JP4705388B2 - Vehicle exterior material and manufacturing method thereof - Google Patents

Description

  The present invention relates to a vehicle exterior material made of a thermoplastic resin material that is injection-molded using a mold having a specific position and a plurality of resin supply ports, has a specific shape, and satisfies specific conditions. The vehicle exterior material is suitable for so-called modular parts. The invention further relates to a method for producing the same. More preferably, the present invention relates to an injection molding method that has a specific shape, a specific position, and a plurality of gates, and sequentially supplies resin to the gates, and a vehicle exterior material manufactured by the manufacturing method. In particular, the present invention relates to a vehicle exterior material capable of providing a modularized component including a light transmission member and a lighting device on the vehicle exterior material.

  2. Description of the Related Art In recent years, in manufacturing vehicles such as automobiles, a manufacturing method in which a large number of parts are integrated and then assembled to a vehicle body, that is, modularization of so-called parts has been expanded. Such modularization can reduce the manufacturing time by reducing the number of components and the management cost at the time of manufacturing. In such modularized parts, the use of resin materials is increasing more than ever. The resin material can easily form a complicated and large member as compared with the metal material. For this reason, the advantages of further reducing the number of parts and eliminating the need for large-scale manufacturing facilities are obtained. In addition, the resin material has an advantage that it is less deformed after hitting and is lighter than the metal material. The latter advantage is advantageous in vehicle exterior parts. Molded products made of resin materials tend to be larger in order to reduce the number of parts and weight. When molding a large injection molded product, how to provide a well-balanced gate is a problem.

  On the other hand, the sequential valve gating method (hereinafter referred to as “SVG method”), in which a plurality of hot runner valves are opened and closed sequentially according to a program, is used for the production of large resin injection molded products. Application is known (see Non-Patent Document 1). The SVG method is sometimes used to form a plurality of molded products having different shapes from a plurality of gates. However, when almost one molded product is formed from a plurality of gates, a high-quality large resin molded product can be produced. Is possible. In the latter, normally, after the molten resin flowing from the previous gate passes, the gate is opened and the resin from the gate is filled with the molten resin flowing. Since such an operation is performed step by step at each gate to supply the molten resin, such molding by the SVG method is usually called cascade molding.

  Cascade forming can suppress weld lines as much as possible. Such suppression increases the degree of freedom in the number of gates, and as a result, large molded products can be injection molded with a relatively low clamping force. The cascade molding by the SVG method does not theoretically require specific characteristics particularly for the resin material. According to this document, it is also known that molding of a bumper was attempted using XENOY (polymer alloy resin made of polycarbonate and polyester) manufactured by GE.

  However, in reality, an increase in the number of gate points causes an increase in manufacturing cost due to an increase in the number of control devices. There are also restrictions on the number of gate points derived from the shape of the molded product. Therefore, in reality, resin materials often require characteristics suitable for such a manufacturing method. On the other hand, as a matter of course, there are characteristics that should be satisfied in the manufacturing process of a target product (for example, an automobile exterior part), and satisfactory characteristics as the product. Vehicle exterior materials are generally required to have high appearance, high impact resistance (particularly surface impact resistance), high rigidity, and low thermal expansion.

  A resin composition comprising an aromatic polycarbonate resin, an ABS resin, and talc having a specific particle diameter, which satisfies a specific linear thermal expansion coefficient, dart impact strength, and load deflection temperature is known ( Patent Document 1). According to this document, it is known that such a resin composition has particularly desirable characteristics for a vehicle body outer panel.

  An automotive side protector manufactured by injection molding a resin composition comprising an aromatic polycarbonate resin, a polyethylene terephthalate resin, an impact modifier, and a specific ratio of mica having a specific particle diameter is known (see Patent Document 2).

  It is known that an aromatic polycarbonate resin, an aromatic polyester resin, a rubbery polymer, a resin composition comprising fine fibers surface-treated with a silane compound, and that the resin composition is suitable for an automobile exterior member such as a bumper. Yes (see Patent Document 3).

  Resin composition comprising aromatic polycarbonate resin, aromatic polyester resin, wollastonite, ethylene-ethyl acrylate copolymer, and copolymer wax of α-olefin and maleic anhydride, and the resin composition for automotive use It is known that it is suitable for (see Patent Document 4).

  A resin composition comprising an aromatic polycarbonate resin, an aromatic polyester resin, and wollastonite that satisfies specific shape conditions is known (see Patent Document 5). According to this document, it is also known that the resin composition is excellent in impact resistance, recyclability and surface appearance (particularly paint appearance) and is suitable for exterior parts for vehicles.

  A large molded article produced by injection press molding a resin composition comprising a filler-reinforced aromatic polycarbonate resin and an aromatic polyester resin is known (see Patent Document 6). Such injection press molding is an extremely effective method for manufacturing large molded articles. The molding method can sufficiently exhibit the characteristics of a resin composition comprising an aromatic polycarbonate resin and an aromatic polyester resin even in a large-sized molded product. However, in the molding method, particularly in the case of a large molded product, the initial investment in facilities is generally large, and other methods may be tried depending on the target product. For example, when the SVG method is adopted as an alternative, it is difficult to say that the document sufficiently disclosed effective knowledge.

Plastics Technology, Dec. 2003, p38 JP-A-2-294358 JP-A-4-224920 JP-A-8-259789 JP-A-9-012847 JP 2002-2657 A JP 2003-171504 A

  An object of the present invention is to provide a vehicle exterior material suitable for manufacturing modularized parts, and a method for manufacturing the same. A more specific object of the present invention is to combine an appropriate molding method and a resin composition suitable for the method in applying cascade molding by the SVG method suitable for manufacturing the vehicle exterior material, and as a result, Furthermore, it is providing the vehicle exterior material which is high quality and low cost. Furthermore, it is an object of the present invention to satisfy that the vehicle exterior material has excellent impact resistance, a low linear expansion coefficient, and excellent appearance (particularly paint appearance). A further object of the present invention is to provide a resin composition suitable for providing such a vehicle exterior material. In addition, the vehicle exterior material is generally painted to develop surface characteristics such as appearance requirements, weather resistance, and scratch resistance, and chemical resistance to coating, coating adhesion strength, and the like are required. .

  As a result of intensive studies to achieve the above object, the present inventor applied a resin composition that satisfies specific conditions to a molded product shape having an appropriate gate arrangement for applying cascade molding by the SVG method. As a result, the inventors have found that this object can be achieved and have completed the present invention.

According to the present invention, the object is (1) a vehicle exterior material manufactured by injection molding a thermoplastic resin material in a mold,
(I) The mold is
(I-1) It has both the following gate-A and gate-B,
(I-2) The gate-B is a gate to which molten resin is supplied so as to merge with the flow after the molten resin flow flowing in from another gate passes, while the gate-A is melted It is a gate where molten resin is supplied without joining the resin flow,
(I-3) Each gate in the mold is provided in a range where there is no other gate within a straight line distance of at least 20 cm on the exterior material surface,
(Ii) The vehicle exterior material is:
(Ii-1) It is mainly composed of a design surface provided on either the front or back surface, and an undesired recess portion or / and a penetrating portion in which the surface is deficient that has retreated from the design surface,
(Iii) The thermoplastic resin material is
(Iii-1) ISO1133 280 ℃ conforming to standards, melt volume rate (MVR value) at 2.16kg load in the range of 15~150cm ^3/10 min,
(Iii-2) The linear expansion coefficient in the range of −30 to 80 ° C. measured at the center of a test piece prepared in accordance with ISO 527-1 is 2 × 10 ^{−5 to} 6 × 10 ⁻⁵ / ° C. In the range of
(Iii-3) The deflection temperature under load measured in accordance with ASTM D-648 at a load of 0.45 MPa is in the range of 110 to 145 ° C.
(Iii-4) The breaking energy in a high-speed surface impact test measured at 23 ° C. using a smooth flat plate-shaped test piece having a thickness of 3 mm is in the range of 3 to 70 J.
This is achieved by a vehicle exterior material characterized in that.

Further, in a more preferred aspect of the present invention, the thermoplastic resin material is composed of 40 to 90% by weight of aromatic polycarbonate (component A), aromatic polyester (component B-1) and styrenic hard resin in 100% by weight of the material. 5 to 35% by weight of at least one polymer (B component) selected from polymers (B-2 component), 1 to 8% by weight of rubbery polymer (C component), and 3 to 3% of inorganic filler (D component). Containing 25% by weight,
This is a vehicle exterior material characterized by the above.

  For the injection molding used in the present invention, an injection molding machine known to those skilled in the art is used. In the present invention, cascade forming by the SVG method is preferably used, but is not limited to this as long as the gate-B satisfies the conditions. For example, it is possible to adjust the arrival time to the gate by adjusting the length and thickness of the runner and satisfy the condition of the gate-B without using the SVG method.

  Furthermore, as long as the conditions of the present invention are satisfied, known molding methods such as injection compression molding, hollow molding, rapid heating / cooling molding, and two-color molding are simultaneously applied to a part or all of the vehicle exterior material as the injection molding method. It is also possible to use it. In particular, hollow molding is used in combination with the thick part of the molded product, and transparent resin material is molded in two colors in the penetration or recess of the vehicle exterior material, and the transparent member that is molded in two colors is molded by injection compression molding. In particular, it is effective to use rapid heating / cooling molding at a site where design properties are particularly necessary.

  The mold for molding the vehicle exterior material of the present invention is supplied with the gate-A to which the molten resin is supplied without being joined to the molten resin flow, and the molten resin is supplied so as to be joined to the flow after the molten resin flow has passed. Each gate is provided in a range where no other gate exists within 20 cm. Further, it is preferable that the vehicle exterior material mainly includes a design surface provided on either the front or back surface and a design-less unnecessary recess or / and a penetrating portion with the surface missing from the design surface. . Furthermore, it is preferable that all the gates of the mold are provided in the recessed portion or / and the penetrating portion that do not require design or / and the end of the molded product.

  After the resin is supplied from the gate-A, the gate-B controls the supply regulating valve provided in the flow path communicating with the gate-B, so that the molten resin flow flowing in from the other gate passes. It is preferable that the gate is supplied with a molten resin so as to join the flow, that is, cascade-molded by a so-called SVG method. Control of such a preparation valve may be performed by any method using a commercially available apparatus. Examples include time control, screw position control, and intracavity pressure control. If the supply of the molten resin at the gate B is too early, a back flow of the molten resin is generated and the flow of the resin is disturbed, so that an appearance defect or a weld line is generated. When the supply is too slow, the molten resin from the other gates is cooled and a large density difference from the resin of the gate-B is generated, so that an appearance defect is likely to occur. Therefore, it is necessary to appropriately control the opening / closing timing of the gate so that these problems do not occur. Furthermore, it is preferable to determine the gate position so that the condition of the opening / closing timing is as tolerant as possible.

  In cascade molding by the SVG method, the molten resin needs to flow to at least another gate except for the gate to which the molten resin is supplied at the end when the molten resin does not pass through the other gate. . In addition, at the gate to which the molten resin is finally supplied, the molten resin needs to flow to the end of the product.

  In the present invention, as long as each gate satisfies the above (i-3), the arrangement is not particularly limited, but the distance between the gate supplied with the molten resin and the gate through which the molten resin passes is partially. In the case of a gate arrangement that is particularly shorter than the others, or when the amount of resin supplied from some gates is reduced due to such an arrangement, the following adverse effects are likely to occur. (I) Control of gate opening / closing tends to be difficult, (ii) Since the amount of supplied resin is smaller than the others, the residence time of the molten resin becomes longer at that portion, and the resin is thermally deteriorated. In addition, even when the amount of resin supplied from the gate to which molten resin is supplied last is small, the above-mentioned problem (ii) occurs.

  Therefore, the resin capacity (Vi) supplied from each gate with respect to the average capacity (Vave) obtained by dividing the total amount of the resin capacity filled in the mold by the number of gate points is preferably 0.5 ≦ Vi / Vave ≦ 1.5. More preferably, 0.6 ≦ Vi / Vave ≦ 1.4, and even more preferably 0.7 ≦ Vi / Vave ≦ 1.3.

On the other hand, when satisfying such a preferable relationship, it is necessary to increase the distance between the gates as the thickness is thinner. Therefore, in the cascade forming by the SVG method, much better fluidity is required than that required in normal multi-point gate forming. The thermoplastic resin material of the present invention provides a satisfactory vehicle exterior material by cascade molding by the SVG method by satisfying such requirements. Further, when the above preferable relationship is satisfied, it is preferable that the thickness of the molded product is as uniform as possible throughout. Therefore, the vehicle exterior material of the present invention preferably has a thickness within ± 50% of the average thickness, and more preferably within ± 30%. In addition, the average thickness of this invention says the value which remove | divided the molded article volume (mm < ³ >) by the surface area (mm < ² >) of the molded article.

  In addition, when the distance between the gate supplied with the molten resin and the gate through which the molten resin passes is too large, the flow of the molten resin tends to be insufficient. Therefore, the above condition (i-3) is that each gate in the mold is provided in a range in which the other gates do not exist within at least 20 cm and do not exist within 80 cm as a linear distance on the exterior material surface. It is more preferable that it is provided in a range that does not exist at least within 25 cm but exists within 70 cm, and more preferably that it is provided in a range that does not exist within at least 25 cm and exists within 60 cm.

The maximum projected area of the vehicle exterior material is preferably a vehicle exterior material in the range of 1,500 to 40,000 cm ² , more preferably 2,000 to 20,000 cm ² , still more preferably 2,200 to 15, 000 cm ² .

  The vehicle exterior material is preferably a vehicle exterior material in which a paint is applied to at least its design surface after molding and subsequently cured in a temperature range of 100 to 140 ° C. to form a coating film. Such a temperature range is more preferably 105 to 135 ° C, still more preferably 115 to 135 ° C. The higher the baking temperature of the paint, the less the difference in color from the steel plate portion, the better the gloss, and as a result, a high-grade coating becomes possible. In a preferred embodiment of the present invention, the vehicle exterior material of the present invention can sufficiently withstand such coating. In recent years, new paints (water-based paints, powder paints, etc.) have been studied due to environmental problems. However, these new paints can also be suitably used for the injection-molded article of the present invention. Furthermore, film insert molding has been actively studied for the purpose of coating-less, but the injection-molded product of the present invention is superior in suitability for film insert molding compared to a normal injection-molded product, and particularly a deep-drawn film. Suitable for insert molding.

  The vehicle exterior material has a surface roughness Ra measured in accordance with JIS B0601-1994 on the design surface, preferably 0.001 to 3 μm, and particularly preferably 0.01 to 1 μm. The surface roughness of the surface of the molded product depends on the mold surface smoothness, molding conditions, mold equipment such as a heat insulating mold and a rapid heating / cooling mold, and a molding material. When the surface roughness Ra is smaller than the above range, these facilities become excessive or the molding stability tends to be lacking. On the other hand, when the surface roughness Ra is larger than the above range, it tends to be insufficient as a vehicle exterior material or requires excessive coating. When Ra is 0.01 to 1 μm, these balances are particularly excellent.

  In addition, the design surface in the vehicle exterior material of the present invention refers to a surface that can be recognized from the outside at least when the vehicle is visually recognized in a travelable state. Of course, the surface roughness other than the design surface may be satisfied.

  Generally, the lower the surface roughness, the smoother and more uniform good appearance is expressed. The vehicle exterior material of the present invention may be partially or mostly used for a vertical member of a vehicle. In that case, a particularly high level of design is required, and a surface roughness of 0.01 to 1 μm is preferable. .

  More preferably, the vehicle exterior material is affixed to the frame with a rubber adhesive. As the rubber adhesive, an adhesive known to those skilled in the art can be used, but a two-component urethane adhesive is preferable. Specific examples of suitable two-component urethane adhesives include, for example, BETAMATE2810 (trade name, combination of A agent and B / S agent) manufactured by DOW AUTOMOTE. A primer is preferably used for the adhesive, and a specific example of the primer is, for example, BETAPRIME5404 (trade name) manufactured by DOW AUTOMOTE.

  The vehicle exterior material is preferably one in which a light transmissive member or a lighting device is attached to at least one of the recessed portion or the through portion. Thereby, the vehicle exterior material can have an even higher function as a module component.

Thermoplastic resin materials used in the present invention is 280 ° C. conforming to ISO1133 standard, melt volume rate (MVR value) at 2.16kg load in the range of 15~150cm ^3/10 min, preferably 18～100Cm ³ / 10 min, more preferably 20～80Cm ^3/10 min. Can not exhibit sufficient flow properties when MVR value is small, but no problem for greater than 150 cm ^3/10 min, it is difficult to substantially other properties, in particular compatibility between impact properties .

The thermoplastic resin material used in the present invention has a linear expansion coefficient of 2 × 10 in the range of −30 to 80 ° C. measured in the flow direction at the center of a test piece prepared in accordance with ISO 527-1. It is in the range of ^{−5 to} 6 × 10 ⁻⁵ / ° C. The lower limit of the linear expansion coefficient is preferably 3 × 10 ⁻⁵ / ° C. The upper limit of the linear expansion coefficient is preferably 5.5 × 10 ⁻⁵ / ° C. When the linear expansion coefficient is larger than this range, the dimensional change of the molded product is large with respect to the temperature change in the use environment, and it is not suitable as a vehicle exterior material. When the linear expansion coefficient is small, there is no particular problem, but it is substantially difficult to achieve compatibility with other characteristics, particularly the appearance of the molded product.

  The thermoplastic resin material used in the present invention has a deflection temperature measured at a load of 0.45 MPa in accordance with ASTM D-648 in the range of 110 to 145 ° C, preferably 120 to 145 ° C, particularly preferably 130. ° C to 145 ° C. When the deflection temperature under load is low, deformation is likely to occur during paint baking. In addition, under a use environment, for example, when a load is applied under a hot sun, it is greatly deflected, and the quality of the vehicle tends to be lowered.

  The thermoplastic resin material used in the present invention has a breaking energy in the range of 3 to 70 J, preferably 30 to 70 J in a high-speed surface impact test measured at 23 ° C. using a 3 mm-thick smooth flat test piece. Especially preferably, it is 50-70J. When the impact strength is low, it is difficult to use as a vehicle exterior material. Although the impact strength has never been high, it is generally difficult to achieve compatibility with other characteristics, particularly fluidity.

  A preferred thermoplastic resin material of the present invention is an aromatic polycarbonate (component A) 40 to 90 wt%, an aromatic polyester (component B-1) and a styrenic hard polymer (component B-2) in 100% by weight of the material. ) Containing at least one polymer (B component) 5 to 35% by weight, rubbery polymer (C component) 1 to 8% by weight, and inorganic filler (D component) 3 to 25% by weight. It will be.

Details of these components will be described below.
(Component A: aromatic polycarbonate)
The aromatic polycarbonate which is the component A is known per se and has been conventionally used for various molded articles. That is, it is obtained by reacting a dihydric phenol and a carbonate precursor. Examples of the reaction method include an interfacial polycondensation method, a melt transesterification method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  The aromatic polycarbonate may be various polycarbonate resins having a high heat resistance or a low water absorption rate, which are polymerized using other dihydric phenols, in addition to the commonly used bisphenol A type polycarbonate. The aromatic polycarbonate may be produced by any production method, and in the case of interfacial polycondensation, a monohydric phenol end-stopper is usually used. The aromatic polycarbonate may be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and further, a copolymer obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol. Polymerized polycarbonate may be used. However, an aromatic polycarbonate composed of a homopolymer of bisphenol A is particularly preferable in terms of excellent impact resistance. The details of the aromatic polycarbonate of the present invention are described in the pamphlet of WO03 / 080728.

  As specific examples of the aromatic polycarbonate having a high heat resistance or a low water absorption, which is polymerized using other dihydric phenols, the following compounds are preferably exemplified.

(1) In 100 mol% of the dihydric phenol component constituting the polycarbonate, 4,4 '-(m-phenylenediisopropylidene) diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferable) 40 to 75 mol%, more preferably 45 to 65 mol%), and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter abbreviated as "BCF") component is 20 to 20 mol. Copolycarbonate which is 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%), And a BCA component in an amount of 5 to 90 mol% (more preferably 10 to 50 mol%, still more preferably 15 to 40 mol%).
(3) In 100 mol% of the dihydric phenol component constituting the polycarbonate, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%), and The 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%). Copolycarbonate.

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production method and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

  As the A component aromatic polycarbonate of the present invention, not only a virgin raw material but also an aromatic polycarbonate regenerated from a used product, that is, a so-called material recycled aromatic polycarbonate can be used. Used products include soundproof walls, glass windows, translucent roofing materials, various glazing materials represented by automobile sunroofs, transparent members such as windshields and automobile headlamp lenses, containers such as water bottles, and optical recording media Etc. are preferred. These do not contain a large amount of additives or other resins, and the desired quality is easily obtained stably. In particular, automobile headlamp lenses, optical recording media, and the like are consumed in large quantities, and regenerated products can be obtained stably. In addition, said virgin raw material is a raw material which is not yet used in the market after the manufacture.

  As the A component aromatic polycarbonate, those having a viscosity average molecular weight of 15,000 to 50,000 can be used, preferably in the range of 16,000 to 23,000, more preferably from 16,000 to 6,000. The range is 21,000. A particularly preferred aromatic polycarbonate having a viscosity average molecular weight in the range of 16,000 to 21,000 is referred to as A 'component. An aromatic polycarbonate having a viscosity average molecular weight in such a suitable range is excellent in balance between fluidity, strength and heat resistance.

  The viscosity average molecular weight may be satisfied as the whole component A, and includes those satisfying such a range by a mixture of two or more kinds having different molecular weights. In particular, mixing of an aromatic polycarbonate having a viscosity average molecular weight exceeding 50,000 (more preferably 80,000 or more, more preferably 100,000 or more) may be advantageous in terms of increasing entropy elasticity at the time of melting. For example, it is effective for reducing jetting, gas injection molding, foam molding (including supercritical fluid), and improvement of injection press moldability. Therefore, the mixing of aromatic polycarbonates having a viscosity average molecular weight exceeding 50,000 is one of the preferred choices when these improvements are required and when these molding methods are applied. Such an effect becomes more prominent as the molecular weight of the aromatic polycarbonate is higher, but the upper limit of the molecular weight is practically 2 million, preferably 300,000, more preferably 200,000. It is preferable that the high molecular weight component is mixed in such an amount that the molecular weight distribution of two or more peaks can be observed in a measuring method such as GPC (gel permeation chromatography).

In the aromatic polycarbonate resin (component A) of the present invention, the amount of phenolic hydroxyl group is preferably 30 eq / ton or less, more preferably 25 eq / ton or less, and further preferably 20 eq / ton or less. Such a value can be substantially 0 eq / ton by sufficiently reacting the terminal terminator. The amount of the phenolic hydroxyl group is determined by performing ¹ H-NMR measurement, and calculating the molar ratio of the dihydric phenol unit having a carbonate bond, the divalent phenol unit having a phenolic hydroxyl group, and the terminal terminator unit. It is calculated | required by converting into the amount of phenolic hydroxyl groups per polymer weight based.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of aromatic polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., and the specific viscosity calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The obtained specific viscosity is inserted by the following equation to determine the viscosity average molecular weight M.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

(B-1 component: aromatic polyester)
The aromatic polyester (component B-1) refers to a polyester containing 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of the aromatic dicarboxylic acid component in 100 mol% of the dicarboxylic acid component. . The diol component of the aromatic polyester is preferably a polyester containing 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of an aliphatic diol or alicyclic diol in 100 mol%. Here, the dicarboxylic acid component indicates a structural unit derived from a dicarboxylic acid of an aromatic polyester or an ester-forming derivative thereof, and the diol component is derived from a diol of an aromatic polyester or an ester-based forming derivative thereof. Indicates the structural unit.

  Examples of the aromatic dicarboxylic acid component include the following. In the following specific examples of the dicarboxylic acid component and the diol component, “component” is abbreviated. That is, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, 4,4′-biphenyl Methanedicarboxylic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-anthracenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, 2,6-anthracenedicarboxylic acid Acid, 4,4-biphenyl ether dicarboxylic acid, 4,4′-biphenylsulfone dicarboxylic acid, 1,2-bis (phenoxy) ethane-4,4′-dicarboxylic acid, 4,4′-biphenylisopropylidenedicarboxylic acid, 4,4′-p-terphenylenedicarboxylic acid and 2,5-pyri Njikarubon acid. Of these, terephthalic acid and 2,6-naphthalenedicarboxylic acid can be preferably used. Other copolymerizable dicarboxylic acids include aliphatic and alicyclic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Mention may be made of acids. Aromatic dicarboxylic acids and copolymerizable dicarboxylic acids can be used alone or in admixture of two or more.

  The diol component of the aromatic polyester includes ethylene glycol, 1,4-butanediol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or Aliphatic diols such as cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, and decamethylene glycol, 1, Examples include alicyclic diols such as 4-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, and cyclohexanediol, and dihydric phenols such as p-xylenediol and bisphenol A. If the amount is even smaller, one or more long-chain diols having a molecular weight of 400 to 6,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, and the like may be copolymerized. These diol components can be used alone or in combination of two or more.

  As the aromatic polyester, those having a logarithmic viscosity value (IV value) of 0.4 to 1.4 dl / g measured at 25 ° C. in o-chlorophenol can be used, but a preferable IV value is 0.45 to 0. .75 dl / g. In particular, 0.45 to 0.60 dl / g is preferable.

  Specific aromatic polyester resins include polyethylene terephthalate (PET), cyclohexanedimethanol copolymerized PET, polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), and polybutylene naphthalate ( PBN), polyethylene-1,2-bis (phenoxy) ethane-4,4′-dicarboxylate, polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, polyethylene naphthalate / terephthalate copolymer Examples thereof include a polymer and a polybutylene naphthalate / terephthalate copolymer. Among them, polyethylene terephthalate (PET) is particularly preferable as an aromatic polyester.

  Such PET has a main repeating unit of ethylene terephthalate, and in 100 mol% of the dicarboxylic acid component, the terephthalic acid component is contained in an amount of 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more. It is a polyester comprising 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of the ethylene glycol component in 100 mol% of the diol component. Other copolymerizable dicarboxylic acid components and diol components are as described above.

  The end group structure of the aromatic polyester used in the present invention is not particularly limited, and even when the ratio of the hydroxyl group and the carboxyl group in the end group is substantially the same, Good. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  About the manufacturing method of the aromatic polyester used for this invention, according to a conventional method, dicarboxylic acid or its ester-forming derivative, and diol or a heating with the presence of the polycondensation catalyst containing titanium, germanium, antimony, etc. The polymerization is carried out by polymerizing the ester-forming derivative and discharging water or lower alcohol produced as a by-product out of the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like, and more specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium. Etc. can be illustrated.

  Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like. The production method of the aromatic polyester can be either batch type or continuous polymerization type.

  Examples of the polycondensation of PET which is a preferred aromatic polyester of the present invention include the following methods. First, a slurry containing terephthalic acid or an ester-forming derivative thereof and ethylene glycol or an ester-forming derivative thereof is prepared. Such a slurry is continuously supplied to the esterification reaction step. The esterification reaction is carried out using an apparatus in which at least two esterification reactors are connected in series under conditions where ethylene glycol is refluxed while water generated by the reaction is removed from the system by a rectification column. . The reaction rate of the esterification reaction is not particularly limited in each stage, but it is preferable that the increase and the degree of esterification reaction rate in each stage are distributed smoothly, and further the esterification reaction formation in the final stage In products, it is usually 90% or more, preferably 93% or more. The esterification product (low-order condensate) is obtained by the above esterification step, and the number average molecular weight of this esterification product is usually 500 to 5,000.

  Such esterification reaction can be carried out without the addition of additives other than dicarboxylic acid containing terephthalic acid as the main component, diol containing ethylene glycol as the main component, and these ester-forming derivatives. It is also possible to carry out in the presence of a polymerization catalyst. Furthermore, the esterification reaction is carried out by tertiary amines such as triethylamine, tri-n-butylamine, and benzyldimethylamine, and quaternary ammonium hydroxides such as tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and trimethylbenzylammonium hydroxide. When a small amount of at least one of basic compounds such as lithium carbonate, sodium carbonate, potassium carbonate, and sodium acetate is added, the proportion of dioxyethylene terephthalate component units in the PET main chain is kept at a relatively low level. It is preferable because it is possible.

  The resulting esterified product is then heated under a reduced pressure in the presence of a polymerization catalyst to a temperature equal to or higher than the melting point of the resulting polyethylene terephthalate, and the resulting glycol is distilled out of the system to cause polycondensation. Supplied to the condensation step. Such a polycondensation reaction in the liquid phase may be performed in one stage or may be performed in a plurality of stages. The logarithmic viscosity value (IV value) reached in each stage of these polycondensation reaction processes is not particularly limited, but it is preferable that the degree of increase in IV value in each stage is smoothly distributed. Furthermore, the IV value of PET obtained from the final stage polycondensation reactor is usually 0.35 to 0.80 dl / g. Suitable PET of the present invention preferably has an IV value of 0.45 to 0.75 dl / g, more preferably 0.45 to 0.60 dl / g.

  An aromatic polyester resin mainly composed of PET having an IV value of 0.45 to 0.60 dl / g is referred to as B-1 'component. More specifically, the B-1 ′ component contains 70 wt% or more, preferably 80 wt% or more of 100 wt% of the aromatic polyester resin, and PET having an IV value of 0.45 to 0.60 dl / g. Polyester resin. PBT, PEN, PBN, etc. are suitably exemplified as the resin contained in the B-1 ′ component other than such PET, and PBT is particularly preferred. When such PBT is contained, the proportion in the B-1 'component is preferably 5 to 20% by weight, more preferably 8 to 15% by weight.

The IV value of PET is calculated from the solution viscosity measured at 25 ° C. after heating and dissolving 1.2 g of PET in 15 cm ³ of o-chlorophenol. Moreover, it is preferable that the density of PET obtained after the polycondensation reaction step is 1.33-1.35 g / cm ³ . In the present invention, the density of PET is measured at a temperature of 23 ° C. by a density gradient tube method using a calcium nitrate solution in accordance with D method of JIS K7112.

  Regarding the detailed conditions of the esterification reaction step and the polycondensation step, for example, JP-A-2001-011198 can be referred to.

  The polycondensation reaction as described above is preferably carried out in the presence of a polymerization catalyst and a stabilizer. Examples of such polymerization catalysts include germanium compounds such as germanium dioxide, germanium tetraethoxide, and germanium tetra n-butoxide, antimony compounds such as antimony trioxide, and titanium compounds such as titanium tetrabutoxide. Widely known as a polymerization catalyst. Among these catalysts, germanium compounds and titanium compounds are more preferably used as polymerization catalysts. Stabilizers include trimethyl phosphate, triethyl phosphate, tri n-butyl phosphate, trioctyl phosphate, triphenyl phosphate, and phosphate esters such as tricresyl phosphate, triphenyl phosphite, trisdodecyl phosphate, and tris. Phosphites such as nonylphenyl phosphite, acidic phosphate esters such as methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, dibutyl phosphate, monobutyl phosphate, and dioctyl phosphate, and phosphorus such as phosphoric acid and polyphosphoric acid Various phosphorus compounds exemplified by the acid are used.

  In the total amount of 100% by weight of the dicarboxylic acid component and the diol component, the catalyst is usually used in the range of 0.0005 to 0.2% by weight (preferably 0.001 to 0.05% by weight) as the weight of the metal in the catalyst. The stabilizer is usually used in the range of 0.001 to 0.1% by weight (preferably 0.002 to 0.02% by weight) as the weight of phosphorus atoms in the stabilizer. These catalyst and stabilizer supply methods can be supplied at the stage of the esterification reaction step, or can be supplied to the first-stage reactor in the polycondensation reaction step.

  The more preferable PET of the present invention satisfies that the content of dioxyethylene terephthalate units is in the range of 1.0 to 5.0 mol% (preferably 1.0 to 2.5 mol%). In this way, the PET obtained from the final polycondensation reactor is usually formed into granules (chips) by a melt extrusion molding method. Such granular PET desirably has an average particle diameter of usually 2 to 5 mm (preferably 2.2 to 4 mm). As the PET of the present invention, granular PET that has undergone the liquid phase polycondensation step in this manner may be used as it is, or a solid phase polycondensation step may be added to increase the IV value.

  As the B-1 component aromatic polyester, not only a virgin raw material but also an aromatic polyester regenerated from a used product can be used. Particularly suitable PET can be used effectively because it is consumed in large quantities and its regeneration system has been established. Examples of the used products include containers represented by PET bottles and blisters, various films, and fibers.

(B-2 component: styrenic hard polymer)
The styrenic hard polymer refers to a polymer or copolymer of an aromatic vinyl compound, or a polymer obtained by copolymerizing with other vinyl monomers copolymerizable therewith. The aromatic vinyl compound is preferably contained at least 30% by weight in 100% by weight of the polymer.

  The hard polymer refers to a polymer having a glass transition temperature of 40 ° C. or higher in an amorphous polymer, and is clearly distinguished from a C-component rubbery polymer having a glass transition temperature of at least 10 ° C. or lower. . In the case of a crystalline polymer, it means a polymer having a melting point of 40 ° C. or higher. These glass transition temperatures and melting points can be determined by differential scanning calorimetry (DSC) measurement in accordance with JIS K7121.

  As the styrenic hard polymer, those having a weight average molecular weight of 40,000 to 250,000 can be used, and more preferably 50,000 to 150,000. The lower limit is more preferably 60,000, and the upper limit is more preferably 110,000, still more preferably 100,000. The molecular weight of the styrenic hard polymer is a standard polystyrene equivalent value by GPC measurement, that is, a calibration line between the retention time and the molecular weight is created by GPC measurement of standard polystyrene, and the retention time value of each polymer is calculated using the calibration line. It is the value converted into molecular weight.

  In the present invention, the aromatic vinyl compound includes styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene, methoxystyrene, mono Examples thereof include bromostyrene, dibromostyrene, fluorostyrene, and tribromostyrene, and styrene is particularly preferable.

  In the present invention, preferred examples of the other vinyl monomer copolymerizable with the aromatic vinyl compound include a vinyl cyanide compound and a (meth) acrylic acid ester compound. Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile, and acrylonitrile is particularly preferable.

  In the present invention, as the (meth) acrylic acid ester compound, specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, amyl (meth ) Acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, phenyl (meth) acrylate, and benzyl ( Examples include (meth) acrylate. The notation of (meth) acrylate indicates that both methacrylate and acrylate are included, and the notation of (meth) acrylic acid ester indicates that both methacrylic acid ester and acrylic acid ester are included. Particularly preferred (meth) acrylic acid ester compounds include methyl methacrylate.

  Examples of other vinyl monomers copolymerizable with aromatic vinyl compounds other than vinyl cyanide compounds and (meth) acrylic acid ester compounds in the present invention include epoxy group-containing methacrylic acid esters such as glycidyl methacrylate, maleimide, N- Maleimide monomers such as methylmaleimide and N-phenylmaleimide, α, β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic acid, and itaconic acid and their anhydrides Can be mentioned.

  Examples of the styrenic hard polymer suitable in the present invention include polystyrene, MS copolymer, AS copolymer, MAS copolymer, and SMA copolymer. Here, the MS copolymer is a copolymer mainly composed of methyl methacrylate and styrene, the AS copolymer is a copolymer mainly composed of acrylonitrile and styrene, and the MAS copolymer is mainly composed of methyl methacrylate, acrylonitrile and styrene. The SMA copolymer and the SMA copolymer are copolymers mainly composed of styrene and maleic anhydride (MA).

  Furthermore, the B-2 component of the present invention may have a high stereoregularity such as syndiotactic polystyrene. Such high stereoregularity can be produced by using a catalyst such as a metallocene catalyst during its production. Furthermore, the B-2 component may be a polymer or copolymer having a narrow molecular weight distribution, a block copolymer, or a polymer or copolymer having high stereoregularity. These polymers can be obtained by methods such as anion living polymerization and radical living polymerization. Furthermore, as the aromatic vinyl polymer or copolymer, various copolymers that are precisely controlled at the molecular level are widely known. For example, a polymer having a comb structure controlled by using a macromonomer is exemplified. As the component B-2, a known precisely controlled copolymer may be used.

  Among these, as the B-2 component, polystyrene or AS copolymer is preferable, and AS copolymer is particularly preferable. The proportion of each monomer component in the B-2 component AS copolymer is 5 to 50% by weight, preferably 15 to 35% by weight of acrylonitrile, assuming that the entire copolymer is 100% by weight. Styrene is 95 to 50% by weight, preferably 85 to 65% by weight. The B-2 component copolymer may be copolymerized with a small proportion of other copolymerizable vinyl compounds in addition to acrylonitrile and styrene. The copolymerization ratio of other vinyl compounds is 15% by weight or less, preferably 10% by weight or less in the component B. A conventionally well-known thing can be used for the polymerization initiator or chain transfer agent etc. which are used for the polymerization reaction of B-2 component as needed.

  The AS copolymer may be produced by any of bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, but is preferably produced by bulk polymerization or suspension polymerization, most preferably Is produced by a bulk polymerization method, and the polymerization method is the most common in the industry. The copolymerization method may be either one-stage copolymerization or multistage copolymerization.

(C component: rubbery polymer)
The rubbery polymer of component C includes a polymer composed of 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 polymer composed of the rubber component. It refers to a copolymer formed by combining other polymer chains. Furthermore, the rubber component refers to a polymer containing at least 35% by weight, more preferably 45% by weight, in 100% by weight of a rubbery polymer. A practical upper limit of the rubber component content is about 90% by weight.

  The rubber polymer is more preferably a copolymer formed by bonding other polymer chains. In the production of a rubbery polymer in which another polymer chain is grafted to a rubber component, it is widely known that not a few polymers or copolymers are not grafted on the rubber component. The component C of the present invention may contain such a free polymer or copolymer.

  More specifically, the rubbery polymer of component C includes SB (styrene-butadiene) copolymer, ABS (acrylonitrile-butadiene-styrene) copolymer, MBS (methyl methacrylate-butadiene-styrene) copolymer, MABS. (Methyl methacrylate-acrylonitrile-butadiene-styrene) copolymer, MB (methyl methacrylate-butadiene) copolymer, ASA (acrylonitrile-styrene-acrylic rubber) copolymer, AES (acrylonitrile-ethylenepropylene rubber-styrene) copolymer Polymer, MA (methyl methacrylate-acrylic rubber) copolymer, MAS (methyl methacrylate-acrylic rubber-styrene) copolymer, methyl methacrylate-acrylic / butadiene rubber copolymer, methyl methacrylate-acrylic Tajiengomu - styrene copolymer, methyl methacrylate - and the like (acrylic silicone IPN rubber) copolymer. These copolymers are preferably core-shell type graft copolymers in which a polymer chain composed of the above monomer is bonded to a polymer core composed of a rubber component.

  The rubber particle diameter of the rubber polymer is preferably 0.1 to 5.0 μm, more preferably 0.2 to 3.0 μm, and particularly preferably 0.2 to 1.5 μm. As the distribution of the rubber particle diameter, either a single distribution or a rubber particle having two or more peaks can be used, and the rubber particles form a single phase in the morphology. Alternatively, it may have a salami structure by containing an occluded phase around the rubber particles.

  In the rubbery polymer of the graft copolymer, the weight ratio of the grafted component to the rubber substrate (graft ratio (% by weight)) is preferably 10 to 100%, more preferably 15 to 70%, still more preferably. 15-40%.

  In the production of the graft copolymer, it is also possible to obtain a mixture of a relatively large amount of styrene-based hard polymer that is not grafted by the production method and a rubbery polymer of the graft copolymer. In the present invention, as the mixture of the B-2 component and the C component, a mixture in which the mixture is produced at the time of production can be used. For example, an ABS resin produced by a bulk polymerization method is a typical example.

  Examples of the rubbery polymer of the present invention include various thermoplastic elastomers composed of a hard segment and a soft segment. Examples of such thermoplastic elastomers include polyester elastomers, polyurethane elastomers, styrene elastomers, and olefin elastomers.

(D component: inorganic filler)
The inorganic filler which is the component D of the present invention can be freely selected from fibrous, flake, spherical and hollow shapes, and is fibrous for improving the strength and impact resistance of the resin composition and dimensional stability. Flakes are preferred. For example, as the fibrous inorganic filler, glass fiber, carbon fiber, metal fiber, ceramic fiber, slag fiber, rock wool, zonotlite, wollastonite, and various whiskers (potassium titanate whisker, aluminum borate whisker, Boron whisker, basic magnesium sulfate whisker and the like) are exemplified, and examples of the flaky inorganic filler include glass flake, metal flake, graphite flake, smectite, kaolin clay, mica and talc. In addition, for example, a hollow filler such as a glass balloon may be crushed by melt-kneading with a resin to obtain an effect of improving rigidity in the same manner as a plate-like inorganic filler. The flaky filler of the present invention includes those that exhibit such effects. These inorganic fillers include those in which different materials are surface-coated. Typical examples of the different materials include metals, alloys, and metal oxides. A coating such as a metal or an alloy can impart high conductivity and may improve the design. In some cases, the metal oxide coating can provide functions such as photoconductivity, and the design can be improved.

  In the present invention, mica, talc, and wollastonite are particularly suitable in terms of impact resistance, appearance, dimensional stability, cost, and the like.

(D 'component)
(Mica)
As the average particle diameter of mica, the average particle diameter (D50 (median diameter of particle size distribution)) measured by a laser diffraction / scattering method is preferably 1 to 50 μm, more preferably 2 to 20 μm, still more preferably 2 10 μm can be used. If the average particle diameter of mica is less than 1 μm, the effect of improving the rigidity is not sufficient, and if it exceeds 50 μm, the rigidity of the rigidity is not sufficiently improved, and the mechanical strength such as impact characteristics is not significantly lowered. As the thickness of mica, a thickness measured by observation with an electron microscope is preferably 0.01 to 1 μm, more preferably 0.03 to 0.3 μm. The aspect ratio is preferably 5 to 200, more preferably 10 to 100. Mica may be a pulverized natural mineral or a synthetic product. The mica may be pulverized by either dry pulverization or wet pulverization. The dry pulverization method is more inexpensive and more common, while the wet pulverization method is effective for pulverizing mica more thinly and finely. As a result, the rigidity improvement effect of the resin composition becomes higher.

(talc)
In the present invention, talc is hydrous magnesium silicate in terms of chemical composition, generally represented by the chemical formula 4SiO ₂ .3MgO.2H ₂ O, and is usually scaly particles having a layered structure. thereof include a SiO ₂ 56 to 65 wt%, the MgO 28 to 35 wt%, and a _{H 2} O about 5 wt%. As other minor components, Fe ₂ O ₃ is 0.03 to 1.2% by weight, Al ₂ O ₃ is 0.05 to 1.5% by weight, CaO is 0.05 to 1.2% by weight, K ₂ O. Is 0.2 wt% or less, Na ₂ O is 0.2 wt% or less. The composition of more preferred _talc, SiO 2: 62-63.5 wt%, MgO: from 31 to 32.5 _{wt%, Fe} 2 O 3: _{0.03~0.15 wt%,} Al _{2 O} 3: 0.05-0.25 weight% and CaO: 0.05-0.25 weight% are preferable. Further, the loss on ignition is preferably 2 to 5.5% by weight.

As for the particle diameter of talc, the average particle diameter measured by the sedimentation method is 0.1 to 50 μm (more preferably 0.1 to 10 μm, still more preferably 0.2 to 5 μm, particularly preferably 0.2 to 3.5 μm). ) Is preferable. Furthermore, it is particularly preferable to use talc having a bulk density of 0.5 (g / cm ³ ) or more as a raw material. The average particle size of talc refers to D50 (median diameter of particle size distribution) measured by an X-ray transmission method which is one of liquid phase precipitation methods. As a specific example of an apparatus for performing such a measurement, Sedigraph 5100 manufactured by Micromeritics Inc. can be cited.

  In addition, there is no particular restriction on the manufacturing method when talc is crushed from raw stone, and the axial flow mill method, the annular mill method, the roll mill method, the ball mill method, the jet mill method, the container rotary compression shearing mill method, etc. are used. can do. Further, the talc after pulverization is preferably classified by various classifiers and having a uniform particle size distribution. There are no particular restrictions on the classifier, impactor type inertial force classifier (variable impactor, etc.), Coanda effect type inertial force classifier (elbow jet, etc.), centrifugal field classifier (multistage cyclone, microplex, dispersion separator) , Accucut, Turbo Classifier, Turboplex, Micron Separator, and Super Separator).

  Further, talc is preferably in an agglomerated state in view of its handleability and the like, and as such a production method, there are a method by deaeration compression, a method of compression using a sizing agent, and the like. In particular, the degassing compression method is preferable in that the sizing agent resin component which is simple and unnecessary is not mixed into the resin composition of the present invention.

(Wollastonite)
The average fiber diameter of wollastonite is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and still more preferably 0.1 to 3 μm. 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. Here, the average fiber diameter is obtained by observing the reinforcing filler with an electron microscope, obtaining 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. A filler to be measured for fiber diameter is randomly extracted from an image obtained by observation with an electron microscope, and the fiber diameter is measured near the center of each filler. The number average fiber diameter is calculated from the obtained measured value. The observation magnification is about 1000 times, and the number of measurement is 500 or more (600 or less is suitable for work). On the other hand, the measurement of average fiber length observes a filler with an optical microscope, calculates | requires individual length, and calculates a number average fiber length from the measured value. Observation with an optical microscope starts by preparing a sample that is dispersed so that fillers do not overlap each other. Observation is performed under the condition of 20 times the objective lens, and the observed image is taken as image data into a CCD camera having about 250,000 pixels. From the obtained image data, the fiber length is calculated using a program for obtaining the maximum distance between two points of the image data using an image analysis apparatus. Under such conditions, the size per pixel corresponds to a length of 1.25 μm, and the number of measurement is 500 or more (600 or less is suitable for work).

The wollastonite of the present invention is a magnetic separator that reflects the iron content mixed in the raw material ore and the iron content mixed due to equipment wear when pulverizing the raw material ore in order to sufficiently reflect the inherent whiteness in the resin composition. It is preferable to remove as much as possible. It is preferable that the iron content in wollastonite is 0.5% by weight or less in terms of Fe ₂ O ₃ by such magnetic separator processing. Wollastonite may be a pulverized natural mineral or a synthetic product.

  The inorganic filler includes silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydride). ) And various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.

(Content of each component)
As described above, the preferred thermoplastic material of the present invention comprises 40-90% by weight of component A, 5-35% by weight of B component, 1-8% by weight of C component, and 3-25 by weight. It consists of D component by weight%. More preferred thermoplastic materials are 100-wt% of which 42-85 wt% A component, 8-32 wt% B component, 1-8 wt% C component, and 4-22 wt% D component Consists of. Further preferred suitable thermoplastic materials are 45-70 wt.% A component, 17-30 wt.% B component, 1-8 wt.% C component, and 5-20 wt. It consists of D component.

  In particular, the preferred thermoplastic material of the present invention is an aromatic polycarbonate having a viscosity average molecular weight in the range of 16,000 to 21,000 (A ′ component) of 45 to 70% by weight, o-chloro. Aromatic polyester (B-1 ′ component) 17 to 30% by weight of rubber having a main component of polyethylene terephthalate having a logarithmic viscosity value (IV value) of 0.45 to 0.60 dl / g measured in phenol at 25 ° C., rubber 1 to 8% by weight of a polymer (C component) and 5 to 25% by weight of at least one inorganic filler (D ′ component) selected from talc, mica and wollastonite is there.

(E component: breakage inhibitor)
The thermoplastic resin material of the present invention can contain a crease inhibitor in order to suppress breakage and cracking of the inorganic filler (component D) and to further improve the thermal stability of the resin material. Such a folding inhibitor includes (i) a lubricant containing a functional group having reactivity with a silicate mineral, and (ii) a lubricant whose surface is previously coated on the silicate mineral. A suitable folding inhibitor is an acidic group-containing lubricant or an alkylalkoxysilane or alkylhydrogensilane having an alkyl group having 60 or less carbon atoms.

  As the acidic group-containing lubricant, the carboxyl group is preferably 0.05 to 10 meq / g, more preferably 0.1 to 6 meq / g, still more preferably 0.5 to 4 meq / g per gram of the carboxyl group-containing lubricant. Carboxy group-containing olefin waxes contained in a concentration are preferred. Furthermore, the molecular weight of the olefin wax is preferably 1,000 to 10,000. Furthermore, a copolymer of an α-olefin and maleic anhydride that satisfies the conditions of such concentration and molecular weight is preferable. Such a copolymer can be produced by melt polymerization or bulk polymerization in the presence of a radical catalyst according to a conventional method. Here, as the α-olefin, those having 10 to 60 carbon atoms as an average value can be preferably exemplified. More preferable examples of the α-olefin include those having an average carbon number of 16 to 60, and more preferably 25 to 55.

  Such a folding inhibitor is preferably 0.01 to 5% by weight in 100% by weight of the thermoplastic resin material, more preferably 0.05 to 3% by weight, and still more preferably 0.05 to 1% by weight.

(Other ingredients)
Further, the thermoplastic resin material of the present invention further includes a flame retardant, a flame retardant aid (for example, sodium antimonate, antimony trioxide, etc.), a char-forming compound (for example, a novolak type) within the range satisfying the above characteristics. Phenolic resins, condensates of pitches and formaldehyde, etc.), nucleating agents (for example, sodium stearate and ethylene-sodium acrylate), anti-dripping agents (such as fluorinated polyolefins having fibril formation ability), thermal stabilizers , Antioxidants (for example, hindered phenol antioxidants, sulfur antioxidants, etc.), ultraviolet absorbers, light stabilizers, mold release agents, antistatic agents, foaming agents, flow modifiers, Antibacterial agent, photocatalytic antifouling agent (fine particle titanium oxide, fine particle zinc oxide, etc.), lubricant, colorant, fluorescent whitening agent, phosphorescent pigment, fluorescent dye, infrared absorber It can be blended such as photochromic agents.

(I) Heat stabilizer It is preferable that various heat stabilizers are blended in the thermoplastic resin material. A phosphorus-based stabilizer is suitable as such a heat stabilizer. Examples of phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine. Such phosphorus stabilizers can be used alone or in combination of two or more.

  Specifically, as the phosphite compound, for example, a trialkyl phosphite such as tridecyl phosphite, a dialkyl monoaryl phosphite such as didecyl monophenyl phosphite, a monoalkyl diaryl phosphite such as monobutyl diphenyl phosphite, Triaryl phosphites such as triphenyl phosphite and tris (2,4-di-tert-butylphenyl) phosphite, distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol Such as diphosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Intererythritol phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite and 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4- Examples include cyclic phosphites such as (di-tert-butylphenyl) phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorthoxenyl phosphate, tributoxyethyl phosphate, and diisopropyl phosphate. Triphenyl phosphate and trimethyl phosphate.

  Preferred examples of the phosphonite compound include tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite and bis (di-tert-butylphenyl) -phenyl-phenylphosphonite. Tetrakis (2,4-di-tert More preferred are -butylphenyl) -biphenylene diphosphonite and bis (2,4-di-tert-butylphenyl) -phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate. An example of the tertiary phosphine is triphenylphosphine.

  The amount of the phosphorus stabilizer is preferably 0.0001 to 1% by weight, more preferably 0.0005 to 0.5% by weight, and 0.002 to 0.3% by weight in 100% by weight of the thermoplastic resin material. Is more preferable.

(Ii) Antioxidant An antioxidant may be blended in the thermoplastic resin material. The antioxidant can improve thermal stability and heat aging resistance during molding of a thermoplastic resin material. Such an antioxidant is preferably a hindered phenol stabilizer. Examples of the hindered phenol stabilizer include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5 ′). -Methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl) -4-hydroxy-5-methylphenyl) propionate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -dimethylethyl } -2,4,8,10-tetraoxaspiro [5,5] undecane, N, N′-hexamethylenebis- (3,5 Di-tert-butyl-4-hydroxyhydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, and tetrakis [ And methylene-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane. All of these are readily available. Of these, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate is preferably used. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types. The blending amount of these antioxidants is preferably 0.0001 to 0.05% by weight in 100% by weight of the thermoplastic resin material.

(Iii) Ultraviolet Absorber Examples of the ultraviolet absorber include benzophenone compounds, benzotriazole compounds, hydroxyphenyltriazine compounds, cyclic imino ester compounds, and cyanoacrylate compounds known as ultraviolet absorbers. More specifically, for example, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethyl) Butyl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotriazol-2-yl ] -4-methyl-6-tert-butylphenol, 2,2'-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] phenol, 2,2′-p-phenylenebis (3,1-benzoxazine-4 − ), And 1,3-bis [(2-cyano-3,3-diphenylacryloyl) oxy] -2,2-bis [[(2-cyano-3,3-diphenylacryloyl) oxy] methyl] propane Is exemplified. Further, hindered amine light stabilizers typified by bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like Can also be used. The blending amount of the ultraviolet absorber and light stabilizer is preferably 0.01 to 1% by weight in 100% by weight of the thermoplastic resin material.

(Iv) Mold Release Agent Examples of the mold release agent include olefin wax, silicone oil, fluorine oil, organopolysiloxane, ester of mono- or polyhydric alcohol and higher fatty acid, paraffin wax, beeswax and the like. Of these, esters of monohydric or polyhydric alcohols and higher fatty acids are preferred. The higher fatty acid preferably contains 60% by weight or more of a fatty acid having 20 or more carbon atoms (more preferably 20 to 32 carbon atoms, still more preferably 26 to 32 carbon atoms). As such a higher fatty acid, a higher fatty acid mainly composed of montanic acid is preferably exemplified. Such higher fatty acids are usually produced by oxidizing montan wax. On the other hand, examples of the monohydric alcohol include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol.

  Examples of the polyhydric alcohol include glycerin, diglycerin, polyglycerin (such as decaglycerin), pentaerythritol, dipentaerythritol, trimethylolpropane, diethylene glycol, and propylene glycol. The alcohol component in the ester of a monohydric or polyhydric alcohol and a higher fatty acid is more preferably a polyhydric alcohol. Among these, glycerin, pentaerythritol, dipentaerythritol, and trimethylolpropane are preferable, and glycerin is particularly preferable.

  The amount of the release agent is preferably 0.001 to 2% by weight, more preferably 0.005 to 1% by weight, still more preferably 0.01 to 1% by weight, particularly 100% by weight of the thermoplastic resin material. Preferably it is 0.01 to 0.5 weight%.

(V) Antistatic agent Examples of the antistatic agent include polyether ester amide, glycerin monostearate, naphthalenesulfonic acid formaldehyde highly condensate alkali (earth) metal salt, dodecylbenzenesulfonic acid alkali (earth) metal salt, Examples include dodecylbenzenesulfonic acid ammonium salt, dodecylbenzenesulfonic acid phosphonium salt, maleic anhydride monoglyceride, and maleic anhydride diglyceride. The blending amount of the antistatic agent is preferably 0.01 to 10% by weight in 100% by weight of the thermoplastic resin material.

(Vi) Flame retardant As the flame retardant, red phosphorus flame retardant represented by stabilized red phosphorus in which red phosphorus or the surface of red phosphorus is microencapsulated using a known thermosetting resin and / or inorganic material; Tetrabromobisphenol 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 , Halogenated flame retardants typified by decabromodiphenyl oxide bisphenol condensate and halogen-containing phosphate ester; triphenyl phosphate as monophosphate compound, resole as condensed phosphate ester Organic phosphate ester flame retardants typified by sinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) and other pentaerythritol diphenyl diphosphates; inorganics such as ammonium polyphosphate, aluminum phosphate, zirconium phosphate Inorganic phosphates, hydrates of inorganic metal compounds such as aluminum hydroxide and magnesium hydroxide, zinc borate, zinc metaborate, magnesium oxide, molybdenum oxide, zirconium oxide, tin oxide, and antimony oxide Flame retardants: potassium perfluorobutanesulfonate, calcium perfluorobutanesulfonate, cesium perfluorobutanesulfonate, potassium diphenylsulfone-3-sulfonate, diphenylsulfone-3,3′-di Organic alkali (earth) metal salt flame retardants typified by potassium sulfonate; (poly) organosiloxane compounds containing phenyl, vinyl and methyl groups, and copolymers of (poly) organosiloxane and polycarbonate resins Examples thereof include silicone-based flame retardants; phosphazene-based flame retardants represented by phenoxyphosphazene oligomers and cyclic phenoxyphosphazene oligomers.

(Vii) Flow modifier As the flow modifier, for example, a plasticizer (represented by, for example, phosphate ester, phosphate ester oligomer, phosphazene oligomer, fatty acid ester, aliphatic polyester, aliphatic polycarbonate, etc.), high Other thermoplastic resins and thermoplastic oligomers having rigidity and high fluidity (for example, having a weight average molecular weight of less than 40,000 obtained by polymerizing at least one component selected from styrene, acrylonitrile, and polymethyl methacrylate) Polymers, represented by oligomers of high-rigidity polycarbonate, etc.), liquid crystal polymers (eg, represented by liquid crystal polyester, etc.), rigid molecules (eg, represented by poly-p-phenylene compounds, etc.), and lubricants (eg, minerals) Oil, synthetic oil, higher fatty acid ester, higher fatty acid ester Amide, polyorganosiloxane, olefin wax, polyalkylene glycol, and fluorine oil).

  Such a flow modifier can be blended in the range of 0.1 to 10% by weight, preferably 1 to 8% by weight, in 100% by weight of the thermoplastic material.

(Manufacture of thermoplastic materials)
Arbitrary methods are employ | adopted for preparation of the thermoplastic material of this invention. For example, the method of premixing A component and another component, melt-kneading after that, and pelletizing can be mentioned. Examples of the premixing means include a Nauter mixer, a V-type blender, a Henschel mixer, a mechanochemical apparatus, and an extrusion mixer. In the premixing, granulation can be performed by an extrusion granulator or a briquetting machine as necessary. After the preliminary mixing, the mixture is melt-kneaded by a melt-kneader represented by a vent type twin-screw extruder and pelletized by a device such as a pelletizer. Other examples of the melt kneader include a Banbury mixer, a kneading roll, and a constant temperature stirring vessel, but a vent type twin screw extruder is preferred.

  In addition, a method of supplying each component independently to a melt kneader represented by a twin screw extruder without premixing each component can also be employed. Moreover, after premixing some components, the method of supplying to a melt-kneader independently of the remaining components is mentioned. In particular, when an inorganic filler is blended, the inorganic filler is preferably supplied from a supply port in the middle of the extruder into the molten resin using a supply device such as a side feeder. The premixing means and granulation are the same as described above. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt kneader.

  Furthermore, in order to prepare a thermoplastic material containing the A component and the B-1 component, it is preferable that the water content contained in the A component and the B-1 component is small before melt kneading. Therefore, it is more preferable to melt-knead after drying either A component or B-1 component or both by methods such as various hot air drying, electromagnetic wave drying, and vacuum drying. The vent suction during melt-kneading is preferably in the range of 1 to 60 kPa, preferably 2 to 30 kPa.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, it is a cylinder more suitably. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

  The vehicle exterior material of the present invention can be obtained by injection molding the pellets of the resin composition thus obtained. The pellet is preferably a single pellet containing all the components constituting the vehicle exterior material. However, it is also possible to obtain the vehicle exterior material of the present invention by mixing pellets having different components at the time of injection molding. It is.

(Method for manufacturing vehicle exterior material)
According to the present invention, a method of manufacturing a vehicle exterior material by injection molding a thermoplastic resin material into a mold,
(I) The mold is
(I-1) It has both the following gate-A and gate-B,
(I-2) The gate-B is a gate to which molten resin is supplied so as to merge with the flow after the molten resin flow flowing in from another gate passes, while the gate-A is melted It is a gate where molten resin is supplied without joining the resin flow,
(I-3) Each gate in the mold is provided in a range where there is no other gate within a straight line distance of at least 20 cm on the exterior material surface,
(Iii) As the thermoplastic resin material,
(Iii-1) ISO1133 280 ℃ conforming to standards, melt volume rate (MVR value) at 2.16kg load in the range of 15~150cm ^3/10 min,
(Iii-2) The linear expansion coefficient in the range of −30 to 80 ° C. measured in the flow direction at the center of the test piece prepared according to ISO 527-1 is 2 × 10 ^{−5 to} 6 × 10 ^{−. In} the range of ⁵ / ° C.
(Iii-3) The deflection temperature under load measured in accordance with ASTM D-648 at a load of 0.45 MPa is in the range of 110 to 145 ° C.
(Iii-4) The breaking energy in a high-speed surface impact test measured at 23 ° C. using a smooth flat plate-shaped test piece having a thickness of 3 mm is in the range of 3 to 70 J.
There is provided a method for manufacturing a vehicle exterior material characterized by using a thermoplastic resin material.
The preferable aspect in each of these requirements is as described above.

In particular, according to the present invention, the mold further comprises (i-4) a gate-B provided with a supply regulating valve provided in a flow path communicating with the gate-B after the resin is supplied from the gate-A. By controlling, there is provided a method for manufacturing a vehicle exterior material, which is a gate to which molten resin is supplied so as to merge with the flow of molten resin flowing from another gate after passing.

  The vehicle exterior material of the present invention is particularly suitable for a molding method suitable for the vehicle exterior material, and satisfies the requirements required for the vehicle exterior material. Therefore, it is possible to provide a vehicle exterior material having higher quality and lower cost, and in particular, a vehicle exterior material suitable for manufacturing modularized parts is provided. As such vehicle exterior materials, more specifically, exterior materials include back panels, fenders, bumpers, door panels, pillars, side protectors, side moldings, rear protectors, rear moldings, various spoilers, bonnets, roof panels, trunk lids, Detachable top, wind reflector, etc. are mentioned. It is particularly suitable for so-called vertical skins such as fenders and door panels. Examples of the vehicle exterior material of the present invention include a motorcycle cowl and a tractor cabin panel. As described above, the present invention is useful, and its industrial effect is extremely great.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

[Examples 1 to 5 and Comparative Examples 1 to 4]
A vehicle exterior material as shown in FIG. 1 was molded from a thermoplastic resin material having the composition shown in Examples 1 to 5 and Comparative Examples 1 to 4 in Table 1. The SVG method was used for molding. Casing molding by the SVG method was possible with the composition of Example 3, and after setting molding conditions so that a weld line hardly occurred in the design surface portion, all samples were manufactured under the same conditions. The state of the obtained molded product was observed and evaluated.
(I) Raw material of thermoplastic material (component A)
PC1: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 19,700 (Panlite L-1225WX (trade name) manufactured by Teijin Chemicals Ltd.)
PC2: Linear aromatic polycarbonate resin powder having a viscosity average molecular weight of 24,500 (Panlite L-1250WQ (trade name) manufactured by Teijin Chemicals Ltd.)
(B component)
PET1: Polyethylene terephthalate resin with an IV value of 0.70 polymerized using a germanium compound polymerization catalyst (TR-4550 (trade name) manufactured by Teijin Chemicals Ltd.)
PET2: Polyethylene terephthalate resin having an IV value of 0.51 polymerized using a germanium compound polymerization catalyst (TR-MB (trade name) manufactured by Teijin Chemicals Ltd.)
PBT1: Polybutylene terephthalate having an IV value of 0.87 (manufactured by Polyplastics Co., Ltd., DURANEX 500FP (trade name))
(C component)
IM1: Ethylene / ethyl acrylate copolymer (manufactured by Nippon Polyolefin Co., Ltd., JEREX A4250 (trade name))
IM2: Butadiene / alkyl methacrylate / styrene copolymer (Rohm and Haas, BTA712 (trade name))
(D component)
WSN: Wollastonite (manufactured by NYCO, NYGLOS4 (trade name))
(E component)
WAX: 1-alkene / maleic anhydride copolymer (Diacarna 30M (trade name) manufactured by Mitsubishi Chemical Corporation)
(Other)
ST: Phosphorus stabilizer (Asahi Denka Kogyo Co., Ltd., ADK STAB PEP-24G (trade name))
COL: Titanium dioxide (made by Taioxide Japan Co., Ltd., RTC30) 25% by weight and carbon black (Mitsubishi Chemical Co., Ltd. # 970) 0.5% by weight are added to PC1 to make a total of 100% by weight. Dry blended and uniformly dispersed

(Manufacture of thermoplastic materials)
The compositions listed in Table 1 were produced by an extruder. The extruder was TEXα-42AW-4V (L / D = 42, barrel number 12) manufactured by Nippon Steel Works. Component B was previously dried with a hopper dryer at 120 ° C. for 4 hours or longer, and charged from the side feeder set at the eighth barrel. D component and WAX were mixed in advance and charged from the side feeder using a weighing machine different from B component. Other ingredients were pre-blended with a Hensyl mixer in advance and charged from the main feeder. Vents were set at the 6th and 10th barrels, and suction was performed at a vacuum level of 6 kPa or less. Other extrusion conditions were: cylinder set temperature: 260 ° C., die set temperature: 270 ° C., discharge rate: 500 kg / hour, and screw rotation speed: 250 rpm.
(Molding of vehicle exterior materials)
The obtained pellets were dried at 120 ° C. for 4 hours to form a molded product shown in FIG. J1300E-C5 manufactured by Nippon Steel Works, Ltd. was used for molding. The cylinder set temperature was 270 ° C., and the mold temperature was 60 ° C. The tip of the sprue was connected to the valve gate of the hot runner, and the valve gate connected to each gate was opened in the following order. That is, the gate (16) at the top of the molded product and the lower gate (15) existing on the axis of symmetry were first opened. Thereafter, the valve was opened so that the molten resin was supplied from the gate 11 immediately after the molten resin from the gate 16 passed through the gate 11. The valve was opened so that the molten resin was supplied from the gate 14 immediately after the molten resin from the gate 15 passed through the gate 14. The linear distance on the exterior material surface from the gate 16 to the gate 11 was about 33.5 cm, and the linear distance on the exterior material surface from the gate 15 to the gate 14 was about 26.8 cm.
(Characteristic evaluation of thermoplastic materials)
(I) MVR (Unit: ^cm 3/10 min): Using the resin pellets prepared above, 280 ° C. conforming to ISO1133 standard, to measure the melt volume rate (MVR value) at 2.16kg load. In the measurement, the thermoplastic material was previously dried at 120 ° C. for 4 hours by a hot air dryer. For the measurement, a melt indexer 2A manufactured by Toyo Seiki Co., Ltd. was used.
(Ii) Linear expansion coefficient (unit: 10 ⁻⁵ / ° C.): In accordance with ISO 527-1 using an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) using the resin pellets produced above. A test piece for evaluation (length 175 mm × width 10 mm × thickness 4 mm) was prepared. The pellets were dried at 120 ° C. for 4 hours for molding, the cylinder set temperature was 270 ° C., and the mold temperature was 60 ° C. The gate of the test piece was at one end in the length direction, and the test was performed under the condition of an injection speed of 20 mm / sec. The obtained test piece was annealed at 120 ° C. for 1 hour, and then the test piece for measuring the linear expansion coefficient (test piece size: length (flow direction) 4 mm × width (right angle direction) 4 mm) from almost the center of the test piece. × Thickness 4 mm) was cut out. The linear expansion coefficient was measured according to JIS K 7197 except that this test piece was used. The measurement was performed from −35 ° C. to 85 ° C., and the dimensional change rate between −30 ° C. and 80 ° C. was taken as the linear expansion coefficient. The measurement was performed using a “TA instrument 2940 type” thermomechanical analyzer (manufactured by TA Instruments) and measuring the flow direction. This measured value was taken as the linear expansion coefficient of the material.
(Iii) Deflection temperature under load (unit: ° C.): A test piece was prepared in the same manner as in (ii) above, and the deflection temperature under load at 0.45 MPa load was measured according to ASTM D-648.
(Iv) Breaking energy (unit: J): A plate test piece for evaluation (length 50 mm × width 50 mm × thickness 3 mm) was prepared in the same manner as (ii) above. The energy (fracture energy) required for the breakage of the plate-like test piece with a high-speed surface impact tester was measured. The test machine uses a high-speed surface impact tester Hydroshot HTM-1 (manufactured by Shimadzu Corporation). The test conditions are a collision speed of the striker of 7 m / second, and the tip of the striker has a radius of 6.35 mm at the tip. And the diameter of the cradle hole was 25.4 mm.

(Evaluation results)
(I) Formability Evaluation Results For the thermoplastic materials of Examples 1 to 5, Comparative Example 2 and Comparative Example 4, a molded product in which weld lines are hardly recognized on the design surface by performing cascade molding by the SVG method. was gotten. The weld line on the design surface was recognized by observation under a strong light source, and the length was about 1 cm. Moreover, when surface roughness Ra was sampled and measured based on JIS B0601-1994 in the design surface, all were between 0.15-0.20 micrometer. Since the appearance of the design surface was uniform, it was judged that any part could satisfy such a value.

  On the other hand, since the fluidity was insufficient in Comparative Example 1, a clear weld line was generated on the design surface even when molded under the same conditions. Such weld lines disappeared when the cylinder set temperature was set to 300 ° C., but silver streaks occurred on the design surface, and a molded product having a good appearance could not be obtained.

  The thermoplastic material of Comparative Example 3 had insufficient impact strength, and was easily damaged when the molded product was placed on the ground with the design surface facing upward and stepped on either of the left and right frame portions.

(II) Evaluation Results of Paintability Coating was performed on molded products made of the thermoplastic materials of Examples 1 to 5, Comparative Example 2 and Comparative Example 4 from which good molded products were obtained. The baking temperature of the coating was 120 ° C. After such coating, the molded article made of the thermoplastic material of Comparative Example 4 was deformed. About Examples 1-5 and the comparative example 2, the coated goods with a favorable coating external appearance were able to be obtained.

(III) Evaluation result of paintability A paint molded product made of the thermoplastic material of Examples 1 to 5 and Comparative Example 2 from which the above-mentioned good paint product was obtained was attached to an aluminum frame with a rubber adhesive and heated. A cycle test was performed. In this test, -30 ° C treatment was performed for 1 hour, 23 ° C treatment for 20 minutes, 80 ° C treatment for 1 hour, and 23 ° C treatment for 20 minutes. It was. The coated molded product made of the thermoplastic material of Examples 1 to 5 had no problem in adhesion with the aluminum frame after the test, but in Comparative Example 2, peeling occurred between the rubber adhesive and the coated product. .

It is the front schematic ([1-A]), side schematic ([1-B]), and cross-sectional schematic ([1-C]) in an A-A 'axis | shaft of the vehicle exterior material created in the Example.

Explanation of symbols

1 Vehicle exterior material body (vertical projection length: 850 mm, lateral projection length: 1000 mm, and wall thickness: 4.5 mm)
2 Design surface 3 Window mounting part (non-design surface)
4 Recessed part for attaching the lamp 5 Recessed part for attaching the handle 11 Upper gate 12 in the frame Sprue connected to the gate 11 (the tip of the sprue is connected to the hot runner valve)
13 In-frame lower gate 14 Sprue connected to gate 13 (the tip of the sprue is connected to a hot runner valve)
15 Recessed gate for grip attachment (Direct gate located on the left and right symmetry axis, the tip of which is connected to the hot runner valve)
16 Molded product tower top gate (located on the axis of symmetry)
17 Sprue connected to the gate 16 (the tip of the sprue is connected to the hot runner valve)

Claims (13)

A vehicle exterior material manufactured by injection molding a thermoplastic resin material into a mold,
(I) The mold is
(I-1) It has both the following gate-A and gate-B,
(I-2) The gate-B is a gate to which molten resin is supplied so as to merge with the flow after the molten resin flow flowing in from the gate-A passes, while the gate-A is melted It is a gate where molten resin is supplied without joining the resin flow,
(I-3) Each gate in the mold is provided in a range where there is no other gate within a straight line distance of at least 20 cm on the exterior material surface,
(Ii) The vehicle exterior material is:
(Ii-1) and the front and back any surface design surface provided, made defective through portion Toka et structure unwanted recess and / or the surface of the design of receding from該意Takumi surface,
(Iii) The thermoplastic resin material is
(Iii-1) ISO1133 280 ℃ conforming to standards, melt volume rate (MVR value) at 2.16kg load ranges of 18 ~ 100 cm ^3/10 min,
(Iii-2) The coefficient of linear expansion in the range of −30 to 80 ° C. measured in the flow direction at the center of a test piece prepared according to ISO 527-1 is 3 × 10 ⁻⁵ to 5.5 ×. In the range of 10 ⁻⁵ / ° C.
(Iii-3) The deflection temperature under load measured in accordance with ASTM D-648 at a load of 0.45 MPa is in the range of 130 to 145 ° C.
(Iii-4) breaking energy in the measured high-speed surface impact test at 23 ° C. with a smooth flat test piece 3mm thick - is Ri range near the 30 ~70J,
(Iii-5) At least 100% by weight of the material selected from aromatic polycarbonate (component A) 40 to 90% by weight, aromatic polyester (component B-1) and styrenic hard polymer (component B-2) One type of polymer (component B) 5 to 35 wt%, rubbery polymer (component C) 1 to 8 wt%, and inorganic filler (component D) 3 to 25 wt%,
A vehicle exterior material characterized by the above. (I-4) Gate-B is controlled by a supply adjustment valve provided in a flow path communicating with Gate-B after resin is supplied from Gate-A. 2. The vehicle exterior material according to claim 1, wherein the vehicle exterior material is a gate to which molten resin is supplied so as to merge with the flow of the molten resin flowing in from the flow. 3. The vehicle exterior material according to claim 1 , wherein all of the gates are provided in a recessed portion or / and a penetrating portion, or / and an end portion of the molded product, which do not require design properties. The vehicle exterior material according to any one of claims 1 to 3 , wherein the vehicle exterior material has a maximum projected area in a range of 1,500 to 40,000 cm ² . The thermoplastic resin material is
A component is an aromatic polycarbonate having a viscosity average molecular weight in the range of 16,000 to 23,000,
B-1 component is an aromatic polyester having a logarithmic viscosity value (IV value) measured at 25 ° C. in o-chlorophenol of 0.45 to 0.75 dl / g,
B-2 component is a styrenic hard polymer having a weight average molecular weight calculated from GPC measurement and converted to standard polystyrene in the range of 50,000 to 150,000,
D component of talc, mica, and at least one vehicle exterior material according to any one of claims 1 to 4 which is an inorganic filler selected from wollastonite. The thermoplastic resin material is composed of 45 to 70% by weight of aromatic polycarbonate (component A ′) having a viscosity average molecular weight of 16,000 to 21,000 in 100% by weight of the material at 25 ° C. in o-chlorophenol. Aromatic polyester (B-1 ′ component) of 17 to 30% by weight having a measured logarithmic viscosity value (IV value) of 0.45 to 0.60 dl / g as a main component, rubber polymer (C Component) 1 to 8% by weight and at least one inorganic filler (D ′ component) selected from talc, mica, and wollastonite 5 to 25% by weight. 1 to the vehicle exterior material according to any one of claims 4. The thermoplastic resin material according to any one of claims 1 to 6 , further comprising 0.01 to 5% by weight of a folding inhibitor (E component) in 100% by weight of the thermoplastic resin material. Vehicle exterior material. The vehicle exterior material has a surface roughness Ra measured in accordance with JIS B0601-1994 on the design surface of 0.001 to 3 μm, and a breaking energy in a high-speed surface impact test measured at 23 ° C. of 3 to 3. The vehicle exterior material according to any one of claims 1 to 7 , which satisfies a range of 70J. The vehicle exterior material, paint is applied to at least the design surface after molding, followed by being cured at a temperature range of 100 to 140 ° C., either of claims 1 to 8 in which the coating film is formed The vehicle exterior material according to claim 1. The vehicle exterior material according to claim 9 , wherein the vehicle exterior material is affixed to the frame with a rubber adhesive. The vehicle exterior material according to claim 9 or 10 , wherein the vehicle exterior material has a light-transmitting member or a lighting device attached to at least one of the recessed portion or the penetration portion. A method of manufacturing a vehicle exterior material by injection molding a thermoplastic resin material into a mold,
(I) The mold is
(I-1) It has both the following gate-A and gate-B,
(I-2) The gate-B is a gate to which molten resin is supplied so as to merge with the flow after the molten resin flow flowing in from the gate-A passes, while the gate-A is melted It is a gate where molten resin is supplied without joining the resin flow,
(I-3) Each gate in the mold is provided in a range where there is no other gate within a straight line distance of at least 20 cm on the exterior material surface,
(Iii) As the thermoplastic resin material,
(Iii-1) ISO1133 280 ℃ conforming to standards, melt volume rate (MVR value) at 2.16kg load ranges of 18 ~ 100 cm ^3/10 min,
(Iii-2) The coefficient of linear expansion in the range of −30 to 80 ° C. measured in the flow direction at the center of a test piece prepared according to ISO 527-1 is 3 × 10 ⁻⁵ to 5.5 ×. In the range of 10 ⁻⁵ / ° C.
(Iii-3) The deflection temperature under load measured in accordance with ASTM D-648 at a load of 0.45 MPa is in the range of 130 to 145 ° C.
(Iii-4) breaking energy in the measured high-speed surface impact test at 23 ° C. with a smooth flat test piece 3mm thick - is Ri range near the 30 ~70J,
(Iii-5) At least 100% by weight of the material selected from aromatic polycarbonate (component A) 40 to 90% by weight, aromatic polyester (component B-1) and styrenic hard polymer (component B-2) One type of polymer (component B) 5 to 35 wt%, rubbery polymer (component C) 1 to 8 wt%, and inorganic filler (component D) 3 to 25 wt%,
The manufacturing method of the vehicle exterior material characterized by using a thermoplastic resin material. (I-4) Gate-B is controlled by a supply adjustment valve provided in a flow path communicating with Gate-B after resin is supplied from Gate-A. 13. The method of manufacturing a vehicle exterior material according to claim 12 , wherein the molten resin flow is supplied to the molten resin so that the molten resin flows after the flow of the molten resin flows.

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