JP2003118379A - Tail gate for automobile - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin rail gate having high strength as a structure and allowing economical production. SOLUTION: In this tail gate for the automobile, an outer panel is formed of a polyphenylene ether/polyamide alloy, while an inner panel is formed of a long fiber reinforced polyamide/polyolefine alloy. Desirably, the polyphenylene ether/polyamide alloy contains 15-60 wt.% of polyphenylene ether (a), 85-40 wt.% of polyamide b, an enough amount of compatibilizer c sufficient for compatibilization, and 5-40 pts.wt. of an impact modifier based on 100 pts.wt. of the sum of a and b. More preferably, polyphenylene ether/polyamide alloy contains 0.5-15 pts.wt. of a conductive filler based on 100 pts.wt. of the sum of a and b.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin tailgate for an automobile, in which an outer panel is made of polyphenylene ether / polyamide alloy and an inner panel is made of long fiber reinforced polyamide / polyolefin alloy.

[0002]

2. Description of the Related Art Conventionally, in a tailgate of an automobile, an outer panel portion is made of a steel plate and an inner panel is made of resin. Recently, tailgates made of resin for both the outer panel and the inner panel have been proposed from the viewpoint of cost reduction due to weight reduction and modularization. The outer panel is polyphenylene ether / polyamide alloy,
Polycarbonate / polybutylene terephthalate alloy and the like have been proposed, but polyphenylene ether / polyamide alloy has high heat resistance, so that it can be applied in-line and has high impact strength. Since strength is required as a support for the inner panel, a molded product made of a glass fiber mat reinforced resin (GMT) has been proposed. Although GMT is advantageous in terms of strength, etc., it is usually stamped and molded, so that it is restricted in shape. It is disadvantageous to provide a rib structure or the like to provide a high-strength component as a structure. In addition, the base resins that have been proposed so far are not so high in heat resistance because they are polypropylene or polycarbonate / polybutylene terephthalate alloy. Therefore, for example, after assembling with an outer panel made of polyphenylene ether / polyamide alloy, , In-line painting could not be done.

[0003]

Under these circumstances, the problems to be solved by the present invention are suitable for weight reduction and modularization of automobiles, have sufficient strength as a structure, and
Even in the manufacturing process, it aims to provide a tailgate for automobiles that allows in-line painting of integrated parts.

[0004]

DISCLOSURE OF THE INVENTION As a result of intensive studies made by the present inventors in view of the above problems, an automobile in which the outer panel is made of polyphenylene ether / polyamide alloy and the inner panel is made of long fiber reinforced polyamide / polyolefin alloy It was thought that the tailgate for automobiles would solve the above-mentioned problems, and came to devise the present invention. That is, in the present invention, the outer panel is made of polyphenylene ether /
The present invention relates to a tailgate for an automobile, which is made of a polyamide alloy and the inner panel is made of a long fiber reinforced polyamide / polyolefin alloy.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The component (a) constituting the polyphenylene ether / polyamide alloy for outer panels of the present invention is polyphenylene ether. Polyphenylene ether is a polymer obtained by oxidatively polymerizing one or more phenol compounds represented by the following general formula (1) with oxygen or an oxygen-containing gas using an oxidative coupling catalyst. (In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and one of them is always a hydrogen atom. .)

Specific examples of R ₁ , R ₂ , R ₃ , R ₄ and R _{5 in} the above general formula include hydrogen, chlorine, bromine, fluorine,
Iodine, methyl, ethyl, n- or iso-propyl,
Examples thereof include pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl, hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl and the like. .

Specific examples of the above general formula include phenol, o-, m-, or p-cresol, 2,6-, 2,
5-, 2,4- or 3,5-dimethylphenol, 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.

The phenol compound of the above general formula is copolymerized with a phenol compound other than the above general formula, for example, a polyvalent hydroxyaromatic compound such as bisphenol-A, tetrabromobisphenol-A, resorcin, hydroquinone and novolac resin. You can also

Preferred polyphenylene ethers are 2,6-dimethylphenol and 2,6-dimethylphenol.
Homopolymer of diphenylphenol, and a large amount of 2,
6-Dimethylphenol and a small amount of 3-methyl-6-t
-Butylphenol or a copolymer of 2,3,6-trimethylphenol may be mentioned.

The oxidative coupling catalyst used in the oxidative polymerization of the phenol compound is not particularly limited, and any catalyst having a polymerization ability can be used.

The component (b) constituting the polyphenylene ether / polyamide alloy for outer panels of the present invention is
It is a polyamide. The polyamide used in the present invention is obtained by polymerizing a lactam or an aminocarboxylic acid and combining an equimolar amount of a saturated aliphatic dicarboxylic acid containing 4 to 12 carbon atoms with an aliphatic diamine containing 2 to 12 carbon atoms. It is one or more polyamide resins selected from homopolyamides and copolyamides that can be produced. If desired, an excess of diamine may be used during the polymerization to provide excess amine end groups over the carboxyl end groups in the polyamide. Conversely, excess dibasic acid can be used to adjust the polyamide carboxyl group end groups to be in excess of the amine end groups. Similarly, these polyamides can be successfully prepared from acid-forming and amine-forming derivatives of the acids and amines such as esters, acid chlorides, amine salts and the like. Typical aliphatic dicarboxylic acids used to make this polyamide include adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid and dodecanedioic acid, while typical aliphatic diamines are hexamethylene. Diamines and octamethylene diamines are included. In addition, these polyamides can be produced by the self-condensation of lactams.

Examples of aliphatic polyamides are polyhexamethylene adipamide (nylon 66), polyhexamethylene azelamide (nylon 69), polyhexamethylene sebacamide (nylon 610), and polyhexamethylene dodecanoamide. (Nylon 612), poly-bis- (p
-Aminocyclohexyl) methane dodecanoamide, polytetramethylene adipamide (nylon 46), nylon 6, nylon 10, nylon 11, nylon 12, nylon 6/66 copolymer, etc.
It may be used in any proportion of one or more species.

Of these polyamides, nylon 46, nylon 6, nylon 66, nylon 1 are preferable.
1, nylon 12, etc. are used. More preferably,
Nylon 6, nylon 66 or a mixture of nylon 6 and nylon 66 in any ratio can be used. The terminal functional groups of these polyamides are preferably those having a large number of amine terminals, those having a large number of carboxy terminals, those in which both are balanced, or a mixture thereof in any desired ratio.

It also includes aromatic polyamide. For example, copolyamides containing aromatic components such as polyhexamethylene isophthalamide (nylon 6I). A thermoplastic copolyamide containing such an aromatic component can be melt-polymerized with an aromatic amino acid and / or an aromatic dicarboxylic acid, for example, para-aminomethylbenzoic acid, para-aminoethylbenzoic acid, terephthalic acid, isophthalic acid, etc. as main constituent components. Means a polyamide.

The diamines which are the 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, etc. can be used. Isocyanates can be used instead of diamine. For example, 4,4 ′ diphenylmethane diisocyanate, tolylene diisocyanate and the like.

The copolymerization component used as necessary is not particularly limited, and may be lactam or ω-containing 4 to 12 carbon atoms.
A unit of amino acid, or a compound derived from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 2 to 12 carbon atoms, for example, ε-caprolactam,
ω-laurolactam, 11-aminoundecanoic acid, 12
-A lactam such as aminododecanoic acid, or an amino acid, a mol salt of the above-mentioned various diamines with adipic acid, azelaic acid, sebacic acid, or the like can be used.

Further, these polyamides may be crystalline or amorphous. Further, these polyamides may be mixed in any ratio.

Component (c) of the polyphenylene ether / polyamide alloy used in the outer panel of the present invention
Is a compatibilizer. Specific preferred examples of the compatibilizer include the following (C1) to (C3).
These may be used alone or in combination of two or more. (C1): Epoxy compound having neither ethylenic unsaturated bond nor acetylenic unsaturated bond (C2): At least one unsaturated group, that is, carbon-carbon double bond or carbon-carbon triple bond in the same molecule. A compound having both a bond and at least one polar group (C
3): In the same molecule, (OR) (wherein R is hydrogen or alkyl, aryl, acyl or carbonyldioxy group) and carboxylic acid, acid halide, acid anhydride, acid halide anhydride, acid ester, A compound having at least two identical or different functional groups selected from acid amide, imide, imide, amino and salts thereof.

The compatibilizer of the (C1) group used in the present invention is 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 epicudolhydrin.

The compatibilizer of the (C2) 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, various groups derived from carboxylic acid, that is, various salts or esters in which a hydrogen atom or a hydroxyl group of a carboxyl group is substituted, an acid amide, an acid anhydride, an imide, an acid azide, an acid halide, Alternatively, examples include functional groups such as oxazoline and nitrile, epoxy groups, amino groups, hydroxyl groups, or isocyanic acid ester groups.
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, an unsaturated alcohol, an unsaturated amine, or an unsaturated isocyanic acid ester is used.

Specifically, maleic acid, maleic anhydride, fumaric acid, maleimide, maleic hydrazide, and a reaction product of maleic anhydride and a diamine are represented by the following chemical formulas (2) and (3). (Wherein R represents an aliphatic or aromatic group), methyl nadic acid anhydride, dichloromaleic anhydride, maleic acid amide, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride Natural oils such as aconitic acid, aconitic acid anhydride, soybean oil, tung oil, castor oil, linseed oil, hemp oil, cottonseed oil, sesame oil, rapeseed oil, peanut oil, camellia oil, olive oil, palm oil, sardine oil, epoxidized natural Oils and fats, 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-ethyl crotonic 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, eleostearic acid, oleic acid, eicosapentaenoic acid, erucic acid,
Unsaturated carboxylic acids such as docosadienoic acid, docosatrienoic acid, docosatetraenoic acid, docosapentaenoic acid, tetracosenoic acid, hexacosenoic acid, hexacodienoic acid, octacosenoic acid, traacontenoic acid, or esters of these unsaturated carboxylic acids, acid amides, Anhydrous, 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 of the general formula C _n H _{2n-5
OH, C n H 2n-7} OH, C n H 2n-9 OH ( where, n is a positive integer) the alcohol represented by the 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
An unsaturated amine in which the H group is replaced with a —NH ₂ group, glycidyl (meth) acrylate, allyl glycidyl ether, etc. may be mentioned.

Further, 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)
Maleic anhydride and phenols are added to those (10,000 or more), those into which an amino group, a carboxylic acid group, a hydroxyl group, an epoxy group and the like are introduced, allyl isocyanate and the like.

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, citraconic acid, citraconic anhydride, aconitic acid are preferred.
Aconitic anhydride and glycidyl (meth) acrylate are used, and more preferably maleic anhydride and fumaric acid are used.

The compatibilizer of the (C3) group used in the present invention is an aliphatic polycarboxylic acid, an acid ester or an acid amide, and has the general formula (R ₇ O) mR ₆ (COO
_{R 8) n (CONR 9 R} 10) l ( wherein, R ₆ is a linear or branched saturated ants files ticks hydrocarbons 2-20
R7 is hydrogen, an alkyl group, an aryl group, an acyl group,
Or particularly preferably a carbonyl dioxy group is hydrogen, R8 is hydrogen, an alkyl group, or a C 1-20 aryl group, preferably 1 to 10, R ₉ and R ₁₀ are hydrogen, an alkyl group, or Aryl group having 1 to 10 carbon atoms,
Preferably 1-6, more preferably 1-4, m =
1 and n + 1 is an integer of 2 or more, preferably 2 or 3
And n is an integer of 0 or more, 1 is an integer of 0 or more, (R ₇ O) is located at the α-position or β-position of the carbonyl group, and at least two carbonyl groups have 2 ~ 6 carbons are present. ) Saturated aliphatic polycarboxylic acid and its derivative compounds represented by (Specifically, ester compounds, amide compounds, anhydrides, hydrates and salts of saturated aliphatic polycarboxylic acids are shown.
Examples of the saturated aliphatic polycarboxylic acid include citric acid, malic acid, agaric acid and the like. Details of these compounds are disclosed in the published patent publication No. 502195, 1986. )

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. Further, when the compatibility improver is blended, a radical initiator may be used together.

Examples of (c) include maleic anhydride, fumaric acid, maleic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, aconitic acid, from the viewpoint of reaction efficiency with polyphenylene ether and polyamide and from an economical point of view. At least one selected from aconitic anhydride, citric acid and malic acid is preferable.

A conductive filler can be added to the polyphenylene ether / polyamide alloy used in the outer panel of the present invention. If an appropriate amount is added to exhibit conductivity, in-line coating can be performed electrostatically without a conductive primer, which is very economically advantageous. As conductive filler, carbon black, carbon fiber, carbon anotube, metal flake, metal fiber, metal coated inorganic filler (talc, kaolin, clay, mica, wollastonite, whiskers, glass flakes, glass fiber, etc.) are listed. However, it is not particularly limited. Among these, carbon black, carbon nanotubes and carbon fibers are preferable.

Examples of the conductive carbon black include acetylene black and furnest black.
Since it is desirable that this carbon black can impart necessary conductivity to the composition with a small amount of addition, acetylene black and oil furnace black, particularly oil furnace black having few impurities and excellent conductivity are preferable. However, among them, especially XCF (Extra Con
ductive Black), SCF (Super Conductive Furnace Blac
k), CF (Conductive Furnace Black) and SAF (Super Abr
asion Furnace Black) can be preferably used. Among them, the BET type specific surface area due to N2 adsorption is 750 m ² / g or more, especially 1000 m ² / g
The above is preferable. For XCF, Ketjen Black EC from Ketjen Black International
(Trademark name), Cabot's "Vulcan XC-72" (Trademark name), and so on.
There are "SC" (trade name), "Vulcan P" (trade name) and Degussa's "Colax L" (trade name), etc., and CF is "Vulcan C" (trade name) of Cabot Co., " Conductive SC "(trademark), SAF is Asahi Carbon's" Asahi # 9 "(trademark),
Examples include Mitsubishi Kasei's "Dia Black A" (trademark) and Cabot's "Vulcan 9" (trademark). You may use these together. The carbon black used in the present invention is
The DBP oil absorption is 70 to 600 ml / 100 g, preferably 300 to 550 ml / 100 g. The amount of carbon black added varies depending on the type of carbon black to be added, but is 0.8 to 10% by weight, preferably 1 to
It is 5% by weight, more preferably 1.5 to 3% by weight. If it is less than 0.8% by weight, conductivity is not sufficiently imparted, and if it exceeds 10% by weight, fluidity and impact strength are remarkably lowered. These carbon blacks are available in one or two
You may use it in mixture of 2 or more types. Fine fibrous carbon such as graphite fibrils can be found in "Plastics worl"
d "(November 1993), pp. 10 et seq. This is a very small fiber composed of crystalline graphite.
Currently commercially available materials have an average diameter of approximately 0.01 μm and an L / D ratio of approximately 500: 1 to 1000:
It is 1. Graphite fibrils are also in principle suitable for the purposes of the invention. These include, for example, International Patent Application Nos. 86/03455, 87/07559,
No. 89/07163, 90/07023 and 90/14221, and JP-A-3-287821.

The polyphenylene ether / polyamide alloy used in the outer panel of the present invention may be further added with an impact resistance improving material. Impact modifiers are rubber-like materials such as natural and synthetic polymers that are elastic at room temperature. Particularly preferred rubbers are ethylene propylene rubber, ethylene-propylene-non-conjugated diene rubber, ethylene-butene-1 rubber, ethylene-butene-1-non-conjugated diene rubber, polybutadiene, styrene-butadiene block copolymer rubber, styrene-butadiene-styrene. Block copolymer rubber, styrene-butadiene copolymer rubber, partially hydrogenated styrene-butadiene-styrene block copolymer rubber, styrene-isoprene block copolymer rubber, partially hydrogenated styrene-isoprene block copolymer rubber, polyurethane rubber, styrene graft- Ethylene-propylene-non-conjugated diene rubber, styrene-graft-ethylene-
Propylene rubber, styrene / acrylonitrile-graft-ethylene-propylene-non-conjugated diene rubber, styrene / acrylonitrile-graft-ethylene-propylene rubber and the like, or a mixture thereof is used. Alternatively, a modified rubber modified with a functional monomer containing another acid or epoxy may be used. The compounding amount of the rubber-like substance is preferably 1 to 50 parts by weight with respect to 100 parts by weight of the total of the components (A) and (B). When the compounding amount of the rubber-like substance exceeds 50 parts by weight, the rigidity of the resin composition is significantly lowered, which is not preferable. As a particularly preferable impact modifier, a saturated rubber elastomer or a partially unsaturated rubber elastomer obtained by using a non-conjugated diene is used. Here, these elastomers have a molecular weight of styrene or styrene and another copolymerization component of 500.
It is preferred to have zero or more segments. Specifically, one styrene-butadiene block copolymer having one or more polystyrene and polybutadiene segments, one styrene-isoprene copolymer having one or more polystyrene and polyisoprene segments, and one polystyrene and isoprene-butadiene copolymer, respectively. A block copolymer obtained by selectively hydrogenating the unsaturated part of the isoprene part or the butadiene part of the block copolymer having one or more, ethylene, propylene, butene,
It is obtained by graft-polymerizing styrene or styrene and another copolymer component to a polyolefin elastomer obtained by copolymerizing a non-conjugated diene component.

The length of the molecular chain of the polystyrene segment or the segment consisting of styrene and another copolymerization component in these elastomers is preferably 5,000 or more in terms of weight average molecular weight. If the polystyrene segment or the segment composed of styrene and another copolymerization component is too short, the elastomer is less likely to stay in the PPE, which may cause poor appearance and the like, which is not preferable. Among them, the preferred impact modifier is a styrene block copolymer in which unsaturated portions of isoprene and butadiene are selectively hydrogenated.

An alkenyl aromatic resin can be blended with the polyphenylene ether / polyamide alloy for the purpose of improving fluidity and rigidity. As the alkenyl aromatic resin, styrene or its derivative such as p
-Methylstyrene, α-methylstyrene, α-methyl-
Examples thereof include homopolymers and copolymers of p-methylstyrene, chlorostyrene, bromostyrene and the like. Further, rubber-modified high impact polystyrene (HIPS) comprising 70 to 99% by weight of the above aromatic vinyl compound and 1 to 30% by weight of diene rubber can be used.

As the polyphenylene ether / polyamide alloy, other components can be used, if necessary, appropriate fillers and stabilizers. The fillers include calcium carbonate, magnesium carbonate, aluminum hydroxide, and hydroxide. Magnesium, zinc oxide, titanium oxide, magnesium oxide, magnesium sulfate, aluminum silicate, magnesium silicate, calcium silicate, silicic acid,
Hydrous calcium silicate, hydrous aluminum silicate, mica, magnesium oxysulfate, glass balun,
There are glass fibers, glass beads, stainless fibers, aramid fibers and the like, but it is possible to mix one or more of these fillers. Further, the filler to be blended is not limited to these. Antioxidants (phosphorus-based antioxidants, phenol-based antioxidants, sulfur-based antioxidants, copper-based antioxidants, hindered amine-based antioxidants, which are usually used as stabilizers in polyphenylene ether, polyamide, and impact modifiers. (Light stabilizer), UV absorber or the like can be used.

The polyphenylene ether / polyamide alloy used in the outer panel of the present invention is preferably (a) polyphenylene ether 15 to 60% by weight and (b) polyamide 85 to 40% by weight. When the amount of polyphenylene ether is 15% by weight or less, heat resistance may be insufficient, and when the amount of polyamide is 40% by weight or less, fluidity may be insufficient. The compatibilizer (c) used in the polyphenylene ether / polyamide alloy is an amount sufficient for compatibilization, and preferably 100 parts by weight of the total amount of (a) and (b) is 100 parts by weight.
It is 0.01 to 2 parts by weight. Further, those containing 5 to 40 parts by weight of the impact resistance improver relative to 100 parts by weight of the total amount of (a) and (b) show preferable impact strength and are preferable.

The long fiber reinforced polyamide / polyolefin alloy used in the inner panel of the present invention is (d) 80 to 50% by weight of polyamide and (e) polyolefin.
Polyamide obtained by melt-blending 20 to 50% by weight /
At least 1 mm in weight average for polyolefin alloy
The glass fiber having the above length is included.

The polyamide (d) forming the long fiber reinforced polyamide / polyolefin alloy used in the inner panel of the present invention is a saturated aliphatic compound containing lactam or aminocarboxylic acid polymerized and an equimolar amount of 4 to 12 carbon atoms. It is one or more polyamide resins selected from homopolyamides and copolyamides, which can be produced by bonding a dicarboxylic acid and an aliphatic diamine containing 2 to 12 carbon atoms. If desired, an excess of diamine may be used during the polymerization to provide excess amine end groups over the carboxyl end groups in the polyamide. vice versa,
It is also possible to use an excess of dibasic acid to adjust the carboxyl end groups of the polyamide to be in excess of the amine end groups. Similarly, these polyamides may be prepared by adding acid- and amine-forming derivatives of the acids and amines, such as esters,
It can be satisfactorily produced from acid chlorides, amine salts and the like. Typical aliphatic dicarboxylic acids used to make this polyamide include adipic acid, pimelic acid, azelaic acid, suberic acid, sebacic acid and dodecanedioic acid, while typical aliphatic diamines are hexamethylene. Diamines and octamethylene diamines are included. In addition, these polyamides can be produced by the self-condensation of lactams.

Examples of aliphatic polyamides are polyhexamethylene adipamide (nylon 66), polyhexamethylene azamide (nylon 69), polyhexamethylene sebacamide (nylon 610), and polyhexamethylene dodecanoamide. (Nylon 612), poly-bis- (p
-Aminocyclohexyl) methane dodecanoamide, polytetramethylene adipamide (nylon 46), nylon 6, nylon 10, nylon 11, nylon 12, nylon 6/66 copolymer, etc.
It may be used in any proportion of one or more species.

Of these polyamides, nylon 46, nylon 6, nylon 66, nylon 1 are preferable.
1, nylon 12, etc. are used. More preferably,
Nylon 6, nylon 66 or a mixture of nylon 6 and nylon 66 in any ratio can be used. The terminal functional groups of these polyamides are preferably those having a large number of amine terminals, those having a large number of carboxy terminals, those in which both are balanced, or a mixture thereof in any desired ratio.

It also includes aromatic polyamide. For example, copolyamides containing aromatic components such as polyhexamethylene isophthalamide (nylon 6I). A thermoplastic copolyamide containing such an aromatic component can be melt-polymerized with an aromatic amino acid and / or an aromatic dicarboxylic acid, for example, para-aminomethylbenzoic acid, para-aminoethylbenzoic acid, terephthalic acid, isophthalic acid, etc. as main constituent components. Means a polyamide.

The diamines which are the 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, etc. can be used. Isocyanates can be used instead of diamine. For example, 4,4 ′ diphenylmethane diisocyanate, tolylene diisocyanate and the like.

The copolymerization component used as necessary is not particularly limited, and may be lactam or ω-containing 4 to 12 carbon atoms.
A unit of amino acid, or a compound derived from an aliphatic dicarboxylic acid having 4 to 12 carbon atoms and an aliphatic diamine having 2 to 12 carbon atoms, for example, ε-caprolactam,
ω-laurolactam, 11-aminoundecanoic acid, 12
-A lactam such as aminododecanoic acid, or an amino acid, a mol salt of the above-mentioned various diamines with adipic acid, azelaic acid, sebacic acid, or the like can be used.

Further, these polyamides may be crystalline or amorphous. Further, these polyamides may be mixed in any ratio. Preferred as the polyamide (d) are nylon 6 and nylon 66.

As the polyolefin (e) forming the long fiber reinforced polyamide / polyolefin alloy used in the inner panel of the present invention, polypropylene (g),
It is at least one resin selected from polyethylene resins such as ethylene homopolymer or ethylene-α-olefin random copolymer, and further modified polyolefin (f). It may also be a mixture of rubber and the like.

The modified polyolefin resin (f) in the present invention is selected from olefin homopolymers or two or more olefin copolymers graft-polymerized with unsaturated carboxylic acid and / or its derivatives, and olefins. In addition, one or more of them and an unsaturated carboxylic acid and / or a derivative thereof are copolymerized.

Examples of the unsaturated carboxylic acid used for modification include maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and the like. As the unsaturated carboxylic acid derivative, these acid anhydrides,
There are esters, amides, imides, metal salts and the like, and specific examples thereof include maleic anhydride, itaconic anhydride, methyl acrylate, ethyl acrylate, butyl acrylate, glycidyl acrylate, methyl methacrylate, ethyl methacrylate, Butyl methacrylate, glycidyl methacrylate, maleic acid monoethyl ester, maleic acid diethyl ester, fumaric acid monomethyl ester, fumaric acid dimethyl ester, acrylamide, methacrylamide,
Examples thereof include maleic acid monoamide, maleic acid diamide, fumaric acid monoamide, maleimide, N-butyl maleimide, sodium methacrylate and the like. Moreover, you may use what produces | generates unsaturated carboxylic acid by dehydration in the process of grafting to polypropylene like citric acid and malic acid. Among these unsaturated carboxylic acids and derivatives thereof, glycidyl esters of acrylic acid and methacrylic acid and maleic anhydride are preferable, and preferable modified polyolefin resin (E) modified by this is ethylene and / or propylene. Modified by graft-polymerizing maleic anhydride to a polyolefin resin having a main polymer structural unit of, by copolymerizing an olefin mainly composed of ethylene and / or propylene with a methacrylic acid glycidyl ester or maleic anhydride Examples include denatured ones. The modified polyolefin (f) used in the present invention is
It is preferable that 0.1 to 10% by weight of the polymer constitutional unit is composed of the unsaturated carboxylic acid or the derivative thereof as described above, especially when these components are introduced into the polymer chain by random copolymerization or block copolymerization. Is 1
10% by weight, 0.1 to 10 in the case of graft polymerization
Weight percent is preferred. If the content of the unsaturated carboxylic acid or its derivative is too small, the mechanical strength such as impact strength and fatigue properties may decrease, and if it is too large, the mechanical strength such as rigidity may decrease.

Examples of the polypropylene (g) in the present invention include propylene homopolymer, ethylene-propylene random copolymer, propylene-α-olefin random copolymer and propylene block copolymer.
Further, these polymers may be blended. Preferred as the polypropylene (g) is a propylene block copolymer. This is because the impact strength is improved. Specific examples of the aforementioned α-olefin include:
1-butene, 2-methyl-1-propene, 2-methyl-
1-butene, 3-methyl-1-butene, 1-hexene,
2-ethyl-1-butene, 2,3-dimethyl-1-butene, 2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-
1-butene, 1-heptene, methyl-1-hexene, dimethyl-1-pentene, ethyl-1-pentene, trimethyl-1-butene, methylethyl-1-butene, 1-octene, methyl-1-pentene, ethyl -1-hexene, dimethyl-1-hexene, propyl-1-heptene, methylethyl-1-heptene, trimethyl-1-pentene, propyl-1-pentene, diethyl-1-butene, 1-nonene, 1-decene, Examples thereof include 1-undecene and 1-dodecene. Among these, 1-butene, 1-pentene, 1-hexene, 1-octene α-
Olefin can be preferably used.

The polyolefin (e) is preferably one containing at least one type of modified polyolefin (f), and more preferably one containing modified polypropylene.

The glass fibers contained in the long fiber reinforced polyamide / polyolefin alloy used in the inner panel of the present invention have a weight average fiber length of at least 1 mm at the stage of molding the inner panel.
It is preferably 2 mm or more. If the fiber length is too short, the mechanical strength of the inner panel of the present invention is insufficient, which is not preferable.

The long fiber reinforced polyamide / polyolefin alloy used for the inner panel of the present invention has at least the weight average fiber length of the glass fibers of 1 mm or more at the stage of molding the inner panel. Is obtained by the pultrusion molding method disclosed in, for example, JP-A-5-9380. The long fiber-reinforced polyamide / polyolefin alloy used for the inner panel is preferably one in which glass fibers have a length of substantially 2 mm or more and are arranged in a state of being substantially parallel to each other. The preferred method for producing long fiber reinforced polyamide / polyolefin alloys is the pull-through molding method. The pultrusion method is basically a method of impregnating a resin while pulling a continuous fiber bundle, and a method of impregnating the resin bundle through an impregnating liquid containing an emulsion, suspension or solution of the resin. A method of spraying the powder on the fiber bundle or passing the fiber bundle through the tank containing the powder to adhere the resin to the fiber and then melting and impregnating the resin, from the extruder etc. while passing the fiber bundle through the crosshead Although a method of supplying a resin to the crosshead and impregnating it is known, any of the known methods can be used in the present invention. Particularly preferred is the method using a crosshead. The impregnation operation of the resin in these pultrusion molding methods is generally carried out in one step, but it may be carried out in two or more steps.

There is no limitation on the shape of the long fiber reinforced polyamide / polyolefin alloy obtained as described above, and any shape such as a strand shape, a sheet shape, a flat plate shape or a pellet shape obtained by cutting the strand into an appropriate length is possible. is there. In particular, it is preferable to use a pellet-like composition having a length of 2 to 50 mm for application to injection molding where molding is easy. In particular, in order to obtain a molded product that is subjected to injection molding where the molding operation is easy and retains excellent strength without impairing the injection moldability, the long fiber reinforced polyamide / polyolefin alloy is formed into pellets with a length of 2 to 50 mm. Preferably, the composition is such that the fibers are arranged in substantially the same length as the pellets.

In the resin composition of the present invention, one or more kinds of other thermoplastic resins may be used in combination or a nucleating agent or a crystallization accelerator may be blended within a range that does not significantly impair the objects and effects thereof. Is possible. Further, in order to impart desired properties depending on the purpose, known substances generally added to thermoplastic resins, for example, antioxidants, heat stabilizers, neutralizers, stabilizers such as UV absorption, antifoam agents, A flame retardant, a flame retardant aid, a dispersant, an antistatic agent, a lubricant, an antiblocking agent such as silica, a colorant such as a dye or a pigment, a plasticizer and the like can be further added. Also glass flakes,
Plates of mica, glass powder, glass beads, talc, clay, alumina, carbon black, wolsenite, etc.
An appropriate amount of powdery or granular inorganic compound or whiskers may be used together.

The inner panel of the present invention is formed by injection molding, injection compression molding or injection press molding using the above-mentioned long fiber reinforced polyamide / polypropylene alloy. Therefore, the rib structure can be easily obtained as compared with the stamping molding of GMT. This makes it possible to improve the strength, which was a weak point of the resin tailgate. In addition, the long fiber reinforced polyamide / polypropylene alloy is far superior to the long fiber reinforced polypropylene in terms of strength, and is significantly improved from the long fiber reinforced polyamide in terms of moisture absorption dimensional change. Equivalent to long fiber reinforced polyamide. The outer panel is also molded by injection molding, injection compression molding or injection press molding using a polyphenylene ether / polyamide alloy. Regarding the adhesion of the inner panel and the outer panel, in addition to bonding with ordinary adhesive, both are alloys containing polyamide,
Adhesion can be achieved by vibration fusion bonding, insert molding during injection molding, or two-color molding, which is very advantageous when modularizing the tailgate.

[0053]

EXAMPLES The present invention will be described below with reference to examples, but these are merely examples and the present invention is not limited to these examples without departing from the present invention.

The method for producing the evaluation sample in the examples will be described below. Method for producing long fiber-reinforced polyamide / polyolefin alloy polyamide / polyolefin alloy for inner panel Polypropylene resin (PP-
1: MI 0.6, EP amount 16%, PP-2: MI
1.6, EP amount 22%, PP-1 15 parts by weight, PP
-2 15 parts by weight), maleic anhydride 0.2 parts by weight,
0.024 parts by weight of a peroxide compound (1,3 bis (t-butyl peroxydiisopropyl) benzene) was supplied from the first supply port of the twin-screw extruder, and a polyamide resin (number average molecular weight 17,000) was supplied from the second supply port. 70 parts by weight and 0.05 part by weight of an antioxidant (GSY-P101 (manufactured by Yoshitomi Fine Chemical Co.)) were supplied and melt-kneaded. The twin-screw extruder used was a cylinder-diameter = 65 mm,
L / D = 37. The cylinder temperature was set to 240 ° C. and the screw rotation speed was 300 rpm.

Method for Producing Long Fiber Reinforced Polyamide / Polyolefin Alloy Using the matrix resin obtained by the above-mentioned method, it was produced by the method described in JP-A-3-121146. The impregnation temperature was 340 ° C., the take-up speed was 6 m, and the glass fiber used had a fiber diameter of 16 μm. Pellets having a glass fiber content of 40% by weight and a pellet length of 9 mm were prepared.

Polyphenylene ether / polyamide alloy for outer panel Each Example and Comparative Example were mixed in a composition as shown in each table,
In a barrel consisting of 12 barrels, the barrel 1 was fed to the polyphenylene ether (2,6
A chloroform solution (concentration: 0.50 g / dl) obtained by homopolymerizing dimethylphenol, 3
22 parts by weight of logarithmic viscosity at 0 degrees centigrade, 0.23 parts by weight of maleic anhydride, impact resistant material (Kreighton G
1650 (made by Clayton Polymer) 16 parts by weight, 0.001 part by weight of peroxide (Perkadox 14 / 40C (made by Kayaku Akzo)) was charged, and a polyamide (A1030BRL (made by Unitika) was introduced into the barrel 6 from the second feed port. )) 30 parts by weight were charged, and polyamide (T-840 (manufactured by Toyobo)) was introduced into the barrel 9 through the third feed port.
22 parts by weight, talc (average particle size 2.64 μm) 1
0 parts by weight, heat stabilizer (ADEKA STAB PEP-36
(Manufactured by Asahi Denka Co., Ltd.) 0.15 parts by weight and zinc stearate 0.5 parts by weight are charged, and a cylinder temperature of 260 is obtained by a twin-screw kneader (TEM-50A manufactured by Toshiba Machine).
It was obtained by melt-kneading at a temperature of ℃ and a screw rotation speed of 300 rpm. An outer panel is formed by injection molding using the polyphenylene ether / polyamide alloy, and an inner panel having a rib structure is formed by injection molding using the long-fiber-reinforced polyamide / polyolefin alloy as a structure. It is possible to obtain a resin tailgate which is excellent in strength and economical in manufacturing.

[0057]

As described above, according to the present invention, it is possible to provide a resin tailgate which is excellent in strength as a structure and economical in manufacturing.

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Claims (6)

[Claims] 1. The outer panel is made of polyphenylene ether / polyamide alloy, and the inner panel is
A tailgate for automobiles, which is made of long fiber reinforced polyamide / polyolefin alloy. 2. The polyphenylene ether / polyamide alloy comprises (a) 15 to 60% by weight of polyphenylene ether and (b) 85 to 40% by weight of polyamide, and a sufficient amount of the compatibilizing agent (c) (a). ) And (b)
The tailgate for an automobile according to claim 1, comprising 5 to 40 parts by weight of an impact resistance improving material with respect to 100 parts by weight. 3. The polyphenylene ether / polyamide alloy contains 0.5 to 15 parts by weight of a conductive filler based on 100 parts by weight of the total amount of (a) and (b). Car tailgate. 4. The automobile tailgate according to claim 1, wherein the long fiber reinforced polyamide / polyolefin alloy is a long fiber reinforced polyamide / polypropylene alloy. 5. Long fiber reinforced polyamide / polypropylene alloy, polyamide / polypropylene alloy
(D) Polyamide 80 to 50% by weight, (e) Polypropylene 20 to 50% by weight, and (d) Polyamide and (e) Polypropylene having a length of 1 mm or more in weight average with respect to 100 parts by weight in total. 5. The tailgate for an automobile according to claim 4, wherein the tailgate is made of a resin containing at least 30% by weight of glass fiber. 6. The component (c) is selected from maleic anhydride, fumaric acid, maleic acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, aconitic acid, aconitic anhydride, citric acid and malic acid. The automobile tailgate according to claim 2 or 3, which is at least one kind.