JPH09302222A - Molded resin for audio equipment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded resin for audio equipment, excellent in acoustic properties and satisfying the requirement for molding and processing characteristics by using a polyphenylene ether, a polyamide and a mica as the principal constituents. SOLUTION: This molded resin contains a polyphenylene ether (A), a polyamide (B) and a mica (C) at a weight ratio of component A to component B of (1:99) to (80:20), with the amount of component C being 1-150 pts.wt. based on 100 pts.wt. total of components A and B. The component A preferably comprises, e.g. a 2,6-dimethylphenol homopolymer. Examples of component B used include a crystalline aliphatic polyamide (e.g. nylon 6) and an aromatic polyamide (e.g. nylon 61). Examples of component C used include margarite, muscovite and biotite. It is desirable that the component C has a weight-mean flake diameter of 5 to 400μm. The obtained molded resin has tan δ values of at least 1.5×10 at 100Hz and at least 4.0×10 at 999Hz in dynamic viscoelasticity measurement at ordinary temperature, and it has a modulus of elasticity of 35,000kg/cm<2> .

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin molding for audio equipment. More specifically, the present invention relates to a resin molding for an audio device, which is mainly used for an acoustic component and has excellent acoustic characteristics and processing characteristics and which contains polyphenylene ether and polyamide as main components.

[0002]

2. Description of the Related Art Conventionally, metal, paper, and
Various resin moldings have been used. In recent years, in order to reduce the processing cost, a method has been attempted in which a thermoplastic resin is molded by injection molding to more economically manufacture a component having a complicated shape than a conventional combination of metal and paper. However, it has not been possible to obtain a molded product satisfying all of the molding processing characteristics, acoustic performance, adhesiveness with an adhesive in the assembly processing step, and heat resistance during processing. For example, a molded product composed mainly of polypropylene with excellent acoustic characteristics does not have sufficient heat resistance and adhesiveness with an adhesive, and a molded product of polyamide resin satisfies the adhesiveness, but changes in sound quality when absorbing water. Is remarkable and the heat resistance is insufficient.

[0003]

In view of the present situation, the problem to be solved by the present invention is to use a resin molded product containing polyamide, polyphenylene ether and mica as main components for parts used for acoustic applications. Another object of the present invention is to provide a resin molded product for an audio device, which has excellent acoustic characteristics and satisfies the molding processing characteristics, the adhesiveness with an adhesive in the processing step, and the heat resistance during processing.

[0004]

That is, the present invention relates to a resin molded product for audio equipment, which contains the following components (A) to (C). (A): Polyphenylene ether (B): Polyamide (C): Mica

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The constituent component (A) of the resin used in the present invention is polyphenylene ether, and one or more of the phenol compounds represented by the following formulas are mixed with oxygen or oxygen using an oxidation coupling catalyst. A polymer obtained by oxidative polymerization with an oxygen-containing gas is preferable.

[0006]

(In the formula, R1 to R5 are independently selected from the group consisting of hydrogen, halogen atoms, hydrocarbon groups and substituted hydrocarbon groups, at least one of which is a hydrogen atom). Specific examples of R1 to R5 include hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, Hydroxymethyl, carboxyethyl,
Methoxycarbonylethyl, cyanoethyl, phenyl,
Chlorophenyl, methylphenyl, dimethylphenyl,
Ethylphenyl, allyl and the like can be mentioned.

Specific examples of the compound represented by the above formula include phenol, o-, m-, or p-cresol, 2,6-, 2,5-, 2,4- or 3,5-dimethyl. Phenol, 2-methyl-6-phenylphenol,
2,6-diphenylphenol, 2,6-diethylphenol, 2-methyl-6-ethylphenol, 2,3
5-, 2,3,6- or 2,4,6-trimethylphenol, 3-methyl-6-t-butylphenol, thymol, 2-methyl-6-allylphenol and the like.

Further, as the component (A), a phenol compound other than the above formula, for example, a polyvalent hydroxy aromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone, and novolak resin, is represented by the above formula. May be used.

The preferred components (A) include:
2,6-dimethylphenol homopolymer, 2,6-diphenylphenol homopolymer, copolymer of a large amount of 2,6-xylenol and small amount of 3-methyl-6-t-butylphenol, large amount And a small amount of 2,3,6-trimethylphenol.

Component (B) of the resin used in the present invention
Is a polyamide, and the polyamide is at least one polyamide selected from crystalline aliphatic polyamides and aromatic polyamides.

The above-mentioned crystalline aliphatic polyamide is, for example, one shown below.

These compounds have an equimolar amount of 4-1 carbon atoms.
Saturated aliphatic dicarboxylic acids containing two and 2 to 12 carbon atoms
In this case, a diamine or the like can be used, if necessary, so as to provide an excess of amine terminal groups over carboxyl terminal groups in the polyamide, if desired. Conversely, dibasic acids can be used to provide excess acid groups. Similarly, these polyamides can be successfully prepared from the acid- and amine-forming derivatives of the acids and amines, such as esters, acid chlorides, amine salts, and the like. Representative aliphatic dicarboxylic acids used to make this polyamide include adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid, and dodecandionic acid, while typical aliphatic diamines include hexamethylene Diamines and octamethylenediamine are included. In addition, these polyamides are derived from lactams or units of ω-amino acids having 4 to 12 carbon atoms, or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and aliphatic diamines having 2 to 12 carbon atoms. Compounds, for example, lactams such as ε-caprolactam, ω-laurolactam, 11-aminoundecanoic acid, 12-aminododecanoic acid, or amino acids, and equimolar salts of the above-mentioned various diamines with adipic acid, azelaic acid, sebacic acid, etc. Can be produced by self-condensation or the like.

Examples of polyamides include polyhexamethylene adipamide (nylon 66), polyhexamethylene azeramid (nylon 69), polyhexamethylene sebasamide (nylon 610), and polyhexamethylene dodecanoamide (nylon 612), poly-bis- (p-aminocyclohexyl) methandodecanamide, polytetramethylene adipamide (nylon 46) or polyamides resulting from ring opening of lactams; ie, polycaprolactam (nylon 6), and polylauryl lactam. included. Further, polyamides produced by polymerizing at least two kinds of amines or acids used in producing the above-mentioned polymer, for example, polymers produced from adipic acid, sebacic acid, and hexamethylenediamine can be used. . Further, copolymers such as nylon 66/6, which is a copolymer of nylon 66 and nylon 6, and nylon 6/12 are included.

Among these crystalline polyamides, nylon 46, nylon 6, nylon 66, nylon 11, nylon 12, and the like are preferably used. More preferably, nylon 6, nylon 66 or a mixture of nylon 6 and nylon 66 in any ratio is used. As the terminal functional groups of these polyamides, those having many amine terminals, those having many carboxy terminals, those having a balance between them, and mixtures having any ratio thereof are suitably used.

The above-mentioned aromatic polyamide is a copolyamide containing an aromatic component such as polyhexamethylene isophthalamide (nylon 6I). The thermoplastic copolyamide containing such an aromatic component can be melt-polymerized with aromatic amino acids and / or aromatic dicarboxylic acids such as paraaminomethylbenzoic acid, paraaminoethylbenzoic acid, terephthalic acid, and isophthalic acid as main components. Mean polyamide.

Diamines as other constituents of the polyamide are hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4
4-trimethylhexamethylenediamine, metaxylylenediamine, paraxylylenediamine, bis (p-aminocyclohexyl) methane, bis (p-aminocyclohexyl) propane, bis (3-methyl, 4-aminocyclohexyl) methane, 1, 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane and the like can be used. Isocyanates can be used instead of diamines. For example, 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate and the like.

The copolymerization component used if necessary is not particularly limited, and may be lactam or ω-C 4 -C 12.
Compounds derived from units of amino acids, or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, and aliphatic diamines having 2 to 12 carbon atoms, for example, ε-caprolactam;
ω-laurolactam, 11-aminoundecanoic acid, 12
-Lactams such as aminododecanoic acid or amino acids, and equimolar salts of the above-mentioned various diamines with adipic acid, azelaic acid and sebacic acid can be used.

Representative examples of thermoplastic aromatic copolyamides comprising these components include copolymerized polyamides of paraaminomethylbenzoic acid and ε-caprolactam (nylon AMBA / 6), 2,2,4- / 2,4 Polyamide (Nylon TMDT, TMDT / 6) containing 4,4-trimethylhexamethylenediamine terephthalate as a main component
I), hexamethylenediamine, isophthalate and / or
Or hexamethylenediamine / terephthalate as a main component, and bis (paraaminocyclohexyl) methane / isophthalate and / or terephthalate or bis (3
-Methyl, 4-aminocyclohexyl) methane isophthalate and / or terephthalate or bis (paraaminocyclohexyl) propaneisophthalate and / or
Or a polyamide (nylon 6I) containing bis (paraaminocyclohexyl) propane terephthalate as a copolymerization component
/ PACM I, nylon 6I / DMPACMI, nylon 6I / PACP I, nylon 6I / 6T / PAC
MI / PACM T, nylon 6I / 6T / DMPA
CM I / DMPACM T, nylon 6I / 6T / P
ACP I / PACP T), which contains hexamethylenediamine / isophthalate or hexamethylenediamine / terephthalate as a main component, ε-caprolactam, 12
Polyamide (nylon) containing aminododecanoic acid, hexamethylenediamine adipate, bis (paraaminocyclohexyl) methane adipate, bis (3-methyl, 4-aminocyclohexyl) methane adipate as a copolymer component 6I, 6I / 6T, 6I / 12, 6
T / 6, 6T / 66, 6I / PACM 6, 6I / DM
PACM 6), bis (para-aminocyclohexyl) methane / isophthalate or bis (3-methyl, 4-aminocyclohexyl) methane, isophthalate as a main component, hexamethylenediamine / dodecane diacid, 12-aminododecanoic acid, etc. (Nylon PACM I / 612, Nylon DMPACM)
I / 12).

Among these aromatic polyamides, amorphous aromatic polyamides are preferably used.

Among the constituent components of the resin used in the present invention,
The content weight ratio of (A) / (B) is preferably 1/99 to 80/20, more preferably 3/97 to 70/30, and most preferably 5/95 to 50/50.
When the amount of component (A) is too small (the amount of component (B) is excessive), the high temperature rigidity may decrease, while when the amount of component (A) is excessive (the amount of component (B) is too small), the impact resistance In some cases, it may not be possible to obtain a preferable molded product having a markedly reduced fluidity.

Component (C) of the resin used in the present invention
Is mica. Here, mica is one of the silicate minerals.
A layered aluminosilicate of the mica family
You. The specific structure is layered ion (Si_TwoO_Five)_n ^2n-During ~
When 1/2 of Si in the above is replaced by Al (SiAlO_Five)
_n ^2n-Become an ion. For example, pearl mica, muscovite, black mica
Mother etc. are mentioned. Pearl mica (margarite)
[CaO / 2Al_TwoO_Three・ 2SiO_Two・ H_TwoO] is Al
³⁺A gibbsite layer centered on ions (SiAlO_Five)
_n ^2n-It is formed by sandwiching the tetrahedral layer ions³⁺(O
H)^-(SiAlO_Five)^3-]_n ^n-Secondary Mica Layer Structure
The former anions overlap, and in the meanwhile, Ca²⁺Ions arranged
Have a structure. Muscovite [K_TwoO ・
3Al_TwoO _Three・ 6 SiO_Two・ 2H_TwoO] (Si_TwoA
10_Five)_n ^2n-1/4 of the Si inside is replaced with Al
Came (Si_ThreeAlO_Ten)_n ^5n-Ions make the gibbsite layer
Sandwich it [Al_Two ³⁺(OH)_Two ^-(Si_TwoAlO_Ten)^Five-]
_n ^n-Anion with a mica layer structure⁺To ion
Is O^2-It has a structure in which 12 ions are coordinated. One of the biotite
Seed phlogopite [K_TwoO.6
MgO / Al_TwoO_Three・ 6 SiO_Two・ 2H_TwoO] (S
i_ThreeAlO_Ten)_n ^{5 n-}Ions sandwich the brucite layer
Anions of the mica layer structure are created, and these layered ions are K⁺
Overlapping with ions in between. Mg in brucite layer
²⁺Coordinate to (OH)^-Some of the ions are often F^-I
Has been replaced by on. Especially from a hot melt
All artificial mica made by F^-Replaced by ions, KM
g_ThreeF_Two(Si_ThreeAlO_Ten). Again these
With some of the cations replaced by Mg and Fe
Can be

The weight average flake diameter of mica is preferably 5 μm or more and 400 μm or less. More preferably 8μ
It is m or more and 200 μm or less. Most preferably 15μ
It is m or more and 90 μm or less. The weight average aspect ratio is preferably 10 or more.

The content of the component (C) is preferably 1 to 150 parts by weight per 100 parts by weight of the total amount of the components (A) and (B). More preferably, it is 10 to 80 parts by weight. Similarly, as the filler for improving the rigidity of the thermoplastic resin composition, talc, clay, glass flakes and the like flaky inorganic filler, and the like,
In either case, the effect of improving the acoustic characteristics is small, and these alone are not preferable.

Addition of the following components to the resin used in the present invention has the effect of further enhancing the acoustic characteristics. That is, a conjugated diene-alkenyl aromatic compound copolymer in which 50% or more of the conjugated diene compound is polymerized with 1, 2 or 3,4 bonds, and the peak temperature of tan δ is -20 ° C or more as a component (A ) ~ 1 to 100 parts by weight of the total amount of the component (C)
By molding using a resin added with 30 parts by weight, a molded body having more excellent acoustic characteristics can be obtained. Examples of the conjugated diene include butadiene and isoprene. Examples of the alkenyl aromatic compound may include styrene. These conjugated diene-alkenyl aromatic compound copolymers are A-
It may be a block copolymer such as B, A-B-A, A-B-A-B or the like, a random copolymer or a partial random copolymer. That is, as the conjugated diene-alkenyl aromatic copolymer, for example, a block copolymer rubber having a styrene block (A) and a butadiene block (B) or an isoprene block (I), for example, SB, SBS, SBSBS, SI. , SIS, IS
I, SISIS block copolymer and the like.

Many methods have been proposed as a method for producing a styrene block copolymer rubber. As a typical method, a lithium catalyst or a lithium catalyst or a method described in Japanese Patent Publication No. 40-2798 is used. A Ziegler type catalyst can be used for block copolymerization in an inert solvent to obtain a copolymer rubber of an aromatic vinyl hydrocarbon (block A) and a conjugated diene hydrocarbon (block B).

Preferably, 65% or more of the conjugated diene compound is a conjugated diene-alkenyl aromatic compound copolymer obtained by polymerizing 1,2 or 3,4 bonds. On the contrary, if the proportion of 1,2 or 3,4 bonds of the conjugated diene compound is 50% or less, the vibration damping effect is insufficient. Especially, when the conjugated diene component is isoprene, it is decomposed by heat. Is markedly low, and impact strength is low, and practicality is poor. From the viewpoint of the function of damping property, it is necessary that the peak temperature of the main dispersion of tan δ (loss tangent) obtained by viscoelasticity measurement with a conjugated diene component is −20 ° C. or higher. When there is a peak only at a temperature lower than −20 ° C., sufficient vibration damping properties cannot be obtained in a normal temperature region, and the acoustic characteristics are not improved so much. In some cases, it is possible to use SIS and SBS together. In the conjugated diene-alkenyl aromatic compound copolymer, the alkenyl aromatic component is 5 to
60% by weight is preferred. More preferably, it is 10 to 40% by weight. When it is 5% by weight or less, the compatibility with polyphenylene ether is insufficient and mechanical performance such as impact strength is lowered, which is not preferable. When this component is added, it is preferably 1 to 20 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If it is too small, the desired effect is not exhibited, and if it is too large, the mechanical strength is significantly decreased, which is not preferable.

In order to improve the impact resistance of the resin used in the present invention, a conjugated diene-alkenyl aromatic copolymer having a Tg of -40 ° C. or lower or a hydrogenated product thereof can be used. Examples of the conjugated diene include butadiene and isoprene. Examples of alker aromatics include styrene. These conjugated diene-alkenyl aromatic compound copolymers are A-
It may be a block copolymer such as B, A-B-A, A-B-A-B or the like, a random copolymer or a partial random copolymer. That is, as the conjugated diene-alkenyl aromatic copolymer, for example, a block copolymer rubber having a styrene block (A) and a butadiene block (B) or an isoprene block (I), for example, SB, SBS, SBSBS, SEBS. , SEP, S
I, SIS, ISI, SISIS block copolymer and S
BR etc. are mentioned. When this component is added, it is preferably 1 to 20 parts by weight based on 100 parts by weight of the total amount of the components (A) and (B). If it is too small, the desired effect is not exhibited, and if it is too large, the mechanical strength is significantly decreased, which is not preferable.

It is preferable to add a necessary amount of a compatibilizing agent to the resin used in the present invention in order to improve the compatibility between the component (A) and the component (B) and improve the mechanical strength. Specific examples thereof include the following (D1) to (D9). (D1): Epoxy compound having no ethylenic or acetylenic unsaturated bond (D2): (i) At least one unsaturated group, that is, carbon-carbon double bond or carbon-carbon triple bond and (ii) in the same molecule. ) Compound having at least one polar group (D3): Oxidized polyolefin wax (D4): In the molecular structure, (i) a carbon atom through an oxygen bridge, and (ii) at least an ethylenic carbon-carbon double bond Alternatively, a silane compound having both a carbon-carbon triple bond and / or a functional group selected from an amino group and a mercapto group, the functional group not directly bonded to a silicon atom (D5): in the same molecule (i ) (OR) (wherein R is hydrogen or an alkyl, aryl, acyl or carbonyldioxy group) and (ii) a carboxylic acid, an acid halide, Compound having at least two identical or different functional groups selected from acid anhydride, acid halide anhydride, acid ester, acid amide, imide, imide, amino and salts thereof (D6): (i) in the same molecule ) Acid halide group and (ii)
Compound having at least one carboxylic acid, carboxylic acid anhydride, acid ester or acid amide group (D7): having a unit of vinyl aromatic compound and a unit of α, β-unsaturated dicarboxylic acid or dicarboxylic acid anhydride A unit of copolymer or vinyl aromatic compound and α,
Copolymer having unit of β-unsaturated dicarboxylic acid imide compound (D8): at least selected from the group consisting of (D1), (D2), (D4), (D5) and (D6) Polyphenylene ether functionalized with one compatibilizing agent (D9): Polyphenylene ether functionalized with at least one compatibilizing agent selected from the group consisting of (D1) to (D7) and a small amount Composition obtained by melt-kneading the above polyamide

As the compatibilizer, since the polyphenylene ether as the component (A) and the polyamide as the component (B) originally have poor affinity, they are melt-kneaded at the same time to obtain polyphenylene ether particles having a particle size of about 10 μm or more. It is compounded in order to improve the drawback that it disperses only in diameter and exhibits only extremely low mechanical properties.

The compatibilizer of the (D1) group used in the present invention is (1) a condensate of polyhydric phenol (for example, bisphenol A, tetrabromobisphenol A, resorcin, etc.) and epichlorohydrin, and coal, propylene glycol, Polyethylene glycol and the like) and a condensate of epicudorhydrin.

The compatibilizer of the (D2) group used in the present invention is an unsaturated group, that is, a carbon-carbon double bond or a carbon-carbon triple bond, and an amide bond contained in a polar group or polyamide resin. , A compound having a functional group showing affinity or chemical reactivity with a carboxyl group or an amino group existing at the chain end in the same molecule. Examples of such a functional group include a carboxylic acid group, a group derived from a carboxylic acid, that is, various salts and esters substituted with a hydrogen atom or a hydroxyl group of a carboxyl group, an acid amide, an acid anhydride, an imide,
Acid azide, acid halide, or oxazoline, functional group such as nitrile, epoxy group, amino group, hydroxyl group,
Or, an isocyanate group and the like, and a compound having both an unsaturated group and a polar group, that is, an unsaturated carboxylic acid, an unsaturated carboxylic acid derivative, an unsaturated epoxy compound,
Unsaturated alcohols, unsaturated amines and unsaturated isocyanates are used.

Specifically, maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide,
A reaction product of maleic anhydride and a diamine, for example,

[0034]

(However, R represents an aliphatic or aromatic group.)
Those having a structure represented by, for example, methylnadic anhydride, dichloromaleic anhydride, maleic amide, itaconic acid, itaconic anhydride, soybean oil, tung oil, castor oil,
Natural oils and fats such as linseed oil, hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, coconut oil, sardine oil, epoxidized natural oils, acrylic acid, butenoic acid,
Crotonic acid, vinyl acetic acid, methacrylic acid, pentenoic acid,
Angelic acid, tiglic acid, 2-pentenoic acid, 3-pentenoic acid, α-ethylacrylic acid, β-methylcrotonic acid, 4-pentenoic acid, 2-hexene, 2-methyl-2-
Pentenoic acid, 3-methyl-2-pentenoic acid, α-ethylcrotonic acid, 2,2-dimethyl-3-butenoic acid, 2-heptenoic acid, 2-octenoic acid, 4-decenoic acid, 9-undecenoic acid, 10 -Undecenoic acid, 4-dodecenoic acid, 5-dodecenoic acid, 4-tetradecenoic acid, 9-tetradecenoic acid,
9-hexadecenoic acid, 2-octadecenoic acid, 9-octadecenoic acid, eicosenoic acid, docosenoic acid, erucic acid, tetracosenoic acid, mycolic acid, 2,4-hexadienoic acid,
Diallylacetic acid, geranium acid, 2,4-decadienoic acid,
2,4-dodecadienoic acid, 9 / 12-hexadecadienoic acid, 9 / 12-octadecadienoic acid, hexadecatrienoic acid, eicosadienoic acid, eicosatrienoic acid, eicosatetraenoic acid, ricinoleic acid, eleostearine acid,
Oleic acid, eicosapentaenoic acid, erucic acid, docosadienoic acid, docosatrienoic acid, docosatetraenoic acid,
Unsaturated carboxylic acids such as docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, traacontenoic acid, or esters of these unsaturated carboxylic acids, acid amides, anhydrides, or allyl alcohol, crotyl alcohol, Methyl vinyl carbinol, allyl carbinol, methyl propenyl carbinol, 4-penten-1-ol, 10-undecen-1-ol, propargyl alcohol, 1.4
-Pentadiene-3-ol, 1.4-hexadiene-
3-ol, 3.5-hexadiene-2-ol, 2
4-hexadiene-1-ol, general formula Cn H2n-5O
Alcohols represented by H, Cn H2n-7OH, Cn H2n-9OH (where n is a positive integer), 3-butene-1,2-
Diol, 2,5-dimethyl-3-hexene-2,5-
Diol, 1.5-hexadiene-3,4-diol,
Unsaturated alcohols such as 2,6-octadiene-4,5-diol or O of such unsaturated alcohols
Examples thereof include unsaturated amines in which the H group is replaced by --NH2 groups, glycidyl (meth) acrylate, allyl glycidyl ether, and the like.

Low polymerization of butadiene, isoprene and the like (for example, those having an average molecular weight of about 500 to 10,000) or high molecular weight compounds (for example, an average molecular weight of 1)
0000 or more) to which maleic anhydride and phenols are added, or those into which an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group, etc. are introduced, and allyl isocyanate.

In the present invention, the definition of a compound having both an unsaturated group and a polar group in the same molecule includes a compound containing two or more unsaturated groups and two or more polar groups (same or different). Needless to say, it is also possible to use two or more specific compounds.

Of these, maleic anhydride, maleic acid, fumaric acid, itaconic anhydride, itaconic acid and glycidyl (meth) acrylate are preferably used, and maleic anhydride and fumaric acid are more preferably used.

The compatibilizer of the (D3) group used in the present invention is usually adjusted by oxidation of a polyolefin wax in the air or in a suspension, and a polyethylene wax or the like is preferable.

The compatibilizing agent of the (D4) group used in the present invention has a) in the molecular structure, a) at least one silicon atom bonded to a carbon atom through a bridge of oxygen, and b)
A silane compound having at least both an ethylenic carbon-carbon double bond or a carbon-carbon triple bond and / or a functional group selected from an amino group and a mercapto group, wherein the functional group is not bonded to a silicon atom; Yes, gamma aminopropitriethoxysilane, 2- (3-cyclohexyl) ethyltrimethoxysilane, and the like can be used.

The compatibilizer of the (D5) group used in the present invention is an aliphatic polycarboxylic acid, an acid ester or an acid amide, and has a general formula (R1 O) m R (COOR
2) n (CONR3R4) l (where R is a linear or branched saturated aliphatic hydrocarbon of 2 to 20).
R1 is hydrogen, an alkyl group, an aryl group, an acyl group,
Or a carbonyldioxy group, particularly preferably hydrogen, R2 is hydrogen, an alkyl group or an aryl group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and R3 and R4 are hydrogen, an alkyl group or an aryl group. And has 1 to 10 carbon atoms,
Preferably 1-6, more preferably 1-4, m =
And n + 1 is an integer of 2 or more, preferably 2 or 3.
Wherein n is an integer of 0 or more, l is an integer of 0 or more, (R1 O) is located at the α-position or β-position of the carbonyl group, and at least two carbonyl groups have 2 to There are 6 carbons. A) a saturated aliphatic polycarboxylic acid and a derivative compound thereof. (Specifically, examples thereof include ester compounds, amide compounds, anhydrides, hydrates, and salts of saturated aliphatic polycarboxylic acids.
Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like. Details of these compounds are disclosed in Published Patent Publication No. 61-502195. )

The compatibilizer of the (D6) group used in the present invention is represented by the general formula ((I) -Z- (II)) (wherein
(I) is at least a compound of the formula: (X—CO) — (where X is
F, Cl, B, I, OH, OR or -O-CO-R;
R is H, an alkyl group or an aryl group), (I
I) is at least a carboxylic acid, an acid anhydride group, an acid amide group, an imide group, a carboxylic ester group, an amino group or a hydroxyl group, and the groups (I) and (II) are divalent hydrocarbon bonds. It is covalently bonded through Z. ). (Specific examples include chloroformyl succinic anhydride, chloroethanoyl succinic anhydride, trimellitic anhydride chloride, trimellitic anhydride acetic anhydride, terephthalic acid chloride, and the like.) It consists of one or more compounds selected from the group.

However, the compatibility improver in the present invention is
The compound is not limited to those exemplified here, and any compound may be used as long as it is used for the purpose of improving the compatibility between PPE and polyamide, and a single or a plurality of compatibilizers may be used at the same time.

If the amount of the compatibility improver is 0.01 to 30 parts by weight with respect to 100 parts by weight of the total of the polyphenylene ether resin and the polyamide resin, the heat stability will be deteriorated or decomposed. It is not preferable because the strength is remarkably reduced due to the above. The preferable blending amount is 0.
It is from 05 to 25 parts by weight.

The compatibilizing agent is preferably at least one selected from the group consisting of maleic anhydride, maleic acid, fumaric acid, itaconic acid, citric acid and malic acid. When compounding the compatibilizer, a radical initiator may be used in combination.

The resin used in the present invention may further include an alkenyl aromatic resin. The resin preferably has an elastic modulus at room temperature of 10,000 kg / cm @ 2 or more, such as styrene, .alpha.-methylstyrene, p-
Polymers or copolymers such as methyl styrene,
Specifically, polystyrene, rubber-reinforced polystyrene, poly-α-methylelstyrene, poly-p-methylstyrene,
Styrene-acrylonitrile copolymer and the like,
Further, a polyphenylene ether grafted with a styrene polymer is also included.

The content of the alkenyl aromatic resin is 60% by weight or less, preferably 1 to 30% by weight. If the content is excessive, the impact resistance and heat resistance of the thermoplastic resin are undesirably reduced.

In addition to mica, various fillers may be used in combination with the resin used in the present invention in order to enhance mechanical strength. Suitable fillers include, for example, calcium carbonate,
Magnesium carbonate, aluminum hydroxide, magnesium hydroxide, zinc oxide, titanium oxide, magnesium oxide, aluminum silicate, magnesium silicate, calcium silicate, silicic acid, hydrous calcium silicate, hydrous aluminum silicate, talc, kaolin, mineral Examples thereof include fibers, xonotlite, potassium titanate whiskers, magnesium oxysulfate, glass balun, glass fibers, glass beads, carbon fibers, inorganic fibers such as stainless fibers, aramid fibers and carbon black. These may be used in combination of two or more.

The resin used in the present invention comprises the constituent components (A) to
The component (C) and, if necessary, a compatibilizer, an impact resistance improver, an alkenyl aromatic resin, and a filler are blended by a known method and melt-kneaded to obtain a blended knead. The order is arbitrary, and after kneading each combination of components separately, all the combinations may be blended and kneaded, or one extruder may be provided with a plurality of feed ports and one or more of each may be provided along the cylinder. The ingredients may be fed sequentially.

The resin used in the present invention may further contain conventional additives such as flame retardants, plasticizers, antioxidants and weather resistance agents. In particular, the additives used for polyphenylene ether or polyamide are most suitable.

The present invention relates to a molded article that is molded from the above-mentioned resin and is used for acoustic purposes. The parts that can be used for concrete audio applications are TVs, radios,
It is used for professional stereos, home stereos, car stereos, speaker frames and chassis for computers, diaphragms (speaker cones), etc. These molded bodies can be molded by a usual thermoplastic resin molding method. Specifically, they are injection molding, press molding, blow molding, and extrusion molding. Of these, injection molding is the most economical and dimensional accurate. Resins based on polyamide, polyphenylene ether and mica are not only suitable for this molding method, but the resulting molded products have acoustic characteristics, mechanical strength, heat resistance during processing, and other peripheral parts. It has excellent performance in terms of adhesion. Usually, the acoustic characteristics are good when the contradictory properties that the elastic modulus of the component is high and the vibration damping is rapid are satisfied. The molded article of the present invention acquires this performance by the combination of polyphenylene ether, polyamide and mica. Usually, ta in dynamic viscoelasticity measurement is used as an index of vibration damping characteristics.
In many cases, nδ is used, and the larger the value, the better the vibration damping characteristic.

Further, these resin moldings have a tan δ value in dynamic viscoelasticity measurement at room temperature of 1.5 × 10 ⁻² or more at 100 Hz and 4.0 × 10 at 999 Hz.
^-When it is ² or more, it exhibits good acoustic characteristics. If it is less than this, the sound does not resonate well, and the performance cannot be sufficiently exhibited as an audio component.

In the resin molded product of the present invention, if the value of tan δ is not less than the above value, the higher the elastic modulus of the molded product, the better the acoustic characteristics. The elastic modulus is preferably 35000 kg / cm ² or more.

[0054]

EXAMPLES The present invention will be described in detail with reference to the following examples, but these are merely examples, and the present invention is not limited thereto.

First, a resin composition for producing a molded product was blended at a cylinder temperature of 260 ° C. (only the molded product composition F was 230 ° C.) using a TEM50 twin-screw kneader manufactured by Toshiba Machine Co., Ltd. with the composition shown in Tables 1 and 2. The molten resin was melt-kneaded and extruded from a die, cooled in a water tank, and pelletized by a strand cutter. Next, after vacuum-drying the pellets at 110 to 130 ° C. for 4 hours, an injection molding machine IS2 manufactured by Toshiba Machine Co., Ltd.
20EN for measuring the mechanical strength under the conditions of a cylinder temperature of 290 ° C. (molded body composition F only 230 ° C.), an injection pressure of 1200 kg / cm ² , and a mold temperature of 80 ° C. (molded body composition F only 50 ° C.). A test piece, speaker frame, and speaker cone were molded.

(1) Impact resistance (Izod impact test) After molding a 3.2 mmt test piece for Izod test with an injection molding machine, insert a notch in accordance with ASTM D256 and perform impact test in an atmosphere of 23 ° C. Was carried out. (2) Bending elastic modulus After molding a 3.2 mmt test piece for bending test with an injection molding machine, it is 23 ° C. in accordance with ASTM D790.
A bending test was performed in an atmosphere. (3) Evaluation of tan δ (acoustic property) by dynamic viscoelasticity measurement The tan δ was evaluated by the following method. First, after crushing the speaker frame and speaker cone obtained above,
After vacuum drying at 140 ° C. for 5 hours, a press sheet having a thickness of 1 mm was prepared at 290 ° C. Cut into a size of 5 mm x 50 mm, and use FT Rheospectler DVE-4 manufactured by Rheology Co., Ltd. at 23 ° C, 100 Hz, 9
Tan delta of 99 Hz was measured. (4) Evaluation of sound quality using speaker frame and speaker cone The sound quality using the molded speaker frame was evaluated. (5) Evaluation of Dimensional Change due to Moisture Absorption of Speaker Frame The dimensional change rate was measured by leaving it at 23 ° C. and 50% RH for 1000 hours. (6) Evaluation of Adhesiveness of Speaker Cone Molded Body and Deformability by Heat During Curing A cloth impregnated with a phenol resin was coated with Sumitomo Chemical Emulsion CXG507S, and heated at 180 ° C. for 1 minute to cure. At this time, the adhesive strength and the deformation due to heat were observed.

The results show the following. All the examples satisfying the conditions of the present invention show satisfactory results in all evaluation items. On the other hand, it can be seen that the molded product made of another resin composition is inferior in any of acoustic characteristics, adhesiveness and dimensional stability and does not have optimum performance as an acoustic component.

[0058]

[Table 1] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− ABCDE Combination * 1 (A) Type PPE-A PPE-A PPE-A PPE-A PPE-B Amount 10 10 17 20 20 (B) Type PA PA PA PA PA Amount 40 40 66 50 53 (C) Type TR2000 TR2000 TR2000 VS-1 Amount 10 10 17 7 (D ) Type MAH MAH MAH MAH MAH Amount 0.3 0.3 0.3 0.2 0.2 (E) Type 300W 200D-GF 300W Amount 40 40-30 20 Znst----0.2 −−−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−

[0059]

[Table 2] −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− FGHIJ formulation * 1 (A) Type PP PPE- A PPE-A PPE-B Amount 60 10 30 20 (B) Type PA PA PS PA Amount 40 60 30 53 (C) Type TR2000 VS-1 Amount 10 7 (D) Type MAH MAH Amount 0.3 0.2 (E) Type 300W TALC 200D 220D 300W Amount 40 40 40 40 20 Znst----0.2 ----------------------------------------------------- −

[0060]

[Table 3] Evaluation of speaker frame ---------------------------------------- Example 1 Example 2 Comparison Example 1 Comparative Example 2 Comparative Example 3 Composition of molded body ABCDI Mechanical strength Impact resistance 3.5 3.0 21 10 5 Flexural modulus 100000 96000 19500 78000 95000 Acoustic characteristic tan δ (× 10 ^-2 ) 100Hz 1.9 1.8 2.2 1.4 1.1 999Hz 6.6 6.0 3.8 5.5 3.2 Sound quality evaluation ◎ ○ × × × Productability evaluation Dimensional change rate (1/1000) 1 1 3 1 0 Adhesiveness of adhesive ◎ ◎ ◎ ◎ ◎ −−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−

[0061]

[Table 4] Evaluation of speaker frame ----------------------------------- Comparative Example 1 Comparative Example 2 Comparative Example Example 3 Comparative Example 4 Comparative Example 5 Molded body composition CDIGH Mechanical strength Impact resistance 21 10 5 2.8 3.0 Flexural modulus 19500 78000 95000 60000 95000 Acoustic characteristic tan δ (× 10 ^-2 ) 100Hz 2.2 1.4 1.1 1.4 1.4 999Hz 3.8 5.5 3.2 5.5 5.7 Sound quality evaluation × × × × △ Productability evaluation Dimensional change rate (1/1000) 3 1 0 3 2 Adhesiveness of adhesive ◎ ◎ ◎ ◎ △ −−−−−−−−−−−−−−−− −−−−−−−−−−−−−−−−−−−−

[0062]

[Table 5]

* 1 Blending values are parts by weight blended. The meanings of the symbols are as follows. (A) PPE-A: A chloroform solution obtained by homopolymerizing 2,6-dimethylphenol (concentration: 0.
Chloroform solution (concentration: 0. 5 g / dl) obtained by homopolymerizing polyphenylene ether PPE-B: 2,6-dimethylphenol having a logarithmic viscosity of 0.46 at 30 ° C.
Polyphenylene ether (B) PA: Nylon 6 having a number average molecular weight of 12000 (C) VS-1: Kuraray Co., Ltd. styrene-isoprene copolymer, trade name HYBRAR (5 g / dl), polyphenylene ether (B) PA having a number average molecular weight of 12000 (Registered trademark), amount of bound styrene 20 wt%, isoprene 1, 2 or 3,
4 bond content 70% Glass transition temperature 8 ° C TR2000: Styrene-butadiene-styrene block copolymer (alkenyl aromatic block copolymer) manufactured by Japan Synthetic Rubber Co., Ltd., trade name TR2000, styrene /
Butadiene weight ratio = 40/60 PS: Sumibrite M58 manufactured by Sumitomo Chemical Co., Ltd.
4 (D) Compatibilizer MAH: Maleic anhydride CA: Citric acid (E) Filler mica 200D: Kuraray Co., Ltd. weight average particle size 90 μm Weight average aspect ratio 50 Mica 300 W: Kuraray Co., Ltd. weight average particle size 30 μm Weight average aspect ratio 40 TALC: Hayashi Kasei Micron White 500
0S GF: Chopped Strand made by Nippon Sheet Glass Co., Ltd.
RES03TP64 (Others) Znst: Zinc stearate WH255: Light Amide WH-255 manufactured by Kyoeisha Yushi-Kagaku Kogyo Co., Ltd.

[0064]

As described above, according to the present invention, by using the resin molded product containing polyamide, polyphenylene ether and mica as the main components in the parts used for the acoustic use, the acoustic properties are excellent, the molding process characteristics, It was possible to provide a resin molded product for an audio device, which satisfies the adhesiveness with an adhesive in the processing step and the heat resistance during processing.

Claims (8)

[Claims] 1. A resin molded product for audio equipment, comprising the following components (A) to (C). (A): Polyphenylene ether (B): Polyamide (C): Mica 2. The (A) component / (B) component content weight ratio is 1/99 to 80/20, and the (C) component content is the total amount of the (A) component and the (B) component. The resin molding according to claim 1, which is 1 to 150 parts by weight per 100 parts by weight. 3. The value of tan δ at 100 Hz is 1.
5 × 10 ^-2 or more and tan at 999 Hz
The resin molded product according to claim 1, wherein the value of δ is 4.0 × 10 ^-2 or more. 4. The elastic modulus at room temperature is 35000 kg /
The resin molded product according to claim 3, having a size of not less than cm ² . 5. The resin molding according to claim 1, which is a frame of a speaker. 6. The resin molded body according to claim 1, which is a diaphragm of a speaker. 7. The resin molding according to claim 1, which is a component of a speaker section of a computer. 8. The resin molded product according to claim 1, which is obtained by injection molding.