JP2003171564A - Injection compression molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a large sized resin injection molded product having an excellent dimensional stability and excellent impact strength and manufactured by an injection compression molding method and to provide a method for enhancing an impact-resistant property of the large sized resin injection molded product not depending on a composition in the resin composition comprising a crystalline thermoplastic polymer and a non-crystalline thermoplastic polymer and particularly reinforced by a reinforcement filler. <P>SOLUTION: The resin composition comprising a total 100 parts by weight of 5-90 parts by weight of a crystalline thermoplastic polymer (a1 component) and 10-95 parts by weight of a non-crystalline thermoplastic polymer (a2 component) is subjected to injection compression molding. Thus obtained injection compression molded product has the maximum projection area of 1,000 cm<SP>2</SP>or more. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a large-sized resin injection molded product. More specifically, it has excellent dimensional stability,
The present invention relates to a large-sized resin injection-molded product manufactured by an injection compression molding method which is also excellent in impact strength, and particularly to the injection-molded product reinforced with a reinforcing filler.

[0002]

2. Description of the Related Art In recent years, the trend toward plasticization in automobile exterior materials has become active again. Exterior materials include back panels, fenders, bumpers, door panels,
Pillars, side protectors, side moldings, various spoilers, bonnets, roof panels, trunk lids, etc. Among them, back panel, fender,
It is active in outer panels that are not yet plasticized such as door panels, bonnets, roof panels, and trunk lids, and is particularly popular in so-called vertical outer panels such as back panels, fenders, and door panels. The advantages of using plastic are that it can be made lighter, the degree of freedom in design can be increased, the cost can be reduced by making a module assembly, and there is no deformation or damage in a light collision. be able to. The point that there is no deformation especially in light collisions is in four-wheel drive multipurpose vehicles that are relatively rough and easy to handle because they run in rough places, large minivans with poor closing, and small cars that need higher functionality as tools. It has suitable characteristics.

On the other hand, the exterior material is required to have good dimensional stability because it is attached to a metal frame made of a steel plate or the like. That is, the exterior material is required to have a low coefficient of linear expansion and a dimensional change due to low water absorption. When the difference in the dimensional change from the frame is large, the exterior material may be distorted and the exterior material may interfere with other parts. In order to prevent such deformation and interference, the attachment of the exterior material to the frame is usually performed in a layout in which the deformation is inconspicuous, and a gap is provided as a deformation allowance. Of course, a material having a relatively small dimensional change is used. However, the dimensional stability may be required to be further reduced for the following reasons. That is, in recent years, four-wheel drive multipurpose vehicles have been crossed over, and there is a demand for a high-class vehicle. Therefore, it is necessary to further reduce the gap. In addition, minivans are becoming larger and the exterior materials are also becoming larger.
Therefore, it may not be possible to provide a further gap as a deformation allowance.

As exterior materials for automobiles, NORYL GTX (trade name) series (polymer alloy of polyamide resin and modified polyphenylene ether resin) already manufactured by GE, Toyota Super Olefin mainly developed by Toyota Motor Corporation Polymer (trade name) series (polymer alloy of polypropylene resin and polyolefin elastomer), polymer alloy of aromatic polyester resin and aromatic polycarbonate, and polymer alloy of polyamide resin and ABS resin are widely known. .. All of these materials satisfy well-balanced requirements such as chemical resistance, heat resistance, impact resistance, appearance, and dimensional stability, which are required for exterior materials for automobiles. Most of them are polymer alloys of a crystalline thermoplastic polymer and an amorphous thermoplastic polymer in order to satisfy such characteristics. These materials have been conventionally injection-molded to produce exterior materials for automobiles, particularly automobile skins.

When a lower dimensional change is required for these materials, a method of increasing the proportion of the amorphous thermoplastic polymer having high dimensional stability can be considered. Further, more preferably, a method of blending or increasing the amount of an inorganic reinforcing filler can be considered. However, the former method causes a decrease in impact resistance in a polymer alloy in which a polyamide resin is combined. The latter method, which is more preferable, causes a decrease in impact resistance in most resin materials. Therefore, there is an idea that the impact resistance of the base is further enhanced and various reinforcing fillers are blended. However, this method also has a limit in achieving contradictory properties only by the composition, and cannot be said to be a sufficiently effective method.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a large-sized resin injection-molded article manufactured by an injection compression molding method which is excellent in dimensional stability and impact strength. Specifically, for resin compositions consisting of crystalline thermoplastic polymers and amorphous thermoplastic polymers, especially resin compositions reinforced with reinforced fillers, improved impact resistance in large resin injection molded products regardless of composition The point is to provide a method to do.

As a result of intensive studies conducted by the present inventors to achieve the above object, surprisingly, a resin composition comprising a crystalline thermoplastic polymer and an amorphous thermoplastic polymer reinforced with a reinforcing filler is surprisingly obtained. It has been found that the larger injection compression-molded product thus formed has a significantly improved impact resistance as compared with a normal injection-molded product of such a resin composition. Conversely, it has been found that the impact resistance of the material may not be sufficiently exhibited in a large injection molded product. The present invention is further studied based on such findings,
It has been completed.

[0008]

The present invention comprises a total of 100 parts by weight of a crystalline thermoplastic polymer (a1 component) of 5 to 90 parts by weight and an amorphous thermoplastic polymer (a2 component) of 10 to 95 parts by weight. Thermoplastic polymer component (component A)
The present invention relates to an injection compression molded product having a maximum projected area of 1000 cm ² or more, which is obtained by injection compression molding a resin composition consisting of 100 parts by weight.

In a preferred embodiment of the present invention, the resin composition further comprises 0.5 to 100 parts by weight of a reinforcing filler (component B) per 100 parts by weight of the a1 component and the a2 component in total. It relates to injection compression molded products.

In a preferred embodiment of the present invention, the resin composition comprises 0.5 to 50 parts by weight of a rubbery polymer (component C) per 100 parts by weight of the a1 component and a2 component in total. It relates to injection compression molded products.

One of preferred embodiments of the present invention relates to the above injection compression molded article, wherein the a1 component is at least one crystalline thermoplastic polymer selected from polyamide and aromatic polyester, and One of the preferred embodiments of the present invention relates to the above injection compression molded article, wherein the a2 component is at least one selected from aromatic polycarbonate, polyphenylene ether, polyarylate, and styrenic polymer.

One of the preferred embodiments of the present invention relates to the injection compression-molded article, wherein the B component is at least one selected from talc and wollastonite.

Furthermore, one of the preferred embodiments of the present invention relates to the above-mentioned injection compression-molded article in which the injection compression-molded article has a gate on the side surface of the molded article. In one of these modes, in the injection compression molding, the melted thermoplastic resin material is filled in a mold cavity having a capacity 1.1 times or more larger than a target capacity of a molded product at least when the supply is completed. The present invention relates to the above injection compression molded product.

Further details of the present invention will be described.

The injection compression molding in the present invention is to supply the molten thermoplastic resin into a mold cavity having a capacity larger than the intended capacity of the molded product at least at the completion of the supply, and after the supply is completed, the mold is completed. This is a molding method in which the cavity volume is reduced to a desired volume of the molded article, and the molded article in the mold cavity is cooled to a temperature at which it can be taken out or lower and then the molded article is taken out. In order to clarify the technical content more clearly, it will be further described below.

The above "at the time of completion of the supply" means at the time of completion of the supply of the resin into the mold cavity (hereinafter sometimes simply referred to as "cavity"). Further, the supply of the resin means that the resin flows at least in appearance. That is, if the supply method is injection molding, it means a normal injection process,
The completion of the supply means the end of the injection process. On the other hand, the pressure-holding process does not seem to be accompanied by the resin flow (although a slight resin flow occurs inside the resin), and since it is a process of compressing the resin, it is necessary to supply the resin into the cavity according to the present invention. Is not included. The supply of the molten resin is an injection molding method, that is, a method of discharging the resin in the cylinder using a piston.

Further, the above-mentioned "at least" means that the cavity volume is larger than the target molded article volume when the resin supply is completed, and it is not required that the cavity volume is larger than the resin supply start. To do. For example, a method may be used in which the cavity volume is expanded with the supply of the resin, the resin is overfilled, and then the cavity volume is reduced to compress the resin. Here, the excess molten resin can be allowed to flow into another space such as a waste cabinet (cavity for inflow of resin other than the product). Further, the excess molten resin can be directly flowed back to the cylinder side. still,
It is also possible to excessively supply the molten resin to the mold cavity, which has a large capacity in advance with respect to the target molded product capacity.

Further, the meaning of "the mold cavity having a capacity larger than the intended capacity of the molded product" is based on the standard that the capacity is the same in the usual molding method in which the cavity capacity does not change. That is, strictly speaking, the volume of the molded product is slightly smaller than the volume of the cavity even in the usual molding method, but in the present invention, such a magnitude relationship does not matter. In the present invention, the degree of the "large capacity" is preferably 1.1 times or more, more preferably 1.2 times or more, and further preferably 1.5 times or more the target molded article capacity. On the other hand, the upper limit is preferably 3 times or less of the intended capacity of the molded product, and 2.
It is more preferably 5 times or less, further preferably 2 times or less.

As a method of expanding the capacity of the cavity (which can be said to be a method of decreasing the capacity to a predetermined value when the operation is in the opposite direction), (i) a method of retracting the movable side mold
Examples include (ii) a method of retracting the movable core plate in the cavity, and (iii) a method of retracting the movable part provided in the cavity.
In particular, the method (i) (so-called type compression method) and the method (ii) (so-called core compression method) are generally used. Since the movable part for expanding the cavity capacity compresses the resin when the capacity is reduced to a predetermined capacity, the movable part will be referred to as a "compression part" hereinafter, and a step of reducing the cavity capacity to a predetermined capacity will be performed. "Compression process"
Sometimes called.

The above-mentioned "after the completion of the supply, the capacity of the mold cavity is reduced to the target molded product capacity" means that the compression process is completed after the completion of the supply of the molten resin, and the start time of the compression process is before and after the completion of the supply. It means that any of them may be used, and that the amount of the resin supplied into the cavity may be in excess of the molded product volume as described above. In particular, it is preferable to start the compression step before the completion of the filling of the molten resin in order to obtain a molded article excellent in appearance, impact resistance and dimensional stability. The time when the compression step and the molten resin filling step overlap is called the overlap time.

As described above, in the injection compression molding of the present invention, the amount of the resin supplied into the cavity may be in excess of the molded product volume. However, in terms of impact resistance and manufacturing cost, it is more preferable that the amount of resin supplied into the cavity be equivalent to the capacity of the molded product. Backflow of the molten resin into the cylinder is likely to be disadvantageous in terms of impact resistance, and the discarded cabinet may be economically inefficient.

In the molding method of the present invention, in order to further improve the appearance of the molded product, the mold cavity can be locally heated to a temperature independent of the mother mold. Examples of the method for increasing the temperature include a method using a heating source and a method using a cavity provided with a heat insulating layer to increase the temperature. Any method is applicable, but a method using a heating source is more preferable. Further, examples of the heating source include an electric heater, an infrared heater, a high frequency induction heating, a heating medium, an ultrasonic heating, a laser heating and the like, and any one or a combination of two or more thereof is selected. As a method for locally improving the appearance by locally raising the temperature of the mold cavity, for example, Japanese Patent Publication No. 19443/1993 discloses a method of eliminating cold marks generated on the surface of a molded article by a heating source.

Further, the temperature for locally raising the temperature of the mold cavity is preferably not less than the glass transition temperature (Tg) of the resin, more preferably Tg + 1 to Tg.
+ 10 ° C range, more preferably Tg + 1 to Tg + 8 ° C
Is the range. The temperature range is preferably 0.1 seconds or longer, more preferably 0.5 seconds or longer. The upper limit is preferably 10 seconds or less, more preferably 5 seconds or less.

A large-sized resin injection-molded article produced by injection compression molding of a resin composition comprising a crystalline thermoplastic polymer and an amorphous thermoplastic polymer, particularly the resin composition reinforced with a reinforcing filler is usually used. Although the cause of achieving good impact resistance as compared with the injection-molded article has not been sufficiently clarified, the following factors can be mentioned. First
In addition, it can be considered that the heat load of a large injection molded product is extremely high. In order for the resin composition comprising the crystalline thermoplastic polymer and the amorphous thermoplastic polymer reinforced with the reinforcing filler to obtain good impact resistance, it is necessary to form a controlled morphology,
In addition, it is necessary to suppress the decomposition reaction that occurs between the polymers. High heat loads are considered to be detrimental to these necessary factors. Secondly, it is considered that the non-uniform internal stress is unlikely to occur. Non-uniform internal stresses can act as defects in the fracture behavior of molded parts. The larger the molded product, the greater the strain generated in the molded product. On the other hand, in injection compression molding, the distortion generated in the molded product is small (the pressure inside the resin is uniform and there is little unevenness). Thirdly, the crystallization behavior of the crystalline thermoplastic polymer is considered. Crystallization is affected by various factors such as thermal history, external forces, and nucleating agents. Injection compression molding produces different thermal history and external forces than normal injection molding. In injection compression molding, cooling of the resin is delayed, and the internal pressure is uniform and has little unevenness. Crystallization behavior may differ depending on these factors. In addition, the behavior can be quite complex if a component with a nucleating effect is included.

Next, the thermoplastic polymer component (component A) used in the present invention will be described. In the following description, the crystalline thermoplastic polymer (a1 component) and the amorphous thermoplastic polymer (a2 component) are combined to form a thermoplastic polymer component (A
Component).

The crystalline thermoplastic polymer (a1 component) in the present invention is not particularly limited as long as it is a crystalline polymer having thermoplasticity, but its melting point is preferably 180 ° C. or higher, more preferably 200 ° C. or higher. . By having such thermal properties, high dimensional stability can be achieved. On the other hand, in consideration of moldability, the melting point is preferably 300 ° C or lower, more preferably 290 ° C or lower. The melting point is the value of the melting point peak when the temperature is raised from room temperature at a temperature rising rate of 20 ° C./min using a DSC device in accordance with JIS K7121. Examples of the crystalline thermoplastic polymer include polyamide, aromatic polyester, polyphenylene sulfide, poly-4-methylpentene-1, and syndiotactic polystyrene.

Among them, the a1 component is more preferably at least one crystalline thermoplastic polymer selected from polyamide and aromatic polyester. Polyamide has good impact resistance and also forms a good polymer alloy with the polyphenylene ether described below.
The aromatic polyester is a crystalline polymer having excellent dimensional stability, and forms a good polymer alloy with the aromatic polycarbonate described later. Aromatic polyesters are particularly preferable in terms of dimensional stability.

The polyamide of the component a1 will be described.
Such polyamides include, for example, (i) by polymerization of a monoamine-monocarboxylic acid containing at least two carbon atoms between an amino group and a carboxylic acid group or a lactam thereof, or (ii) between two amino groups. Polymerization of a dicarboxylic acid containing at least two carbon atoms with a dicarboxylic acid in a substantially equimolar ratio, or (iii) polymerization of a monoaminocarboxylic acid or lactam thereof with a substantially equimolar ratio of a diamine and a dicarboxylic acid. It is manufactured by The dicarboxylic acid may be in the form of its functional derivative, such as an ester or acid chloride.

The "substantially equimolar" proportions (of the diamines and dicarboxylic acids) mentioned above are (i) exactly equimolar proportions and (ii) in the conventional art for stabilizing the viscosity of the resulting polyamide. It is meant to include both in proportions that deviate somewhat from the equimolar amounts used. Examples of monoaminomonocarboxylic acids or lactams thereof useful in the production of polyamides are such compounds containing 2 to 16 carbon atoms between the amino and carboxylic acid groups, in the case of lactam the carbon atoms being It forms a ring with the -CO-NH- group. Specific examples of aminocarboxylic acids and lactams include aminocaproic acid, butyrolactam, pivalolactam, caprolactam, capryllactam, enantolactam, undecanolactam, dodecanolactam, and 3- and 4-aminobenzoic acid.

Suitable diamines for use in making polyamides include diamines having straight and branched chain alkyl groups, aryl groups and alkyl-aryl groups. Examples of such diamines are those represented by the following general formula (1) H ₂ N (CH ₂ ) _n NH ₂ (1) (wherein n is an integer of 2 to 16), such as trimethylene diamine, Tetramethylenediamine, pentamethylenediamine, octamethylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, m-phenylenediamine, m
-Including xylylenediamine and the like, and hexamethylenediamine is particularly preferable.

The dicarboxylic acid in the polyamide can be an aromatic dicarboxylic acid such as isophthalic acid and terephthalic acid. Preferred dicarboxylic acids are those represented by the following general formula (2) HOOC-Y-COOH (2) (wherein Y represents a divalent aliphatic group containing at least 2 carbon atoms), and examples thereof include sebacic acid. , Octadecanoic acid, suberic acid, glutaric acid, pimelic acid and adipic acid, with adipic acid being particularly preferred.

Typical examples of polyamides (nylons) useful in the present invention are so-called polyamide 46, polyamide 6, polyamide 66, polyamide 11 and polyamide 1.
2, polyamide 63, polyamide 64, polyamide 61
0 and polyamide 612 and obtained from terephthalic acid and / or isophthalic acid and trimethylhexamethylenediamine, adipic acid and m-
Polyamides derived from xylylenediamine, adipic acid and / or azelaic acid and 2,2-bis- (p-
Aminocyclohexyl) propane-derived polyamide, terephthalic acid and / or isophthalic acid and /
Or a polyamide obtained from adipic acid and hexamethylenediamine, a polyamide obtained from terephthalic acid and / or isophthalic acid and hexamethylenediamine and 2-methylpentamethylenediamine, and from terephthalic acid and 4,4′-diamino-dicyclohexylmethane The resulting polyamide is included. Preferred polyamides are polyamide 6, polyamide 66, polyamide 61
0 and polyamide 46, and most preferably polyamide 66.

The aromatic polyester as the component a1 will be described. Aromatic polyester is an aromatic dicarboxylic acid in which 70 mol% or more, preferably 90 mol% or more, and most preferably 99 mol% or more of the dicarboxylic acid component and 100 mol% of the dicarboxylic acid component forming the polyester are aromatic dicarboxylic acids. It is a polyester.

Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid and 2,5-
Dichloroterephthalic acid, 2-methylterephthalic acid, 4,
4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid, 4,4-diphenoxyethane dicarboxylic acid, 5
-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid and the like can be mentioned. These dicarboxylic acids can be used alone or in admixture of two or more.

In addition to the above aromatic dicarboxylic acid, the aromatic polyester of the present invention can be copolymerized with less than 30 mol% of an aliphatic dicarboxylic acid component. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,
4-cyclohexanedicarboxylic acid and the like can be mentioned.

Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,
2-dimethyl-1,3-propanediol, trans-
Or cis-2,2,4,4-tetramethyl-1,3-
Cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,
6-hexanediol, 1,4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2
-Hydroxyethyl ether) and the like. These may be used alone or in combination of two or more. The dihydric phenol in the diol component is 3
It is preferably 0 mol% or less.

The types and composition ratios of the above aromatic dicarboxylic acid, aliphatic dicarboxylic acid and diol components are preferably selected so as to satisfy the more preferable melting point peak temperature conditions of the present invention.

Specific aromatic polyesters include polyethylene terephthalate (PET), polypropylene terephthalate and polybutylene terephthalate (PB).
T), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (P
BN), polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate, etc., as well as polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, etc. Polymerized polyester can be used.

Further, the terminal group structure of the aromatic polyester used in the present invention is not particularly limited, and in the case where the ratio of the hydroxyl group and the carboxyl group in the terminal group is almost the same amount, or when one ratio is large. May be Further, those terminal groups may be blocked by reacting a compound having reactivity with such terminal groups.

Regarding the method for producing the aromatic polyester used in the present invention, the dicarboxylic acid component and the diol component are heated under heating in the presence of a polycondensation catalyst containing titanium, germanium, antimony, etc. according to a conventional method. Is polymerized, and by-produced water or lower alcohol is discharged to the outside of the system. For example, as the germanium-based polymerization catalyst, germanium oxide, hydroxide, halide, alcoholate, phenolate and the like can be exemplified,
More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxy germanium and the like can be exemplified. Further, in the present invention, compounds such as manganese, zinc, calcium and magnesium used in the transesterification reaction which is a prior stage of polycondensation which is conventionally known can be used in combination, and phosphoric acid or phosphorus after the transesterification reaction is completed. It is also possible to deactivate such a catalyst with an acid compound or the like for polycondensation. Further, the method for producing the aromatic polyester may be either a batch method or a continuous polymerization method.

Furthermore, polybutylene terephthalate is particularly suitable among the above aromatic polyesters. The polybutylene terephthalate of the present invention is a polymer obtained by polycondensation reaction of terephthalic acid or its derivative and 1,4-butanediol or its derivative. As mentioned above, other dicarboxylic acid components and other alkylenes are used. Includes copolymers of glycol components.

The terminal group structure of polybutylene terephthalate is not particularly limited as in the above, but it is more preferable that the terminal carboxyl group is less than the terminal hydroxyl group.

Regarding the manufacturing method, the above-mentioned various methods can be adopted, but the following is preferable. As a manufacturing method, a continuous polymerization method is more preferable. This is because the quality stability is high and the cost is advantageous. Furthermore, it is preferable to use an organic titanium compound as the polymerization catalyst. This is because there is a tendency that the effect on the transesterification reaction is small.

Preferred examples of the organic titanium compound include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitate, and a reaction product of trimellitic anhydride with trimellitic anhydride. And so on. The amount of the organic titanium compound used is 3 with respect to the acid component whose titanium atom constitutes polybutylene terephthalate.
The ratio of about 12 mg atomic% is preferable.

The molecular weight of the aromatic polyester resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35 ° C. with o-chlorophenol as a solvent is 0.5-1.
It is preferably 5 and particularly preferably 0.6 to 1.2.
Is.

The amorphous thermoplastic polymer (a2 component) in the present invention is not particularly limited as long as it is a thermoplastic amorphous polymer, but its glass transition temperature is 100.
It is preferably at least ° C, more preferably at least 120 ° C. By having such thermal properties, high dimensional stability can be achieved. On the other hand, in consideration of moldability, the glass transition temperature is preferably 250 ° C or lower, more preferably 200 ° C or lower. The glass transition temperature is JIS K
Compliant with 7121, using a DSC device from room temperature to 20 ° C
It is a value measured by raising the temperature at a temperature raising rate of / min. The glass transition temperature is a temperature that can be grasped as a2 component as a whole. For example, when polyphenylene ether and polystyrene are contained as a2 components, it means a glass transition temperature in such a polymer alloy. Examples of such amorphous thermoplastic polymers include aromatic polycarbonates, polyphenylene ethers, polyarylates, styrenic polymers, polyether sulfones, and cyclic polyolefins.

Among them, as the component a2, aromatic polycarbonate, polyphenylene ether, polyarylate,
And at least one selected from styrenic polymers
More preferred are some amorphous thermoplastic polymers. Aromatic polycarbonates have good impact resistance. While polyphenylene ether has a high glass transition temperature and is advantageous in terms of dimensional stability, it has excellent compatibility with polystyrene and the like, and can control a wide range of properties. Polyarylate has properties in impact resistance and glass transition temperature which are intermediate between those of aromatic polycarbonate and polyphenylene ether. The styrene-based polymer has good moldability and good compatibility with the above-mentioned amorphous polymer. Aromatic polycarbonate is particularly preferable in terms of impact resistance.

The aromatic polycarbonate as the component a2 will be described. The a2 component aromatic polycarbonate used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor, and the reaction method includes an interfacial polycondensation method, a melt transesterification method, and a carbonate prepolymer. The solid phase transesterification method, the ring-opening polymerization method of a cyclic carbonate compound, etc. can be mentioned.

As a typical example of the dihydric phenol,
2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A), 2,2-bis {(4-hydroxy-3-methyl) phenyl} propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4
-Hydroxyphenyl) -3-methylbutane, 9,9-
Bis {(4-hydroxy-3-methyl) phenyl} fluorene, 2,2-bis (4-hydroxyphenyl)-
3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4
-Hydroxyphenyl) -3,3,5-trimethylcyclohexane, α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene and the like can be mentioned. In particular, a homopolymer of bisphenol A can be mentioned. Such an aromatic polycarbonate resin is particularly preferable because it has excellent impact resistance.

As the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples thereof include phosgene, diphenyl carbonate or dihaloformate of dihydric phenol.

In producing an aromatic polycarbonate by reacting the above dihydric phenol with the carbonate precursor by an interfacial polycondensation method or a melt transesterification method,
If necessary, a catalyst, a terminal stopper, an antioxidant for preventing the dihydric phenol from oxidizing and the like may be used. The aromatic polycarbonate may be a branched polycarbonate obtained by copolymerizing a trifunctional or higher polyfunctional aromatic compound. Examples of trifunctional or higher polyfunctional aromatic compounds include 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane. Can be used.

When a polyfunctional compound which produces a branched polycarbonate is contained, such a proportion is 0.001 to 1 mol%, preferably 0.001 of the total amount of the aromatic polycarbonate.
It is 5 to 0.5 mol%, particularly preferably 0.01 to 0.3 mol%. Further, particularly in the case of the melt transesterification method, a branched structure may occur as a side reaction, and the amount of the branched structure is 0.
001 to 1 mol%, preferably 0.005 to 0.5 mol%, particularly preferably 0.01 to 0.3 mol%. The ratio can be calculated by ¹ H-NMR measurement.

Further, it may be a polyester carbonate obtained by copolymerizing an aromatic or aliphatic difunctional carboxylic acid. Examples of the aliphatic bifunctional carboxylic acid include an aliphatic bifunctional carboxylic acid having 8 to 20 carbon atoms, preferably 10 to 12 carbon atoms. The aliphatic difunctional carboxylic acid may be linear, branched or cyclic. The aliphatic difunctional carboxylic acid is preferably α, ω-dicarboxylic acid. Preferred examples of the aliphatic difunctional carboxylic acid include linear saturated aliphatic dicarboxylic acids such as sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, and icosanedioic acid.

The aromatic polycarbonate is a mixture of two or more of the above-mentioned polycarbonates having different dihydric phenols, polycarbonates containing a branching component, various polyester carbonates, and various aromatic polycarbonates such as polycarbonate-polyorganosiloxane copolymers. It may be one. Further, various kinds of polycarbonates having different production methods shown below, polycarbonates having different terminal stoppers, and the like can be used as a mixture of two or more kinds.

In the polymerization reaction of aromatic polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction between a dihydric phenol and phosgene, which is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, tertiary amines such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds,
It is also possible to use a catalyst such as a quaternary phosphonium compound. At that time, the reaction temperature is usually 0 to 40 ° C., and the reaction time is 1
The pH during the reaction is preferably maintained at 9 or higher for about 0 minutes to 5 hours.

Further, in such a polymerization reaction, a terminal stopper is usually used. Monofunctional phenols can be used as such an end terminator. Specific examples of monofunctional phenols include, for example, phenol and p-tert.
-Butylphenol, p-cumylphenol and isooctylphenol. Moreover, you may use a terminal terminator individually or in mixture of 2 or more types.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, which is produced by mixing the dihydric phenol and the carbonate ester while heating in the presence of an inert gas. It is carried out by a method of distilling alcohol or phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol to be produced, but is usually in the range of 120 to 350 ° C. In the latter stage of the reaction, the system was set at 1.33 × 10 ³ -1.
The alcohol or phenol produced by reducing the pressure to about 3.3 Pa is easily distilled. Reaction time is usually 1 to 4
It's about time.

Examples of the carbonate ester include an optionally substituted ester such as an aryl group having 6 to 10 carbon atoms, an aralkyl group or an alkyl group having 1 to 4 carbon atoms, and among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to accelerate the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol, and water. A catalyst such as an alkaline earth metal compound such as calcium oxide, barium hydroxide or magnesium hydroxide, or a nitrogen-containing basic compound such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine or triethylamine can be used. In addition, alkali (earth) metal alkoxides, alkali (earth)
It is possible to use a catalyst which is usually used for esterification reaction and transesterification reaction of organic acid salts of metals, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds and the like. The catalyst may be used alone or in combination of two or more kinds. The amount of these polymerization catalysts used is preferably 1 × 10 ⁻⁸ to 1 × 1 with ^respect to 1 mol of the dihydric phenol as a raw material.
It is selected in the range of 0 ^-3 equivalent, more preferably 1 x 10 ^{-7 to} 5 x 10 ^-4 equivalent.

In the reaction by the melt transesterification method, in order to reduce the phenolic terminal group, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenylcarbonate and 2-ethoxycarbonylphenylcarbonate are added at the latter stage or after the completion of the polycondensation reaction. Compounds such as phenyl carbonate can be added.

Further, in the melt transesterification method, it is preferable to use a deactivator which neutralizes the activity of the catalyst. The amount of the deactivator is 0.5 to 1 mol of the remaining catalyst.
It is preferably used in a proportion of 50 mol. Further, it is used in a proportion of 0.01 to 500 ppm, more preferably 0.01 to 300 ppm, and particularly preferably 0.01 to 100 ppm, relative to the polycarbonate after polymerization. Preferable examples of the quenching agent include phosphonium salts such as dodecylbenzenesulfonic acid tetrabutylphosphonium salt and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

Although the viscosity average molecular weight of the aromatic polycarbonate is not specified, when the viscosity average molecular weight is less than 10,000, the strength and the like decrease, and when it exceeds 50,000, the molding processability decreases. 1,000-5
Those of 10,000 are preferable, and 12,000 to 30,000
It is more preferable that it is 00, and even more preferable that it be 18,000.
It is 0-28,000. In this case, it is naturally possible to mix with a polycarbonate having a viscosity average molecular weight outside the above range.

The viscosity average molecular weight as used in the present invention is calculated by the following formula at a specific viscosity of 20 ml at 100 ml of methylene chloride.
Was obtained from a solution in which 0.7 g of aromatic polycarbonate was dissolved using an Ostwald viscometer. Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀ [t ₀ is the number of seconds of methylene chloride drop, and t is the sample Solution drop seconds] The calculated specific viscosity is inserted by the following equation to obtain a viscosity average molecular weight M
Ask for. η _SP /c=[η]+0.45×[η] ² c (however, [η]
Is the intrinsic viscosity) [η] = 1.23 × 10 ⁻⁴ M ^0.83 c = 0.7

Examples of the aromatic polycarbonate in the present invention include the following. That is, it is composed of an aromatic polycarbonate (PC) having a viscosity average molecular weight of 70,000 to 300,000 and an aromatic polycarbonate (PC) having a viscosity average molecular weight of 10,000 to 30,000, and has a viscosity average molecular weight of 16,0.
An aromatic polycarbonate having an amount of from 0 to 35,000 (hereinafter sometimes referred to as "high molecular weight component-containing aromatic polycarbonate") can also be used.

The aromatic polycarbonate containing a high molecular weight component is more advantageous at the time of injection compression molding because the entropy elasticity of the polymer is increased by the presence of PC. For example, appearance defects such as cold marks can be further reduced, and the condition range of injection compression molding can be broadened accordingly. On the other hand, the low molecular weight component of the PC component lowers the overall melt viscosity, promotes the relaxation of the resin, and enables molding with lower distortion. The same effect is also observed in the aromatic polycarbonate containing a branched component.

The aromatic polycarbonate containing a high molecular weight component can be obtained by mixing the above PC and PC in various ratios and adjusting them so as to satisfy a predetermined molecular weight range. Preferably, the aromatic polycarbonate 1 containing a high molecular weight component
PC is 2 to 40% by weight in 00% by weight,
Particularly preferably, PC is 5 to 20% by weight.

The polyphenylene ether as the component a2 will be described. The a2 component polyphenylene ether used in the present invention is a polymer or copolymer of a nucleus-substituted phenol having a phenylene ether structure (hereinafter simply referred to as PPE).
It may be referred to as a polymer).

Typical examples of the nucleus-substituted phenol polymer having a phenylene ether structure include poly (2,6-dimethyl-1,4-phenylene) ether and poly (2-methyl-6-ethyl-1,4-). 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-hydroxyethyl-1,4-phenylene) ether , Poly (2-methyl-6-chloroethyl-1,4-phenylene) ether and the like. Among these, poly (2,6-dimethyl-
1,4-phenylene) ether is particularly preferred.

Typical examples of the nuclear-substituted phenol copolymer having a phenylene ether structure are copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, and 2,6-dimethylphenol and o. -Copolymer with cresol or copolymer of 2,6-dimethylphenol with 2,3,6-trimethylphenol and o-cresol.

The method for producing the above PPE polymer is not particularly limited, but for example, US Pat. No. 4,788,27.
According to the method described in Japanese Patent No. 7 (Japanese Patent Application No. 62-77570), 2,6
It can be produced by oxidative coupling polymerization of xylenol.

Although various molecular weights and molecular weight distributions of PPE polymers can be used, the molecular weight is 0.5 g / dl chloroform solution, and the reduced viscosity at 30 ° C. is 0.20 to 0.70 dl / The range of g is preferable, and the range of 0.30 to 0.55 dl / g is more preferable.

In the PPE polymer of the present invention, various other phenylene ether units, which have been proposed to be present in the PPE polymer, have been proposed so far as long as they do not violate the gist of the present invention. May be included as. Examples of those proposed to coexist in a small amount include Japanese Patent Application No. 63-12698 and Japanese Patent Application Laid-Open No. 63-12698.
A 2- (dialkylaminomethyl) -6-methylphenylene ether unit, a 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit, and the like described in JP-A-301222 are mentioned. Also, a small amount of diphenoquinone or the like is bonded to the main chain of the PPE polymer is included.

Further, the PPE polymer has the following α, β-
It may also include PPE polymers modified with ethylenically unsaturated compounds such as unsaturated carboxylic acids or their anhydrides. When the PPE polymer modified by using these is used, it is possible to provide a molded article having excellent compatibility with a polyamide or a styrene polymer and having good impact resistance.
Examples of α, β-unsaturated carboxylic acids or anhydrides thereof include JP-B-49-2343 and JP-B-3-5248.
No. 6, etc., maleic anhydride, phthalic acid, itaconic anhydride, glutaconic anhydride, citraconic anhydride,
Examples thereof include aconitic anhydride, hymic acid anhydride, 5-norbornene-2-methyl-2-carboxylic acid, maleic acid and fumaric acid, but are not limited thereto, and maleic anhydride is particularly preferable.

The reaction of an α, β-unsaturated carboxylic acid such as maleic anhydride or its anhydride with a PPE polymer is carried out by mixing the two in the presence or absence of an organic peroxide, and then mixing them with PP.
It can be produced by heating to a temperature not lower than the glass transition temperature of the E polymer. When the resin composition of the present invention is produced, a PPE polymer to which an α, β-unsaturated carboxylic acid such as maleic anhydride or its anhydride is bound in advance may be used. At the same time when the resin composition is produced,
A method of reacting with a PPE polymer by adding an α, β-unsaturated carboxylic acid such as maleic anhydride or an anhydride thereof may be used.

The polyarylate of the component a2 will be described. The polyarylate of the a2 component used in the present invention is
It is obtained from an aromatic dicarboxylic acid or its derivative and a dihydric phenol or its derivative. The aromatic dicarboxylic acid used for preparing the polyarylate may be any one as long as it reacts with the dihydric phenol to give a satisfactory polymer, and one kind or a mixture of two or more kinds is used.

As a preferred aromatic dicarboxylic acid component,
Examples include terephthalic acid and isophthalic acid. It may also be a mixture of these.

Specific examples of the dihydric phenol component include:
2,2-bis (4-hydroxyphenyl) propane,
4,4'-dihydroxydiphenyl sulfone, 4,4 '
-Dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenylmethane, 2,2'-bis (4hydroxy-3,5-dimethylphenyl) propane, 1 , 1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxydiphenyl, hydroquinone and the like. Although these dihydric phenol components are para-substituted, other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

Among the above preferred polyarylates, the aromatic dicarboxylic acid component is terephthalic acid and isophthalic acid, and the dihydric phenol component is 2,2.
-Bis (4-hydroxyphenyl) propane (bisphenol A) may be mentioned. The ratio of terephthalic acid and isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 1/9 (molar ratio), and particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

Other typical polyarylates include those in which the aromatic dicarboxylic acid component is terephthalic acid and the dihydric phenol component is bisphenol A and hydroquinone. The ratio of such bisphenol A and hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and 60/4.
0 to 70/30 is more preferable.

The viscosity average molecular weight of polyarylate is about 7,
The range of 000 to 100,000 is preferable from the viewpoint of physical properties and moldability. As the polyarylate, those produced by any of the interfacial polycondensation method and the transesterification method can be selected.

The styrene polymer as the component a2 will be described. The styrene-based polymer as the component a2 used in the present invention is obtained by polymerizing a styrene-based monomer and, if necessary, another vinyl monomer copolymerizable therewith.

Examples of the styrene-based monomer include styrene and α
-Methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, monobromostyrene, dibromostyrene, fluorostyrene, tribromostyrene. And the like, and styrene is particularly preferable. These may be used alone or in combination of two or more.

Other vinyl monomers copolymerizable with the styrene-based monomer include vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, and methyl (meth).
Acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate,
Amyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, cyclohexyl (meth)
Acrylate, alkyl ester of (meth) acrylic acid such as dodecyl (meth) acrylate, aryl ester of (meth) acrylic acid such as phenyl (meth) acrylate, benzyl (meth) acrylate (where (meth) acrylate and (meth)) The expression of acrylic acid is
Acrylate and methacrylate, as well as containing both acrylic acid and methacrylic acid), epoxy group-containing methacrylic acid ester such as glycidyl methacrylate, maleimide, N-methylmaleimide, N-
Examples thereof include maleimide-based monomers such as phenylmaleimide, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid and itaconic acid, and anhydrides thereof.

Examples of the styrene-based polymer include polystyrene, acrylonitrile-styrene copolymer (AS copolymer), styrene-methylmethacrylate copolymer (MS copolymer), methylmethacrylate
Examples thereof include acrylonitrile / styrene copolymer (MAS copolymer), styrene / maleic anhydride copolymer (SMA copolymer), or a mixture thereof. The styrene-based polymer is a polymer or copolymer having a narrow molecular weight distribution obtained by a method such as anion living polymerization or radical living polymerization, a block copolymer, and a polymer having high stereoregularity, or a copolymer. It is also possible to use. These may be used alone or in combination of two or more. Of these, polystyrene and AS copolymer are preferable. Polystyrene is particularly excellent in compatibility with polyphenylene ether, and AS copolymer is excellent in compatibility with aromatic polycarbonate.

The molecular weight of the styrenic polymer is 1 expressed as the weight average molecular weight (Mw) calculated by GPC measurement (gel permeation chromatography measurement).
50,000 to 500,000 is preferable, 50,000
To 250,000 are more preferable, and 70,000 to 20
10,000 is especially preferred. The weight average molecular weight shown here is calculated as a value in terms of polystyrene by GPC measurement using a calibration straight line using a standard polystyrene resin.

When the styrene-based polymer is a copolymer, the ratio of styrene-based monomer is 100
It is preferably 20 mol% or more in the mol% and 30
It is more preferably at least mol%, still more preferably at least 40 mol%. The upper limit is 90 mol% or less, preferably 8
When it is 5 mol% or less, the advantage as a copolymer is easily obtained. For example, in an AS polymer, the molar ratio of styrene to acrylonitrile (St / AN) is St / A
The range of N = 30/70 to 85/15 is preferable, and St /
The range of AN = 45 / 55-80 / 20 is more preferable,
The range of St / AN = 50/50 to 75/25 is more preferable.

Among the above, preferable combinations of the a1 component and the a2 component are as follows. Firstly, a combination of polyamide as the a1 component and polyphenylene ether as the a2 component may be mentioned, and such a combination may further comprise polystyrene as the a2 component. Secondly, an aromatic polyester and a as the a1 component
The two components include combinations of aromatic polycarbonates, and such combinations may further include an AS copolymer as the a2 component. In particular, a combination of an aromatic polyester as the a1 component and an aromatic polycarbonate as the a2 component is preferable because the dimensional change due to water absorption is small.

Next, the reinforcing filler which is the component B of the present invention will be described. Various inorganic fillers and heat-resistant organic fillers can be used as the reinforcing filler of the present invention. As the reinforcing filler, a plate-like and / or fibrous inorganic filler is more preferable. This is because such a reinforcing filler has a particularly high effect of reducing dimensional change.

Specific examples of the plate-like inorganic filler include:
Examples thereof include talc, mica, glass flakes, metal flakes, graphite flakes, smectite, kaolin and the like. In addition, for example, a hollow filler such as a glass balloon may be crushed by melt-kneading with a resin to obtain the same rigidity improving effect as the plate-like inorganic filler. The plate-like filler of the present invention includes those exhibiting such effects. Further, as the fibrous inorganic filler, specifically, glass fiber, carbon fiber, heat-resistant organic fiber, metal fiber,
Ceramic fiber, slag fiber, rock wool, wollastonite, xonotlite, potassium titanate whiskers,
Examples thereof include aluminum borate whiskers, boron whiskers, and basic magnesium sulfate whiskers. Examples of the plate-like inorganic filler and the fibrous inorganic filler include those obtained by surface-coating different materials. Typical different materials are metals, alloys, metal oxides and the like. The coating of metal or alloy can give high conductivity,
In addition, the designability may be improved. In some cases, the metal oxide coating can impart a function such as photoconductivity, and the design can be improved.

The average particle diameter of the plate-like inorganic filler is 0.
05-50 μm is preferable, 0.05-10 μm is more preferable, 0.05-5 μm is further preferable, 0.05
˜2 μm is particularly preferred. The average particle diameter is D50 measured by an X-ray transmission method which is one of liquid phase sedimentation methods.
(Median diameter of particle size distribution). As a specific example of an apparatus for performing such measurement, Se manufactured by Micromeritics Co., Ltd.
digraph5100 etc. can be mentioned.

Talc is suitable as the plate-like inorganic filler. Further, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. If the bulk density is low, problems such as a decrease in thermal stability may occur during melt-kneading. As a method of granulating talc to increase the bulk density, there are a method using a binder and a method not using it substantially. In the method using a binder, a liquid in which a resin serving as a binder is dissolved or dispersed and talc are uniformly mixed with a mixer such as a super mixer, and then dried. A uniform mixture of other liquid and talc is granulated through a granulator and then dried. In any case, drying may be omitted. The method that does not use a binder is usually a deaeration compression method. A representative example of such a method is a method of roller-compressing with a briquetting machine while degassing. On the other hand, especially in the case of talc ground using a grinding aid such as water, rolling granulation or agglomeration granulation is preferable. Furthermore, it is preferable that the talc is thereafter dried to sufficiently remove components such as water. Preferable examples of such talc include a granulated product obtained by granulating a slurry composed of a mixture of water and ground talc by a method such as rolling granulation and then drying.

From the viewpoint of impact resistance, the average particle size of talc is particularly preferably in the range of 0.1 to 1.5 μm. It is considered that this is because the crystals of the crystalline polymer are more finely crystallized. Specific examples of such more preferable talc include H produced by IMI-FABI, Italy.
iTalc HTP ultra10C, and HiT
Examples thereof include alc HTP ultra5C, SG2000 and SG1000 manufactured by Nippon Talc Co., Ltd.

The fiber diameter of the fibrous inorganic filler is 0.1 to 1
0 μm is preferable, 0.1 to 5 μm is more preferable,
0.1 to 3 μm is more preferable. The aspect ratio (average fiber length / average fiber diameter) is preferably 3 or more. The upper limit of the aspect ratio is 30 or less. That is, as a preferred embodiment of the fibrous inorganic filler, the fiber diameter is 0.
Examples thereof include fibrous inorganic fillers having a 1 to 10 μm and an aspect ratio of 3 to 30. Here, the fiber diameter is obtained by observing the inorganic filler with an electron microscope, obtaining the individual fiber diameters, and calculating the number average fiber diameter from the measured values. The electron microscope is used because it is difficult for an optical microscope to accurately measure the size of a target level. The fiber diameter is, with respect to the image obtained by observing with an electron microscope, the filler to be measured for the fiber diameter is randomly extracted, the fiber diameter is measured in the vicinity of the central portion, and the number average fiber is obtained from the measured values. Calculate the diameter. The observation magnification is approximately 1000 times, and the number of measurements is 500 or more. On the other hand, in the measurement of the average fiber length, the filler is observed with an optical microscope, the individual lengths are obtained, and the number average fiber length is calculated from the measured value. Observation with an optical microscope
Start by preparing a dispersed sample so that the fillers do not overlap too much. The observation is performed under the condition of 20 times the objective lens, and the observed image is captured as image data in a CCD camera having about 250,000 pixels. The fiber length is calculated from the obtained image data by using an image analyzer and a program for obtaining the maximum distance between two points of the image data. Under such a condition, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more.

As the above fibrous inorganic filler, wollastonite, various whiskers, carbon fibers and the like are preferable, and wollastonite is particularly preferable.

The resin composition forming the injection compression-molded article of the present invention comprises a crystalline thermoplastic polymer (a1 component) 5 to 90.
Parts by weight, and amorphous thermoplastic polymer (a2 component) 1
It comprises 0 to 95 parts by weight in total of 100 parts by weight (thermoplastic polymer component (A component)).

The lower limit of the proportion of the a1 component in the thermoplastic polymer component (A component) is preferably 10 parts by weight or more, more preferably 15 parts by weight or more, still more preferably 20 parts by weight or more, per 100 parts by weight of the A component. . On the other hand, a1
The upper limit of the ratio of the components is 8 per 100 parts by weight of the component A.
The amount is preferably 0 parts by weight or less, more preferably 70 parts by weight or less. The lower limit of the proportion of the component a2 is preferably 20 parts by weight or more, and more preferably 30 parts by weight or more per 100 parts by weight of the component A. On the other hand, the upper limit of the proportion of the component a2 is preferably 90 parts by weight or less, more preferably 85 parts by weight or less, still more preferably 80 parts by weight or less, per 100 parts by weight of the component A.

The lower limit of the ratio of the B component is the A component 10
Per 0 parts by weight, 1 part by weight or more is preferable, 5 parts by weight or more is more preferable, 10 parts by weight or more is further preferable, 15
It is particularly preferable that the amount is at least parts by weight. The upper limit of the proportion of component B is preferably 70 parts by weight or less, more preferably 60 parts by weight or less, and even more preferably 50 parts by weight or less, per 100 parts by weight of component A.

The thermoplastic polymer component of the present invention includes
It may contain various block copolymers or graft copolymers formed by combining crystalline thermoplastic polymers and amorphous thermoplastic polymers. Further, it may include various block polymers formed by combining any one of the crystalline thermoplastic polymer, the amorphous thermoplastic polymer, and the polymers formed by combining these with a rubber-like polymer described below. Such a polymer component formed by bonding different kinds of polymers is produced as a compatibilizer between the polymers when it is mixed as a part of the raw material when producing the resin composition, or when producing the resin composition. It may be generated by a chemical reaction. In the present invention, when a polymer component to which such a different kind of polymer is bound is present, the crystalline thermoplastic polymer portion is used as the a1 component, the amorphous thermoplastic polymer portion is used as the a2 component, and the rubber polymer portion described below is used. Is reflected as a C component in the composition ratio. This is because each block in the polymer component formed by binding such different polymers has the properties of each polymer not a little. Therefore, the component A of the present invention contains a compatibilizer composed of a polymer in which such a different polymer is bound.

The resin composition constituting the injection compression-molded product of the present invention can further contain a rubbery polymer (component C) in addition to the above-mentioned components A and B. Since the presence of such a rubbery polymer greatly contributes to the improvement of impact resistance, it is more preferable to include the rubbery polymer.

The rubbery polymer means a rubber component having a glass transition temperature of 10 ° C. or lower, preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and a monomer component copolymerizable with the rubber component. It means a polymer obtained by copolymerizing and. As the rubber component, polybutadiene, polyisoprene, a diene-based copolymer (for example, a random copolymer and a block copolymer of styrene / butadiene, an acrylonitrile / butadiene copolymer, and an acrylic / butadiene rubber (acrylic acid alkyl ester or Copolymer of alkyl methacrylate and butadiene)),
Copolymers of ethylene and α-olefins (for example, ethylene / propylene random copolymers and block copolymers, ethylene / butene random copolymers and block copolymers), ethylene and unsaturated carboxylic acid esters Copolymers (eg ethylene / methacrylate copolymers and ethylene / butyl acrylate copolymers), ethylene / aliphatic vinyl copolymers (eg ethylene / vinyl acetate copolymers), ethylene / propylene And non-conjugated diene terpolymers (eg ethylene / propylene / hexadiene copolymers), acrylic rubbers (eg polybutyl acrylate, poly (2
-Ethylhexyl acrylate), and a copolymer of butyl acrylate and 2-ethylhexyl acrylate), and a silicone rubber (for example, polyorganosiloxane rubber, polyorganosiloxane rubber component and polyalkyl (meth) acrylate rubber component) IPN type rubbers; that is, rubbers having a structure in which two rubber components are intertwined with each other so that they cannot be separated, and IPN type rubbers composed of a polyorganosiloxane rubber component and a polyisobutylene rubber component).

The monomer component to be copolymerized with the rubber component is a styrene-based monomer, a vinyl cyanide compound,
Preferable examples include (meth) acrylic acid ester compounds and (meth) acrylic acid compounds. Other monomer components include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimides, N-methylmaleimide, maleimide-based monomers such as N-phenylmaleimide, acrylic acid, methacrylic acid, maleic acid, maleic anhydride. Examples thereof include α, β-unsaturated carboxylic acids such as acid, phthalic acid, and itaconic acid, and their anhydrides.

More specifically, SB (styrene-butadiene) polymer, ABS (acrylonitrile-butadiene-styrene) polymer, MBS (methyl methacrylate-).
Butadiene-styrene) polymer, MABS (methyl methacrylate-acrylonitrile-butadiene-styrene) polymer, MB (methyl methacrylate-butadiene) polymer, ASA (acrylonitrile-styrene-acrylic rubber) polymer, AES (acrylonitrile-ethylene propylene rubber) -Styrene) polymer, MA (methyl methacrylate-acrylic rubber) polymer, MAS (methyl methacrylate-acrylic rubber-styrene) polymer,
Examples thereof include a methyl methacrylate-acrylic / butadiene rubber copolymer, a methyl methacrylate-acrylic / butadiene rubber-styrene copolymer, and a methyl methacrylate- (acrylic / silicone IPN rubber) polymer.

Other rubbery polymers include various thermoplastic elastomers such as styrene-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyurethane-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyamide-based thermoplastic elastomers.

The proportion of the rubber component in the above rubbery polymer is preferably 5 to 95% by weight, more preferably 10 to 90%.
%, More preferably 50 to 85% by weight. Similarly, in the case of a thermoplastic elastomer, the proportion of the soft segment is preferably 5 to 95% by weight, more preferably 10 to 9%.
It is 0% by weight, more preferably 50 to 85% by weight. The proportion of the rubber-like polymer (component C) is preferably 0.5 to 50 parts by weight, more preferably 1 to 30 parts by weight, still more preferably 2 to 20 parts by weight, per 100 parts by weight of the component A. The ratio of the rubber component contained in the rubbery polymer is preferably 0.3 to 40 parts by weight, more preferably 0.5 to 24 parts by weight, and 1 to 15 parts by weight per 100 parts by weight of the component A.
More preferably parts by weight.

Further, the resin composition constituting the injection compression molded article of the present invention may contain a melt elasticity effect modifier. The effect of such a modifier improves the melt elasticity and enables the appearance improvement during injection compression molding. Other examples include prevention of uneven thickness by improving melt elasticity during gas-assisted injection molding, and prevention of jetting during injection molding due to the ballast effect.

The effect of modifying the melt elasticity is basically obtained by a high molecular weight polymer, and in the case of a polymer or copolymer of an ethylenically unsaturated compound, its weight average molecular weight is 1,000,000 to 20,000,000, more preferably 200
Those of 10 to 10 million are preferable. Representative examples of the polymer or copolymer of the ethylenically unsaturated compound include polystyrene, polymethylmethacrylate, poly (acrylonitrile-styrene) copolymer, and polytetrafluoroethylene. Among them, polytetrafluoroethylene is preferable. This is because the longer the relaxation time is, the more advantageous it is to obtain the effect, and for that purpose, it is more preferable that the softening temperature and the melting point are higher than the molding processing temperature of the thermoplastic resin composition of the present invention.

Such polytetrafluoroethylene (hereinafter may be simply referred to as PTFE) is widely used as a melt dripping inhibitor or the like as PTFE having a fibril-forming ability. P having such fibril forming ability
Commercially available products of TFE include, for example, Teflon 6J manufactured by Mitsui DuPont Fluorochemical Co., Ltd. and Daikin Chemical Industry Co., Ltd.
Polyflon MPA FA500, F-201L and the like. Commercially available aqueous dispersions of PTFE include Fluon AD-1, AD-936 manufactured by Asahi IC Polymers Co., Ltd., Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui DuPont Fluoro. Representative examples thereof include Teflon 30J manufactured by Chemical Co., Ltd.

Further, PTFE may be used in a mixed form with a resin. The mixed form of PTFE is (1) a method of mixing an aqueous dispersion of PTFE and an aqueous dispersion or solution of an organic polymer and coprecipitating to obtain a coaggregation mixture (Japanese Patent Laid-Open No. 60-258263). Kaisho 6
3-154744, etc.),
(2) a method of mixing an aqueous dispersion of PTFE with dried organic polymer particles (a method described in JP-A-4-272957), (3) an aqueous dispersion of PTFE and an organic polymer particle solution A method of uniformly mixing and simultaneously removing the respective media from the mixture (Japanese Patent Laid-Open No. 06-2202).
No. 10, JP-A-08-188653 and the like), and (4) a method of polymerizing a monomer forming an organic polymer in an aqueous dispersion of PTFE (JP-A-9-9).
5583), and (5) PT
After uniformly mixing the aqueous dispersion of FE and the organic polymer dispersion,
Further, those obtained by a method of polymerizing a vinyl-based monomer in the mixed dispersion and then obtaining a mixture (method described in JP-A No. 11-29679) can be used. Commercially available products of these mixed forms of PTFE include "Metabrene A3000" (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and "BLEND manufactured by GE Specialty Chemicals.
EX B449 "(trade name) and the like.

The composition ratio of such a melt elasticity effect modifier is
0.01 to 20% by weight is preferable in 100% by weight of the resin composition, more preferably 0.05 to 10% by weight, and 0.1 to 10% by weight.
5% by weight is more preferable.

Further, in the present invention, a breakage suppressing agent for suppressing breakage of the reinforcing filler (component B) can be included. As the fold suppressing agent, there can be used a component selected from (i) a lubricant containing a functional group having reactivity with the reinforcing filler, and (ii) a lubricant whose surface is previously coated on the reinforcing filler. Among them, as a suitable bending inhibitor, an olefin wax containing a carboxyl group and / or a carboxylic acid anhydride group is preferable, and α-
A copolymer of an olefin and maleic anhydride is more preferable. Such a bending inhibitor is 0.1% in 100% by weight of the resin composition.
01 to 5% by weight is preferable, 0.05 to 3% by weight is more preferable, and 0.05 to 1% by weight is further preferable.

The resin composition constituting the injection compression-molded article of the present invention further contains a flame retardant, a flame retardant aid (eg, sodium antimonate, antimony trioxide, etc.) as long as the object of the present invention is not impaired. ), A char-forming compound (for example, a novolac type phenol resin, a condensate of pitches and formaldehyde, etc.), a nucleating agent (for example, sodium stearate, ethylene-sodium acrylate, etc.), a heat stabilizer, an antioxidant ( For example, hindered phenol-based antioxidants, sulfur-based antioxidants, etc.),
UV absorbers, light stabilizers, mold release agents, antistatic agents, foaming agents, flow modifiers, antibacterial agents, photocatalytic antifouling agents (particulate titanium oxide, particulate zinc oxide, etc.), lubricants, colorants, fluorescence enhancement A whitening agent, a phosphorescent pigment, a fluorescent dye, an infrared absorbing agent, a photochromic agent, etc. can be added.

Examples of the heat stabilizer include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and their esters. Specific examples thereof include triphenylphosphite, tris (nonylphenyl) phosphite and tris (2 , 4-di-t-butylphenyl) phosphite, tridecylphosphite, trioctylphosphite, trioctadecylphosphite, didecylmonophenylphosphite,
Dioctyl monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, bis (2,6-di-t
-Butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-
Ethylphenyl) pentaerythritol diphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octylphosphite, bis (nonylphenyl) pentaerythritol diphosphite, bis (2,2
4-di-t-butylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tributyl phosphate, triethyl phosphate, trimethyl phosphate, triphenyl phosphate, diphenyl monoorthoxenyl phosphate, dibutyl phosphate, dioctyl phosphate,
Examples thereof include diisopropyl phosphate, tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylenediphosphosphinate, dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. These heat stabilizers may be used alone or
You may use it in mixture of 2 or more types. The composition ratio of the heat stabilizer is preferably 0.0001 to 1% by weight, more preferably 0.0005 to 0.5% by weight, and further preferably 0.001 to 0.1% by weight in 100% by weight of the resin composition. preferable.

Specific examples of the phenolic antioxidants include, for example, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate and 2-tert-butyl-6-. (3'-ter
t-Butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyl Oxy] -1,
1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, and tetrakis [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) Propionate] methane and the like can be preferably mentioned, and n-octadecyl-β
More preferred is-(4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate.

Specific examples of the sulfur antioxidant of the present invention include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, dimyristyl-3,3'-. Thiodipropionate, distearyl-3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, pentaerythritol tetra (β
-Lauryl thiopropionate) ester, bis [2-
Methyl-4- (3-laurylthiopropionyloxy)
-5-tert-butylphenyl] sulfide, octadecyl disulfide, mercaptobenzimidazole,
2-mercapto-6-methylbenzimidazole, 1,
1'-thiobis (2-naphthol) and the like can be mentioned. More preferably, a pentaerythritol tetra ((beta) -lauryl thiopropionate) ester can be mentioned.

Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,
Examples thereof include benzophenone-based UV absorbers represented by 2'-dihydroxy-4,4'-dimethoxybenzophenone and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane.

Examples of the ultraviolet absorber include 2-
(2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazole, 2
-(2'-hydroxy-3 ', 5'-bis (α, α'-
Dimethylbenzyl) phenylbenzotriazole, 2,
2'methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], methyl-3- [3-tert-butyl-5- (2H -Benzotriazol-2-yl) -4
-A benzotriazole-based ultraviolet absorber represented by a condensate of -hydroxyphenyl propionate-polyethylene glycol can be mentioned.

Further, as the ultraviolet absorber, for example, 2-
(4,6-diphenyl-1,3,5-triazine-2-
Yl) -5-hexyloxyphenol, 2- (4,6
Examples thereof include hydroxyphenyltriazine compounds such as -bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

Further, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl)- 1,2,3,4-butanetetracarboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-
2,4-Diyl] [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene [(2,2,6,6
-Tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane, and other hindered amine-based light stabilizers may also be included. When such a light stabilizer is used in combination with the above-mentioned ultraviolet absorber and various antioxidants, it exhibits better performance in terms of weather resistance and the like.

The composition ratio of the phenol-based antioxidant or the sulfur-based antioxidant is 100% by weight of the resin composition,
0.001 to 2% by weight is preferable, 0.005 to 1% by weight is more preferable, and 0.01 to 0.5% by weight is further preferable.

The composition ratio of the ultraviolet absorber and the light stabilizer is 0.001 to 100% by weight of the resin composition.
It is preferably 2% by weight, more preferably 0.005 to 1% by weight, further preferably 0.01 to 1% by weight, and particularly preferably 0.01 to 0.5% by weight.

As the releasing agent, for example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc.), those modified with a functional group-containing compound such as acid modification may also be used. Can be used), fluorine compounds (fluorine oil represented by polyfluoroalkyl ether, etc.), paraffin wax, beeswax and the like. Preferred releasing agents include saturated fatty acid esters and polyolefin waxes such as glycerin monostearate, glycerin distearate, glycerin tristearate and the like glycerin fatty acid esters, decaglycerin decasterate and decaglycerin tetrastearate, etc. Polyglycerin fatty acid esters, lower fatty acid esters such as stearyl stearate, higher fatty acid esters such as sebacic acid behenate, and erythritol esters such as pentaerythritol tetrastearate are used. The release agent is the resin composition 1 of the present invention.
0.001 to 2% by weight is preferable in 0.00% by weight, more preferably 0.005 to 1% by weight, still more preferably 0.00.
It is from 1 to 1% by weight, particularly preferably from 0.01 to 0.5% by weight.

Examples of the antistatic agent include polyether ester amide, glycerin monostearate, ammonium dodecylbenzenesulfonate, phosphonium dodecylbenzenesulfonate, sodium alkylsulfonate, monoglyceride maleate, diglyceride maleate. And so on.

Further, as the flame retardant, red phosphorus or a red phosphorus flame retardant represented by stabilized red phosphorus whose surface is microencapsulated by using a known thermosetting resin and / or an inorganic material; tetra Brombisphenol A,
Tetrabromobisphenol A oligomer, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, brominated bisphenol polycarbonate, brominated polystyrene, brominated crosslinked polystyrene, brominated polyphenylene ether, polydibromophenylene ether, decabromodiphenyl oxide Halogen flame retardants typified by bisphenol condensates and halogen-containing phosphates; triphenyl phosphate as monophosphate compounds, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) as condensed phosphates, and other penta Organic phosphate ester flame retardants represented by erythritol diphenyl diphosphate; polyphosphoric acid Inorganic phosphates such as ammonium salts, aluminum phosphates and zirconium phosphates, hydrates of inorganic metal compounds such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc metaborate, magnesium oxide, molybdenum oxide, oxidation Inorganic flame retardants represented by zirconium, tin oxide, antimony oxide, etc .; potassium perfluorobutane sulfonate, calcium perfluorobutane sulfonate, cesium perfluorobutane sulfonate, diphenyl sulfone-3-potassium sulfonate, diphenyl sulfone- Organic alkaline (earth) metal salt flame retardants represented by potassium 3,3'-disulfonate; (poly) organosiloxane compounds containing phenyl group, vinyl group and methyl group, (poly) organosiloxane and polycarbonate resin The weight of , And the like phosphazene flame retardants typified by phenoxy phosphazene oligomers and cyclic phenoxy phosphazene oligomers; silicone flame retardants typified by the body.

Any method may be employed to produce the resin composition constituting the injection compression molded article of the present invention. For example, after the components a1 and a2, and optionally the components B, C and other additives are thoroughly mixed using a premixing means such as a V-type blender, a Henschel mixer, a mechanochemical device, an extrusion mixer, Granulate using an extrusion granulator or briquetting machine as needed,
Then, a method of melt-kneading with a melt-kneader typified by a vent type twin-screw extruder and pelletizing with a device such as a pelletizer can be mentioned.

In addition, a method of supplying each component independently to a melt-kneader represented by a vent type twin-screw extruder, or pre-mixing a part of each component and then melt-kneading independently of the remaining components The method of supplying to the machine is also included. As a premixing method, for example, when a powder having a form of A is included as a component A, a method of blending a part of the powder with an additive to be blended to form a masterbatch of the additive diluted with the powder is used. Can be mentioned. Furthermore, a method in which one component is independently supplied from the middle of the melt extruder may be used. In addition, when there are liquid components,
A so-called liquid injection device or a liquid addition device can be used for supplying to the melt extruder.

The injection-compression molded product of the present invention can be obtained by injection-compressing the pellets of the resin composition thus obtained. Incidentally, such pellets are preferably a single pellet containing all the components constituting the injection compression molded product, but pellets having different components are mixed at the time of injection compression molding to obtain the injection compression molded product of the present invention. It is also possible. In such injection molding, not only the normal cold runner molding method but also the hot runner molding method is possible, and the application of the method is preferable. Since the present invention is a large-sized molded product, the weight of the cold runner portion becomes large, which is not economical. On the other hand, the injection compression molded product of the present invention is valuable in that a molded product having good impact resistance can be obtained even in such a hot runner having a high heat load. Further, in the present invention, gas-assisted injection molding, foam molding (including by injection of supercritical fluid), insert molding, in-mold molding, local high temperature mold molding (including heat insulation mold molding), two-color molding, sandwich. A molded product can be obtained by using molding, ultra-high speed injection molding or the like together.

The maximum compression area of the injection compression-molded article of the present invention is 1000 cm ² or more, more preferably 20.
It is at least 00 cm ² . On the other hand, the upper limit is 50,000
cm ² or less is appropriate, 25,000cm ² or less being more preferred. The thickness of the injection compression molded product is 0.5 to
The range of 10 mm is preferable, 1-8 mm is more preferable, 1.5-7 mm is further preferable, and 2-6 mm is particularly preferable. Further, the flow length is preferably 30 cm or more, and 35
cm or more is more preferable. The upper limit is preferably 150 cm or less, and more preferably 100 cm or less. Furthermore, the present invention has a very suitable effect in an injection-molded product having a gate on the side surface of the molded product, which tends to have a large flow length. Therefore, a preferable embodiment of the injection-molded article of the present invention is an injection compression-molded article having a gate on the side surface of the molded article.

INDUSTRIAL APPLICABILITY The present invention makes it possible to provide a large-sized resin injection-molded article having excellent dimensional stability and sufficient impact resistance. In particular, the present invention provides a large-sized resin injection-molded product having the following characteristics in impact resistance.

That is, from a large injection molded product obtained by injection molding without performing injection compression molding, a test piece of 50 mm in length and 50 mm in width is cut out so as to include the flow end, and the high speed of the test piece is measured. The breaking energy (J) of the surface impact test is (E2). On the other hand, from the same molded product obtained by injection compression molding, the same portion as the above is cut out as a test piece, and the breaking energy (J) in the high-speed surface impact test on the test piece is defined as (E1). At this time, the E1 satisfies at least 1.1 times or more of E2, more preferably 1.2 times or more, and further preferably 1.3 times or more. Incidentally, the upper limit is a case where a completely filled molded product cannot be obtained by normal injection molding (that is, breaking energy is 0).

In the high speed surface impact test, the test piece was attached to a pedestal having a circular hole with a diameter of 25.4 mm.
It is performed at a punching speed of 5 m / sec and a measurement temperature of 23 ° C. using a hammer core having a hemispherical tip with a diameter of 12.7 mm.

The injection compression-molded article of the present invention may be subjected to surface treatment such as coating, painting, plating, printing and sealing on the molded article. In automobile exterior materials, particularly automobile exterior panels, which are effective uses of the present invention, resin molded articles are usually coated. The baking temperature is often 12
Although the temperature is 0 ° C. or higher, in a preferred embodiment of the components a1 and a2, the injection compression molded article of the present invention can sufficiently withstand such coating. Further, in recent years, new paints (water-based paints, powder paints, etc.) have been studied due to environmental problems, and these new paints can be suitably used for the injection compression molded article of the present invention. Further, although film insert molding has been actively studied for the purpose of coatingless, the injection compression molded product of the present invention is excellent in suitability for film insert molding as compared with a normal injection molded product, and particularly in a deep drawing shape. It is suitable for film insert molding.

The injection-compression-molded article of the present invention thus obtained is suitable as an automobile exterior material, particularly an outer panel, as already described. It is particularly suitable for so-called vertical skins such as fenders and door panels.

[0133]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The molding conditions and the main evaluations are shown below. (1) Injection compression molding conditions The injection compression molding machine is a hydraulic circuit and control system that enables injection compression of a mold compression type injection molding machine (J1300E-C5 manufactured by Japan Steel Works, Ltd.) with a mold clamping force of 12700 kN. Was used. Injection compression molded products are
The molded product had a projected area of about 2100 cm ² and a thickness of 3 mm with the rear door of an automobile being about 1/2 scale.
The molded product had a gate on the side surface of the molded product. The shape of such a molded product is shown in FIG. The compression stroke in injection compression molding was 2 mm. Further, the molten resin was filled in the cavity that had been retracted by 2 mm from the final mold clamping position in advance. Therefore, the mold cavity having a volume 1.7 times the intended volume of the molded product was filled with the resin for the volume of the molded product. The filling was performed at a single injection speed of 20 mm / sec. The compression process was started 0.5 seconds before the end of filling (that is, the overlap time was 0.5 seconds), and was performed at a speed of about 2 mm / sec. The compression pressure was set to 30 MPa at maximum. The molding was performed with a valve gate type hot runner having a diameter of 3 mm, and the conditions were such that the valve was closed immediately after the completion of filling and no holding pressure was applied. The cooling time was 60 seconds. The mold temperature was controlled as a series circuit using a water circulation mold temperature controller. Although the molding cycle was not always constant due to the time taken to remove the sample, it was carried out for about 110 seconds. The temperature in the hopper dryer during molding was 100 ° C. Molding was carried out continuously for 20 shots, and the following high-speed surface impact test and linear expansion coefficient were measured from the samples of 6th to 15th shots, and the coating test used 16th to 20th shots.

(2) Evaluation of injection compression molded product (i) High-speed surface impact test As shown in FIG. 1, four test pieces each having a length of 50 mm and a width of 50 mm from the central portion including the flow end were tested from the injection compression molded product. I cut out the dots. This portion was a plate-like body that was slightly curved. The plate-like body is placed in an environment of 23 ° C. and 50% RH for 1
After leaving it for a week to adjust the condition of the test piece, a high-speed surface impact test was performed. A high-speed surface impact tester Hydroshot HTM-1 (manufactured by Shimadzu Corporation) is used as a tester, and in the test, the tip of the hammer is hemispherical and the diameter of the hammer is 12.7 mm and the hole diameter of the pedestal is 25. A 4 mm cradle was used. There are two levels of impact velocity of the hammer, 5 m / sec and 15 m / sec, and two measurement temperatures of 23 ° C. and -30 ° C. (Note that the above four samples are random for each level. Extracted). At each level, 10 test pieces were measured and the average value was calculated. -30 ℃
Was measured as follows. A stainless steel container was prepared and filled with polyethylene beads. Further test pieces were embedded in such beads. This is to reduce the effect of uneven heat conduction. This stainless steel container
It was stored in a freezer at 30 ° C, and the test piece was set to -30 ° C. During the test, the test piece was quickly taken out from the freezer, mounted on an impact tester, and tested. The temperature of the test piece is almost -3
It was confirmed by thermography that the test was performed at 0 ° C.

(Ii) Measurement of linear expansion coefficient Samples for measuring linear expansion coefficient (length 4 mm × width 4 mm) from the region as shown in FIG. Was cut out using a Bernas cutter. After annealing the sample at 120 ° C. for 5 hours, a TMA device (thermo-mechanical analyzer: TA Instrument) was manufactured by a method based on JIS K7197.
The linear expansion coefficient in the lateral direction (the direction perpendicular to the flow direction) of the molded product was determined using TA2200 manufactured by Nte. Measurement is -4
Performed from 0 ℃ to 100 ℃, the coefficient of linear expansion is -30 ℃ to 90 ℃
The value was calculated from the slope at ° C. Temperature rising rate is 2 ℃
/ Min. The measurement was performed at a total of 6 points, and the average value was calculated.

(Example 1) Polyamide 66 resin (Asahi Kasei
45 parts by weight of Leona 1200S manufactured by Kogyo Co., Ltd., polyphe
Nylene ether resin (Zairon X9 manufactured by Asahi Kasei Corporation)
102) 55 parts by weight for a total of 100 parts by weight of carb
Black (acetylene black, Denki Kagaku Kogyo Co., Ltd.)
DENKA BLACK) 2 parts by weight and about 30% by weight of soot
Acid-modified hydrogenated styrene-butadien containing Tylene units
-Styrene triblock copolymer (KR made by Shell Co.
ATON FG1901X) 22 parts by weight in a tumbler
After pre-mixing, twin-screw extruder with same-direction vent (Co., Ltd.)
With TEX-α manufactured by Japan Steel Works, screw diameter 30 mm)
Screw rotation speed 150 rpm, cylinder temperature 280
Extruded at ℃ and vent suction degree of 3 kPa to obtain pellets.
Dry the pellets in a vacuum dryer at 100 ° C for 12 hours
½ scale of automobile rear door panel shown in Fig. 1
A molded product was molded. Molding conditions are cylinder temperature 280
℃, mold temperature 80 ℃, and hot runner temperature
It was set to 300 ° C. High-speed surface impact test destruction of the obtained molded product
Energy (E1) is shown in Table 1. The coefficient of linear expansion is
8 x 10^-Five℃ ^-1Met.

(Comparative Example 1) When molding the above-mentioned molded article, injection molding was not carried out, and a usual injection molding method was used in which the cavity was clamped in the final mold with resin, under substantially the same conditions as in Example 1. Molded. After the filling, the hot runner valve was opened and the holding pressure was 100 MPa for 12 seconds. The high-speed surface impact test breaking energy (E2) of the obtained molded product is shown in Table 1. The linear expansion coefficient is 10 × 10.
It was ^-5 ° C ^-1 .

(Example 2) The large injection compression molded article obtained in Example 1 was used as a PPG commonly used in the United States for automobile outer panels.
Powder coated with paint. The paint adhered well to the resin. In addition, the paint appearance was at a level where it could be used as an outer panel for automobiles without any problems.

Comparative Example 2 The large-sized injection compression-molded article obtained in Comparative Example 1 was powder-coated with the PPG paint as in Example 2. Peeling of the coating film was confirmed near the gate of the molded product.

(Example 3) Aromatic polycarbonate resin (Panlite L-1250WP manufactured by Teijin Chemicals Ltd.) 30
30 parts by weight of PBT resin (1100211S manufactured by Changchun Synthetic Resin Factory Co., Ltd.), 10 parts by weight of compatibilizer (TKS-7300 manufactured by Kuraray Co., Ltd.), talc (IMI
Fabi S. p. A's Hitalc Ultra5
c) 25 parts by weight, rubbery polymer (SEP manufactured by Kuraray Co., Ltd.)
TON2005) 5 parts by weight, and phosphate heat stabilizer (Adeka Stub PEP-8 manufactured by Asahi Denka Co., Ltd.)
After 0.2 parts by weight was uniformly mixed with a tumbler, extrusion was carried out by substantially the same method and conditions as in Example 1 except that the vent suction degree was set to 30 kPa to obtain pellets.

The compatibilizer was 70% by weight of polybutylene terephthalate (PBT) component and hydrogenated styrene.
(Butadiene-isoprene copolymer) -30% by weight of styrene triblock copolymer (hydrogenated SBIS) component, 35% by weight of block copolymer component formed by combining PBT block and hydrogenated SBIS block,
It comprises 55% by weight of PBT and 10% by weight of hydrogenated SBIS (having a hydroxyl group at the terminal). Therefore, the above composition is expressed according to the present invention,
A total of 100 parts by weight of 55 parts by weight of a1 component (polybutylene terephthalate) and 45 parts by weight of a2 component (aromatic polycarbonate), 37 parts by weight of B component (talc), 12 parts by weight of C component (hydrogenated SBIS), and It consists of a stabilizer.

The obtained pellets were heated at 120 ° C. in a hot air dryer.
And dried for 5 hours to form a 1/2 scale molded product of the automobile rear door panel shown in FIG. The molding conditions were a cylinder temperature of 270 ° C., a mold temperature of 120 ° C., and a hot runner temperature of 290 ° C. The high-speed surface impact test breaking energy (E1) of the obtained molded product is shown in Table 2. The linear expansion coefficient was 4 × 10 ^-5 ° C ^-1 .

(Comparative Example 3) In molding the above-mentioned molded article, injection compression molding was not carried out, and a usual injection molding method of filling resin into the cavity closed by final mold was carried out under substantially the same conditions as in Example 3. Molded. After the filling, the hot runner valve was opened and the holding pressure was 100 MPa for 12 seconds. The high-speed surface impact test breaking energy (E2) of the obtained molded product is shown in Table 2. The linear expansion coefficient is 5 × 10 ^-5
The temperature was ^-1 .

Example 4 The large-sized injection compression molded product obtained in Example 3 was coated with a water-based paint commonly used in Europe for automobile outer panels. The paint adhered well to the resin. In addition, the paint appearance was at a level where it could be used as an outer panel for automobiles without any problems.

Comparative Example 4 The large injection compression-molded article obtained in Comparative Example 3 was coated with a water-based paint commonly used in Europe for automobile outer panels. Uneven coating occurred on the appearance of the molded product.

Example 5 Pellets were obtained in the same manner as in Example 3 except that the proportion of talc in Example 3 was changed from 25 parts by weight to 20 parts by weight. Expressed in accordance with the present invention, such a composition has a B component of 55 parts by weight (polybutylene terephthalate) and an a2 component (aromatic polycarbonate) of 45 parts by weight based on 100 parts by weight of B.
30 parts by weight of component (talc), C component (hydrogenated SBIS) 1
2 parts by weight and a stabilizer. The pellets were molded under the same conditions as in Example 3 to obtain a large injection compression molded product.
High-speed surface impact test fracture energy (E1
) Is shown in Table 3. The linear expansion coefficient was 5 × 10 ^-5 ° C ^-1 .

(Comparative Example 5) In molding the above-mentioned molded article, the injection compression molding was not carried out and the ordinary injection molding method of filling the resin into the cavity closed in the final mold was carried out under the same conditions as in Example 5. Molded. After the filling, the hot runner valve was opened and the holding pressure was 100 MPa for 12 seconds. Table 3 shows the breaking energy (E2) of the high-speed surface impact test of the obtained molded product. The linear expansion coefficient is 5 × 10 ^-5
The temperature was ^-1 .

Example 6 Pellets were obtained in the same manner as in Example 3 except that the reinforcing filler was changed from 25 parts by weight of talc to 15 parts by weight of wollastonite (NYGLOS4 manufactured by Nyco Minerals Co., Ltd.). It was Expressed in accordance with the present invention, such a composition has a total of 100 parts by weight of 55 parts by weight of a1 component (polybutylene terephthalate) and 45 parts by weight of a2 component (aromatic polycarbonate), and 22 parts by weight of B component (wollastonite), It comprises 12 parts by weight of C component (hydrogenated SBIS) and a stabilizer.
The pellets were molded under the same conditions as in Example 3 to obtain a large injection compression molded product. Table 4 shows the breaking energy (E1) of the high speed surface impact test of the obtained molded product. The linear expansion coefficient was 7 × 10 ^-5 ° C ^-1 .

(Comparative Example 6) In molding the above-mentioned molded article, injection compression molding was not carried out, and a usual injection molding method of filling the resin into the cavity closed in the final mold was carried out under substantially the same conditions as in Example 5. Molded. After the filling, the hot runner valve was opened and the holding pressure was 100 MPa for 12 seconds. The high-speed surface impact test breaking energy (E2) of the obtained molded product is shown in Table 4. The linear expansion coefficient is 8 × 10 ^-5
The temperature was ^-1 .

[0150]

[Table 1]

[0151]

[Table 2]

[0152]

[Table 3]

[0153]

[Table 4]

As is clear from these experiments, it is understood that the large-sized injection compression-molded article obtained in the present invention can achieve impact strength without sacrificing the linear expansion coefficient. Conversely speaking, it is possible to achieve a better linear expansion coefficient while having the same impact strength as the conventional one. In addition, it can be seen that other added values such as appearance can be easily added.

[0155]

INDUSTRIAL APPLICABILITY The injection compression-molded product of the present invention has excellent impact strength, and also has a high level of dimensional stability and appearance, and can be used in buildings, building materials, agricultural materials, marine materials, vehicles, electricity, It is widely used in various fields such as electronic devices, machines, and other fields, and in particular, it provides a molded article suitable for exterior materials for vehicles such as automobiles, and particularly for automobile outer panels. Effects are extremely large.

[Brief description of drawings]

FIG. 1 shows a 1/2 scale molded product of an automobile rear door panel molded in an example. [1-A] shows a front view (a view projected on the platen surface at the time of molding. Therefore, such an area becomes the maximum projected area. The gate is located below the molded product), [1-B] Is bottom view, [1-C]
Is a side view.

[Explanation of symbols]

1 Injection compression molded product main body 2 Molded product ridgeline (not clear because it is not an acute angle) 3 Molded product gate (film gate) 4 Hot runner nozzle part (diameter 3 mmφ) 5 Molded product ridgeline (acute angle) 6 Molding Size of resin in vertical direction of product (38 cm) 7 Size of resin in horizontal direction of molded product (55 cm) 8 Cutout portion of test piece for measuring linear expansion coefficient 9 Cutout portion of test piece for high-speed surface impact test measurement (50
mm 4 pieces of 50 mm pieces) 10 Ridge line of molded product (not clear because it is not acute angle) 11 Size of molded product in height direction (12 cm)

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08L 77/00 C08L 77/00 // B29K 101: 12 B29K 101: 12 B29L 31:30 B29L 31:30 F term (reference) 4F206 AA13 AA24 AA27 AA28 AA29 AA32 AB16 AH24 AH25 JA03 JN33 JQ81 JQ83 4J002 AC02Y AC03Y AC06Y AC07X BB06Y BB07Y BB15Y BB17X BC02W BC03W BC03X BC04W BC05Y BC06W BC07W BC08W BC09W BC11W BC12W BC13W BG04Y BG05Y BH01W BN06Y BN07Y BN12Y BN14Y BN15Y BN16Y BP01Y BP02Y CF03Y CF05X CF06X CF07X CF08X CF09X CF16W CG01W CH07W CK02Y CL00Y CL01X CL03X CL05X CN01X CP02Y DA016 DA026 DA066 DE186 DG046 DJ006 DJ036 DJ046 DJ056 DK006 DL006 DM006 FA016 FA046 FA066 FA106 FD050FD100FD

Claims (8)

[Claims] 1. A crystalline thermoplastic polymer (a1 component) 5
˜90 parts by weight and 10 to 95 parts by weight of the amorphous thermoplastic polymer (a2 component) in total 100 parts by weight, the maximum projected area obtained by injection compression molding is 1
Injection compression molded product of 000 cm ² or more. 2. The injection compression according to claim 1, wherein the resin composition further comprises 0.5 to 100 parts by weight of a reinforcing filler (component B) per 100 parts by weight of the a1 component and the a2 component in total. Molding. 3. The injection according to claim 1, wherein the resin composition further comprises 0.5 to 50 parts by weight of a rubbery polymer (component C) per 100 parts by weight of component A. Compression molded product. 4. The injection compression-molded article according to claim 1, wherein the a1 component is at least one crystalline thermoplastic polymer selected from polyamide and aromatic polyester. 5. The injection compression molded article according to claim 1, wherein the component a2 is at least one selected from aromatic polycarbonate, polyphenylene ether, polyarylate, and styrene polymer. . 6. The component B is at least one selected from talc and wollastonite.
An injection compression molded article according to any one of 1. 7. The injection compression molded product according to claim 1, wherein the injection compression molded product has a gate on a side surface portion of the molded product. 8. The injection compression molding is to fill a molten thermoplastic resin material into a mold cavity having a volume 1.1 times or more larger than an intended volume of a molded product at least when the supply is completed. The injection compression molded article according to any one of claims 1 to 7.