration-damping thermoplastic resin composition according to claim 4, wherein the component b is 4,4 ′-(m-phenylenediisopropylidene) diphenol.