JP3237254B2 - Damping composite - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composite having excellent vibration damping properties, moldability and physical properties.

[0002]

2. Description of the Related Art In recent years, noise and vibration caused by transportation such as automobiles have become a serious social problem, and low vibration and low noise are also required inside automobiles. Also in ordinary households, reduction of noise and vibration generated from office equipment such as a copying machine and a printer has become an important issue. Furthermore, due to changes in lifestyle, household electric appliances are also becoming larger, and low vibration and low noise of refrigerators, washing machines, and vacuum cleaners are required. Hitherto, styrene resins and general-purpose engineering plastics such as polyamide resins, polyester resins, and polycarbonate resins have been widely adopted as automotive parts, electric / electronic parts, and OA equipment parts. We cannot satisfy the demand.

[0003]

The present invention has been made in view of the above-mentioned problems of the prior art, and has not only physical properties equal to or higher than those of conventional styrene resins and general-purpose engineering plastics, but also excellent vibration damping performance. It is an object of the present invention to provide a thermoplastic resin composite.

[0004]

According to the present invention, there is provided an acrylic acid ester monomer and / or methacrylic acid ester monomer in an amount of 10 to 95% by weight and another monomer copolymerizable therewith with 90 to 5% by weight. 2 to 50 parts by weight of a copolymer (A) having a glass transition point of 0 ° C. or higher and a styrene resin,
Selected from the group of polyamide resin and polycarbonate
At least one thermoplastic resin (B) [Note that the above was
(Excluding the component (A) ) 100 to 100 parts by weight of a resin (A + B) consisting of 98 to 50 parts by weight, and filler (C) having a major axis (t) / minor axis (d) of 1.5 to 8 to 2 to 250 parts by weight The present invention provides a vibration damping composite characterized by mixing parts.

[0005] First, the copolymer (A) will be described.
Acrylic ester monomer and methacrylic ester monomer which are constituent components of the copolymer (A) of the present invention (hereinafter, when these are collectively described, they are referred to as "acrylic ester monomer"). Is an ester of acrylic acid or methacrylic acid with an aliphatic, alicyclic or aromatic unsubstituted alcohol. The term “unsubstituted” as used herein means having no group other than a hydrocarbon group.

Examples of the acrylate and methacrylate monomers include methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, isobutyl acrylate, n-butyl methacrylate, isobutyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, acrylic acid Heptyl, heptyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, octyl acrylate, octyl methacrylate, n-nonyl acrylate, isononyl methacrylate, n-nonyl methacrylate, decyl acrylate, decyl methacrylate, Undecyl acrylate, undecyl methacrylate, dodecyl acrylate, dodecyl methacrylate, n-amyl acrylate, isoamyl acrylate, n-amyl methacrylate,
Examples include isoamyl methacrylate, lauryl acrylate, lauryl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, and cyclohexyl methacrylate.

[0007] Among the acrylic ester monomers, preferred are alkyl acrylate and alkyl methacrylate having an alkyl group having 4 to 12 carbon atoms, more preferably ethyl acrylate and n-acrylate. Butyl, isononyl acrylate, methyl methacrylate, ethyl methacrylate and the like. These monomers can be used alone or in combination of two or more. The proportion of these acrylic ester monomers in the total monomers is 10 to 95% by weight, preferably 20 to 90% by weight, more preferably 3 to 95% by weight.
It is from 5 to 85% by weight, particularly preferably from 40 to 80% by weight. When the use amount of the acrylic ester monomer is less than 10% by weight, the vibration damping property of the vibration damping composite becomes low, and when it exceeds 95% by weight, the impact resistance of the vibration damping composite becomes low.

In the present invention, other monomers that can be copolymerized with the acrylic ester monomer include:
Aromatic vinyl monomer, vinyl cyanide monomer, ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer, ethylenically unsaturated carboxylic acid amide monomer, ethylenically unsaturated acid monomer, ethylene Ethylenically unsaturated sulfonic acid ester monomer, ethylenically unsaturated alcohol and its ester monomer, ethylenically unsaturated ether monomer, ethylenically unsaturated amine monomer, ethylenically unsaturated silane monomer, halogen Examples include vinyl chloride monomers and conjugated diene monomers, and one or more of these are used.

Examples of the aromatic vinyl monomer include:
Styrene, α-methylstyrene, o-methylstyrene,
p-methylstyrene, o-ethylstyrene, p-ethylstyrene, α-chlorostyrene, p-chlorostyrene,
p-methoxystyrene, p-aminostyrene, p-acetoxystyrene, sodium styrenesulfonate, α-
Examples thereof include vinyl naphthalene, sodium 1-vinyl naphthalene-4-sulfonate, 2-vinyl fluorene, 2-vinyl pyridine, and 4-vinyl pyridine, and styrene is particularly preferable. Examples of the vinyl cyanide monomer include acrylonitrile, α-chloroacrylonitrile,
α-methoxyacrylonitrile, methacrylonitrile,
There are α-chloromethacrylonitrile, α-methoxymethacrylonitrile, vinylidene cyanide and the like, and acrylonitrile is particularly preferred.

Examples of the ethylenically unsaturated carboxylic acid hydroxyalkyl ester monomer include hydroxyethyl acrylate, hydroxyethyl methacrylate,
Examples include hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl acrylate, and hydroxybutyl methacrylate. Examples of the ethylenically unsaturated carboxylic acid amide monomer include acrylamide, methacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide,
-Butoxyethylacrylamide, N-butoxyethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, Nn-propoxymethylacrylamide, Nn-propoxymethylmethacrylamide, N-methylacrylamide, N -Methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide,
N, N-diethylacrylamide, N, N-diethylmethacrylamide and the like.

The ethylenically unsaturated acid monomers include:
Ethylenically unsaturated carboxylic acids, ethylenically unsaturated sulfonic acids and the like are used. Examples of ethylenically unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, fumaric acid, fumaric anhydride, maleic acid, maleic anhydride, and the like.Examples of ethylenically unsaturated sulfonic acids include vinyl sulfone Acid and isoprenesulfonic acid. The ethylenically unsaturated acid monomer may be neutralized with, for example, an alkali metal such as sodium or potassium, ammonia, or the like. Examples of the ethylenically unsaturated sulfonic acid ester monomer include alkyl vinyl sulfonic acid and alkyl isoprene sulfonic acid. Examples of the ethylenically unsaturated alcohol and its ester monomer, allyl alcohol, methallyl alcohol, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl stearate,
Vinyl benzoate, allyl acetate, methallyl caproate,
Examples include allyl laurate, allyl benzoate, vinyl alkyl sulfonate, allyl alkyl sulfonate, vinyl aryl sulfonate and the like.

Examples of the ethylenically unsaturated ether monomer include methyl vinyl ether, ethyl, vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, methyl allyl ether and ethyl allyl ether. Examples of the ethylenically unsaturated amine monomer include vinyl dimethylamine, vinyl diethylamine,
Examples include vinyldiphenylamine, allyldimethylamine, and methallyldiethylamine. Examples of the ethylenically unsaturated silane monomer include vinyltriethylsilane, methylvinyldichlorosilane, dimethylallylchlorosilane, vinyltrichlorosilane, and the like.

Examples of the vinyl halide monomer include:
Examples include vinyl chloride, vinylidene chloride, 1,2-dichloroethylene, vinyl bromide, vinylidene bromide, and 1,2-dibromoethylene. Examples of the conjugated diene monomer include:
1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-neopentyl-1,3-butadiene, 2-chloro-1,3-
Butadiene, 1,2-dichloro-1,3-butadiene,
2,3-dichloro-1,3-butadiene, 2-bromo-
There are 1,3-butadiene, 2-cyano-1,3-butadiene, substituted straight-chain conjugated pentadienes, straight-chain and side-chain conjugated hexadienes, and 1,3-butadiene is particularly preferred.

In the present invention, among other monomers that can be copolymerized with the acrylic ester monomer, preferred are aromatic vinyl monomers, vinyl cyanide monomers and And ethylenically unsaturated acid monomers. The proportion of the other monomer in the total monomer is 5
To 90% by weight, preferably 10 to 80% by weight, more preferably 15 to 65% by weight, particularly preferably 20% by weight.
６０60% by weight. When the proportion of the other monomer exceeds 90% by weight, the impact resistance of the vibration damping composite becomes low, and when it is less than 5% by weight, the vibration damping property of the vibration damping composite becomes low. The copolymer (A) can be synthesized by, for example, solution polymerization or emulsion polymerization using heat and a catalyst, and has a number average molecular weight of usually 10,000 to 500,000, preferably 20,000 or more, more preferably 30,000 or more. is there. If the number average molecular weight is less than 10,000, the impact resistance is not sufficient when blended with a thermoplastic resin to form a vibration damping composite.

The glass transition point of the copolymer (A) is determined by the ratio of the constituent monomers. In the present invention,
The copolymer (A) has a glass transition point of 0 ° C. or higher, preferably 10 ° C. or higher, more preferably 20 ° C. or higher. When the copolymer (A) having a temperature of less than 0 ° C. is used, a vibration damping composite having sufficient vibration damping properties cannot be obtained at a temperature of room temperature or higher. In the present invention, the glass transition point of the copolymer (A) is determined by a differential scanning calorimeter (DC) manufactured by Rigaku Corporation.
The measurement was performed using S) under the conditions of a temperature increase rate of 20 ° C./min, a nitrogen atmosphere, and a sample amount of 20 mg.

[0016] The thermoplastic resin (B) of the present invention, the
Styrenic resins other than component (A), especially aromatic vinyl
Monomer-vinyl cyanide monomer copolymer, polyamide
Selected from the group of resin and polycarbonate
Both are one type. Here, the aromatic vinyl monomer-vinyl cyanide monomer copolymer is obtained by copolymerizing an aromatic vinyl monomer and a vinyl cyanide monomer, and is usually used. And AS resins, which may be obtained by polymerizing an aromatic vinyl monomer or a vinyl cyanide monomer in the presence of a rubbery polymer, or a mixture thereof.

Further, as the polyamide resin, H ₂ N-
_{(CH 2) x-NH 2} ( wherein, x is 3-12 integer) linear diamine represented by HOOC- (CH ₂₎ y-CO
Those produced by condensation with a linear diamine acid represented by OH (where y is an integer of 2 to 12) or those produced by ring-opening polymerization of a lactam can be used. Preferred examples of these polyamide resins include nylon 6,6, nylon 6,10, nylon 6,12, nylon 4,6, nylon 3,4, nylon 6,9, nylon 6, nylon 12, nylon 11, nylon 4 and the like. In addition, nylon 6/6, 1
0, nylon 6/6, 12, nylon 6/4, 6, nylon 6/12, nylon 6/6, 6, nylon 6/6,
Copolymers such as 6/6, 10, nylon 6/4, 6/6, 6, nylon 6/6, 6/6, 12, nylon 6/4, 6/10, nylon 6/4, 6/12 Polyamides can be mentioned. Furthermore, nylon 6/6, T (T
Is a terephthalic acid component), a semi-aromatic polyamide resin obtained from an aromatic dicarboxylic acid such as terephthalic acid or isophthalic acid and meta-xylylenediamine or an aliphatic diamine, and obtained from meta-xylylenediamine and the above-mentioned linear dicarboxylic acid. polyamides, etc. polyetheramide can be exemplified.

Further, as the polycarbonate resin,
Examples thereof include an aromatic polycarbonate resin, an aliphatic polycarbonate resin, and an aliphatic-aromatic polycarbonate resin. Generally, a polymer obtained by polymerizing bisphenols such as 2,2-bis (4-oxyphenyl) alkane, bis (4-oxyphenyl) ether, bis (4-oxyphenyl) sulfone sulfide or sulfoxide is used. It is a polymer using a bisphenol compound which is a coalesced or copolymer and is optionally substituted with halogen. About the kind and production method of polycarbonate resin, Nikkan Kogyo Shimbun (published in 1944)
(Issued on September 30, 1998) can be referred to.

In the present invention, the amount of the copolymer (A) used is 2 to 50 parts by weight, preferably 5 to 45 parts by weight.
More preferably, it is 10 to 40 parts by weight. If the amount is less than 2 parts by weight, the vibration-damping property of the composition is low, and if it exceeds 50 parts by weight, the impact resistance of the vibration-damping composite becomes low. On the other hand, the amount of the thermoplastic resin (B) used is 50 to 98 parts by weight, preferably 5 to 98 parts by weight.
It is 5 to 95 parts by weight, more preferably 60 to 90 parts by weight.

The vibration-damping composite of the present invention exhibits vibration damping property excellent by mixing specific filler (C), physical properties, impact resistance and rigidity, the molding processability. The average diameter of the filler (C) in claim 1 is preferably from 0.1 to 800 μm.
m, and in each filler, the longest point is called the major axis (t), and the shortest point is the minor axis (d), and t / d is 1.5 to 8. As long as the filler satisfies this condition, it may be organic or inorganic. The shape may be fibrous, scaly, or any other shape. Examples of the fibrous material include glass fiber, carbon fiber, metal fiber, and ceramic fiber. Examples of scaly ones include mica, glass flake, and mica. In addition, there are lumps such as whiskers and needle-like metal acid compounds.

A scaly (flat) one has good damping properties,
Physical properties and moldability depend on t / d. Fibrous materials exhibit good rigidity, but have low impact resistance and vibration damping properties. That is, it depends on the value of t / d. The filler has an average diameter of 0.1 to 800 μm, preferably 0.1 to 70 μm.
0 μm, more preferably 0.1 to 600 μm.
If the average diameter is less than 0.1 μm, the impact resistance is low,
If it exceeds 0 μm, the vibration damping property, impact resistance and rigidity are low. The t / d of the filler is between 1.5 and 8. Preferably 1.5 to
7, more preferably 1.5 to 6.5. When t / d is less than 1.5, impact resistance and rigidity are low, and t / d is 8
If it exceeds 300, the vibration damping property and the formability will deteriorate.

The vibration-damping composite of the present invention, [(A) +
(B)] / (C) and various additives used as required, for example, a single screw extruder, a twin screw extruder, a rubber mill, a Brabender mixer, a Banbury mixer, a pressure kneader, a mixing roll, and the like. And by heating and mixing. The obtained composition is molded by a roll, an extruder, and an injection molding machine and used as a vibration damping material. As an example, regarding the production of the vibration damping composite of the present invention, using an extruder having a large L / D (L: screw length, D: diameter), [(A) + (B)] / ( Knead C).

[0023]

The present invention will now be described more specifically with reference to examples. Preparation of copolymer (A) In a reaction vessel, 200 parts of polymerization water, 0.2 parts of potassium carbonate, 0.03 parts of sodium acid sulfite, 2.0 parts of sodium laurate, 0.3 parts of potassium sulphate, and Table 1 Was polymerized at 50 ° C. for 5 hours.

[0024]

[Table 1]

The glass transition point (Tg) measured by DSC, heated at 20 ° C. / hr.

[0026] Examples 1 to 11 and Comparative Examples 1 to 8 Table 1 copolymer, nylon-6 and other following thermoplastic resins, glass fibers, glass beads, glass flakes Table 2
The pellets were prepared by kneading with the compositions shown in Nos. 1 to 4, and injection molding was performed to prepare test pieces. Nylon-6; aramid Chemical Co. P C; Idemitsu Co. A-3000 AS resin; JSR Co., Ltd.

[0027]

[Table 2]

[0028]

[Table 3]

[0029]

[Table 4]

The impact resistance was measured according to (Izod impact strength) ASTM D-256. (Kg ・ cm
/ Cm, with notch)-Flexural modulus Measured according to ASTM D-760. (Kg / cm
² )-MFR Measured according to JIS K7210. (G / 10 minutes,
(240 ° C.) Loss coefficient: Measured by a resonance method using a sheet having a thickness of 2 mm.

[0031]

Industrial Applicability The vibration damping composite of the present invention is a material having excellent physical properties and workability and reducing the generation of vibration and noise, and is useful for automobile parts, electric / electronic parts, and OA equipment parts. .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI // (C08L 25/12 (C08L 25/12 33:06) 33:06) (C08L 69/00 (C08L 69/00 33: 06) 33:06) (C08L 77/00 (C08L 77/00 33:06) 33:06) (56) References JP-A-3-182545 (JP, A) JP-A-4-15259 (JP, A JP-A-63-308051 (JP, A) JP-A-63-118344 (JP, A) JP-A-5-112726 (JP, A) JP-A-58-39828 (JP, A) 80454 (JP, A) JP-A-5-272588 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 33/00-33/26 C08L 69/00-69/00 C08L 77/00-77/12 C08K 7/00-7/28

Claims (1)

(57) [Claims] 1. A glass transition point of 10 to 95% by weight of an acrylic acid ester monomer and / or methacrylic acid ester monomer and 90 to 5% by weight of another monomer copolymerizable therewith has a glass transition point of 0. C. or higher copolymer (A) 2-5
0 parts by weight of styrene resin, polyamide resin and poly
At least one thermoplastic resin (B) selected from the group of carbonates (but excluding the component (A))
To 100 parts by weight of the resin (A + B) consisting of 50 parts by weight,
When one filler is taken out, the longest both ends distance is t,
Major axis (t) / minor axis (d) when the shortest distance is d
1. A vibration damping composite characterized by mixing 2 to 250 parts by weight of a filler (C) having a particle size of 1.5 to 8.