JPH0532844A - Thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which is light in wt. and excellent in vibration-damping properties. stiffness, and impact strength. CONSTITUTION:The title compsn. comprises a thermoplastic polyurethane, an alkyl alpha,beta-unsatd. carboxylate polymer, a rubberlike polymer, and a copolymer of a vinyl cyanide monomer, an arom. vinyl monomer, and, if necessary, a monomer copolymerizable with these monomers. The compsn., being light in wt., easily moldable, and excellent in vibration-damping properties, can be used as a structure.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition which is excellent in vibration damping performance, has high rigidity and impact strength, is lightweight, and can be easily molded.

[0002]

2. Description of the Related Art In recent years, environmental problems such as noise and vibration have come to the fore, and there is a demand for reduction of noise and vibration in the fields of automobiles, electric equipment, housing, etc. For example, in the automobile field, damping materials are used or required for oil pans, head covers, dash panels, etc. around the engine, and in the electrical equipment field, solid transmission noise and vibration generated from a vibration source. Is becoming a problem, and quietness, which is a function that overcomes these problems, has become one of the important performances as a product. Further, in the fields of automobiles and information equipment, it is desired to reduce the weight of the structure in association with the vibration damping property from the viewpoint of energy saving.

As the vibration-damping material and the vibration-damping material, it is desirable that the structure itself has a vibration damping property, but in general, a material having a high rigidity that can be a structure has a small vibration damping property, and conversely, a vibration damping property. It is difficult to use a resin composition having a vibration damping property as a structure as it is, because a material having high properties has a trade-off relationship of low rigidity. As one of means for overcoming the problem, Japanese Patent Laid-Open No. 54-4325
As disclosed in Japanese Patent No. 1 etc., a resin composition having a vibration damping property is
There is a sandwich type damping steel plate sandwiched between two steel plates. However, since there is a large difference in the heat shrinkage rate between the metal and the resin, the vibration damping property and the physical property are deteriorated due to poor adhesion. Also, since it is a multi-layer composite material, it has a difficulty in workability,
Moreover, a large-scale compound device is required for processing. Further, since the steel sheet itself has a large specific gravity, it is not preferable when the structure is required to be lightweight.

Further, as disclosed in Japanese Patent Application Laid-Open No. 55-153831, there is used a filler such as glass filler or talc (mainly calcium carbonate) in order to increase the rigidity of a resin having vibration damping performance and low rigidity. There is also a method of adding. Although the rigidity of the resin is improved, the impact resistance is not sufficient, and the anisotropy of the impact resistance is largely observed, so that the use conditions and applications are limited. Furthermore, the surface gloss is significantly reduced, and the addition of filler increases the specific gravity.
It is not preferable when weight reduction is required as in the case of the vibration damping steel plate. It is also not advantageous from the viewpoint of recyclability.

A thermoplastic elastomer, such as polyurethane, may be used as a material having a vibration-proof property and a vibration-damping property. However, when it is used alone, its rigidity is insufficient to be used as a structure. Further, a composition of polyurethane and polymethacrylate is known in JP-A-53-148196, but the balance between impact strength and rigidity is not sufficient for use as a structure. Further, in Japanese Patent Publication No. 36-19492, etc., ABS
Although a combination of (acrylonitrile-butadiene-styrene) and polyurethane is known, the balance between vibration damping property, rigidity and heat resistance is not sufficient. Furthermore, JP-A-56-1
In JP 09236, a combination of ABS and polymethacrylate is also known, but the balance between impact strength and vibration damping performance was not sufficient.

[0006]

DISCLOSURE OF THE INVENTION The present invention is excellent in vibration damping performance, and has rigidity and impact resistance strength capable of forming a structure.
Another object of the present invention is to provide a thermoplastic resin composition which is lightweight and can be easily molded.

[0007]

[Means for Solving the Problems] In order to solve the above-mentioned problems, the inventors of the present invention have made earnest studies and have found means for solving the above-mentioned problems. That is, the present invention provides a thermoplastic polyurethane (I), an α, β-unsaturated carboxylic acid alkyl ester polymer (II), a rubbery polymer, a vinyl cyanide monomer, an aromatic vinyl monomer, and A thermoplastic resin composition comprising a copolymer (III) comprising a monomer copolymerizable with these as required, and having excellent vibration damping properties, rigidity, and impact resistance. ..

The present invention will be described in more detail. Regarding the thermoplastic polyurethane (I) in the present invention, as a type, polyester type, polyether type, polycaprolactone type, polycarbonate type (polycarbonate type)
It is possible to use those having a structure such as, and from the viewpoint of mechanical strength after blending, a polycarbonate type is preferable. In terms of hardness, JIS K
7311, JIS A, preferably 60-9
5, more preferably 60 to 90, even more preferably 65.
~ 85.

In the present invention, the α, β-unsaturated carboxylic acid alkyl ester polymer (II) means an α, β-unsaturated carboxylic acid alkyl ester monomer, and, if necessary, a copolymerizable monomer. It consists of the body, α,
β-unsaturated carboxylic acid alkyl ester polymer (II)
The sum of the α, β-unsaturated carboxylic acid alkyl ester monomer units is preferably 75% by weight or more.
Specific examples of the α, β-unsaturated carboxylic acid alkyl ester monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, Dodecyl acrylate, isopropyl acrylate, isobutyl acrylate, acrylic acid-sec
-Butyl acrylic acid 2-ethylhexyl, acrylic acid 2
-Pentyl, 2-hexyl acrylate, 2-acrylic acid
Hepsyl, acrylic acid 2-methylbutyl acrylic acid 3-
Methyl butyl, 3-methoxybutyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, dodecyl methacrylate, isopropyl methacrylate, methacrylic acid Acid isoptyl, methacrylic acid-
sec-butyl, 2-ethylhexyl methacrylate, 2-pentyl methacrylate, 2-hexyl methacrylate,
2-Heptyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, methacrylic acid 3
-Methoxybutyl and the like can be mentioned. The α, β-unsaturated carboxylic acid alkyl ester monomer and the monomer copolymerizable with are, for example, acrylonitrile, methacrylonitrile,
Vinyl cyanide monomer such as chloroacrylonitrile, aromatic vinyl monomer such as styrene α-methylstyrene, α-chlorostyrene, dimethylstyrene, vinyltoluene, and maleimide unit such as n-phenylmaleimide and n-cyclohexylmaleimide And unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid and maleic anhydride. Further, when the obtained resin composition requires high rigidity and high vibration damping performance, methyl methacrylate is preferable as the kind of the monomer, and as the amount,
α, β-unsaturated carboxylic acid alkyl ester polymer (I
The methyl methacrylate unit in I) is preferably 75% by weight or more, more preferably 80% by weight or more, and further preferably 90% by weight or more.

The rubbery polymer (B), vinyl cyanide monomer (A), aromatic vinyl monomer (S) in the present invention,
And a rubbery polymer (B) in a copolymer (III) comprising a monomer (M) copolymerizable therewith
Specific examples of polybutadiene, polyisoprene,
Dichloro rubber such as polychloroprene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer, saturated rubber such as ethylene-propylene copolymer, acrylic rubber such as butyl acrylate-methyl methacrylate copolymer, trifluoro Examples thereof include fluororubbers such as ethylene-vinylidene fluoride copolymer and the like, and specific examples of the vinyl cyanide monomer (A) include acrylonitrile, methacrylonitrile, chloroacrylonitrile and the like,
Specific examples of the aromatic vinyl monomer (S) include styrene, α-methylstyrene, chlorostyrene, dimethylstyrene, vinyltoluene and the like, and of the monomer (M) copolymerizable therewith. Specific examples include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, beptyl acrylate, octyl acrylate, dodecyl acrylate, isopropyl acrylate, isobutyl acrylate, and acrylic. Acid-sec-butyl acrylic acid 2
-Ethylhexyl, 2-pentyl acrylate, 2-hexyl acrylate, 2-hepsyl acrylate, 2-methylbutyl acrylate 3-methylbutyl acrylate, 3-methoxybutyl acrylate, methyl methacrylate, ethyl methacrylate, methacrylic acid Propyl, butyl methacrylate, pentyl methacrylate, hexyl methacrylate,
Heptyl methacrylate, octyl methacrylate, dodecyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, -sec-butyl methacrylate, 2-ethylhexyl methacrylate, 2-pentyl methacrylate, 2-hexyl methacrylate, 2-heptyl methacrylate. , 2-methylbutyl methacrylate, methacrylic acid 3
-Α-β-unsaturated carboxylic acid alkyl ester monomers such as methylbutyl and 3-methoxybutyl methacrylate, n
Examples thereof include maleimide monomers such as -phenylmaleimide and n-cyclohexylmaleimide, unsaturated carboxylic acid monomers such as acrylic acid, methacrylic acid, maleic acid and maleic anhydride.

The copolymer (III) may be in the form of random, block, graft or the like, but it is preferably grafted from the viewpoint of impact strength. As for the molecular weight of the copolymer (III), the acetone-soluble component in the copolymer (III) is in the range of 5,000 to 500,000 in terms of polystyrene equivalent weight average molecular weight by GPC (gel permeation chromatography). It is preferable to be present, and it is more preferable to be in the range of 10,000 to 200,000. If it is less than 5,000, the rigidity and impact strength are inferior, and if it exceeds 500,000, the physical properties are deteriorated due to poor dispersion of the copolymer (III) in the resin composition after blending, and good forming processability is obtained. Things get difficult.

Further, regarding the composition of the copolymer (III), (A) / {(A) + (S) + (M)} = 0.10-0.
34 is preferable, and 0.11 to 0.29 is more preferable. When it is smaller than 0.10 or larger than 0.34, the compatibility between the α, β-unsaturated carboxylic acid ester polymer (II) and the copolymer (III) is poor and sufficient mechanical strength is obtained. Becomes difficult.

The vibration damping material preferably has a loss coefficient η at the operating temperature of 0.05 or more, more preferably 0.06 or more, still more preferably 0.08 or more.
Further, in order to use a resin composition having a vibration damping property as a structure, it is preferable that the ASTM D790 flexural modulus of rigidity is 10000 kgf / cm ² or more, more preferably 15000 kgf / cm ² or more, and further preferably 20000 kgf / cm ² or more,
As for impact strength, ASTM D256 Izod impact strength (1/4 inch with notch) is 5 kg · cm / cm
It is preferably not less than 8 kg · c.
m / cm or more, more preferably 10 kg · cm / cm
That is all.

Further, in order to obtain a resin which is lightweight and has little impact resistance anisotropy, it is preferable not to add a filler such as glass filler or talc. Further, in order to have easy moldability, it is preferable that the resin composition is not a multilayer composite material such as a vibration damping steel plate but a single layer material and is thermoplastic. As a preferable condition for use as a structure, the loss coefficient η is 0.05 or more, the flexural modulus is 10,000 kgf / cm ² or more,
In order to satisfy both of the Izod impact strength of 5 kg · cm / cm or more, as a guideline, the thermoplastic polyurethane (I) is 5 to 70 parts by weight, more preferably 5
To 30 parts by weight, 5 to 94 parts by weight of α, β-unsaturated carboxylic acid alkyl ester polymer (II), more preferably 40 to 90 parts by weight, and 1 to 70 parts of copolymer (III).
Parts by weight, more preferably 5 to 30 parts by weight, (I) +
The total amount of (II) + (III) may be 100 parts by weight, and they may be blended so as to satisfy the above physical properties. If the amount of the thermoplastic polyurethane (I) is less than 5 parts by weight, the vibration damping property is insufficient, and if it is more than 70 parts by weight, the rigidity is insufficient and it becomes difficult to obtain a structure. Further, when the copolymer (III) is less than 1% by weight, the impact resistance strength is insufficient, and when it exceeds 70% by weight, sufficient vibration damping performance cannot be obtained, and the rigidity is insufficient to obtain a structure. Becomes difficult and the fluidity becomes insufficient, resulting in deterioration of moldability.

Further, (B) / {(I) + (II) + (I
II)} = 0.005 to 0.70 is preferable, and if less than 0.005, the impact strength is insufficient.
If it exceeds 0.70, it becomes difficult to use it as a structure because the rigidity is insufficient, and the fluidity is remarkably reduced.
Moldability becomes difficult. Further, the graft ratio of the copolymer (III) is preferably 20% or more. 20%
If it is below the range, the compatibility after blending may be poor, and impact resistance may be insufficient. The graft ratio as referred to in the present invention is obtained from the following formula by dissolving a constant weight of the copolymer (III) in acetone, centrifuging the acetone insoluble matter, drying and weighing.

[0016]

[Equation 1]

The average particle size of the copolymer (III) is preferably in the range of 0.03 to 1 μm, and when the average particle size is smaller than 0.03 μm or exceeds 1 μm, the impact resistance is insufficient. There is. Further, the average particle size of the thermoplastic polyurethane (I) after blending is preferably in the range of 1 to 10 μm in terms of vibration damping property,
More preferably in the range of 0.01-5 μm,
It is more preferably 0.01 to 1 μm. When the average particle diameter of the dispersion layer exceeds 10 μm, the vibration damping property decreases,
If it is less than 0.01 μm, the impact resistance is poor. The average particle diameter in the present invention is obtained by an electron micrograph of an ultrathin section of the resin composition, and the particle diameter of the dispersion layer is represented by the arithmetic mean of the long diameter and the short diameter of the dispersion layer. ..

The blending method of the thermoplastic polyurethane (I), the α, β-unsaturated carboxylic acid ester polymer (II) and the copolymer (III) may be selected from known kneading methods. Forming a mixture of powders, beads, flakes, chips, or pellets (I), (II), (III) into a composition by a roll mill, a kneader, a Banbury mixer, a single screw extruder, a twin screw extruder, or the like. You can In some cases, the latexes after polymerization are mixed with each other,
A method of kneading after precipitation, washing and drying can also be used.

It is optional to add known heat stabilizers, ultraviolet absorbers, lubricants, release agents, flame retardants and antistatic agents to the resin composition of the present invention. However, the processing temperature at the time of preparing the resin composition of the present invention by melt-kneading, or the molding processing temperature also means to prevent thermal decomposition of the thermoplastic polyurethane (I) or the resin composition of the present invention prepared after kneading. , 240 ° C. or lower, and more preferably 220 ° C. or lower.

[0020]

The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. The parts used below are parts by weight. (Production Method of Copolymer III-1) The average particle size is 0.3.
45 parts by weight of polybutadiene latex (rubber solid content) of μm (hereinafter all parts by weight are all parts), deionized water 100
And 0.3 part of potassium rosinate were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen.
A mixture of 11 parts of acrylonitrile, 44 parts of styrene, 0.5 part of t-dodecyl mercaptan, 0.2 part of cumene hydroperoxide, and 50 parts of deionized water and 0.1 parts of sodium formaldehyde sulfoxynate.
Parts, 0.005 parts of ferrous sulfate, and 0.05 parts of disodium ethylenediaminetetraacetate were dissolved in the solution for 7 hours with continuous addition to carry out polymerization. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. Polymerization rate is 9
It was 8%. The obtained polymerized latex was flaked by salt folding, dehydration and drying. (Production Method of Copolymer III-2) Copolymer III-1
To produce a copolymer III-2 in which the amount of rubber was changed to 25 parts. 25 parts of polybutadiene latex having an average particle diameter of 0.3 μm, 100 parts of deionized water, potassium rosinate of 0.1.
Three parts were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen. 15 parts of acrylonitrile,
60 parts of styrene, 0.7 part of t-dodecyl mercaptan,
A mixture of cumene hydroperoxide (0.2 parts), deionized water (50 parts), sodium formaldehyde sulfoxide (0.1 parts) and ferrous sulfate (0.005)
And 0.05 part of disodium ethylenediaminetetraacetate were dissolved in the solution for 7 hours with continuous addition to carry out polymerization. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. The polymerization rate was 98%. The polymerized latex obtained was subjected to salt folding, dehydration,
It was dried and made into flakes. (Production Method of Copolymer III-3) Copolymer III-1
To produce a copolymer III-3 in which the amount of rubber was changed to 10 parts. 10 parts of polybutadiene latex having an average particle size of 0.3 μm, 100 parts of deionized water, potassium rosinate of 0.
Three parts were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen. 18 parts acrylonitrile,
72 parts of styrene, 1.0 part of t-dodecyl mercaptan,
A mixture of cumene hydroperoxide (0.2 parts), deionized water (50 parts), sodium formaldehyde sulfoxide (0.1 parts) and ferrous sulfate (0.005)
And 0.05 part of disodium ethylenediaminetetraacetate were dissolved in the solution for 7 hours with continuous addition to carry out polymerization. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. The polymerization rate was 98%. The polymerized latex obtained was subjected to salt folding, dehydration,
It was dried and made into flakes. (Production Method of Copolymer III-4) Copolymer III-1
Of (A) / {(A) + (S) + (M)} = 0.29 was produced. The average particle size is 0.
45 parts of 3 μm polybutadiene latex, 100 parts of deionized water, and 0.3 parts of potassium rosinate were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen. Acrylonitrile 16 parts, styrene 39 parts, t-
Mixture of 0.5 parts of dodecyl mercaptan and 0.2 parts of cumene hydroperoxide, and deionized water 5
An aqueous solution prepared by dissolving 0.1 part of sodium formaldehyde sulfoxynate, 0.005 part of ferrous sulfate and 0.05 part of disodium ethylenediaminetetraacetate in 0 part of the mixture was continuously added for 7 hours with stirring to perform polymerization. went. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. The polymerization rate was 99%. The obtained polymerized latex was subjected to salt folding, dehydration and drying in the same manner as the copolymer III-1 to form flakes.

[0021]

Examples 1 to 15 and Comparative Examples 1 to 6 As thermoplastic polyurethane, 10 parts of Desmopan 590 (manufactured by Bayer, polyester type, hardness 90), and 65 parts of Delpet 80N (manufactured by Asahi Kasei) as PMMA were used. Polymer III-1
Was blended and extruded at 220 ° C. while kneading with a twin-screw extruder to pelletize the resin composition of Example 1. Using this composition, dumbbells and strips (for vibration damping, flexural modulus, and Izod impact measurement) were molded by an injection molding machine at 220 ° C., and physical properties thereof were measured.

Examples 2 to 15 and Comparative Examples 1 to 5 were extruded and pelletized in the same manner as in Example 1. Examples 2 to 15, Comparative Examples 1 to 6
Was molded and evaluated in the same manner as in Example 1. However, the thermoplastic polyurethane used is E180 (manufactured by Nippon Miractolan Co., polyester type, hardness 80), E98.
0 (manufactured by Nippon Miractolan, polycarbonate type, hardness 80), E990 (manufactured by Nippon Miractolan, polycarbonate type, hardness 80), E390 (manufactured by Nippon Miractolan, polyether type, hardness 90), E590 (manufactured by Nippon Miractolan, Polycaprolactone-based, hardness 90), Resamine P8765 (manufactured by Dainichiseika Kogyo KK, polycarbonate, hardness 65) 120B (Styrac ABS, manufactured by Asahi Kasei) was used. (Test Method) (Izod Impact Strength) Measured at 23 ° C. according to ASTM D256 (1/4 inch with notch). (Flexural Modulus) Measured at 23 ° C. according to ASTM D790. (Method of measuring vibration damping performance (loss coefficient η)) The loss coefficient of a dumbbell (ASTM D638 type I: thickness 3 mm) molded by an injection molding machine was 2 at 23 ° C.
Channel FFT (Fast Fourier Transform) device (2032
(Type: manufactured by B & K Co., Ltd.) was used to measure by a half-width method by a cantilever method with non-contact random vibration, and a value in terms of 500 Hz was obtained.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

EFFECT OF THE INVENTION The resin composition of the present invention is characterized in that it is excellent in vibration damping performance, has high rigidity and impact resistance, is lightweight, and can be easily molded. INDUSTRIAL APPLICABILITY Since the resin composition of the invention can be used as a structure, it can be suitably used for a housing such as a vacuum cleaner and a shaver in a field where vibration damping property is required, for example, for household appliance applications where integral molding is performed. Above all very useful.

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[Procedure amendment]

[Submission date] August 27, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0004

[Correction method] Change

[Correction content]

Further, as disclosed in Japanese Patent Application Laid-Open No. 55-153831, there is used a filler such as glass filler or talc (mainly calcium carbonate) in order to increase the rigidity of a resin having vibration damping performance and low rigidity. There is also a method of adding. Indeed although the rigidity of the resin is improved, the impact strength is insufficient, and usage conditions for the anisotropy of impact strength is observed large applications Ru limited. Furthermore, the surface gloss is significantly reduced, and the addition of filler increases the specific gravity.
It is not preferable when weight reduction is required as in the case of the vibration damping steel plate. It is also not advantageous from the viewpoint of recyclability.

[Procedure Amendment 2]

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The α, β-unsaturated carboxylic acid alkyl ester polymer (II) in the present invention means an α, β-unsaturated carboxylic acid alkyl ester monomer and, if necessary, a copolymerizable monomer. It consists of the body, α,
β-unsaturated carboxylic acid alkyl ester polymer (II)
The sum of the α, β-unsaturated carboxylic acid alkyl ester monomer units is preferably 75% by weight or more.
Specific examples of the α, β-unsaturated carboxylic acid alkyl ester monomer include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, Dodecyl acrylate, isopropyl acrylate, isobutyl acrylate, acrylic acid-sec
- butyl, 2-ethylhexyl acrylate, acrylic acid 2-pentyl, acrylic acid 2-hexyl, acrylic acid 2
- Hepsyl, acrylic acid 2-methylbutyl, acrylic acid 3-methylbutyl, 3-methoxybutyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, dodecyl methacrylate, isopropyl methacrylate, isobutoxide chill,-sec-butyl methacrylate, 2-ethylhexyl methacrylate, 2-pentyl methacrylate, 2-hexyl methacrylate, 2-heptyl, methacrylic Examples thereof include 2-methylbutyl acid, 3-methylbutyl methacrylate, 3-methoxybutyl methacrylate and the like. The monomer copolymerizable with the α, β-unsaturated carboxylic acid alkyl ester monomer includes, for example, vinyl cyanide monomers such as acrylonitrile, methacrylonitrile, and chloroacrylonitrile, styrene , α-methylstyrene, Aromatic vinyl monomers such as α-chlorostyrene, dimethylstyrene and vinyltoluene, maleimide monomers such as n-phenylmaleimide and n-cyclohexylmaleimide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like Examples include saturated carboxylic acid monomers. Further, when the obtained resin composition requires high rigidity and high vibration damping performance, methyl methacrylate is preferable as the type of monomer, and the amount thereof is α, β-unsaturated carboxylic acid alkyl ester weight. In the combined (II), the methyl methacrylate unit content is preferably 75% by weight or more, more preferably 80% by weight or more, still more preferably 90% by weight or more.

[Procedure 3]

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[Correction method] Change

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The rubbery polymer (B), vinyl cyanide monomer (A), aromatic vinyl monomer (S) in the present invention,
And a rubbery polymer (B) in a copolymer (III) comprising a monomer (M) copolymerizable therewith
Specific examples of polybutadiene, polyisoprene,
Dichloro rubber such as polychloroprene, butadiene-styrene copolymer and butadiene-acrylonitrile copolymer, saturated rubber such as ethylene-propylene copolymer, acrylic rubber such as butyl acrylate-methyl methacrylate copolymer, trifluoro Examples thereof include fluororubbers such as ethylene-vinylidene fluoride copolymer and the like, and specific examples of the vinyl cyanide monomer (A) include acrylonitrile, methacrylonitrile, chloroacrylonitrile and the like,
Specific examples of the aromatic vinyl monomer (S) include styrene, α-methylstyrene, α -chlorostyrene, dimethylstyrene, vinyltoluene and the like, and a monomer (M specific examples of), methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, pentyl acrylate, hexyl acrylate, f heptyl, octyl acrylate, dodecyl acrylate, isopropyl acrylate, Isobutyl, acrylic acid-sec-butyl , acrylic acid 2-ethylhexyl, acrylic acid 2-pentyl, acrylic acid 2-hexyl, acrylic acid 2-heptyl, acrylic acid 2-methylbutyl , acrylic acid 3-methylbutyl, acrylic acid 3-methoxy Butyl, methyl methacrylate, ethyl methacrylate , Propyl methacrylate, butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, octyl methacrylate, dodecyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, -s
ec-butyl, 2-ethylhexyl methacrylate, 2-pentyl methacrylate, 2-hexyl methacrylate, 2-heptyl methacrylate, 2-methylbutyl methacrylate, 3-methylbutyl methacrylate, 3-methacrylic acid
Α, β-Unsaturated carboxylic acid alkyl ester monomers such as methoxybutyl, maleimide monomers such as n-phenylmaleimide and n-cyclohexylmaleimide, Unsaturation of acrylic acid, methacrylic acid, maleic acid, maleic anhydride, etc. Examples thereof include carboxylic acid monomers.

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The copolymer (III) may be in the form of random, block, graft or the like, but it is preferably grafted from the viewpoint of impact strength. As for the molecular weight of this copolymer (III), the acetone - soluble component in the copolymer (III) is in the range of 5,000 to 500,000 in terms of polystyrene equivalent weight average molecular weight by GPC (gel permeation chromatography). Preferably,
Is more preferably in the range. If it is less than 5000, the rigidity and impact strength are poor, and if it exceeds 500000,
Copolymer (III) in resin composition after blending
Resulting dispersion properties decreased due to bad, but also good growth
It becomes difficult to obtain a form workability.

[Procedure Amendment 5]

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Further, in order to obtain a resin which is lightweight and has little impact resistance anisotropy, it is preferable not to add a filler such as glass filler or talc. Further, in order to have easy moldability, it is preferable that the resin composition is not a multilayer composite material such as a vibration damping steel plate but a single layer material and is thermoplastic. As a preferable condition for use as a structure, the loss coefficient η is 0.05 or more, the flexural modulus is 10,000 kgf / cm ² or more,
In order to satisfy both of the Izod impact strength of 5 kg · cm / cm or more, as a guideline, the thermoplastic polyurethane (I) is 5 to 70 parts by weight, more preferably 5
To 30 parts by weight, 5 to 94 parts by weight of α, β-unsaturated carboxylic acid alkyl ester polymer (II), more preferably 40 to 90 parts by weight, and 1 to 70 parts of copolymer (III).
Parts by weight, more preferably 5 to 30 parts by weight, (I) +
The total amount of (II) + (III) should be 100 parts by weight, and blended so as to satisfy the above physical properties. If the amount of the thermoplastic polyurethane (I) is less than 5 parts by weight, the vibration damping property is insufficient, and if it is more than 70 parts by weight, the rigidity is insufficient and it becomes difficult to obtain a structure. Further, if the copolymer (III) is less than 1% by weight, the impact strength will be insufficient, and if it exceeds 70% by weight, sufficient vibration damping performance cannot be obtained and the rigidity will be insufficient. As a result, it becomes difficult to obtain a structure, and further, the fluidity is insufficient, so that the moldability is deteriorated.

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The average particle size of the copolymer (III) is preferably in the range of 0.03 to 1 μm, and when the average particle size is smaller than 0.03 μm or exceeds 1 μm, the impact resistance is insufficient. There is. Further, the average particle diameter of the thermoplastic polyurethane (I) after the blend in terms of vibration damping property, preferably in the range of 0.01 10 .mu.m, more preferably in the range of 0.01 to 5 [mu] m, It is more preferably 0.01 to 1 μm. If the average particle diameter of the dispersion layer exceeds 10 μm, the vibration damping property is deteriorated, and if it is smaller than 0.01 μm, the impact strength is poor. The average particle diameter in the present invention is obtained by an electron micrograph of an ultrathin section of the resin composition, and the particle diameter of the dispersion layer is represented by the arithmetic mean of the long diameter and the short diameter of the dispersion layer. ..

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The blending method of the thermoplastic polyurethane (I), the α, β-unsaturated carboxylic acid alkyl ester polymer (II) and the copolymer (III) may be selected from known kneading methods. Forming a mixture of powders, beads, flakes, chips, or pellets (I), (II), (III) by a roll mill, a kneader, a Banbury mixer, a single-screw extruder, a twin-screw extruder, etc. You can In some cases, a method may be used in which the latexes after polymerization are mixed, precipitated, washed, dried, and then kneaded.

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[0020]

The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. The parts used below are parts by weight. (Production Method of Copolymer III-1) The average particle size is 0.3.
45 parts by weight of polybutadiene latex (rubber solid content) of μm (hereinafter all parts by weight are all parts), deionized water 100
And 0.3 part of potassium rosinate were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen.
A mixture of 11 parts of acrylonitrile, 44 parts of styrene, 0.5 part of t-dodecyl mercaptan, 0.2 part of cumene hydroperoxide, and 50 parts of deionized water and 0.1 parts of sodium formaldehyde sulfoxynate.
Parts, 0.005 parts of ferrous sulfate, and 0.05 parts of disodium ethylenediaminetetraacetate were dissolved in the solution for 7 hours with continuous addition to carry out polymerization. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. Polymerization rate is 9
It was 8%. The resulting polymer latex is salted out, dehydrated,
It was dried and made into flakes. (Production Method of Copolymer III-2) Copolymer III-1
To produce a copolymer III-2 in which the amount of rubber was changed to 25 parts. 25 parts of polybutadiene latex having an average particle diameter of 0.3 μm, 100 parts of deionized water, potassium rosinate of 0.1.
Three parts were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen. 15 parts of acrylonitrile,
60 parts of styrene, 0.7 part of t-dodecyl mercaptan,
A mixture of cumene hydroperoxide (0.2 part), deionized water (50 parts), sodium formaldehyde sulfoxynate (0.1 part) and ferric sulfate (0.005)
And 0.05 part of disodium ethylenediaminetetraacetate were dissolved in the solution for 7 hours with continuous additional addition to carry out polymerization. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. The polymerization rate was 98%. The resulting polymer latex is a copolymer III-1 in the same manner as in salting, dehydrated and flaked and dried. (Production Method of Copolymer III-3) Copolymer III-1
To produce a copolymer III-3 in which the amount of rubber was changed to 10 parts. 10 parts of polybutadiene latex having an average particle size of 0.3 μm, 100 parts of deionized water, potassium rosinate of 0.
Three parts were charged into a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen. 18 parts acrylonitrile,
72 parts of styrene, 1.0 part of t-dodecyl mercaptan,
A mixture of cumene hydroperoxide (0.2 parts), deionized water (50 parts), sodium formaldehyde sulfoxide (0.1 parts) and ferrous sulfate (0.005)
And 0.05 part of disodium ethylenediaminetetraacetate were dissolved in the solution for 7 hours with continuous additional addition to carry out polymerization. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. The polymerization rate was 98%. The resulting polymer latex is a copolymer III-1 in the same manner as in salting, dehydrated and flaked and dried. (Production Method of Copolymer III-4) Copolymer III-1
Of (A) / {(A) + (S) + (M)} = 0.29 was produced. The average particle size is 0.
45 parts of 3 μm polybutadiene latex, 100 parts of deionized water, and 0.3 parts of potassium rosinate were charged in a polymerization tank equipped with a reflux condenser, and the temperature was raised to 70 ° C. while substituting the gas phase with nitrogen. Acrylonitrile 16 parts, styrene 39 parts, t-
Mixture of 0.5 parts of dodecyl mercaptan and 0.2 parts of cumene hydroperoxide, and deionized water 5
An aqueous solution prepared by dissolving 0.1 part of sodium formaldehyde sulfoxynate, 0.005 part of ferrous sulfate, and 0.05 part of disodium ethylenediaminetetraacetate in 0 part was continuously added for 7 hours with stirring to perform polymerization. went. During this period, the reaction temperature was controlled at 70 ° C., and after the addition was completed, post-polymerization was carried out for 1 hour to complete the reaction. The polymerization rate was 99%. The resulting polymer latex is a copolymer III-1 in the same manner as in salting, dehydrated and flaked and dried.

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[0021]

[Examples 1 to 15 and Comparative Examples 1 to 6] As thermoplastic polyurethane, Desmopan 590 (Bayer, polyester, hardness 90) 2 0 parts, DELPET 80N as PMMA (manufactured by Asahi Kasei Corporation) 5 5 parts , Copolymer III-1
Was blended and extruded at 220 ° C. while kneading with a twin-screw extruder to pelletize the resin composition of Example 1. Using this composition, a damper and a strip (for damping property, flexural modulus, and Izod impact measurement) were molded by an injection molding machine at 220 ° C., and their physical properties were measured.

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Examples 2 to 15 and Comparative Examples 1 to 5 were extruded and pelletized in the same manner as in Example 1. Examples 2 to 15, Comparative Examples 1 to 6
Was molded and evaluated in the same manner as in Example 1. However, the thermoplastic polyurethane used is E180 (manufactured by Nippon Miractolan Co., polyester type, hardness 80), E98.
0 (manufactured by Nippon Miractolan, polycarbonate type, hardness 80), E990 (manufactured by Nippon Miractolan, polycarbonate type, hardness 80), E390 (manufactured by Nippon Miractolan, polyether type, hardness 90), E590 (manufactured by Nippon Miractolan, Polycaprolactone type, hardness 90), Resamine P8765 (Dainichi Seika Kogyo Co., Ltd., polycarbonate type, hardness 65) ABS is 120B (styrac A)
BS, manufactured by Asahi Kasei) was used. (Test Method) (Izod Impact Strength) Measured at 23 ° C. according to ASTM D256 (1/4 inch with notch). (Flexural Modulus) Measured at 23 ° C. according to ASTM D790. (Method of measuring vibration damping performance (loss coefficient η)) The loss coefficient of a damper (ASTM D638 type I: thickness 3 mm) molded by an injection molding machine was 2 at 23 ° C.
Channel FFT (Fast Fourier Transform) device (2032
(Type: manufactured by B & K Co., Ltd.) was used to measure by a half-width method by a cantilever method with non-contact random vibration, and a value in terms of 500 Hz was obtained.

Claims (1)

Claim: What is claimed is: 1. A thermoplastic polyurethane (I), α, β
-Unsaturated carboxylic acid alkyl ester polymer (II)
And a rubbery polymer, a vinyl cyanide monomer, an aromatic vinyl monomer, and a copolymer (III) composed of a monomer copolymerizable therewith, if necessary. A thermoplastic resin composition which is excellent and has excellent rigidity and impact resistance.