JP2002173545A - Polymer alloy molding and method for injection molding thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To improve the strengths of product and dimensional accuracy of a molding demanded in a polymer alloy by improving a molding method without impairing the degree of freedom of a resin composition of a polymer alloy molding constituted of at least a polyamide-based resin and a polyphenylene ether-based resin and a product design, to be specific, in order to obtain especially a thin molding, to provide a molding method with which a polymer alloy is readily packed into a cavity of mold, occurrence of bad conditions such as warpage and sink mark mainly occurring after molding, is controlled and which can be applied to a thicker or thinner molding. SOLUTION: This polymer alloy molding is characterized in that the resin components of the polymer alloy are constituted of at least a polyamide-based resin component and a polyphenylene ether-based resin component, >=0.2 wt.% of carbon dioxide is dissolved or absorbed in the polymer alloy and the polymer alloy is packed into the cavity of mold.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer alloy molded article and an injection molding method thereof.

[0002]

2. Description of the Related Art Metal components such as steel and aluminum have been used as materials for various components constituting an exterior of an automobile such as a front fender, a rear fender, a door panel, a hood and a hood. On the other hand, among the components that make up the exterior, such as outside door handles, bumpers, aero parts, and motorcycle cowls, relatively small parts are polyacetal, polycarbonate, and ABS.
Resins such as resin, polyamide, and polypropylene have been widely used as materials.

[0003] In recent years, front fenders, rear fenders, which have conventionally been mainly made of metal, have been used for the purpose of expanding the degree of freedom of design, reducing the weight of parts, simplifying the manufacturing process, and reducing the energy consumption required for manufacturing. Consideration is being given to using resin for door panels, hoods and hoods. In addition, conventionally, an outside door handle manufactured using polyacetal, polycarbonate, polyamide, or the like,
Demands for bumpers and aero parts have also been increasing in terms of better paintability, heat resistance to withstand an ambient temperature of about 150 ° C., high rigidity, and impact characteristics. Therefore, in order to satisfy these requirements, a polymer alloy made of a polyamide-based resin and a polyphenylene ether-based resin (hereinafter abbreviated as “PA / PPE-based polymer alloy”) has been devised.

On the other hand, in order to further reduce the weight, exterior parts such as front fenders, rear fenders, door panels, hoods, hoods, bumpers, aero parts, motorcycle cowls, and the like are becoming thinner every year. There is a need for a means of obtaining a thin molded article. When the thickness of the molded product becomes thin, it becomes difficult to fill the resin to the flow end portion.

As measures to improve the molding conditions, the resin temperature is increased to lower the viscosity of the resin to secure the flow length, the mold temperature is increased to reduce the solidification speed of the resin, and the injection speed is increased. It is common to fill the resin to the flow end before the resin solidifies. However, the setting range of the resin temperature when molding a polymer alloy containing a crystalline resin component such as polyamide is narrow, and is usually in a range of 5 to 30 ° C. higher than the melting point of the crystalline resin component, and is often 10 to 10 ° C. higher than the melting point. It is carried out at a temperature higher by 20 ° C.

This is because the viscosity of the resin is so high that it is difficult to fill the resin up to a temperature range of about 5 ° C. higher than the melting point of the crystalline resin component. It can be said that the temperature range is easy to perform. When the unmelted portion is mixed in the molded product, there is a concern that a problem such as a decrease in strength may occur. On the other hand, the resin temperature during molding is 30
If the temperature is higher than ℃, the decomposition of the resin is promoted, and the appearance of the molded product, called silver (or “silver streak”), may deteriorate, and the molded product itself may be discolored. Mold stains are more likely to occur. This is not preferable because it may cause deterioration of the resin, may deteriorate the working environment, and may cause the mold to be disassembled and cleaned.

On the other hand, when the solidification rate of the resin is reduced by increasing the temperature of the mold, the cooling time of the resin filled in the mold becomes longer. become longer. Also, the energy consumption for keeping the mold at a high temperature cannot be ignored. JP-A-62-58287, "Injection molding method of rubber-reinforced polystyrene resin", and JP-A-62-58287 disclose an injection molding method for extremely increasing the surface temperature of the mold only when the resin is filled into the mold cavity.
No. 58288, "ABS resin injection molding method". Injection molding to obtain a crystalline resin molded product that has a smooth surface and good mold transferability by inserting an inductor between the molds and heating the mold surface with both molds open. Is the law.

In these injection molding methods, during a molding cycle, a step of inserting an inductor or a high-frequency induction heating coil between molds, heating the mold surface, and pulling out the inductor or the high-frequency induction heating coil from between the molds. is necessary. In addition, since the molding cycle is extended due to the step of heating the surface of the mold, there is a problem in productivity, and the amount of electricity consumed in high-frequency induction heating is excessive, which is not preferable from the viewpoint of energy saving. In addition, the injection molding method involving high-frequency induction heating is not preferable because it is limited to a molded product having a relatively flat shape because it limits the degree of freedom in product design of the molded product.

On the other hand, under molding conditions for increasing the injection speed,
A high injection pressure is required during resin injection, which results in a large amount of distortion remaining in the molded product. The molding distortion remaining in the molded article is also called “residual distortion”. This residual strain is gradually relaxed after molding, but this is often due to deformation and shrinkage of the molded product. This is also seen when the mold structure, molding conditions, etc., are not appropriate. In addition, the rise in resin temperature due to shear heat cannot be ignored, and the decomposition gas of the resin stays at the end of the flow, thereby impeding the flow of the resin and causing contamination of the mold. It can be said that there is a limit.

On the other hand, as a mold design for easily obtaining a thin molded product, it is conceivable to increase the number of gates. However, an increase in the number of gates means that the number of sprues and runners that do not become a product increases, and that the weld line increases in the product part. Increasing the number of sprue and runner portions is not preferable because it increases the amount of unnecessary parts that do not become a product and is generated in each molding cycle. Further, an increase in the weld line is not preferable because it causes a reduction in product strength, particularly impact strength.

On the other hand, when commercializing a thin-walled molded product,
By reducing the molecular weight of the resin used and improving the fluidity, it has been found that a desired product shape is obtained and dimensional accuracy is ensured. However, a crystalline resin having a small molecular weight improves rigidity but decreases toughness and impact resistance, and also tends to have a shorter life with respect to fatigue due to repeated loading and the like. While sacrificing the properties of the resin,
There are many examples of commercialization.

[0012] The pressure applied to the resin filled in the mold cavity is not limited to a thin molded product, but the pressure distribution may be uneven near the gate and at the end of the flow. This means that it is difficult to transmit a sufficient pressure to the end portion of the flow, which causes poor appearance of the end portion of the flow, generation of voids, sink marks, expansion of molding shrinkage and unevenness. On the other hand, in a molded product having a certain thickness such as an outside door handle, sink is likely to occur on the surface of the molded product due to volume shrinkage after molding. For this reason, a design method such as reducing the average thickness of a product is often selected as a shape obtained by hollowing out the back side of the design surface (the opposite side of the design surface). Also, increase the number of gate points,
Product design for suppressing deformation of a molded product by making the wall thickness as uniform as possible is also generally performed.

However, the ribs and the like provided for compensating for the decrease in strength while reducing the thickness of the molded product cause linear sink marks on the design surface, complicating the mold structure. Depending on the shrinkage of the resin and the magnitude and direction of the load applied to the molded product, stress concentrates on the rib itself, which may cause destruction, and there are cases where it is difficult to obtain a product having a desired shape. On the other hand, new injection molding methods such as a high-speed injection molding method and a gas assist molding method have been proposed.

In the high-speed injection molding method, the crystalline resin is injected at a high speed to prevent the melt viscosity from rising due to cooling from the mold, reduce the melt viscosity with a high shear force, and reduce the pressure difference in the cavity. Has the effect of doing Further, the effect of reducing the injection time is obtained, and the productivity is also improved. However, it is necessary to pay attention to the deterioration of the resin due to the heat generated by shearing, the generation of burrs due to high-speed injection, and the occurrence of resin burn due to adiabatic compression in the gas reservoir at the end of the mold cavity.

In the gas assist molding method, generally, a hollow portion is formed in a molded article by injecting a compressed gas into a resin. The compressed gas has a pressure-holding effect from the inside of the molded article, and has the effect of suppressing the occurrence of sink marks on the molded article. The pressure-holding effect of the compressed gas is lower than the pressure-holding effect in the usual injection molding method, and the pressure-holding effect can be expected up to the end of the flow. For this reason, the residual distortion is small, the deformation of the molded product such as warpage can be reduced, and the dimensional accuracy can be expected to be improved. However, depending on the shape of the molded product, there are cases where the installation location of the gas injection port is limited, and the effect may not be sufficiently exhibited.

On the other hand, in J.I. Appl. Polym. Sc
i. , Vol. 30, 2633 (1985), it is known that when carbon dioxide is absorbed into a resin, it acts as a plasticizer for the resin and lowers the glass transition temperature. It has not been widely applied to processing. Japanese Unexamined Patent Publication No. Hei 5-318541 discloses a method in which a gas such as carbon dioxide or nitrogen is contained in a thermoplastic resin, and the resin is filled in the cavity while removing the gas in the cavity. To obtain a molded article without deterioration in strength and appearance. However, in this method, when carbon dioxide is used as the gas, the amount of the gas contained in the resin is small at a maximum of about 0.18% by weight, and it is difficult to obtain a sufficient fluidity improving effect. It can be said that it is difficult to obtain accuracy and dimensional stability.

In addition, WO 98/52734 discloses that
In injection molding of thermoplastic resin,
Shows a method of filling molten resin whose viscosity has been reduced by dissolving more than 1% by weight into a mold cavity that has been pressurized with a gas such as carbon dioxide at a pressure higher than the pressure at which foaming does not occur at the flow front of the molten resin. The mold surface reproducibility, glossiness, and weld lines are less noticeable.
It is described that it is effective for reproducibility of a sharp edge on a mold surface and reproducibility of irregularities on a fine mold surface.

However, the pressure (hereinafter referred to as "holding pressure") applied to the resin after filling the resin into the mold cavity as described in the examples of the publication is 89 to 9 of the filling pressure.
It is in the range of 3%. However, the holding pressure equivalent to 89 to 93% of the filling pressure may cause burrs, and it is difficult for foamed parts to be formed inside the molded product, and sinks, warpage, etc.
It is difficult to solve the problems mainly occurring after molding.

[0019]

DISCLOSURE OF THE INVENTION The present inventors have improved the molding method without impairing the resin composition and the degree of freedom of product design of a polymer alloy molded product composed of at least a polyamide resin and a polyphenylene ether resin. Accordingly, it is an object of the present invention to improve the product strength and dimensional accuracy of a molded product required for a polymer alloy. Specifically, the present invention, in particular, to obtain a thin molded product, it is easy to fill the mold cavity, warpage, suppress the occurrence of defects such as sinks mainly occurring after molding, more thickness, or, An object of the present invention is to provide a molding method that enables application to a thinner molded product.

[0020]

Means for Solving the Problems The present inventor has improved the molding method without impairing the resin composition and the degree of freedom in product design of a polymer alloy molded product composed of at least a polyamide resin and a polyphenylene ether resin. In order to improve the product strength and dimensional accuracy of molded products required for polymer alloys, it is easy to fill the mold cavity and suppress the occurrence of defects mainly after molding such as warpage and sink marks Therefore, an injection molding method which enables application to a molded product having a larger thickness or a smaller thickness was studied.

As a result, the injection molding method of a molded product obtained by dissolving or absorbing 0.2% by weight or more of carbon dioxide in a polymer alloy and then filling it into a mold cavity has a problem such as warpage or sink mark. The inventor has found that a problem mainly occurring after molding is solved, and has completed the present invention. That is, the present invention provides: The polymer alloy resin component is composed of at least a polyamide resin component and a polyphenylene ether resin component. After dissolving or absorbing 0.2% by weight or more of carbon dioxide in the polymer alloy, the polymer alloy is introduced into the mold cavity. A polymer alloy molded product obtained by filling,

2. 2. The polymer alloy molded article according to the above item 1, wherein the polyphenylene ether-based resin component is a modified polyphenylene ether-based resin modified with a styrene-based resin composition and / or a rubber-like polymer. 3. The polymer according to item 1 or 2, wherein 100 parts by weight of the polymer alloy is composed of 30 to 98 parts by weight of the polyamide resin component and 70 to 2 parts by weight of the polyphenylene ether resin component.
Alloy molded products,

4. The polymer alloy is
2. The alloy according to claim 1, wherein at least one kind of organic and / or inorganic filler is added to the alloy.
4. The polymer alloy molded article according to any one of items 1 to 3, The polymer alloy according to any one of claims 1 to 4, wherein the polymer alloy molded article has a foamed portion inside and a non-foamed layer which is not substantially foamed in a surface layer portion. Alloy molded products,

6. 6. The polymer alloy molded article according to the above item 5, wherein the polymer alloy molded article has a substantially non-foamed non-foamed layer having a thickness of 500 μm or more in a surface layer portion. After filling a mold cavity with a polymer alloy in which 0.2% by weight or more of carbon dioxide is dissolved or absorbed, the method includes a step of holding the polymer alloy under a pressure of 30% or more of the filling pressure. 2. The method of injection-molding a polymer alloy molded article according to the above item 1, wherein

8. After filling a mold cavity with a polymer alloy in which 0.2% by weight or more of carbon dioxide is dissolved or absorbed, a step of holding the polymer alloy under pressure by a pressure of 85% or less of the filling pressure is performed. 8. The method for injection-molding a polymer alloy molded article according to 7 above, wherein 9. The method for injection-molding a polymer alloy molded article according to the above item 7 or 8, wherein the polymer alloy in a molten state is filled in a mold cavity adjusted or maintained at a pressure of not less than atmospheric pressure and not more than 15 MPa. .

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be specifically described below. In the present invention, the polymer alloy refers to a composite resin material in which two or more resin compositions are physically mixed. In the polymer alloy used in the molded article of the present invention, the resin component of the polymer alloy is composed of at least a polyamide (hereinafter abbreviated as “PA”) resin and a polyphenylene ether (hereinafter abbreviated as “PPE”) resin. It is characterized by being.

The polymer alloy in the present invention is characterized in that it is a polymer alloy in which at least a PA resin and a PPE resin are physically mixed (hereinafter abbreviated as “PA / PPE polymer alloy”). . This is PA
/ PPE polymer alloy has low specific gravity, and
Excellent rigidity, impact resistance and paintability, high temperature (around 150 ° C)
This is because it has heat resistance enough to withstand baking coating.

As the PA resin used in the present invention, any resin having an amide bond {—NH—C (＝ O)} in the polymer main chain can be used. Generally, PA resins are obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but are not limited thereto.

The above-mentioned diamines are roughly classified into aliphatic, alicyclic and aromatic diamines, and specific examples thereof include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, and the like. 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnanomethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4
-Bisaminomethylcyclohexane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine.

The dicarboxylic acids are roughly classified into aliphatic,
Alicyclic and aromatic dicarboxylic acids are mentioned, and specific examples are adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,1,3-tridecandioic acid,
1,3-cyclohexanedicarboxylic acid, terephthalic acid,
Examples include isophthalic acid, naphthalenedicarboxylic acid, and dimer acid. As lactams, specifically, ε-
Caprolactam, enantholactam, ω-laurolactam and the like.

Examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8
-Aminooctanoic acid, 9-aminonanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, 13-aminotridecanoic acid and the like. In the present invention,
Any of these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids may be used alone or in the form of a mixture of two or more, and any of the copolymerized PAs obtained by polycondensation may be used.

Further, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and ω-aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight by an extruder or the like can also be suitably used. it can. Particularly, PA resins that can be usefully used in the present invention include PA resins.
6, PA6,6, PA4,6, PA11, PA12, P
A6,10, PA6,12, PA6 / 6,6, PA6 /
6, 12, PA6 / MXD (m-xylylenediamine), PA6, T, PA6, I, PA6 / 6, T, PA
6/6, I, PA6, 6/6, T, PA6, 6/6,
I, PA6 / 6, T / 6, I, PA6, 6/6, T /
6, I, PA6 / 12/6, T, PA6, 6/12 /
6, T, PA6 / 12/6, I, PA6, 6/12 /
6, I and the like. PAs obtained by copolymerizing a plurality of PAs with an extruder or the like can also be used. Preferred PAs are PA6, PA6,6, and mixtures thereof.

The preferred number average molecular weight of the PA resin used in the present invention is from 5,000 to 100,000, more preferably from 10,000 to 30,000. PA resin in the present invention is not limited to these,
It may be a mixture of a plurality of PA resins having different molecular weights. For example, a low molecular weight P having a number average molecular weight of 10,000 or less
A, a mixture of a high molecular weight PA of 30,000 or more, a low molecular weight PA of a number average molecular weight of 10,000 or less,
It is a mixture of about 00 general PAs.

The PA end groups participate in the reaction with the functionalized polyphenylene ether. PA resins generally have an amino group and a carboxyl group as terminal groups. Generally, when the carboxyl group concentration exceeds the amino group concentration, the impact resistance generally decreases, the flowability increases, and If the amino group concentration exceeds the carboxyl group concentration, the impact resistance is improved and the fluidity is reduced. These preferred ratios are 9/1 to 1/9, more preferably 8/2 to 1/9, and still more preferably 6/4 to 1/9 in amino / carboxyl group ratio.
/ 9.

The concentration of the terminal amino group is preferably at least 10 meq / kg. More preferably, it is 30 meq / kg or more. These PAs
As a method for adjusting the terminal group of the system resin, a known method that is apparent to those skilled in the art may be used. For example, addition of a diamine or a dicarboxylic acid, addition of a monocarboxylic acid, or the like during polymerization of a PA-based resin may be mentioned. In addition, a metal-based stabilizer can be used for the purpose of improving the heat stability of the PA-based resin.

Specific examples of the metal-based stabilizer include CuI,
Examples thereof include CuCl ₂ , copper acetate, potassium iodide, and cerium stearate, and these may be used in combination.
The preferred compounding amount of the metal-based stabilizer is 0.001 to 1 part by weight based on 100 parts by weight of the PA-based resin. The PPE resin used in the present invention is a homopolymer or a copolymer having a repeating unit represented by the general formula (1) and / or (2).

[0037]

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[0038]

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(Where R1, R2, R3, R4, R
5, R6 independently represents an alkyl group having 1 to 4 carbon atoms, an aryl group, halogen, or hydrogen. However, R5 and R6 are not simultaneously hydrogen. Representative examples of the homopolymer of the PPE resin include poly (2,6-dimethyl-1,4-phenylene) ether,
Poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-)
1,4-phenylene) ether, poly (2,6-di-n)
-Propyl-1,4-phenylene) ether, poly (2
-Methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-)
Phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl) -1, 4
And homopolymers such as (phenylene) ether.

Among them, poly (2,6-dimethyl-1,1)
4-phenylene) ether is preferred.
Nos. 2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit described in JP-A-01222 and the like as a partial structure. Containing polyphenylene ethers are particularly preferred. Here, the PPE copolymer is a copolymer having a phenylene ether structure as a main unit unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or a copolymer of 2,6-dimethylphenol and o-cresol.
There are copolymers of dimethylphenol with 2,3,6-trimethylphenol and o-cresol.

In the present invention, a part or all of the PPE-based resin may be used as described in JP-A-2-276823 and JP-A-63-1988.
It can be used in place of a modified PPE resin modified with a compound having a carbon-carbon double bond as described in 108059 and JP-A-59-59724. In the present invention, the PA / PPE-based polymer
The PPE resin constituting the alloy may be a modified PPE resin modified with a styrene resin composition, a rubbery polymer, or the like.

Here, the styrene resin composition is a polymer obtained by polymerizing a styrene resin, a styrene compound, or a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. It is preferred that they are united. Specific examples of the styrene resin include a polystyrene (hereinafter abbreviated as “PS”) resin, a rubber-reinforced polystyrene (hereinafter abbreviated as “HIPS”) resin, and an acrylonitrile / styrene copolymer (hereinafter abbreviated as “AS resin”). ), Acrylonitrile / butadiene / styrene copolymer (hereinafter abbreviated as “ABS resin”), and other styrene copolymers. Particularly preferred are PS-based resins and HIPS-based resins.

Specific examples of the styrene compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, pt
tert-Butylstyrene, ethylstyrene and the like can be mentioned, and styrene is most preferable. Examples of the compound copolymerizable with the styrene compound include methyl methacrylate, methacrylic acid esters such as ethyl methacrylate, acrylonitrile, unsaturated nitrile compounds such as methacrylonitrile, and acid anhydrides such as maleic anhydride. And used together with styrenic compounds. The amount of the copolymerizable compound to be used is preferably 20% by weight or less, more preferably 15% by weight or less, based on the total amount with the styrene compound.

Examples of the rubbery polymer include a conjugated diene rubber, a copolymer of a conjugated diene and an aromatic vinyl compound, and an ethylene-propylene copolymer rubber. Specifically, polybutadiene and a styrene-butadiene copolymer are particularly preferred. When an unsaturated rubbery polymer is used, it is preferable to use a partially hydrogenated rubber. The rubbery polymer in the present invention is a natural or synthetic polymer material which is elastic at room temperature. For example, a block copolymer of an aromatic vinyl compound and a conjugated diene compound, a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound, and a copolymer of ethylene and an α-olefin also used as an impact modifier. Polymers, copolymers of ethylene, α-olefin and polyene, and the like can be used, and one or more of these can be used.

The block copolymer of the aromatic vinyl compound and the conjugated diene compound comprises one, preferably two or more polymer blocks mainly composed of the aromatic vinyl compound and a polymer block mainly composed of the conjugated diene compound. Contains at least one. Further, in the block polymer of the aromatic vinyl compound and the conjugated diene compound, the weight ratio between the aromatic vinyl compound and the conjugated diene compound is preferably 10/90 to 90/10. More preferably, 15 / 85-8
0/20. More preferably, 15 / 85-65 /
35. These may be blended by mixing two or more kinds having different weight ratios of the aromatic vinyl compound and the conjugated diene compound. Further, those containing mineral oil or the like can also be used.

As the aromatic vinyl compound, styrene, α
-Methylstyrene, vinyltoluene and the like. One or more compounds selected from these are used, and styrene is particularly preferred. Examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like. One or more compounds selected from these are used, but butadiene, isoprene and a combination thereof are preferable.

The molecular structure of the block copolymer is linear,
Any of branched or radial or a combination thereof may be used. When butadiene is used as the conjugated diene compound, the microstructure of the polybutadiene block portion has a 1,2-vinyl content or 1,2-vinyl content and 3,3 The total amount of 4-vinyl content is preferably from 5 to 80%, more preferably from 10 to 70%. A hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound is a polymer block mainly composed of a diene compound obtained by subjecting a block copolymer of an aromatic vinyl compound and a conjugated diene compound to hydrogenation treatment. Is controlled in the range of more than 0 to 100%.

The copolymer of ethylene and an α-olefin refers to a copolymer of ethylene and an unsaturated hydrocarbon compound having 3 to 20 carbon atoms, and specific examples of the α-olefin include propylene and butene. 1, pentene-1, hexene-1, heptene-1, octene-1, 4-methylbutene-1,4-methylpentene-1 and the like, and preferred are propylene, butene-1, and octene-1. Propylene and octene-1 are particularly preferred. The weight ratio of ethylene to α-olefin is preferably from 95/5 to 5/95, more preferably from 95/5 to 60/95.
40. The Mooney viscosity (ML1 + 4, 121 ° C.) of the copolymer of ethylene and α-olefin is preferably 1 to 100, more preferably 1 to 50. The preferred rubbery polymer is a copolymer of ethylene and an α-olefin.

The polyene of the copolymer of ethylene, α-olefin and polyene refers to a non-conjugated diene such as 1,4-hexadiene, dicyclopentadiene and norbornadiene. The polyene content is desirably about 0.1 to 8%. The definition of α-olefin and the weight ratio of ethylene to α-olefin are the same as above. Mooney viscosity of copolymer of ethylene, α-olefin and polyene (ML1 +
(4, 121 ° C.) is preferably from 1 to 100, more preferably from 1 to 50.

The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method. For example, US Pat. No. 3,306,687
US Pat. No. 3,308,875, which can be easily produced by oxidative polymerization of 2,6-dimethylphenol, for example, using a complex of cuprous chloride and an amine according to Hay described in No. 4 as a catalyst.
Nos. 3,257,357 and 3,257,358, Japanese Patent Publication No. 52-17880, and Japanese Patent Application Laid-Open No. Sho 50-50.
It can be easily produced by the methods described in JP-A-51197 and JP-A-63-152628.

In the present invention, crystalline polyphenylene ether having a melting point can be used as the polyphenylene ether-based resin. Documents showing the relationship between crystalline polyphenylene ether and its melting point include, for example, Jo
urnal of Polymer Science,
Part A-2 (6), pages 1141-1148 (196
8 years), European Polymer Jour
nal (9) pp. 293-300 (1973), Pol
ymer (19), pp. 81-84 (1978).

The polymer alloy in the present invention is PA
It is a polymer alloy made of a PPE resin and a PPE resin. It has the advantages of PA resin and the advantages of PPE resin such as flame retardancy, heat resistance, dimensional stability, and acid and alkali resistance. In order to maintain the polymer content, when the resin component of the polymer alloy is 100 parts by weight, PA
Preferably, the PPE resin composition comprises 30 to 98 parts by weight of the PPE resin component and 70 to 2 parts by weight of the PPE resin component, more preferably 50 to 90 parts by weight of the PA resin component. Is composed of 10 to 50 parts by weight.

A compatibilizer can be added to the polymer alloy according to the present invention. The type of the compatibilizer is not limited, but is an adduct of a copolymer of an aromatic vinyl compound and a conjugated diene compound, α, β-unsaturated dicarboxylic acid or a derivative thereof, and an aromatic vinyl compound, For example, styrene, α-methylstyrene, a compound such as vinyltoluene and a conjugated diene compound such as butadiene, isoprene, a copolymer composed of 1,3-pentadiene and the like, preferably a copolymer composed of styrene and butadiene, α, It is preferably a copolymer to which an adduct of β-unsaturated dicarboxylic acid or a derivative thereof is added.

The α, β-unsaturated dicarboxylic acids or derivatives thereof used herein include maleic acid, maleic anhydride, monomethyl maleate, metal salts of monomethyl maleate, fumaric acid, monomethyl fumarate, succinic acid , Succinic anhydride, itaconic acid, acrylic acid, methacrylic acid, hymic acid, hymic acid anhydride,
Crotonic acid, phthalic acid, phthalic anhydride, metal salts of methacrylic acid, metal salts of acrylic acid, maleimide, phthalimide, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, vinyl glycidyl ether, glycidyl itaconate, etc. Most preferred is maleic anhydride.

The amount of the α, β-unsaturated dicarboxylic acid or derivative thereof added to the above copolymer is 0.01 to 20 mol.
It is preferably in the range of 1%, more preferably in the range of 0.05 to 10 mol%. The amount of the compatibilizer is determined according to the polymer alloy 1 according to the present invention.
It is preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, based on 00 parts by weight.

The polymer alloy molded article according to the present invention is required to satisfy the performance required for the molded article.
It is possible to add a thermoplastic elastomer to the polymer alloy as a modifier. Although the kind of the thermoplastic elastomer is not limited, styrene-based (hereinafter abbreviated as “SBC”), olefin-based (hereinafter abbreviated as “TPO”), polyvinyl chloride-based (hereinafter abbreviated as “TPVC”), urethane System (hereinafter abbreviated as "TPU"), polyester system (hereinafter abbreviated as "TPEE"), PA system (hereinafter "TPU").
Abbreviated as "PAE").

The amount of the thermoplastic elastomer is based on 100 parts by weight of the polymer alloy according to the present invention.
It is preferably 0.5 to 40 parts by weight, more preferably 1 to 20 parts by weight. It is also possible to use the compatibilizer and a thermoplastic elastomer together. In the polymer alloy of the present invention, additives that are usually used as needed, such as antioxidants, flame retardants, mold release agents, lubricants, and heat stable, as long as the characteristics and effects of the present invention are not impaired. Agents, weathering stabilizers, rust inhibitors, fillers, coloring agents, antibacterial agents, metal deactivators, slip agents, various coloring agents, fungicides, etc., if necessary, one or more kinds may be added. it can.

As the above flame retardant, an organic phosphoric ester compound, an inorganic phosphorus compound, an aromatic halogen flame retardant, a silicon flame retardant and the like can be considered. In addition, as other additives, one of carbon fiber, metal fiber, and graphite is used.
By selecting more than one kind, the electric resistance value of the crystalline resin can be reduced. This is preferable because it is possible to prevent small powder such as dust from adhering to a molded article made of a polymer alloy by static electricity.

An inorganic or organic filler may be added to the polymer alloy according to the present invention for the purpose of imparting specific gravity, strength, and ensuring dimensional accuracy. Examples of the specific gravity imparting agent include inorganic salts, oxides, and metal powders such as barium sulfate, red iron oxide, and tungsten powder. In addition, as a strength imparting agent, glass fiber, carbon fiber, metal fiber, aramid fiber, potassium titanate, asbestos, silicon carbide, ceramic, silicon nitride, barium sulfate, calcium sulfate, carbon whisker, kaolin, clay, pyrophyllite , Bentonite, sericite, zeolite, mica, mica, nepheline sinite, talc, atalpargite, wollastonite, slag fiber, ferrite, graphite, silicon, calcium, calcium carbonate, magnesium carbonate, dolomite, zinc oxide, gypsum, Glass beads,
Glass powder, glass balloon, quartz, quartz glass,
Alumina and the like can be considered.

The shape of the inorganic or organic filler is not limited, and a fibrous, plate-like or spherical shape can be arbitrarily selected. Examples of the carbon fibers mentioned above include polyacrylonitrile-based carbon fibers, pitch-based carbon fibers, chop fibers, milled fibers, graphite, and carbon whiskers. The preferred fiber diameter of the polyacrylonitrile-based carbon fiber and the pitch-based carbon fiber is 5 μm to 20 μm, more preferably 5 to 13 μm, and the aspect ratio is 10 or more. Further, a preferable sizing agent is an epoxy resin, and the sizing agent is 1% based on carbon fiber.
~ 5% is preferred.

The graphite preferably has a carbon purity of 80% by weight and a particle size of 100 μm or less. As the carbon whiskers, carbon-coated potassium titanate is preferable, and the fiber diameter is 0.1 to 10 μm. These carbon-based fillers can improve the adhesion to the resin and the handleability by using various known coupling agents and / or sizing agents.

Further, two or more of the above-mentioned inorganic or organic fillers can be used in combination. Further, if necessary, it can be used after being pre-treated with a silane-based or titanium-based coupling agent. The amount of the inorganic or organic filler added to the polymer alloy of the present invention is not limited, but the specific gravity of the polymer alloy is adjusted, rigidity is improved, and dimensional accuracy is secured. In order to sufficiently obtain the effect of adding an additive, such as suppressing deformation such as warpage, 5% by weight
The above addition amount is preferred, and more preferably 10% by weight.
That is, the addition amount is as described above.

If the amount is less than 5% by weight, the effect of adding the above-mentioned filler is small, which is not preferable. Here, the added amount of the filler refers to a ratio when the total amount of the polymer alloy to which the filler is added is 100% by weight, and when there are two or more fillers, the total added amount is Point. In the present invention, the amount of the inorganic or organic filler to be added refers to the amount of the inorganic filler to be added when one kind is added, and to the total amount of the addition when two or more kinds of the inorganic filler are added. Further, the amount of the inorganic or organic filler added indicates a ratio when the total amount of the resin component, the inorganic or organic filler, and other additives is 100% by weight.

Preparation of these compositions can be achieved by conventionally known techniques such as Brabender, kneader, Banbury mixer, extruder and the like, and an extruder is particularly preferred. The molded article of the polymer alloy of the present invention is a molded article, a part, and a product of a minimum unit constituted by the polymer alloy, and includes, for example, an automobile part.Specifically, a bumper, a front fender, Exterior parts such as rear fenders, door panels, various malls, emblems, engine hoods, wheel caps, roofs, spoilers, outside door handles, roof rails, various aero parts, motorcycle cowls, instrument panels, and consoles Suitable for interior parts such as boxes, trims and inner door handles.

Further, it can be suitably used as an interior / exterior component of electric / electronic equipment, and specifically includes various computers and their peripheral devices, other OA devices, televisions, videos, cabinets for various disk players, refrigerators and the like. Suitable for parts use. In addition, it refers to the minimum unit of molded articles, parts and products made of polymer alloy used for containers, household goods, electrical products, general machinery, piping parts, precision machinery, tools, industrial parts, transportation equipment, etc. It may be a molded product or product requiring secondary processing such as a plate.

The injection molding method according to the present invention is characterized in that 0.2% by weight or more of carbon dioxide is dissolved or absorbed in a polymer alloy and then filled into a mold cavity. This is 0.2% by weight of polymer alloy
This is because, by dissolving the above carbon dioxide, the fluidity at the time of filling the polymer alloy into the mold cavity is improved, and it is possible to suppress an increase in the filling pressure. This is supposedly because carbon dioxide is efficiently dispersed as a plasticizer in the molten polymer alloy.
As a result, there is no need to raise the temperature of the resin more than necessary, so there is no need to worry about thermal decomposition and deterioration of the resin, and it is not necessary to raise the temperature of the mold more than necessary.

Further, since the filling pressure at the time of filling the polymer alloy into the mold cavity is reduced, deformation of the molded article such as warpage after molding is reduced as compared with the conventional molding method. This is considered to be due to the fact that the filling pressure during filling into the mold cavity is lower than that of the conventional molding method, so that residual strain hardly remains in the molded product. This facilitates injection molding with a polymer alloy that has a high viscosity when molten, and improves the quality of molded products.
It is expected that a resin composition, which has not been realized until now because of increased flexibility in product design and high viscosity at the time of melting, can be realized.

When the amount of carbon dioxide dissolved or absorbed is less than 0.2% by weight, it is difficult to obtain the effect of improving the fluidity by dissolving or absorbing carbon dioxide, and sufficient dimensional accuracy is obtained. It is not preferable because it becomes difficult to obtain dimensional stability. In the present invention, the polymer
The method is characterized by dissolving or absorbing 0.2% by weight or more of carbon dioxide in an alloy, and the method is to mix the crystalline resin in a molten state in a heating cylinder of an injection molding machine. A method of mixing the crystalline resin in a molten state from a nozzle portion of a molding machine, providing equipment for supplying carbon dioxide between a mold and a nozzle of the molding machine, and mixing the crystalline resin in a molten state. Method, a method in which resin pellets are granulated in a state where carbon dioxide is mixed with a crystalline resin in a molten state in advance, and injection molding is performed using the granules, or a method in which the resin pellets are previously formed in a closed container such as a hopper of a molding machine. A method of absorbing carbon is conceivable.

Carbon dioxide is used as the polymer in the present invention.
Easy to disperse uniformly in alloy, easy to dissolve or absorb 0.2% by weight or more in short time, easy to adjust absorption or dissolution, easy setup before molding, molding machine hopper Considering that there is no need to provide a pressure-resistant structure for the parts, etc., the carbon dioxide supply can be placed in the heating cylinder of the injection molding machine, at the nozzle of the molding machine, or at any position between the nozzle of the molding machine and the mold. Preferably, a method for dissolving or absorbing carbon dioxide in the polymer alloy in a molten state by providing equipment for the above is preferable.

In the present invention, the amount of carbon dioxide dissolved or absorbed is measured by the following method. 1. Immediately after molding, the weight of the molded article is measured (M1). 2. Put the molded product in a hot air dryer kept at 100 ° C.
After leaving for 8 hours or more to allow carbon dioxide to evaporate, the weight of the molded article taken out of the hot air dryer is measured (M2). 3. The amount of carbon dioxide dissolved or absorbed (% by weight)
It is calculated from (M1−M2) ÷ M2 × 100.

In the present invention, the molded article made of the polymer alloy preferably has a foamed portion inside. The foamed portion is formed by appropriately foaming carbon dioxide dissolved or absorbed in the polymer alloy when the polymer alloy cools and solidifies in the mold cavity and causes volume shrinkage. I imagine that. By forming the foamed portion inside the molded article, it is considered that the volume shrinkage of the polymer alloy is supplemented from the inside of the molded article, and the occurrence of sink marks on the molded article surface is suppressed.
The foamed portion is different from that obtained by adding a foaming agent to the polymer alloy.

Since the molded article made of the polymer alloy has a foamed portion inside, the occurrence of defects such as sink marks which occur after molding is suppressed, and the molded article made of the thermoplastic resin composition is formed into a thicker molded article. It can be expected to be applied to products and increase the degree of freedom in product design. In the present invention, the molded article made of the polymer alloy preferably has a foamed portion inside, but more preferably has a non-foamed layer having a thickness of 500 μm or more on the surface layer of the molded article. This means that the thickness of the non-foamed layer is 500 μm
If it is less than this, a swelling phenomenon occurs on the surface of the molded article, and the mechanical strength may be lowered, which is not preferable.

The thickness of the non-foamed layer can be adjusted by the holding pressure and the holding time. The higher the holding pressure and the longer the holding time, the thicker the non-foamed layer tends to be. However, if the holding pressure is too high or if the holding time is too long, when the polymer alloy is cooled and solidified in the mold cavity, carbon dioxide dissolved in the polymer alloy is formed. It is difficult to form a foamed portion inside the product, and there is a possibility that sinks may occur on the surface of the molded product.

Here, the foamed portion refers to a portion where a void or whitening phenomenon due to foaming is observed when the cross section of the molded product is magnified and observed 10 to 20 times by an optical microscope or the like. It refers to a void due to foaming or a portion where no whitening phenomenon is observed. Normally, the injection molding method has a step of filling the resin into the mold cavity and then holding the resin in the cavity under pressure. This step is referred to as a "holding step", and the degree of the pressure is referred to as "holding pressure". In the injection molding method of the polymer alloy according to the present invention, after filling the polymer alloy into the mold cavity, the filling pressure is reduced. It is preferable that the resin in the mold cavity is held under pressure by a pressure of 30% or more.

In the present invention, the holding pressure is 30% of the filling pressure.
If it is less than 1, the thickness of the non-foamed layer formed on the surface layer of the molded article becomes thin, and the proportion of the foamed portion in an arbitrary cross section becomes large. On the other hand, when the holding pressure exceeds 85% of the filling pressure, burrs may be generated, and a foamed portion may not be easily formed inside the molded product, and sink and warpage may easily occur after molding.

An injection molded article made of a crystalline resin in which 0.2% by weight or more of carbon dioxide is dissolved or absorbed forms a non-foamed layer having an appropriate thickness on the surface layer of the molded article, and is formed inside the molded article. In order to have an appropriate foaming portion, the preferable range of the holding pressure in the injection molding process is in the range of 30 to 85% with respect to the filling pressure, and more preferably in the range of 30 to 80%. And most preferably in the range of 30-75%.

Although the holding time is not limited, if the holding time is extremely short, the carbon dioxide dissolved or absorbed in the crystalline resin before filling into the mold cavity expands. This is not preferable because a swelling phenomenon may occur in the molded product. Specifically, the dwell time is preferably 3 seconds or more, more preferably 5 seconds or more, and most preferably 7 seconds or more.

Here, the filling pressure refers to a resin pressure generated when the molten resin is charged into the mold cavity. Specifically, the screw pressure in the in-line type injection molding machine and the plunger position in the pre-plasticization type injection molding machine indicate the resin pressure generated when moving from the measurement position to the PV switching position. In the present invention, the injection molding method of a polymer alloy is a usual molding and processing method of a thermoplastic resin. In addition to a commonly used injection molding method, a hollow injection molding method, a gas assist molding method, a blow molding method Methods, injection and compression molding methods, and the like.

In the injection molding method of the molded article using the polymer alloy of the present invention, when the polymer alloy having dissolved or absorbed carbon dioxide is filled in the mold cavity,
It is preferable that the inside of the mold cavity is adjusted or held by the pressurized gas at a pressure higher than the pressure at which foaming does not occur at the flow front of the polymer alloy, so that a foamed pattern is not generated on the surface of the molded product. The pressure of the pressurized gas may be a minimum pressure at which the foaming pattern on the surface of the molded product disappears, the amount of gas used during the molding cycle is minimized, and the structure of the mold cavity seal and gas supply device is reduced. It is preferable that the gas pressure is low for simplification. Gas pressure is 15MP
If it exceeds a, the mold may open due to gas pressure, and problems such as difficulty in sealing the mold cavity are likely to occur. Therefore, the pressure of the gas for pressurizing the mold cavity is preferably not less than atmospheric pressure and not more than 15 MPa, more preferably not more than 10 MPa.

At this time, as the gas for adjusting or maintaining the inside of the mold cavity to a constant pressure, a single substance or a mixture of various gases such as nitrogen inert to the polymer alloy can be used. Carbon dioxide with high solubility in polymer alloys,
Hydrocarbons and gases in which hydrogen has been partially replaced by fluorine are preferred. Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the examples.

The resin used for injection molding was PA / PPE
Polymer alloy (“Zylon A0501” manufactured by Asahi Kasei Corporation) and “Zylon AG511”
POM resin (Tenac-C manufactured by Asahi Kasei Corporation)
4520 "), polycarbonate (hereinafter abbreviated as" PC ") resin (" Panlite G-3 "manufactured by Teijin Chemicals Limited)
430 ") and a PA resin (" Leona 13G23 "manufactured by Asahi Kasei Corporation).

Composition A was prepared by adding 29.5 parts by weight of PA6 resin, 49.5 parts by weight of PPE resin, and 100 parts by weight of a resin composition comprising 1.0 part by weight of a compatibilizer to 2 parts of glass fiber.
It is a PA6 / PPE polymer alloy added with 0% by weight. Composition B is composed of 50.0 parts by weight of PA6 resin, PPE
It is a PA6 / PPE polymer alloy obtained by adding 30% by weight of glass fiber to 100 parts by weight of a resin composition comprising 50.0 parts by weight of a resin.

Composition C was 47.0 parts by weight of PA6 resin,
10% by weight of glass fiber based on 100 parts by weight of a resin composition comprising 47.0 parts by weight of a PPE resin, 5.0 parts by weight of a hydrogenated styrene-butadiene block copolymer (HTR), and 1.0 part by weight of a compatibilizer. It is a PA6 / PPE polymer alloy added. Composition D is a resin comprising 47.0 parts by weight of PA6 resin, 47.0 parts by weight of PPE resin, 5.0 parts by weight of hydrogenated styrene-butadiene block copolymer (HTR), and 1.0 part by weight of a compatibilizer. It is a PA6 / PPE-based polymer alloy obtained by adding 15% by weight of glass fiber to 100 parts by weight of the composition.

Composition E was composed of 47.0 parts by weight of PA6 resin,
20 parts by weight of glass fiber is added to 100 parts by weight of a resin composition comprising 47.0 parts by weight of a PPE resin, 5.0 parts by weight of a hydrogenated styrene-butadiene block copolymer (HTR), and 1.0 part by weight of a compatibilizer. It is a PA6 / PPE polymer alloy added. Each of the above-mentioned resins is in a pellet form before molding. The molding machine used was “TUPARL TR50S2” manufactured by Sodick Plustech, and “SG125-HP” manufactured by Sumitomo Heavy Industries, Ltd. The cylinder temperature during injection molding was 2 for PA / PPE polymer alloys.
80 ° C, POM resin 190 ° C, PC resin 290
° C, PA66 resin was 280 ° C. Mold temperature is 80
° C.

[0085]

Reference Examples 1 to 5 Composition A, Composition B, Composition C,
Using the composition D and the composition E, predetermined molded articles and test pieces were prepared by injection molding, and the specific gravity, flexural modulus, heat deformation temperature, paint adhesion, falling weight impact strength, and water absorption were measured. Table 1 shows the results. Reference Example, Reference Comparative Example when the following, specific gravity, flexural modulus, heat deformation temperature, paint adhesion, bending strength under any temperature environment, falling weight impact strength, water absorption, the following The method was carried out by the method described above.

The specific gravity was measured in accordance with ASTM standard "D 792" by obtaining a tank type test piece by injection molding. The flexural modulus is measured according to ISO standard “178 (JIS“ K
7171 ")", a sample was obtained by injection molding and measured. The heat distortion temperature is 0.455
The heat distortion temperature under a load of MPa is determined according to ASTM standard "D64
According to 8 ", a tongue-shaped test piece was obtained by injection molding.
The measurement was performed.

The paint adhesion was determined by injection molding.
A flat molded product having a size of 60 mm × 60 mm and a thickness of 3 mm is prepared.
After immersion for 0 hours, evaluation was made by performing a cross-cut peel test. In the cross-cut peeling test, a sample was prepared by applying a coating process to the surface of a flat molded product, and the adhesion of the coating film was determined by J.
The test was performed according to the cross cut tape method according to the IS standard “K5400”.

The coating process of the coating film is performed by applying a conductive primer to a flat molded product, applying an intermediate coating with a polyester resin coating by electrostatic coating, and then overcoating with an amino alkyd resin coating (at 150 ° C. for 30 minutes). (Baking coating). After completion of the coating step, the thickness of the paint film is about 5 μm for the conductive primer, about 35 μm for the middle coat, and about 35 μm for the top coat, and is about 75 μm in total. The adhesion of the coating film was measured with a cutter knife at 10 ×
10. A total of 100 cuts are made in a grid pattern, a cellophane adhesive tape is stuck on the grid, and the tape is completely adhered to the coating by rubbing with an eraser. After 1 to 2 minutes, the cellophane adhesive tape was peeled off, and the number of grids in which the coating film did not peel off was measured.

The bending strength under each temperature environment was determined by the ISO
A tank type test piece according to the standard “178 (JIS“ K7171 ”)” was obtained by injection molding, and the measurement was performed according to the same standard except for the ambient temperature conditions. The falling weight impact strength was measured by a Dupont type impact test and was measured in a completely dry state. The test piece was a flat plate having a size of 75 mm × 75 mm and a thickness of 3 mm, and was prepared by injection molding.
The measurement temperature is 23 ° C., the diameter of the missile is イ ン チ inch, and the outer diameter and inner diameter of the pedestal are φ48 mm and φ44 mm, respectively. According to ASTM standard “D570”, the water absorption
A test piece was obtained by injection molding and measured. It can be said that the smaller the water absorption, the smaller the dimensional change and rigidity change due to moisture absorption. Each measurement result,
Table 1 shows the determination results.

[0090]

[Reference Comparative Examples 1 to 3] "Tenac-C 4520",
"Panlight G-3430", "Leona 13G2
In the same manner as in Reference Examples 1 to 5, predetermined molded articles and test pieces were prepared by injection molding using "3", and specific gravity, flexural modulus, heat deformation temperature, paint adhesion, falling weight impact strength, water absorption The rate was measured. Table 1 shows the results. Table 1 shows the results.

[0091]

[Table 1]

[0092]

Examples 1 to 3 Using "Zylon AG511",
After absorbing carbon dioxide so that the absorption amount becomes 0.44 to 0.88% by weight, it was filled into a mold cavity to obtain a box-shaped model molded product shown in FIG. The cylinder temperature of the molding machine was 285 ° C., the number of gate points at this time was two, and the thickness of the box-shaped model molded product where the gate was installed was 1.8 mm. The minimum value of the resin pressure required for filling the resin in the molten state into the mold cavity was measured so as not to leave an unfilled portion. The measured value was a value obtained by converting a read value of a gauge pressure of an injection molding machine into a resin pressure. Table 2 shows the measurement results.

[0093]

[Comparative Example 1] As in Examples 1 to 3, "Zylon AG5
Using "11", carbon dioxide was absorbed so that the absorption amount became 0.12% by weight, and then filled into a mold cavity to obtain a box-shaped model molded product shown in FIG. The cylinder temperature of the molding machine was 285 ° C., and the number of gate points at this time was two. We tried to measure the minimum value of the resin pressure required to fill the molten resin into the mold cavity so as not to leave unfilled parts, but even if the resin pressure was 220 MPa, unfilled parts remained As a result, a box-shaped model molded product was not obtained. Table 2 shows the measurement results.

[0094]

[Comparative Example 2] As in Examples 1 to 3, "Zylon AG5
11 "was used to fill the mold cavity by the same method as ordinary injection molding without absorbing carbon dioxide, thereby obtaining a box-shaped model molded product shown in FIG. The cylinder temperature of the molding machine was 295 ° C., and the number of gate points at this time was two. An attempt was made to measure the minimum value of the resin pressure required to fill the molten resin into the mold cavity so as not to leave unfilled portions.
Even at 20 MPa, an unfilled portion remained, and a box-shaped model molded product was not obtained. Table 2 shows the measurement results.
Shown in

[0095]

[Comparative Example 3] As in Examples 1 to 3, "Zylon AG5
11 ", and without absorbing carbon dioxide, was filled in a mold cavity by the same method as in ordinary injection molding to obtain a box-shaped model molded product shown in FIG.
The cylinder temperature of the molding machine was 295 ° C., and the number of gate points at this time was three. Not to leave unfilled parts
An attempt was made to measure the minimum value of the resin pressure required to fill the molten resin into the mold cavity. However, even if the resin pressure was 220 MPa, unfilled portions remained, and a box-shaped model molded product Did not come to get. Table 2 shows the measurement results.

[0096]

[Table 2]

[0097]

Embodiments 4 and 5 Using "Zylon A0501",
After absorbing carbon dioxide so that the absorption amount becomes 0.66 to 0.92% by weight, it was filled into a mold cavity to obtain a box-shaped model molded product shown in FIG. The cylinder temperature of the molding machine was 285 ° C., and the number of gates at this time was two, and the thickness of the box-shaped model molded product where the gate was installed was 1.2 mm.

The minimum value of the resin pressure required for filling the resin in the molten state into the mold cavity was measured so as not to leave unfilled portions. The measured value was a value obtained by converting a read value of a gauge pressure of an injection molding machine into a resin pressure. The flatness of the molded product can be measured using a three-dimensional measuring machine (“AE12 manufactured by Mitutoyo Corporation”).
2 ”) and a measurement program (“ Geopak40 ”manufactured by the company)
0 ") by plotting the measurement position arbitrarily set on the back surface of the gate installation surface of the box-shaped model molded article shown in FIG. Table 3 shows the measurement results.

[0099]

Embodiments 6 and 7 In the same manner as in Embodiments 4 and 5, "Zylon A"
Using “5011,” the carbon dioxide is absorbed so that the absorption amount becomes 0.62 to 0.88% by weight, and then filled into a mold cavity, thereby forming the box-shaped model molded product shown in FIG. I got The cylinder temperature of the molding machine was 285 ° C., the number of gate points was 3 at this time, and the thickness of the surface of the box-shaped model molded product on which the gate was installed was 1.2 mm. The minimum value of the resin pressure necessary to fill the molten resin into the mold cavity and the flatness of the box-shaped model molded product were measured. Table 3 shows the measurement results.

[0100]

Comparative Example 4 In the same manner as in Examples 4 to 7, "Zylon A05
01 ", without absorbing carbon dioxide, and filling the mold cavity by the same method as in normal injection molding to obtain the box-shaped model molded article shown in FIG.
The cylinder temperature of the molding machine was 295 ° C., the number of gate points at this time was two, and the thickness of the surface of the box-shaped model molded product on which the gate was installed was 1.2 mm. We tried to measure the minimum value of the resin pressure required to fill the molten resin into the mold cavity so as not to leave unfilled parts, but even if the resin pressure was 220 MPa, unfilled parts remained As a result, a box-shaped model molded product was not obtained.
Table 3 shows the measurement results.

[0101]

Comparative Example 5 "Zylon A05" was prepared in the same manner as in Examples 4 to 7.
01 ", without absorbing carbon dioxide, and filling the mold cavity by the same method as in normal injection molding to obtain the box-shaped model molded article shown in FIG.
The cylinder temperature of the molding machine was 295 ° C., the number of gate points was 3 at this time, and the thickness of the surface of the box model molded product on which the gate was installed was 1.2 mm. The flatness of the box-shaped model molded product was measured as the minimum value of the resin pressure required for filling the molten resin into the mold cavity. Table 3 shows the measurement results.

[0102]

[Table 3]

[0103]

According to the method of the present invention, by improving the molding method without impairing the resin composition of the polymer alloy molded article and the degree of freedom in product design, the molded article product required for the polymer alloy is improved. It is possible to improve strength and dimensional accuracy. Furthermore, the present invention facilitates the filling of the mold cavity, suppresses the occurrence of defects mainly occurring after molding, such as warpage and sink marks occurring in molded products, and enables application to thicker molded products. .

[Brief description of the drawings]

FIG. 1 shows a perspective view of a box-shaped model molded product.

FIG. 2 shows a top view of a box-shaped model molded product.

FIG. 3 shows a bottom view of a box-shaped model molded product.

[Explanation of symbols]

 1 box-shaped model molded product 2 rib 3 gate 4 flatness measurement position

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 71/12 C08L 71/12 77/00 77/00 // B29K 71:00 B29K 71:00 77:00 77:00 F-term (reference) 4F074 AA13B AA71 AA77 AA98 AC00 AC34 BA32 CA26 DA08 DA35 DA59 4F206 AA29 AA32 JA07 JL02 JM04 JM05 JN11 JN21 4J002 CH07X CL01W CL03W CL06Y DA016 DA026 DA066 DA116 DE106 DJ006 016 FA04Y FA046 FA066 FA086 FA106 FD01Y FD016 FD130 GN00

Claims (9)

[Claims] 1. The polymer / alloy resin component is composed of at least a polyamide-based resin component and a polyphenylene ether-based resin component.
After dissolving or absorbing 2% by weight or more of carbon dioxide,
A polymer alloy molded product obtained by filling a mold cavity. 2. A polyphenylene ether-based resin component comprising:
The polymer / alloy molded product according to claim 1, which is a modified polyphenylene ether-based resin modified with a styrene-based resin composition and / or a rubber-like polymer. 3. The method according to claim 1, wherein 100 parts by weight of the polymer alloy comprises 30 to 98 parts by weight of the polyamide resin component and 70 to 2 parts by weight of the polyphenylene ether resin component. 3. The polymer alloy molded article according to 2. 4. The polymer alloy according to claim 1, wherein at least one kind of organic and / or inorganic filler is added to the polymer alloy. Polymer alloy molded products. 5. The polymer alloy molded article according to claim 1, wherein the molded article has a foamed portion inside and a non-foamed layer which is not substantially foamed in a surface layer portion. A polymer alloy molded product according to the above item. 6. A polymer alloy molded article having 5
The polymer alloy molded article according to claim 5, further comprising a substantially non-foamed non-foamed layer having a thickness of 00 µm or more. 7. A mold cavity is filled with a polymer alloy in which 0.2% by weight or more of carbon dioxide is dissolved or absorbed, and then the polymer alloy is pressurized with a pressure that is 30% or more of the filling pressure. The injection molding method for a polymer alloy molded product according to claim 1, further comprising a holding step. 8. After filling a mold cavity with a polymer alloy in which 0.2% by weight or more of carbon dioxide is dissolved or absorbed, the polymer alloy is applied by a pressure of 85% or less of the filling pressure. The method of injection molding a polymer alloy molded product according to claim 7, further comprising a step of maintaining pressure. 9. A polymer alloy molded article according to claim 7, wherein the polymer alloy in a molten state is filled into a mold cavity adjusted or maintained at a pressure not lower than atmospheric pressure and not higher than 15 MPa. Injection molding method.