JP2017141347A - Resin composition for automobile exterior and outer panel - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition suitable for automobile exterior and outer panel which has heat resistance in a level to which a coating material for automobile body requiring high temperature baking at 140°C or higher can be applied so as to keep consistency of coating appearance and weather-resistance discoloration of a metal portion of an automobile body, keeps good surface property even after coating, has small reduction in impact strength resistance by coating baking, suppresses linear expansion property by heat and a moisture content, is excellent in rigidity, chemical resistance and coating film adhesion, is light-weight and has a high degree of design freedom, and is excellent in workability.SOLUTION: There is provided a resin composition suitable for automobile exterior and outer panel which is formed from (A) an amorphous polyester resin, (B) an aromatic polycarbonate resin and (C) a high heat resistant aromatic polycarbonate resin, where (A) is 5-82 pts.wt. and a total amount of (B) and (C) is 95-18 pts.wt. with respect to 100 pts.wt. of the total amount of the three resins and a weight ratio of (B) and (C) is 0/100 to 75/25.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition based on an aromatic polycarbonate / aromatic polyester having excellent heat resistance and improved impact resistance. Further, the dimensional change of the molded body due to temperature is suppressed, and the dimensional change of the molded body due to humidity is also suppressed. The present invention relates to a small thermoplastic resin composition for automobile exterior and outer panels.

  In recent years, automobiles are required to greatly improve energy use efficiency due to energy problems and environmental problems. In order to contribute to the achievement by reducing the weight, there is a great demand for resin conversion of metal parts.

  In addition, metal plates used for large automobile exteriors and outer plates are usually shaped by pressing, but for reasons such as increased need for design and aerodynamic characteristics, it is difficult to apply complex shapes that are difficult to press. There is a growing demand. In this case as well, replacement of the material with a resin that can be molded into a complicated shape is required. From the viewpoint of productivity and reduction of energy consumption during processing, time-efficient production is necessary, and in recent years, there has been an increasing demand for replacement with thermoplastic resins.

  Conventional thermoplastic resin compositions used for automobile members include (heat resistant) acrylonitrile-butadiene-styrene resin (ABS), an alloy of aromatic polycarbonate resin (PC) and ABS resin (PC / ABS), or talc glass. Resin compositions based on polypropylene resin (PP) filled with fibers and the like are known. These have been used effectively because they are inexpensive and have good impact resistance in a low temperature environment. However, in many cases, the rigidity is insufficient to replace the metal, and it is necessary to increase the thickness of the product in order to prevent deformation due to a load applied to the member during actual use. Also, in applications where exposed to severe sunlight such as a horizontal surface of a spoiler, there is a case where it is not suitable for use because it may be deformed when the member temperature rises.

  Therefore, PC and polyethylene terephthalate resin (PET) or polybutylene terephthalate resin (PBT) are materials that have appropriate rigidity and have sufficient heat resistance that does not deform even when the member temperature rises under severe sunlight irradiation. Alloys with aromatic polyester resins such as these have been proposed. Among them, a resin composition based on a PC / PET alloy has been proposed because warpage during molding is suppressed and a large product can be easily obtained (Patent Documents 1 to 3). Here, when a large molded article made of the PC / PET resin composition is used in a metal automobile body, the coefficient of linear expansion (thermal coefficient of thermal expansion) depending on the temperature of the metal and the PC / PET resin composition is used. Due to the difference, the molded body that is distorted or expanded at a high temperature may come into contact with the metal part and be damaged. In order to avoid this, there were cases where the design was restricted, such as a large gap. A resin composition composed of PC, PET, mineral filler, and bisol-modified PET has been proposed in order to eliminate such problems and to realize a thin molded body and promote weight reduction (Patent Document 4). . The molded body made of this resin composition has a low coefficient of thermal linear expansion and is lightened by thinning, but it has sufficient rigidity and excellent resistance to deformation under load and heat in the actual use environment. Have However, when the molded parts are used after being coated, the resin composition has a heat-resistant temperature of about 120 to 130 ° C., and the intermediate coating or clear coating of the automobile body (metal sheet metal, etc.) It is difficult to suppress deformation of the molded body at a baking temperature of 140 ° C. or higher applied to the melamine resin paint or acid epoxy resin paint used in the process. Therefore, it has been necessary to paint using another paint and a separate process capable of being baked at a low temperature of 120 ° C. or lower. In this case, since the painting system of the parts composed of the automobile body and the molded body is different, it is necessary to make difficult adjustments to fill a subtle difference in color that occurs between them. In addition, even if the initial color tone adjustment is good, there may be a problem that the weather discoloration behaviors of the automobile body and the parts made of the molded body are different.

  Patent Documents 5 and 6 include a polyamide (PA) / polyphenylene ether resin (PPE) alloy (PA / PPE) as a base, blended with polystyrene (PSt) and rubber to increase impact strength, A resin composition in which a heat-like expansion coefficient is suppressed to a low level by blending a filler is disclosed. These resin compositions have a high heat-resistant temperature, and the molded product is suppressed from thermal deformation at a high temperature of 140 ° C. or higher. Therefore, a method has been proposed in which the molded body of these resin compositions is assembled in advance and integrated with a metal automobile body that has been subjected to electrodeposition coating, and then subjected to a baking treatment by applying a paint for the automobile body ( So-called in-line painting). Alternatively, even if in-line painting is difficult, a method of painting a paint for an automobile body in a separate process has been proposed (so-called off-line painting). In the two types of coating methods, since the resin parts and the coating system used for the automobile body match, not only the initial color difference but also the expansion of the color difference due to weathering discoloration can be eliminated. However, these resin compositions mainly composed of PA sometimes have a problem of high hygroscopicity. That is, deformation due to moisture absorption may be a problem in humid regions such as Southeast Asia. In addition, problems such as the occurrence of defects during coating due to moisture absorption and the occurrence of defects after coating due to insufficient adhesion to the coating film due to the PA forming a continuous phase in the alloy being a crystalline resin. .

  As with the PA / PPE alloy, the heat-resistant temperature is increased, while on the other hand, as a method of eliminating the above-mentioned defects due to humidity changes and the coating defects due to the crystalline resin occupying the continuous phase, A resin composition using a high heat-resistant polycarbonate resin having an alicyclic structure, optionally a polycarbonate resin other than the high heat-resistant polycarbonate resin, PET, an elastomeric polymer, a filler, and / or a reinforcing material has been proposed (Patent Document 7). ). Parts obtained by molding this resin composition are assumed to be applied with the paint for automobile bodies as in the case of PA / PPE. Although details of the paint for the automobile body to be used are not specified in Patent Document 7, the obtained parts can maintain a good surface smoothness even after in-line coating, and have a painted surface with an excellent appearance. You can get. However, while the inventors have studied, the impact strength of the molded product is reduced while being held in a high temperature environment of 140 ° C. or higher in a baking process such as a melamine resin paint or an acid epoxy resin paint. We faced a problem that declined significantly.

JP 2011-231280 A JP 2010-222393 A JP 2002-121373 A JP 2010-254739 A JP-A-6-287446 Japanese Patent Laid-Open No. 5-179135 JP-T-2004-526848

  INDUSTRIAL APPLICABILITY The present invention can be applied to a paint for an automobile body that requires high-temperature baking at 140 ° C. or higher in order to produce a resin molded body that can maintain the consistency of paint appearance and weather resistance discoloration with a metal part of the automobile body. It has a high level of heat resistance, maintains good surface properties even after painting, has little impact strength reduction due to paint baking, suppresses linear expansion due to heat and moisture, and has rigidity, chemical resistance, and coating adhesion An object of the present invention is to provide a resin composition for an automobile exterior / outer plate member that is excellent in performance, is lightweight, has a high degree of design freedom, and is excellent in workability.

  In order to solve the above problems, the present inventors have conducted extensive investigations on the problem that the impact strength is significantly reduced by high-temperature baking at 140 ° C. or higher, particularly in the resin composition described in Patent Document 2, It has been found that the crystallinity of the PET phase dispersed and present in a continuous phase composed of a high heat-resistant polycarbonate resin and other polycarbonate resins is caused by a large change after coating baking.

  Therefore, as a result of further earnest studies, the present inventors have found that an amorphous polyester having a heat of crystal melting of a specific value or less, a high heat-resistant aromatic polycarbonate resin (HHPC) having a specific deflection temperature, and necessary. Based on an alloy with an aromatic polycarbonate resin (PC) other than HHPC that has a specific deflection temperature under load, impact strength is reduced by suppressing the change in crystallinity of the aromatic polyester phase after painting and baking. The present inventors have found that the above-mentioned problems can be solved by suppressing the above, and have reached the present invention.

That is, the resin composition of the present invention is
[1] A resin composition for an automobile exterior / outer plate comprising (A) an amorphous polyester resin, (B) an aromatic polycarbonate resin, and (C) a highly heat-resistant aromatic polycarbonate resin, wherein (A) and (B ) And (C) is 100 parts by weight, whereas (A) is 5 to 82 parts by weight, and (B) and (C) is 18 to 95 parts by weight. B) / (C) has a weight ratio of 0/100 to 75/25, and (A) has a heat of crystal melting of 10 J / g or more in the range of 180 to 300 ° C. by thermal analysis using a differential scanning calorimeter. The deflection temperature under load (Method A) measured according to ASTM D648 is 110 ° C. or higher and lower than 145 ° C., and the deflection temperature under load (Method A) (C) is 145 ° C. or higher. The present invention relates to a resin composition for exterior and outer panels of an automobile.
[2] Further, the present invention relates to the resin composition for an automobile exterior / outer plate, wherein the deflection temperature under load (Method B) is 130 ° C. or higher.
[3] Further, (A) the non-crystalline polyester resin contains (a1) 70 to 80 mol% terephthalic acid and (a2) 20 to 30 mol% dicarboxylic acid other than terephthalic acid.
A resin comprising: (a) a unit derived from a dicarboxylic acid; and (b1) a unit derived from diol (b) consisting of 80 to 100 mol% of ethylene glycol and (b3) another copolymerizable diol of 0 to 20 mol%. The present invention relates to a resin composition for an automobile exterior / outer plate.
[4] Further, (A) the non-crystalline polyester resin comprises (a) a unit derived from (a1) a dicarboxylic acid comprising (a1) 70 to 80 mol% of terephthalic acid and (a2) 20 to 30 mol% of isophthalic acid; The present invention relates to the resin composition for an automobile exterior / outer plate, which is a resin containing a unit derived from diol (b) consisting of 100 mol% of ethylene glycol.
[5] (A) The non-crystalline polyester resin comprises (a) units derived from (a1) dicarboxylic acid comprising (a1) 80 to 100 mol% terephthalic acid and (a2) 0 to 20 mol% dicarboxylic acid other than terephthalic acid, (B1) ethylene glycol 60 to 80 mol% and (b2) one or more diols 20 to 40 mol% selected from the group consisting of aliphatic diols having 3 to 10 carbon atoms or alicyclic diols having 6 to 21 carbon atoms And (b3) a resin composition containing (b) a diol-derived unit consisting of 0 to 20 mol% of another copolymerizable diol.
[6] (A) The non-crystalline polyester resin comprises (a) a unit derived from (a) dicarboxylic acid consisting of 100 mol% of terephthalic acid, (b1) 60 to 80 mol% of ethylene glycol, and (b2) neopentyl. A resin comprising 20 to 40 mol% of one or more diols selected from the group consisting of glycol or cyclohexanedimethanol, and (b3) a diol-derived unit consisting of 0 to 20 mol% of other copolymerizable diols The present invention relates to a resin composition for an automobile exterior / outer plate.
[7] The present invention further relates to (D) the resin composition for an automotive exterior / outer plate, further comprising 2.5 to 50 parts by weight of a plate-like filler.

  By using the resin composition of the present invention, heat resistance at a level that can be applied to automobile body paints that require high-temperature baking at 140 ° C. or higher in order to maintain the consistency of paint appearance and weather resistance discoloration with metal parts of the automobile body. Maintain good surface properties after painting, impact resistance strength drop due to paint baking is small, linear expansion due to heat and moisture is suppressed, and excellent rigidity, chemical resistance and coating film adhesion Thus, it is possible to provide a molded article suitable for an automobile exterior / outer plate member that is lightweight and has a high degree of design freedom and excellent workability.

  Hereinafter, preferred embodiments of the present invention will be described, but the present invention is not limited to the following descriptions.

In the resin composition of the present invention, (A) non-crystalline polyester, (B) deflection temperature under load (edgewise, hereinafter referred to as DTUL) (Method A) measured based on ASTM D648 is 110 ° C. or higher and lower than 140 ° C. An aromatic polycarbonate, (C) DTUL (Method A) is a resin composition for automobile exterior and outer panels, comprising a highly heat-resistant aromatic polycarbonate having a temperature of 145 ° C or higher,
(A) Amorphous polyester is characterized by not having a heat of crystal melting (ΔHc) of 10 J / g or more in the range of 180 to 300 ° C. by thermal analysis using a differential scanning calorimeter (DSC).

  The resin composition of the present invention has good heat resistance and has a DTUL (Method B) of 130 ° C. in order to suppress thermal deformation during baking of paints for automobile bodies such as melamine resin paints and acid epoxy resin paints. It is preferable that it is above, More preferably, it is 139 degreeC or more, More preferably, it is 145 degreeC or more. In the case of subjecting to so-called on-line coating, which is carried out from electrodeposition coating reaching a higher temperature, the DTUL (Method B) is preferably 170 ° C. or higher, more preferably 180 ° C. or higher. The upper limit is not limited, but from the viewpoint of moldability, the upper limit is preferably 220 ° C, more preferably 200 ° C, and further 190 ° C.

As a countermeasure against deformation caused by the difference in the thermal linear expansion coefficient between the molded product obtained from the resin composition of the present invention and the metal part, without excessively increasing the fitting with the metal part of the automobile body, the thermal linear expansion coefficient difference In order to suppress the gap required as a measure against physical interference due to the above and to enhance the design, the linear expansion coefficient of the resin composition of the present invention is preferably 6.5 × 10 ⁻⁵ or less, and 6.1 × 10 6. More preferably, it is ⁻⁵ or less. The linear expansion coefficient is determined by processing the resin composition of the present invention into a type A1 dumbbell defined in ISO 20553, cutting out a test piece by cutting, and a direction parallel to the flow direction of the molten resin during molding (MD ) Based on ISO 11359-2. In the present invention, the linear expansion coefficient measured in the same manner as described above in the direction (TD) perpendicular to the flow direction of the molten resin during molding is within ± 0 + 1 within the linear expansion coefficient measured by MD. Is preferred.

  Since the resin composition of the present invention is used after being molded into an automobile exterior / skin member, the flexural modulus of the resin composition of the present invention is 2900 MPa or more in order to ensure the product rigidity of the molded product and the final product. It is preferable that Moreover, the resin composition of this invention can also adjust the said bending elastic modulus according to the predetermined objective. For example, for the purpose of weight reduction, 3500 MPa or more is preferable so that the molded body can have a thickness of less than 3 mm while maintaining product rigidity, and in particular when the thickness is set to about 1.5 to 2.5 mm, 4000 MPa. The above is more preferable, and 5000 MPa or more is more preferable. In the present invention, the flexural modulus is measured based on ISO 178.

  Below, although it demonstrates about the compounding component of this invention, the "weight part" used with the usage-amount is (A) non-crystalline polyester resin, (B) aromatic polycarbonate resin, and (C) highly heat-resistant aromatic polycarbonate. The total amount of resin was 100 parts by weight.

The amount of the (A) non-crystalline polyester resin used in the present invention is preferably 5 to 82 parts by weight from the viewpoints of impact resistance, heat resistance, dimensional stability, chemical resistance, thermal stability, and moldability.
The lower limit of the amount of (A) used is more preferably 10 parts by weight and more preferably 20 parts by weight from the viewpoints of thermal stability and molding processability.
The upper limit of the amount of (A) used is more preferably 50 parts by weight and more preferably 40 parts by weight from the viewpoint of impact resistance and heat resistance.

The resin composition of the present invention may contain (B) an aromatic polycarbonate resin.
(B) The amount of the aromatic polycarbonate resin used is preferably 0 to 50 parts by weight from the viewpoint of a balance between heat resistance, molding processability and impact resistance.
The lower limit of the amount of (B) used is more preferably 5 parts by weight and more preferably 10 parts by weight from the viewpoints of impact resistance and molding processability.
The upper limit of the amount of (B) used is more preferably 40 parts by weight and more preferably 30 parts by weight from the viewpoint of heat resistance.

(C) The amount of the high heat-resistant aromatic polycarbonate resin used is preferably 10 to 90 parts by weight from the viewpoint of a balance between heat resistance, molding processability and impact resistance.
In order not to impair heat resistance, the lower limit of the amount of (C) used is more preferably 20 parts by weight, more preferably 30 parts by weight, and particularly preferably 40 parts by weight.
The upper limit of the amount of (C) used is more preferably 80 parts by weight, more preferably 70 parts by weight, and particularly preferably 60 parts by weight, from the viewpoint of impact resistance and moldability.

In the resin composition of the present invention, from the viewpoint of the balance of heat resistance, impact resistance, and fluidity, the total amount of (B) and (C) is 18 to 95 parts by weight, and (B) / (C) The weight ratio is adjusted to 0/100 to 75/25.
The lower limit of the total amount of (B) and (C) is preferably 40 parts by weight, more preferably 55 parts by weight, and the upper limit is preferably 85 parts by weight, more preferably 75 parts by weight.
The lower limit of the weight ratio (B) / (C) is preferably 15/85, more preferably 25/75, even more preferably 35/65, and the upper limit is preferably 75/25, more preferably 65/35. preferable.

The resin composition of the present invention may contain (D) a plate-like filler in order to achieve a good balance between impact resistance and rigidity, heat resistance, thermal linear expansion, and surface appearance.
(D) As a usage-amount of a plate-shaped filler, 2.5-50 weight part is preferable.
The lower limit of the amount of use of (D) is preferably 4.5 parts by weight, more preferably 5.5 parts by weight, and 6.5 parts by weight or more in order to keep the thermal expansion coefficient low and increase rigidity and heat resistance. Is more preferable.
The upper limit of the amount of (D) used is more preferably 34 parts by weight, more preferably 29 parts by weight or less, still more preferably 24 parts by weight or less, in order to improve the surface appearance without reducing impact resistance. 15 parts by weight or less is particularly preferable.

The resin composition of the present invention may contain (E) an elastomer in order to improve impact resistance, particularly impact resistance in a low temperature environment.
(E) The amount of the elastomer used is preferably 0.5 to 10 parts by weight in order to achieve a good balance between impact resistance, heat resistance and thermal linear expansion.
From the viewpoint of impact resistance, the lower limit of the amount of (E) used is more preferably 1 part by weight, and even more preferably 3 parts by weight.
The upper limit of the amount of use of (E) is more preferably 7 parts by weight and further preferably 5.5 parts by weight so as not to deteriorate the heat resistance and the thermal linear expansibility.

The resin composition of the present invention is produced by the metal compound contained in the raw material in order to suppress the deterioration of the mechanical properties, the thermal stability during the molding process, or the appearance defect of the molded product due to the generation of decomposition gas. As a supplement, (F) a phosphorus compound may be included.
(F) As for a phosphorus compound, 0-2 weight part is preferable.
The lower limit of the amount of (F) used is more preferably 0.002 parts by weight, still more preferably 0.01 parts by weight, and particularly preferably 0.1 parts by weight.
The upper limit of the amount of (F) used is preferably 2 parts by weight, more preferably 1 part by weight, and even more preferably 0.5 parts by weight, in order to suppress poor appearance of the molded body.

  The resin composition of this invention may contain 0.5-15 weight part of (G) amorphous thermoplastic resins other than a polycarbonate-type resin.

  The concentration of the antimony element (Sb) contained in the resin composition of the present invention is 20 ppm or less in order to maintain the thermal stability during the molding process and to suppress the deterioration of the mechanical properties and the heat resistance of the molded body. Is preferable, 10 ppm or less is more preferable, and 4 ppm or less is particularly preferable.

  The concentration of germanium element (Ge) contained in the resin composition of the present invention is 200 ppm or less in order to maintain the thermal stability during the molding process and to suppress the deterioration of the mechanical properties and the heat resistance of the molded body. Is preferable, 100 ppm or less is more preferable, and 50 ppm is particularly preferable.

<(A) Amorphous polyester resin>
The (A) non-crystalline polyester resin used in the present invention is 10 J // within a range of 180 to 300 ° C. when measured at a heating rate of 10 ° C./min by thermal analysis using a differential scanning calorimeter (DSC). It is a requirement that no peak having a heat of crystal melting of g or more is detected. In thermal analysis by DSC, it is preferable that a crystal melting heat peak of 5 J / g or more is not detected, and it is more preferable that a crystal melting heat peak of 2 J / g or more is not detected.

  When a crystal melting heat peak of 10 J / g or more is detected when thermal analysis is performed by DSC under the above-mentioned conditions, it has crystallinity to the extent that it affects the physical properties of the molded body. That is, the degree of crystallinity of the polyester phase forming a dispersed phase in the resin composition is applied to the obtained molded body while it is subjected to a baking process under a high temperature condition of usually 130 ° C. or higher. Rise. As a result, the elastic modulus of the resin composition is increased and the specific gravity of the polyester phase is changed, so that the polyester phase, (C) a high heat-resistant aromatic polycarbonate resin, and (B) aromatic Distortion and stress concentration occur around the interface with the continuous phase formed by the polycarbonate resin. This leads to a decrease in impact resistance of the molded body. On the other hand, if a crystal melting heat peak of 10 J / g or more is not detected, the crystallinity is low enough not to substantially give physical properties, and the resistance to resistance caused by the above-described promotion of crystallization of the polyester phase is low. Does not cause impact degradation.

  The (A) non-crystalline polyester resin used in the present invention is a polycondensate having an ester bond in the main chain and has a structure derived from a combination of a dicarboxylic acid unit and a diol unit, or one or more per molecule. There are those having a structure derived from a compound unit having both a carboxylic acid group and one or more hydroxyl groups, or a combination thereof. In order to improve the heat resistance and thermal stability of the resulting resin composition, the dicarboxylic acid is an aromatic dicarboxylic acid and / or the diol is an aromatic diol, or directly as a substituent on the aromatic ring. Alternatively, it is possible to use an aromatic compound in which one or more carboxylic acids are bonded to one or more carboxylic acids via a hydrocarbon chain or the like, and directly or via a hydrocarbon chain or the like. A polycondensate of an aromatic dicarboxylic acid and a diol is preferably used because it can be easily obtained industrially.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like. As the dicarboxylic acid not containing an aromatic ring, aliphatic dicarboxylic acids such as itaconic acid, succinic acid, adipic acid, sebacic acid, and cyclohexanedicarboxylic acid can be used.

  Examples of aromatic diols include catechol, resorcinol, hydroquinone, 2,2-bis (4-hydroxyphenyl) propane ("bisphenol A") and 1,1-bis- (4-hydroxyphenyl) -3, 3, 5 -Bisphenol compounds such as trimethylcyclohexane ("Bisphenol TMC"), biphenol compounds such as 4,4'-biphenol, and the like.

  Examples of diols having no aromatic ring include ethylene glycol (EG), 1,2-propanediol, 1,3-propanediol (also known as trimethylene glycol), 1,4-butanediol, dimethylpropanediol, and methylpentane. Examples thereof include diol, cyclohexanediol, cyclohexanedimethanol, and nonanediol. As an aromatic compound in which one or more carboxylic acids are bonded directly or through a hydrocarbon chain as a substituent on the aromatic ring, and similarly one or more hydroxyl groups are bonded directly or through a hydrocarbon chain, for example, hydroxy Benzoic acid or the like can be used. An aliphatic compound having one or more carboxylic acids and one or more hydroxyl groups in one molecule can also be used, and examples thereof include lactic acid, hydroxybutyric acid, and hydroxyhexanoic acid. These can also be used in combination.

From the viewpoint of mechanical properties, fluidity, heat resistance, or impact resistance in the coating baking process, the (A) non-crystalline polyester resin of the present invention has either or both of (a) a dicarboxylic acid and (b) a diol. It is preferably denatured.
The modification means that (a) dicarboxylic acid and / or (b) diol is substituted with another group.

(A) As (A) non-crystalline polyester resin in which dicarboxylic acid is modified, for example,
(A1) 10-95 mol% of terephthalic acid and (a2) 5-90 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 80 to 100 mol% of ethylene glycol and (b3) 0 to 20 mol% of other copolymerizable diols
Those containing units derived from diol (b) consisting of
(A1) 50 to 90 mol% of terephthalic acid and (a2) 10 to 50 mol% of dicarboxylic acid other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 80 to 100 mol% of ethylene glycol and (b3) 0 to 20 mol% of other copolymerizable diols
And more preferably those containing units derived from diol (b) consisting of
(A1) 70-80 mol% of terephthalic acid and (a2) 20-30 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 80 to 100 mol% of ethylene glycol and (b3) 0 to 20 mol% of other copolymerizable diols
And more preferably those containing units derived from diol (b) consisting of
(A1) 70-80 mol% terephthalic acid and (a2) 20-30 mol% isophthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) Ethylene glycol 100 mol%
Particularly preferred are those containing a unit derived from diol (b).

(B) As the (A) non-crystalline polyester resin in which the diol is modified, for example,
(A1) 80-100 mol% of terephthalic acid and (a2) 0-20 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 10 to 95 mol% ethylene glycol
(B2) 5 to 90 mol% of one or more diols selected from the group consisting of aliphatic diols having 3 to 10 carbon atoms or alicyclic diols having 6 to 21 carbon atoms;
(B3) Other copolymerizable diol 0 to 20 mol%
(B) a unit containing a diol-derived unit consisting of
(A1) 80-100 mol% of terephthalic acid and (a2) 0-20 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) Ethylene glycol 50 to 90 mol%
(B2) 10 to 50 mol% of one or more diols selected from the group consisting of aliphatic diols having 3 to 10 carbon atoms or alicyclic diols having 6 to 21 carbon atoms;
(B3) Other copolymerizable diol 0 to 20 mol%
(B) a unit containing a diol-derived unit consisting of
(A1) 80-100 mol% of terephthalic acid and (a2) 0-20 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 60-80 mol% ethylene glycol
(B2) 20 to 40 mol% of one or more diols selected from the group consisting of aliphatic diols having 3 to 10 carbon atoms or alicyclic diols having 6 to 21 carbon atoms;
(B3) Other copolymerizable diol 0 to 20 mol%
(B) a unit containing a diol-derived unit consisting of
(A1) 100 mol% terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 60-80 mol% ethylene glycol
(B2) One or more diols selected from the group consisting of neopentyl glycol or cyclohexanedimethanol 20 to 40 mol%
(B3) Other copolymerizable diol 0 to 20 mol%
Those comprising (b) a diol-derived unit consisting of

(A) The logarithmic viscosity (IV value) of the amorphous polyester resin is not particularly limited, but is preferably 0.4 or more, more preferably 0.5 or more, and further preferably 0.6 or more from the viewpoint of impact resistance. preferable. The logarithmic viscosity (IV value) of (A) is preferably 1.5 or less, more preferably 1.2 or less, and even more preferably 1.0 or less, from the viewpoint of moldability.
The IV value is measured by using a Ubbelohde viscometer in a mixed solvent of tetrachloroethane / phenol = 50/50 (weight ratio) as a solution having a concentration of 0.5 g / dl at 25 ° C. and (A). .

  (A) The non-crystalline polyester resin is preferably produced using a polymerization catalyst selected from the group consisting of a germanium catalyst, a titanium catalyst, an aluminum catalyst and an antimony catalyst, and the thermal stability and molding process of the resin composition From the viewpoint of suppressing the generation of cracked gas at the time, those produced using a germanium catalyst or a titanium catalyst are more preferred, and those produced using a germanium catalyst are more preferred.

When the polymerization catalyst residue remaining in (A) causes a transesterification reaction when melt-kneaded with (B) aromatic polycarbonate resin or (C) highly heat-resistant aromatic polycarbonate resin, resulting in deterioration of physical properties or poor appearance There is.
The germanium metal content in (A) is preferably 5 to 500 ppm, more preferably 10 to 400 ppm, because it may cause a transesterification reaction when melt-kneading, resulting in deterioration of physical properties and poor appearance.
The titanium metal content in (A) is preferably 100 ppm or less, more preferably 20 ppm or less, and more preferably 1.5 ppm or less because it may cause a transesterification reaction when melt-kneading and may cause deterioration in physical properties and appearance defects. Is more preferable.
The aluminum metal content in (A) is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 20 ppm or less because it may cause a transesterification reaction when melt-kneaded, resulting in deterioration of physical properties and poor appearance. preferable.
The antimony metal content in (A) is preferably 100 ppm or less, more preferably 50 ppm or less, and even more preferably 6 ppm or less because it may cause a transesterification reaction when melt-kneaded, resulting in deterioration of physical properties and poor appearance. preferable.

  Examples of germanium catalysts include germanium oxides such as germanium dioxide, germanium alkoxides such as germanium tetraethoxide and germanium tetraisopropoxide, germanium hydroxide and alkali metal salts thereof, germanium glycolate, germanium chloride, and germanium acetate. However, these are used alone or in combination of two or more. Among these germanium catalysts, germanium dioxide is particularly preferable because unnecessary residues are not generated.

  As the titanium catalyst, tetraethoxy titanium, titanium alkoxide treated with an alcohol having 2 to 10 carbon atoms, or the like can be used. In order to increase the thermal stability at the time of molding, for example, the titanium alkoxide or the titanium alkoxide and an aromatic polyvalent carboxylic acid such as benzenedicarboxylic acid, benzenetricarboxylic acid, benzenetetracarboxylic acid, or an acid anhydride thereof. (A) an amorphous polyester resin obtained by polymerizing in the presence of a titanium-phosphorus catalyst obtained by reacting a phosphorus compound represented by the following formula 1 or a salt thereof with a titanium compound obtained by the reaction: Preferably, it can be used.

(Wherein R ¹ represents an unsubstituted or substituted hydrocarbon group having 6 to 20 carbon atoms, and p is 1 or 2)

  For the same reason, (A) an amorphous polyester resin polymerized in the presence of a compound represented by the following formula 2 can be used more preferably.

(Wherein R ² and R ³ each independently represents an unsubstituted or substituted alkyl group having 2 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms)

  On the other hand, when the non-crystalline polyester resin (A) obtained by using an antimony compound that is commercially available at a low cost as a catalyst is simply used, it often becomes a problem that the appearance of the molded article is impaired. Therefore, in order to avoid this, it is preferable to use a phosphorus compound (F) described later in detail. The amount of the phosphorus compound (F) used is as described above.

<(B) Aromatic polycarbonate resin>
The resin composition of the present invention may contain (B) an aromatic polycarbonate resin from the viewpoint of toughness, impact resistance, and mechanical properties. (B) The aromatic polycarbonate resin is a resin usually obtained by the reaction of dihydric phenol and phosgene, or the reaction of dihydric phenol and carbonic acid diester, or the reaction of dihaloformate of dihydric phenol. Among these, a polycarbonate made of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferable because it easily develops impact resistance. It is particularly preferable to use a polycarbonate that substantially contains only 2,2-bis (4-hydroxyphenyl) propane-derived units and carbonate bonds.
The deflection temperature under load (Method A) (B) is 110 ° C. or higher and lower than 145 ° C., preferably 110 ° C. or higher and 140 ° C. or lower, from the viewpoint of the balance between impact resistance and heat resistance.
The weight average molecular weight of (B) is preferably 20,000 to 200,000 from the viewpoints of impact resistance, chemical resistance, moldability, and the like.
The lower limit of the weight average molecular weight (hereinafter also referred to as GPC molecular weight) of (B) is preferably 40,000, more preferably 45,000, from the viewpoint of impact resistance and chemical resistance.
The upper limit of the weight average molecular weight of (B) is preferably 150,000, more preferably 100,000, more preferably 80,000 and particularly preferably 60,000 from the viewpoint of moldability.

<(C) High heat resistant aromatic polycarbonate resin>
The (C) high heat-resistant aromatic polycarbonate resin used in the present invention is a resin composition having a heat resistance capable of withstanding the baking temperature of a melamine resin paint or acid epoxy resin paint at 130 ° C. or higher, or an electrodeposition coating temperature at 170 ° C. or higher. To grant.
From the viewpoint of heat resistance, the deflection temperature under load (C) (C) is preferably 145 ° C. or higher, more preferably 155 ° C. or higher, and even more preferably 170 ° C. or higher.
Further, the deflection temperature under load (C) (Method A) is preferably 250 ° C. or lower, more preferably 220 ° C. or lower, and further preferably 200 ° C. or lower, from the viewpoint of moldability.
The weight average molecular weight of (C) is preferably 20,000 to 200,000. Furthermore, from the viewpoint of impact resistance and chemical resistance, 40,000 or more is more preferable, 50,000 or more is more preferable, and 55,000 or more is particularly preferable. Further, from the viewpoint of moldability, 100,000 or less is more preferable, 80,000 or less is more preferable, and 70,000 or less is particularly preferable.

  The (C) high heat-resistant aromatic polycarbonate resin used in the present invention is at least one selected from the group consisting of bis (hydroxyaryl) cycloalkane, bis (hydroxyaryl) fluorene, bis (hydroxyaryl) adamantane, and dihydroxytetraarylmethane. A polycarbonate containing one as a monomer unit can be preferably used. These are more preferably contained in combination with the 2,2-bis (4-hydroxyphenyl) propane monomer unit in order to achieve good impact resistance.

  As the bis (hydroxyaryl) cycloalkane, substituted or unsubstituted bis (hydroxyphenyl) cyclohexane can be more preferably used. 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4 -Hydroxyphenyl) -4-isopropylcyclohexane and the like, and in particular, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane ("bisphenol TMC") can be preferably used. 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) propane are used in combination, and 1,1-bis- (4- The molar fraction of the hydroxyphenyl) -3,3,5-trimethylcyclohexane monomer unit is preferably 10 to 90% from the balance of impact resistance, heat resistance and processability. The lower limit of the mole fraction is preferably 30%, particularly preferably 50%, and the upper limit is more preferably 85%, and particularly preferably 70%.

  As the bis (hydroxyaryl) fluorene, a substituted or unsubstituted bis ((hydroxyalkoxy) phenyl) fluorene compound, bis (hydroxyphenyl) fluorene compound, or the like can be preferably used. The bis ((hydroxyalkoxy) phenyl) fluorene compound is preferably a bis (4- (2-hydroxyethoxy) phenyl) fluorene compound, which is used in combination with a dihydroxybenzene compound and / or a dihydroxynaphthalene compound. Can be used. The dihydroxybenzene compound can be selected from hydroquinone, resorcinol, and catechol. Specifically, 2,6-naphthalenediol can be selected as the dihydroxynaphthalene compound. As the bis (hydroxyphenyl) fluorene compound, a bis (4-hydroxyphenyl) fluorene compound, particularly 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (“bisphenol BCF”) is preferably used. it can. For example, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and 2,2-bis (4-hydroxyphenyl) propane are used in combination, among which 9,9-bis (4-hydroxy-3-methyl) The molar fraction of phenyl) fluorene is preferably 10 to 90% from the balance of impact resistance, heat resistance and workability. The lower limit is preferably 25%, more preferably 40%, particularly preferably 60%, and the upper limit is further preferably 85%, particularly preferably 70%. Also, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene and α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene (“bisphenol M”) are used in combination. , 9-bis (4-hydroxy-3-methylphenyl) fluorene monomer unit may have a molar fraction of 10 to 90%.

  As the bis (hydroxyaryl) adamantane, substituted or unsubstituted bis (hydroxyphenyl) adamantane can be preferably used, and examples thereof include 1,3-bis (4-hydroxyphenyl) -5,7-dimethyladamantane. In particular, 2,2-bis (4-hydroxyphenyl) adamantane can be preferably used. 2,2-bis (4-hydroxyphenyl) adamantane and 1,1-bis (4-hydroxyphenyl) cyclohexane ("bisphenol Z") are used in combination, among which 2,2-bis (4-hydroxyphenyl) adamantane The molar fraction of the monomer units is preferably 10 to 90% from the balance of impact resistance, heat resistance and processability. The lower limit is preferably 30%, particularly preferably 50%, and the upper limit is further preferably 90%, particularly preferably 80%. Furthermore, α, ω-bis (hydroxyphenylpropyl) -polydimethylsiloxane and / or 1,1,1-tris (4-hydroxyphenyl) ethane can be used in combination.

  As the dihydroxytetraarylmethane, substituted or unsubstituted dihydroxytetraphenylmethane can be preferably used, and 4,4′-dihydroxytetraphenylmethane (“bisphenol BP”) can be particularly preferably used. 4,4′-dihydroxytetraphenylmethane and 2,2-bis (4-hydroxyphenyl) propane and / or α, α′-bis (4-hydroxyphenyl) -m-diisopropylbenzene, The molar fraction of the 4,4′-dihydroxytetraphenylmethane monomer unit is preferably 10 to 90% from the balance of impact resistance, heat resistance and processability. The lower limit is further 30%, particularly 45%, and the upper limit is further preferably 90%, and particularly preferably 80%.

  Among these, an aromatic polycarbonate composed of 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and 2,2-bis (4-hydroxyphenyl) propane is industrially used. Are easily available and preferable.

<(D) Plate filler>
The resin composition of the present invention may contain (D) a plate-like filler in order to suppress the coefficient of thermal expansion of a molded product obtained from the resin composition and to reduce the in-plane anisotropy of the molded product. .
(D) The plate-like filler is an alkaline inorganic substance containing silicon element, and is preferably a silicate mineral. In the present invention, at least one selected from mica, talc or kaolin can be used particularly preferably.
(D) The shape of the plate filler is preferably a flat plate shape or a scale shape.
(D) A plate-like filler having a volume average particle diameter (MV) determined by a laser diffraction method of 0.5 to 45 μm can be preferably used, and the ratio of the MV to the thickness, that is, the aspect ratio is The thing of 5-200 can be used preferably. In order to suppress the thermal linear expansion coefficient and improve the heat resistance, the MV is preferably 1 μm or more, more preferably 2 μm or more, and further 5 μm or more, and preferably 45 μm so as not to greatly deteriorate the impact resistance. Hereinafter, it is more preferably 35 μm or less, and even more preferably 25 μm or less. In order to achieve a good balance between the effect of suppressing the linear expansion coefficient and the heat resistance and impact resistance, the aspect ratio is more preferably 10 or more, further preferably 50 or more, more preferably 150 or less, and still more preferably 100. Hereinafter, more preferably 80 or less. Mica is preferably used from the balance between the linear expansion coefficient suppressing effect and the impact resistance.

  (D) The plate-like filler is an alkaline inorganic substance as described above. In the resin composition of the present invention, (B) an aromatic polycarbonate resin or (C) at a high temperature during compound production or molding. When contacted with a high heat-resistant aromatic polycarbonate resin, it may act as a decomposition catalyst for them. If the decomposition is severe, carbon dioxide gas is generated, which may cause appearance defects such as silver streak during molding. In order to suppress such decomposition action, it is preferable that (D) the constituent element of the plate-like filler does not substantially contain an alkaline earth metal. Such alkaline earth metals include calcium, magnesium, barium and the like. From such conditions, in the present invention, as the (D) plate-like filler, white mica, silk mica and the like are preferably used, and white mica is particularly preferably used. Here, “substantially contains” means that the filler contains an alkaline earth metal element in excess of 5% by weight.

  In the present invention, (D) the plate-like filler is dispersed in water after mining, at the time of pulverization, or after pulverization, and then the aqueous phase is subjected to a method such as wet vibration sieving, sedimentation separation, wet cyclone, filtration or centrifugation. What separated and dried is preferable. This is because impurities contained in the filler may act as a decomposition catalyst for (B) aromatic polycarbonate resin or (C) highly heat-resistant aromatic polycarbonate resin. It is preferable to remove these impurities from the filler. In addition, since a fine powder having a high aspect ratio is realized and it is easy to balance the mechanical properties such as impact resistance and the effect of suppressing the linear expansion coefficient, a filler manufactured by a wet pulverization method using water during pulverization is preferable. Used. As such a wet pulverization method, a wet ball mill, a wet roller mill, a wet micron mill, a water jet pulverization, a wet grinding with a stone mortar, or the like can be used.

  In the present invention, the (D) plate-like filler can be used after being surface-treated with a silane coupling agent, a titanium coupling agent, an aluminum coupling agent, etc., but from the viewpoint of cost and surface appearance, those without surface treatment are used. More preferably, it can be used.

<(E) Elastomer>
The resin composition of the present invention may contain (E) an elastomer for the purpose of improving impact resistance, particularly impact resistance at low temperatures. Examples of (E) include (E1) graft copolymers and (E2) ethylene copolymers. The (E1) graft copolymer and the (E2) ethylene copolymer can be used in combination.

<(E1) Graft copolymer>
The (E1) graft copolymer that can be used in the present invention is obtained by graft polymerization of a monomer in the presence of a rubber-like polymer.
The glass transition temperature of the rubber-like polymer is preferably −10 ° C. or lower, more preferably −30 ° C. or lower, and particularly preferably −50 ° C. or lower, from the viewpoint of impact resistance at low temperatures.
The rubbery polymer is preferably crosslinked.
The amount of the rubbery polymer in (E1) is preferably 40 to 95% by weight, with (E1) being 100% by weight. From the viewpoint of impact resistance and the viewpoint of suppressing the generation of gas during molding, it is more preferably 50% by weight or more, and further preferably 65% by weight or more.
The amount is 90% by weight or less in order to stably develop impact resistance by controlling the dispersed particle size of (E1) to a submicron size or less and ensuring a dispersed state in basic particle units described later. Is more preferable, and 85% by weight or less is more preferable.

  Examples of the rubber-like polymer include polybutadiene, hydrogenated polybutadiene, acrylic acid ester copolymer, butadiene-styrene copolymer, butadiene-acrylic acid ester copolymer, polyorganosiloxane, polyorganosiloxane-acrylic acid ester complex, And polyorganosiloxane-butadiene composites can be used. From the viewpoint of impact resistance at low temperature, polybutadiene, polyorganosiloxane, and polyorganosiloxane-acrylic acid ester complex are more preferable, and polybutadiene and polyorganosiloxane are particularly preferable.

  In the present invention, (E1) the graft copolymer is one kind selected from the group consisting of an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester compound in the presence of the rubbery polymer. Those obtained by polymerizing the above monomers in one or more stages are preferred. In order to stably exhibit impact resistance, the monomer is preferably composed mainly of methyl methacrylate, and methyl methacrylate (MMA) and ethyl acrylate, butyl acrylate, butyl methacrylate, styrene, or the like, MMA in all monomers excluding the combined portion is preferably 50% by weight or more, more preferably 70% by weight or more, further 80% by weight or more, preferably 98% by weight or less, more preferably 95% by weight or less. Use as follows. Further, for the same reason, styrene and acrylonitrile, which are mainly polymerized in one or more stages, can be used. In this case, styrene in all monomers except the rubber-like polymer portion is preferably 50 wt. % Or more, more preferably 60% by weight or more, further preferably 70% by weight or more, preferably 90% by weight or less, more preferably 80% by weight or less.

  In the present invention, as the (E1) graft copolymer, a rubbery polymer whose volume average particle diameter is adjusted to 70 to 320 nm using a production method such as emulsion polymerization can be preferably used. In order to realize excellent impact resistance with addition of a small amount, the lower limit is more preferably 100 nm, still more preferably 150 nm, and the upper limit is preferably 320 nm, more preferably 250 nm. In the resin composition of the present invention, the effect of improving impact resistance is maximized by dispersing the (E1) graft copolymer in a basic unit having a particle size designed in advance.

<(E2) Ethylene copolymer>
The (E2) ethylene-based copolymer that can be used in the present invention, like the (E1) graft copolymer, improves the impact resistance particularly in a low-temperature environment, and also has fluidity during molding. It is a component for making the quality good.

  In the present invention, the (E2) ethylene copolymer is composed of ethylene as a monomer unit and another unsaturated monomer copolymerizable with ethylene. As the unsaturated monomer, acrylic acid lower alkyl esters such as ethyl acrylate and methyl acrylate, propylene, and the like can be used. However, the unsaturated monomer can be well dispersed in the resin composition of the present invention to cause molding defects such as delamination. In order not to cause it, it is preferable to use a copolymer with ethyl acrylate. The ratio of ethylene in the total amount of ethylene and unsaturated monomer is preferably 10% by weight or more, more preferably 50% by weight or more, and even more preferably 70% by weight or more in order to sufficiently exhibit impact resistance. In order to avoid molding defects such as delamination, the content is preferably 90% by weight or less, more preferably 85% by weight or less, and further 80% by weight or less.

The embrittlement temperature (F50) of (E2) measured based on JIS K7216 is preferably −30 ° C. or less, more preferably −50 ° C. or less, and further preferably −70 ° C. or less from the viewpoint of impact resistance.
The melting point of (E2) measured based on JIS K7121 is preferably 80 ° C. or higher, more preferably 90 ° C. or higher, in order to suppress the ease of handling during the production of the resin composition and the sticky feeling of the molded product. From a viewpoint of property, 130 degrees C or less is preferable and 100 degrees C or less is more preferable.

The melt flow rate of (E2) measured based on JIS K7210 is preferably 1 g / 10 min or more, more preferably 5 g / 10 min or more, and further preferably 10 g / 10 min or more in order to improve the fluidity at the time of molding. In order not to impair the heat resistance, 400 g / 10 min or less is preferable, 50 g / 10 min or less is more preferable, and 30 g / 10 min or less is more preferable.
Note that JIS is Japanese Industrial Standard.

<(F) Phosphorus compound>
The phosphorus compound (F) in the present invention is a component that, as its effect, improves the heat and humidity resistance and the thermal stability during molding, acidic phosphoric acid, acidic phosphoric acid ester represented by the above formula 1, or these A salt with an alkali metal, an alkaline earth metal, aluminum, zinc, or the like, an oxaphosphorine compound, a phosphite ester, a phosphonic acid derivative, a phosphinic acid derivative, or the like can be used.
Examples of the salt of acidic phosphoric acid include sodium dihydrogen pyrophosphate, sodium dihydrogen phosphate, calcium dihydrogen phosphate and the like.
As an example of the said acidic phosphate ester or its salt, the compound represented by following formula 3-5 can be mentioned.
Examples of the oxaphospholine compound include a compound represented by the following formula 6 and derivatives thereof.
Examples of the phosphite include compounds represented by the following formula 7.
Examples of the phosphonic acid derivative include aluminum salts and zinc salts such as n-octadecylphosphonic acid and benzylphosphonic acid.
Examples of the phosphinic acid derivative include aluminum salts and zinc salts such as diphenylphosphinic acid and diethylphosphinic acid.

  As a more preferable (F) phosphorus compound, an acidic phosphate represented by the following formula 3 or calcium dihydrogen phosphate can be used.

(Where q is 1 or 2)

When it is necessary to apply electrostatic coating to the molded body obtained from the resin composition of the present invention, carbon-based conductive fillers such as carbon fiber, carbon nanotube (CNT), graphite, graphene, ketjen black, and carbon particles Metal fibers such as stainless steel and aluminum can be blended in the resin composition of the present invention to impart conductivity. In addition, an electrostatic primer can be applied to the molded body obtained from the resin composition of the present invention to a sufficient extent in advance to impart conductivity to the surface of the molded body. The electrostatic primer is, for example, a conductor such as conductive carbon black, graphite, silver, nickel, copper, for example, active methylene-based block polyisocyanate / chlorinated polyolefin combined resin, etc., for example, xylene, toluene, cyclohexane, etc. Hydrocarbon solvents, alcohol solvents such as methyl alcohol and isopropyl alcohol, ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone, and isophorone, such as ester solvents such as ethyl acetate, butyl acetate, and ethylene glycol monoethyl ether acetate It is obtained by diluting with a solvent or a mixed solvent thereof.
In the present invention, a method based on blending of carbon-based conductive fillers and metal fibers and a method based on electrostatic primer coating can be combined. Here, electrostatic coating means that a positive or negative voltage is applied to a molded article obtained from the metal member and the resin composition of the present invention, and a reverse polarity voltage is applied to the mist side when spraying the paint mist. The paint mist is charged to the opposite charge by applying it, and the paint mist is adsorbed to the metal member and the molded article of the present invention by using the action of the electrostatic attraction generated to efficiently and uniformly form a coating film. Is the method.

<(G) Amorphous thermoplastic resin>
The resin composition of the present invention comprises (G) an amorphous thermoplastic resin such as (meth) acrylic resin, acrylonitrile-styrene copolymer resin (AS), polystyrene resin, polypropylene resin, polybutylene terephthalate resin, and fluororesin. Can be included. (G) The amorphous thermoplastic resin preferably has a glass transition temperature of 150 ° C. or higher from the viewpoint of thermal decomposition resistance and heat resistance. For example, polyetherimide resin, polyphenylene ether resin, polysulfone resin / polyphenyl Examples thereof include polysulfone resins such as sulfone resins and polyethersulfone resins, phthalmaleimide copolymerized (meth) acrylic resins, (phenyl) imidized (meth) acrylic resins, and polyarylate resins. Also, a mixed product such as a polymer alloy with another polymer or a polymer blend can be used.

<(H) Other additives>
(H) Other additives can be blended with the resin composition of the present invention as required. (H) Other additives include known light stabilizers, antioxidants, heat stabilizers, flame retardants, plasticizers, lubricants, mold release agents, ultraviolet absorbers, antistatic agents, pigments / dyes, inorganic fillers. , Long fiber fillers, pH adjusters, fluidity improvers and the like.

  As known light stabilizers, benzophenone compounds, triazine compounds, benzotriazole compounds, and the like can be used. As a known release agent, stearyl stearate, pentaerythritol tetrastearate, montanic acid ester, diglyceryl stearate, glycerin monobehenate, or the like can be used.

  In the present invention, the resin composition of the present invention is melted in an impregnation die or an extruder into continuous fibers such as glass fibers, carbon fibers, stainless fibers, and aramid fibers, preferably those obtained by opening these continuous fiber bundles. After impregnation, long fiber pellets obtained by collecting the fibers into the resin composition of the present invention by pelletizing can be used. A resin composition having excellent impact resistance can be obtained when the length of the recovered fiber and the pellet length are substantially matched, which is preferable. When stainless steel fibers are used, the electromagnetic wave shielding effect may be excellent, which is preferable.

<Method for producing resin composition>
The resin composition of the present invention can be produced by any method. For example, blending using a blender, super mixer, etc., single screw or multi screw screw extruder, etc. (A) and (C), if necessary (B), and further according to the desired purpose ( D), (E), (F), (G), and (H) are appropriately selected and manufactured by kneading.

<Method of molding resin composition>
The resin composition of the present invention can be molded by any method. For example, it can be molded by injection molding, injection compression molding, extrusion molding, blow molding, compression molding or the like. A molding method by injection molding or injection compression molding is preferable because it can efficiently produce a molded body having a complicated shape such as a rib or a clip seat. In order to obtain a large molded article with a good appearance, it is preferable to perform injection molding or injection compression molding using a hot runner mold / timing gate.

Thus, the resin composition of the present invention can be formed into a molded body for an automobile exterior / outer plate by applying the molding method as described above. In particular, a molded body having a projected area of 40,000 mm ² or more and an average thickness of 5 mm or less can be obtained. In order to increase the replacement area from metal and reduce the vehicle weight efficiently, the projected area is more preferably 60,000 mm ² or more, and more preferably 100,000 mm ² or more. In order to reduce the weight of the member itself, the average thickness is more preferably 3.5 mm or less, further preferably 3 mm or less, more preferably 2.5 mm or less, and further preferably 2 mm or less. In order not to reduce the product rigidity too much, the average thickness is preferably 1 mm or more, and more preferably 1.5 mm or more. The thickness said here is the average thickness of the top surface of the molded body. In order to further secure product rigidity, the molded body can be provided with a rib structure on the back surface. In order to suppress sink marks generated on the design surface of the top surface, the thickness of the rib is preferably 1/2 or less of the top surface, and more preferably 1 / 2.5 or less. On the other hand, in order to prevent short shots in the rib portion, the thickness is preferably 0.3 mm or more, more preferably 0.5 mm or more, and further preferably 0.6 mm or more. In the present invention, “sink” refers to a recess that is not intended in design and that occurs on the design surface or the like due to volume shrinkage accompanying cooling of the resin.

  In general, the projection area and thickness can be values set at the time of designing a molded body structure in CAD (Computer Assisted Design). If the set values are unknown, 3D scanning or the like can be used. Thus, the compact structure can be digitized and analyzed by CAD or CAE (Computer Assisted Engineering) software based on the data.

  Since the resin composition of the present invention is excellent in heat resistance, even if a paint for an automobile body such as a melamine paint or an acid epoxy paint is suitably applied and baked at 130 ° C. or higher to cure the coating film, Without excessive deformation, the surface appearance after coating can be kept good, and the impact resistance can be kept even after baking. Therefore, it is possible to apply in-line coating after assembling the molded body to a metal automobile body as necessary, or to apply only the molded body off-line separately from the automobile body. The molded body obtained from the resin composition of the present invention has a reduced thermal linear expansion coefficient, excellent mechanical properties such as impact resistance, and excellent appearance, and therefore has a garnish, spoiler, fender, roof, trunklit, and fuel lit. -It can be suitably used as an exterior / skin member for automobiles such as doors and tailgates. The molded body obtained from the resin composition of the present invention is excellent in durability and has a lower specific gravity than metal, and thus can contribute to weight reduction of an automobile and is excellent in consideration of the environment. Moreover, since it can shape | mold by injection molding or injection compression molding, it can contribute to the improvement of the design property of a motor vehicle.

In the following, examples that more specifically represent the present invention will be described, but the present invention is not limited thereto.
“Parts” and “%” in the following measurement conditions and examples represent “parts by weight” and “% by weight”, respectively.
First, materials used and measurement methods will be described below.

<Materials used>
(A) Amorphous polyester resin A-1: Cyclohexanedimethanol-modified polyethylene terephthalate resin (noncrystalline polyester resin) containing terephthalic acid units, ethylene glycol (EG) units, and cyclohexanedimethanol (CHDM) units: IV Value 0.65, heat of crystal melting 0 J / g (heat of crystal melting in the range of 180 to 300 ° C. when measured at a heating rate of 10 ° C./min by thermal analysis by DSC. The same applies to (A) below) EG unit / CHDM unit = 69/31 (mol / mol), containing germanium element at 100 ppm or less, and content of antimony element is below detection limit.
A-2: Neopentyl glycol-modified polyethylene terephthalate resin (non-crystalline polyester resin) containing a terephthalic acid unit, an ethylene glycol (EG) unit, and a neopentyl glycol (NPG) unit, IV value: 0.78, crystal melting Heat 0 J / g, EG unit / NPG unit = 67/33 (mol / mol), containing 100 ppm or less of germanium element, and the content of antimony (Sb) element is below the detection limit.
A-3: Isophthalic acid-modified polyethylene terephthalate resin (non-crystalline polyester resin) containing terephthalic acid (TPA) unit, isophthalic acid (IPA) unit, and ethylene glycol unit, IV value: 0.64, crystal melting heat 0J / G, TPA unit / IPA unit = 77/23 (mol / mol), containing 100 ppm or less of germanium element, and the content of antimony element is below the detection limit.
A-4: Polyethylene terephthalate resin, IV value: 0.70, crystal melting heat 37 J / g Germanium element is contained in 100 ppm or less, and content of antimony element is below detection limit.
The contents of germanium (Ge) element and antimony (Sb) element are determined by fluorescent X-ray measurement, and the measurement limit of antimony (Sb) element is 1 ppm.

(B) Aromatic polycarbonate resin B-1: Bisphenol A polycarbonate resin, GPC molecular weight 49,700, deflection temperature under load (Method A) 130 ° C.

(C) High heat-resistant aromatic polycarbonate resin C-1: Bisphenol A-bisphenol TMC copolymer polycarbonate resin, GPC molecular weight 58,400, deflection temperature under load (Method A) 172 ° C., bisphenol A unit / bisphenol TMC unit = 40/60 (Mol / mol)

(D) Plate-like filler D-1: natural white mica wet / dry combined pulverized product, volume average particle size: 5.4 μm, aspect ratio unknown D-2: natural white mica wet pulverized product, volume average particle size: 20 μm, Aspect ratio 70
The volume average particle diameter was measured by Nikkiso Co., Ltd. Microtrac “MT-3000”, and the aspect ratio was determined by scanning electron microscope (SEM) observation.

(E) Elastomer E-1: Graft copolymer obtained by graft polymerization of methyl methacrylate / butyl acrylate based on polybutadiene as a rubber-like polymer, volume average particle diameter 200 nm.
E-2: Ethylene / ethyl acrylate copolymer, density 0.94, embrittlement temperature <−75 ° C.

(H) Other additives H-1: phenolic antioxidant, pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate]
H-2: Phosphorous antioxidant, pentaerythritol bis (diphenyl) phosphate H-3: Montanate ester release agent H-4: Epoxy heat stabilizer, bisphenol A epoxy resin H-5: Pigment, carbon black

<Measurement method>
(Intrinsic viscosity (IV value))
Using a mixed solvent of tetrachloroethane / phenol = 50/50 (weight ratio), it was adjusted to a solution having an aromatic polyester (A) concentration of 0.5 g / dl, and calculated from the logarithmic viscosity obtained by measurement at 25 ° C. .

(Weight average molecular weight)
The polymer sample was made into a 20 mg / 10 ml chloroform solution, and the solution was subjected to gel permeation chromatography (GPC) analysis to determine the weight average molecular weight. GPC system (manufactured by Waters) is used, and polystyrene gel columns “Shodex K-806” and K805 (manufactured by Showa Denko KK) are used as columns, and chloroform is used as an eluent at 30 ° C., in terms of polystyrene. Analyzed.

(Melt flow rate (MFR))
According to ISO 1133, measurement was performed at 280 ° C. under a load of 21.18 N. For the measurement, pellets dried at 110 ° C. for 5 hours or more were used.

(Spiral flow length (SFL))
An injection molding machine “FAS-150B” (manufactured by FANUC CORPORATION) was used, molding was performed using a spiral mold having a thickness of 3 mm at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C., and the flow length was evaluated. For the measurement, pellets dried at 130 ° C. for 5 hours or more were used.

(Deflection temperature under load (Method A))
Based on ASTM D648, measurement was performed edgewise by Method A (1.8 MPa load).

(Deflection temperature under load (Method B))
Based on ASTM D648, measurement was performed edgewise by method B (0.45 MPa load).

(Heat sag)
In accordance with JIS K 7195, however, the molded body was measured using the ASTM D638 95 Type-I test piece, and the displacement amount at an overhang amount of 100 mm was measured. Evaluation was performed at 140 ° C and 150 ° C.

(Surface appearance)
The appearance of a molded product of 120 mm x 120 mm x 3 mm flat plate molded by staying at a cylinder temperature of 280 ° C and a mold temperature of 80 ° C for 2 minutes using an injection molding machine "FN-1000" (Nissei Plastic Industry Co., Ltd.) It was observed with the naked eye and evaluated according to the following criteria.
◎: No flash or roughness on the surface is observed. ○: Flash or roughness on the surface is observed in 10% or less of the total area. Δ: Flash or roughness on the surface exceeds 10% of the total area and 25% or less. Observed in x: Surface flash or roughness observed over 25% of the total area

(Linear expansion coefficient)
For each of the resin flow direction (MD) and the orthogonal direction (TD), the linear expansion coefficient was measured in a temperature range of −30 to 80 ° C. by thermodynamic analysis (TMA) in accordance with ISO 11359: 1999 (E). The test piece was 7 mm × 4 mm × thickness 4 mm. At this time, the test direction (MD or TD) was aligned and cut so as to be 7 mm.

(Bending test)
According to ISO 178, the bending strength and the flexural modulus were measured at a test speed of 5 mm / min and 23 ° C.

(Shock resistance strength)
40 or more flat plates with a thickness of 6 cm × 6 cm × 3 mm were prepared, and 20 or more test pieces with and without heat treatment at 150 ° C. × 60 minutes were prepared, assuming the maximum heat load when painting the paint for an automobile body. In accordance with ASTM D2794 (for plastics), the weight is 4.5 kg, the maximum non-destructive height is obtained by measuring in a -30 ° C. environment, and the gravitational acceleration (9.807 m / s ² ) × the weight of the weight is dropped. X Based on the maximum non-destructive height, it was converted into an energy value (unit: J), which was designated as impact strength.

(specific gravity)
In accordance with ISO 1183-1, the liquid immersion method was used.

(Examples 1-9, Comparative Example 1)
(Resin composition)
Table 1 shows (A) non-crystalline polyester resin, (B) aromatic polycarbonate resin, (C) highly heat-resistant aromatic polycarbonate resin, (D) plate-like filler, (E) elastomer, and (H) other additives. The mixture was premixed at the ratio shown in FIG. 1 and melt-kneaded at 290 ° C. using a twin-screw extruder “TEX-44SS” (manufactured by Nippon Steel Works, Ltd.) to produce pellets. At this time, (D) the plate-like filler was supplied from the side feeder. Using the obtained pellets, test pieces were prepared with an injection molding machine “FN-1000” (manufactured by Nissei Plastic Industry Co., Ltd.) set at a cylinder temperature of 290 ° C. and a mold temperature of 100 ° C. The physical properties shown in were evaluated. Similarly, an injection molding machine “FN-1000” (manufactured by Nissei Plastic Industry Co., Ltd.) is used to produce a flat plate of 200 mm × 150 mm × 3 mm thickness, cut out into 60 mm × 60 mm squares, and the impact resistance strength is increased by the above method. evaluated. Further, the melt flow rate and the spiral flow length were determined by the above methods. The evaluation results are shown in Table 2.

  As seen in Table 1, the molded body of Comparative Example 1 obtained in Examples 1-9, whereas the impact strength after heat treatment at 150 ° C. × 60 minutes decreased to less than 50% compared to before heat treatment. It can be seen that all of the obtained molded bodies retain 65% or more, and have a heat resistance of a level that can be applied to automobile body paints that require high-temperature baking at 140 ° C. or higher.

In addition, from the results of the physical properties shown in Table 1, all of the molded bodies obtained in Examples 1 to 9 maintain good surface properties after coating, and the impact strength strength drop due to coating baking is small. It can be seen that the molded article has excellent workability, linear expansion due to moisture and moisture, excellent rigidity, chemical resistance and coating film adhesion, light weight and high design freedom.
Therefore, it turns out that the molded object obtained in Examples 1-9 is a resin molded object which can maintain the consistency of the coating external appearance with a metal site | part of a motor vehicle main body, and a weather resistance discoloration.

The resin composition of the present invention is suitably used for exterior / skin members for automobiles such as passenger cars where design and appearance are particularly important, and for exterior / skin members for automobiles that have been baked. The

Claims (7)

(A) Non-crystalline polyester resin, (B) Aromatic polycarbonate resin, (C) Resin composition for automobile exterior / outer plate comprising highly heat-resistant aromatic polycarbonate resin,
Whereas the total amount of (A), (B) and (C) is 100 parts by weight,
(A) is 5 to 82 parts by weight,
The total amount of (B) and (C) is 18 to 95 parts by weight,
The weight ratio of (B) / (C) is 0/100 to 75/25,
(A) does not have a heat of crystal fusion of 10 J / g or more in the range of 180 to 300 ° C. by thermal analysis using a differential scanning calorimeter,
The deflection temperature under load (Method A) measured based on ASTM D648 (Method A) is 110 ° C. or higher and lower than 145 ° C.,
(C) Deflection temperature under load (Method A) is 145 ° C. or higher.   The resin composition for automotive exterior / exterior panels according to claim 1, wherein the deflection temperature under load (Method B) is 130 ° C or higher. (A) Non-crystalline polyester resin
(A1) 70-80 mol% of terephthalic acid and (a2) 20-30 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) 80 to 100 mol% of ethylene glycol and (b3) 0 to 20 mol% of other copolymerizable diols
The resin composition for automobile exterior / outer panels according to claim 1, wherein the resin composition comprises a unit derived from diol (b). (A) Non-crystalline polyester resin
(A1) 70-80 mol% terephthalic acid and (a2) 20-30 mol% isophthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) Ethylene glycol 100 mol%
The resin composition for automobile exterior / outer panels according to claim 1, wherein the resin composition comprises a unit derived from diol (b). (A) Non-crystalline polyester resin
(A1) 80-100 mol% of terephthalic acid and (a2) 0-20 mol% of dicarboxylic acids other than terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) ethylene glycol 60 to 80 mol% and (b2) one or more diols 20 to 40 mol% selected from the group consisting of aliphatic diols having 3 to 10 carbon atoms or alicyclic diols having 6 to 21 carbon atoms When,
(B3) Other copolymerizable diol 0 to 20 mol%
The resin composition for an automobile exterior / outer plate according to claim 1, wherein the resin composition comprises (b) a diol-derived unit. (A) Non-crystalline polyester resin
(A1) 100 mol% terephthalic acid
(A) a unit derived from a dicarboxylic acid consisting of:
(B1) ethylene glycol 60 to 80 mol%, and (b2) one or more diols 20 to 40 mol% selected from the group consisting of neopentyl glycol or cyclohexanedimethanol,
(B3) Other copolymerizable diol 0 to 20 mol%
The resin composition for an automobile exterior / outer plate according to claim 1, wherein the resin composition comprises (b) a diol-derived unit. Furthermore, (D) The resin composition for motor vehicle exterior and outer plates in any one of Claims 1-6 containing 2.5-50 weight part of plate-shaped fillers.