JP5408853B2 - Polyester resin composition and resin substrate formed by molding the same - Google Patents

Description

  The present invention relates to a polyester resin composition for a resin substrate, on which a metal vapor deposition layer and a hard coat layer are provided in this order. More specifically, it is possible to provide a metal vapor deposition layer and a hard coat layer in this order directly on the surface, and excellent impact resistance, chemical resistance, high cycle performance, dimensional stability, fluidity, and metallic tone. The present invention relates to a polyester resin composition for a resinous substrate, which is a product having a high-class glossy, deep, and color design, and a resinous substrate formed by molding the polyester resin composition.

  Thermoplastic resin is lighter than metal, has a high degree of freedom in design, and is excellent in productivity, so it has a wide range of parts such as electrical / electronic / OA equipment parts, machine parts, vehicle parts, building materials, and household goods. Used in the field. In particular, in the case of housing members such as electrical / electronic / OA equipment parts, machine parts, vehicle parts, and resin products where appearance is important, excellent impact resistance, chemical resistance, high cycle performance, dimensional stability, etc. In addition to the above characteristics, there is a growing demand for a design property having a glossy, deep, and color tone with a high-class metallic tone.

  On the other hand, a beautiful design is imparted by forming a metal layer on the surface of the resin substrate by a method such as wet plating, dry plating, metal spraying, painting, hot stamping. Among them, wet plating is excellent in terms of appearance and adhesion, and thus has been adopted in many cases. However, from the viewpoint of environmental measures, dry plating methods such as vacuum deposition and ion plating have attracted attention in recent years.

  Such resin products are applied to various design parts and mechanism parts, mainly automobile parts such as automobile parts. In particular, polyester resin and polycarbonate resin are excellent in mechanical strength, and among these parts, they are used in various handles for outer or inner, and various improvements have been proposed.

  For example, multi-phase polymer molding composed of thermoplastic resins such as fluoropolymer, polyimide, polycarbonate, polyester, polymethyl methacrylate, polyphenylene oxide, silicone, and fillers such as polyarylene sulfide, oxidized polyarylene sulfide, polyimide, and aromatic polyester. Parts that have been metallized by sputtering have been proposed (for example, see Patent Document 1). However, in this method, a part having excellent impact resistance, chemical resistance, dimensional stability and fluidity has not been obtained yet.

  In addition, a resin composition containing a polybutylene terephthalate resin having a terminal carboxyl group amount of 50 meq / kg or less, a polycarbonate resin, and an inorganic filler having an average primary particle diameter of 10 μm or less is molded to form a resin substrate. A resinous light reflector in which a light-reflecting metal layer is directly formed at least partially has been proposed (see, for example, Patent Document 2).

  The polybutylene terephthalate resin (A) is replaced with any one of an aromatic polycarbonate resin (B-1), a polyethylene terephthalate resin (B-2), and a polycyclohexylenedimethylene terephthalate-based polyester resin (B-3), or Metal directly on a resin substrate comprising a mixture of these resins (B) and a polyester resin composition containing barium sulfate (C) having an average particle size of 0.2 to 1.5 μm and a pH of 7.0 to 7.5. A resinous light reflector having a deposited film formed thereon has also been proposed (see, for example, Patent Document 3).

  However, the resinous light reflectors described in Patent Documents 2 and 3 have a problem that they are both low in impact resistance and poor in practicality.

  Further, a light-reflecting metal layer is formed directly on a resin substrate formed by molding a resin composition containing a thermoplastic polyester resin, a composite rubber-based graft polymer and / or a compound having an organosiloxane structure, and an inorganic reinforcing material. A thermoplastic resin reflector has been proposed (see, for example, Patent Document 4). And the polyester resin composition which mix | blended the polyethylene terephthalate resin (B), the thermoplastic polyester elastomer (C), the calcined kaolin (D), and the non-fibrous inorganic filler (E) with the polybutylene terephthalate resin (A). There has been proposed a light reflector in which a metal substrate is formed on a molded resin base (see, for example, Patent Document 5).

  However, even the light reflectors described in Patent Documents 4 and 5 have a problem that they cannot have both excellent impact resistance and dimensional stability, and their use is limited.

JP-A-9-216310 Japanese Patent Laid-Open No. 11-101905 JP-A-2005-146103 JP 2003-12903 A JP 2006-265331 A

  The present invention solves the above-mentioned problems of the prior art and has excellent impact resistance, chemical resistance, high cycle performance, dimensional stability, fluidity, as well as providing a metal layer on the surface, Resin substrate having a metallic glossy gloss, depth, and color tone design, specifically, a polyester resin composition for a resin substrate in which a metal vapor-deposited layer and a hard coat layer are directly provided on the surface in this order. And providing a resin substrate formed by molding the resin composition.

  As a result of intensive studies on the resin composition having an effect for such a specific use, the present inventors have included a specific amount of a polyester resin and a polycarbonate resin, and combined use of a thermoplastic elastomer, a metal vapor deposition layer The present inventors have found that even if it is directly provided on the surface, it has an excellent surface property that exhibits a beautiful appearance.

  Furthermore, even if a hard coat layer is provided on this metal vapor-deposited layer, the resin substrate is also excellent in resistance to chemicals (chemical resistance) such as a hard coat. The present invention has been completed by finding that the protective layer can be provided with an excellent effect and the above-mentioned problems are solved.

  The gist of the present invention is a polyester resin composition for a resinous substrate in which a metal vapor deposition layer and a hard coat layer are provided in this order on the surface, and the polyester resin composition is a polycarbonate with respect to 100 parts by weight of the polyester resin (A). The present invention relates to a polyester resin composition containing 5 to 100 parts by weight of a resin (B) and 0.5 to 40 parts by weight of a thermoplastic elastomer (C), and a resin substrate formed by molding the polyester resin composition.

  The resin substrate of the present invention and the resin substrate formed by molding the resin composition and having a metal vapor deposition layer and a hard coat layer in this order can directly deposit the metal layer on the surface of the molded product in a relatively simple process. Since the hard coat layer is provided on the metal layer, a resin product with stable quality can be obtained.

  In addition, the resin substrate of the present invention has excellent impact resistance, chemical resistance, high cycle performance, dimensional stability, fluidity, and metallic, high-grade gloss, depth, and color design. Therefore, it is excellent as a resin base for interior parts and exterior parts for vehicles and aircraft, especially outer or inner handles. In addition, it is expected to be used as a resin substrate in resin products in a wide range of fields such as electric / electronic / OA equipment parts, mobile phones, machine parts, building members, recreational goods and miscellaneous goods.

The present invention will be described in detail below.
The polyester resin (A) used in the present invention is preferably a thermoplastic polyester resin obtained by polycondensation of at least one glycol component or oxycarboxylic acid with at least one aromatic dicarboxylic acid component as the main acid component.

  Specifically, for example, polybutylene terephthalate, polybutylene terephthalate copolymer containing polytetramethylene oxide glycol residue in the main chain, polybutylene naphthalate, polycyclohexanedimethanol terephthalate, polyethylene terephthalate, polyethylene naphthalate, etc. It is done. Of these, polybutylene terephthalate (PBT) and polyethylene terephthalate (PET) are preferable.

  Examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyldicarboxylic acid, adipic acid, sebacic acid, dodecin diacid, and ester forming properties thereof. Derivatives and the like. Of these, aromatic dicarboxylic acids or ester-forming derivatives thereof are preferable, and terephthalic acid or terephthalic acid diester is particularly preferable.

  Examples of the glycol component include ethylene glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol and the like, C2-C10 α, ω-alkylene glycol, neopentyl glycol, 1,4-cyclohexanediol, Examples include 1,4-cyclohexanedimethanol, bisphenol A polyoxyethylene glycol, polyoxytetramethylene glycol, and ester-forming derivatives thereof.

  Of these, α, ω-alkylene glycols such as ethylene glycol and 1,4-butanediol are preferred. Furthermore, polytetramethylene oxide glycol or the like can be used as a part of the glycol component. Moreover, any copolymer may be sufficient if 70 mol% or more of all the acid components or all the diol components which form polyester are single components.

  In particular, the polyester resin (A) used in the present invention preferably has an intrinsic viscosity of 0.4 to 2.0 measured at 25 ° C. in a mixed solvent of phenol and tetrachloroethane (weight ratio = 50/50). . If the intrinsic viscosity is too low, the mechanical strength becomes insufficient. Conversely, if the intrinsic viscosity is too high, the fluidity is remarkably lowered. Therefore, the intrinsic viscosity is 0.5 to 1.8, particularly 0.7 to 1.5. It is preferable that

  As the polyester resin (A) used in the present invention, not only virgin raw materials but also PET and PBT recycled from used products, so-called material recycled PET and PBT can be used. Spent products include mainly containers, films, sheets, fibers, etc., but more suitable are containers such as PET bottles. In addition, as recycled PET and PBT, non-conforming products, pulverized products obtained from sprues, runners, etc., or pellets obtained by melting them can be used.

  As the polycarbonate resin (B) used in the present invention, aromatic polycarbonate, aliphatic polycarbonate, and aromatic-aliphatic polycarbonate can be used, and aromatic polycarbonate is particularly preferable. The aromatic polycarbonate resin is a thermoplastic aromatic polycarbonate polymer or copolymer produced by reacting an aromatic dihydroxy compound with phosgene or a diester of carbonic acid.

  Examples of the aromatic dihydroxy compound include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -P-diisopropylbenzene, hydroquinone, resorcinol, 4, 4-dihydroxydiphenyl etc. are mentioned, Preferably bisphenol A is mentioned.

  Furthermore, in order to improve the flame retardancy, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above-mentioned aromatic dihydroxy compound, a polymer having both ends phenolic OH groups having a siloxane structure, or an oligomer thereof is used. Also good.

  The polycarbonate resin (B) used in the present invention is preferably a polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other And polycarbonate copolymers derived from aromatic dihydroxy compounds. The polycarbonate resin may be used alone or in combination of two or more at any ratio.

  The molecular weight of the polycarbonate resin (B) is arbitrary, and may be appropriately selected and determined. Usually, methylene chloride is used as a solvent, and the one having a viscosity average molecular weight (Mv) converted from the solution viscosity measured at a temperature of 25 ° C. is 14,000 to 30,000. If the Mv is too low, the mechanical strength is remarkably lowered. Conversely, if the Mv is too high, the fluidity is remarkably lowered. Therefore, Mv is preferably 15000 to 28000, particularly 16000 to 26000.

  The method for producing the polycarbonate resin used in the present invention is arbitrary and is not particularly limited. Specifically, any conventionally known method such as a phosgene method (interfacial polymerization method), a melting method (transesterification method) or the like can be used. Furthermore, the aromatic polycarbonate resin which adjusted the amount of OH groups of the terminal group manufactured by the melting method can be used.

  Furthermore, the polycarbonate resin (B) used in the present invention can be not only a virgin raw material but also an aromatic polycarbonate resin regenerated from a used product, that is, a so-called material recycled aromatic polycarbonate resin. Used products include optical recording media such as optical disks, light guide plates, automobile window glass and automobile headlamp lenses, vehicle transparent members such as windshields, containers such as water bottles, glasses lenses, soundproof walls and glass windows, waves A building member such as a plate is preferred. In addition, as the recycled polycarbonate resin, non-conforming product, pulverized product obtained from sprue or runner, or pellets obtained by melting them can be used.

  The resin composition of the present invention uses 5 to 100 parts by weight, preferably 10 to 80 parts by weight of the polycarbonate resin (B) with respect to 100 parts by weight of the polyester resin (A). If the polycarbonate resin (B) is less than 5 parts by weight, the impact resistance and dimensional stability are lowered. Conversely, if it exceeds 100 parts by weight, the chemical resistance to the thinner in the hard coat paint applied on the metal deposition layer is reduced. Sex is reduced.

  The thermoplastic elastomer (C) used in the present invention preferably has a glass transition temperature of 0 ° C. or lower, more preferably −20 ° C. or lower, and a rubber polymer is copolymerized with a monomer component copolymerizable therewith. Also includes polymers. As the thermoplastic elastomer (C) used in the present invention, any conventionally known elastomer which can be generally blended into a polyester resin composition, a polycarbonate resin composition or the like to improve its impact resistance can be used.

  Examples of the thermoplastic elastomer (C) include polybutadiene, polyisoprene, diene copolymers (styrene / butadiene copolymer, acrylonitrile / butadiene copolymer, acrylic / butadiene rubber, etc.), copolymers of ethylene and α-olefin. Polymer (ethylene / propylene copolymer, ethylene / butene copolymer, ethylene / octene copolymer, etc.), copolymer of ethylene and unsaturated carboxylic acid ester (ethylene / methacrylate copolymer, ethylene / butyl acrylate) Copolymers), copolymers of ethylene and aliphatic vinyl compounds, terpolymers of ethylene, propylene and non-conjugated dienes, acrylic rubber (polybutyl acrylate, poly (2-ethylhexyl acrylate), butyl acrylate 2- Ethylhexyl acrylate copolymer Body, etc.), silicone rubber (a polyorganosiloxane rubber, a polyorganosiloxane rubber and a polyalkyl (meth) IPN type composite rubber consisting of acrylate rubber), and the like.

  These may be used alone or in combination of two or more. “(Meth) acrylate” means “acrylate” and “methacrylate”, and “(meth) acrylic acid” described later means “acrylic acid” and “methacrylic acid”.

  Further, as the thermoplastic elastomer (C) used in the present invention, a copolymer obtained by polymerizing a monomer component with a rubber polymer may be used. Preferred examples of this monomer include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, and the like. Other monomer components include epoxy group-containing (meth) acrylic acid ester compounds such as glycidyl (meth) acrylate; maleimide compounds such as maleimide, N-methylmaleimide, N-phenylmaleimide; maleic acid, phthalic acid, itacon Examples include α, β-unsaturated carboxylic acid compounds such as acids and anhydrides thereof (eg, maleic anhydride). These monomer components may be used alone or in combination of two or more.

  The thermoplastic elastomer (C) used in the present invention is of the core / shell type graft copolymer type because the molded article having impact resistance and a metal vapor-deposited layer exhibits high-grade gloss, depth and color tone. Is preferred. Among them, at least one selected from butadiene-containing rubber, butyl acrylate-containing rubber, and silicone rubber is used as a rubber polymer core layer, and at least one selected from acrylic acid ester, methacrylic acid ester, and aromatic vinyl compound around it. A core / shell type graft copolymer comprising a shell layer formed by copolymerizing the above monomer components is particularly preferred.

  More specifically, methyl methacrylate-butadiene-styrene polymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene polymer (MABS), methyl methacrylate-butadiene polymer (MB), methyl methacrylate-acrylic rubber polymer ( MA), methyl methacrylate-acrylic rubber-styrene polymer (MAS), methyl methacrylate-acrylic butadiene rubber copolymer, methyl methacrylate-acrylic butadiene rubber-styrene copolymer, methyl methacrylate- (acrylic silicone IPN (interpenetrating) polymer network) rubber) polymer and the like. Such rubbery polymers may be used alone or in combination of two or more.

  Specific examples of other rubbery polymers include styrene-butadiene-styrene block copolymer (SBS), styrene-ethylene / butylene-styrene block copolymer (SEBS), and styrene-ethylene / propylene-styrene block copolymer. Examples thereof include a combination (SEPS), an acrylonitrile-butadiene-styrene polymer (ABS), an acrylonitrile-styrene-acrylic rubber polymer (ASA), and an acrylonitrile-ethylenepropylene rubber-styrene polymer (AES).

  The resin composition of the present invention is 0.5 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 2 to 20 parts by weight of the thermoplastic elastomer (C) with respect to 100 parts by weight of the polyester resin (A). Blend. If the thermoplastic elastomer (C) is less than 0.5 parts by weight, the impact resistance improvement effect is small, and if it exceeds 40 parts by weight, the load deflection temperature decreases, and the metal is deposited when the metal substrate is directly subjected to metal vapor deposition. High-quality gloss, depth, and color tone may not be obtained.

  In the present invention, an inorganic filler (D) can be further used. Specific examples of the inorganic filler (D) include quartz, talc, kaolin, mica, clay, hydrotalcite, mica, graphite, glass beads, calcium carbonate, calcium sulfate, barium carbonate, barium sulfate, and carbonate. Examples thereof include magnesium, magnesium sulfate, calcium silicate, titanium oxide, zinc oxide, magnesium oxide, silicon oxide, calcium titanate, magnesium titanate, and barium titanate.

  These may be used alone or in combination of two or more at any ratio. Among them, talc is preferable because the effect of the present invention becomes remarkable. The inorganic filler (D) may be subjected to a surface treatment as necessary. The average particle diameter of the inorganic filler (D) is arbitrary, and may be appropriately selected and determined. However, if the average particle diameter of the inorganic filler (D) is too large, the surface smoothness of the resin substrate is lowered. When the metal is directly deposited on the surface, there may be a case where a glossy, deep, and color tone having a high-quality metallic tone cannot be obtained. Therefore, the average particle diameter is preferably 20 μm or less, particularly 10 μm or less.

  When the inorganic filler (D) is used, the blending amount thereof may be appropriately selected and determined, but it is usually preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyester resin (A). If the blending amount is too small, the crystallization speed becomes insufficient and the molding cycle may be lowered. On the other hand, even if the amount is too large, the inorganic filler (D) is relatively raised on the surface of the resin base, and when a metal vapor deposition layer is provided directly on the surface of the resin base, there is a metallic-like high-class feeling. Gloss, depth, and color tone may not be obtained. Therefore, the compounding amount of the inorganic filler (D) is preferably 0.3 to 15 parts by weight, particularly 0.5 to 10 parts by weight, with respect to 100 parts by weight of the polyester resin (A).

  In addition, the polyester resin composition of the present invention may use other resin components and various resin additives in addition to the components described above as long as the effects of the present invention are not impaired. Specifically, for example, various resin additives include phosphorous heat stabilizers, hindered phenolic antioxidants, flame retardants, weather resistance improvers, antistatic agents, mold release agents, antifogging agents, lubricants and antistatic agents. Examples include blocking agents, fluidity improvers, plasticizers, dispersants, antibacterial agents, fillers and fillers.

  The polyester resin composition of the present invention uses various mixers such as a tumbler and a Henschel mixer, and after previously mixing the above components, a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder It can be produced by any conventionally known method such as melt kneading with a machine, a kneader or the like.

  The polyester resin composition of the present invention is a resin composition for a resin substrate for providing a metal vapor deposition layer and a hard coat layer in this order directly on the surface, and this resin substrate has an excellent design. It is suitable as a resin substrate for resin products.

  The resin substrate of the present invention can be obtained from the above-described polyester resin composition of the present invention by any conventionally known resin molding method. Specific examples include resin molding methods such as injection molding, injection compression molding, gas assist molding, and injection blow molding.

  Among them, in order to suppress the occurrence of sink marks in the thick part and to form a resin substrate having a particularly excellent appearance, a gas assist molding method (gas injection molding method) described in JP-A-2004-352737 and the like It is preferable to make a hollow resin molded body by using, since the effect of the present invention becomes more remarkable.

  Even if a metal vapor deposition layer and a hard coat layer are directly provided in this order without providing an adhesive layer and a base layer on the surface of the resin substrate of the present invention, a beautiful appearance is exhibited. However, if necessary, a metal vapor-deposited layer or the like may be provided after treating the surface of the resin substrate by any conventionally known pretreatment method, specifically, for example, oxidation treatment, reverse sputtering treatment or the like.

  The formation method of the metal vapor deposition layer is a conventionally known arbitrary method, specifically, for example, (a) various vacuum vapor deposition methods such as electron beam heating method, resistance heating method, flash vapor deposition method, (b) plasma vapor deposition method (c) Various sputtering methods such as bipolar sputtering method, DC sputtering method, DC magnetron sputtering method, high frequency sputtering method, magnetron sputtering method, ion beam sputtering method, bias sputtering method, etc. (d) DC (Direct Current) method, RF method, multi-cathode PVD (Physical Vapor Deposition) methods such as various ion plating methods such as a method, an activation reaction method, an HCD (Hollow Cathode Discharge) method, a field evaporation method, a high frequency ion plating method, and a reactive ion plating method. It is done.

  The metal species to be vapor-deposited is arbitrary and may be appropriately selected and determined. Specifically, for example, metals such as gold, platinum, silver, chromium, nickel, phosphoric nickel, aluminum, copper, beryllium, beryllium copper, and zinc Or these metal compounds and alloys are mentioned. Among these, aluminum is preferable from the viewpoint of metal appearance and cost.

  The thickness of the metal vapor deposition layer is arbitrary, and may be appropriately selected and determined. The thickness is excellent as long as it has excellent light reflectivity and a glossy, deep, and color appearance with a high-quality metallic tone on the surface. However, if it is too thin, the desired appearance may not be obtained. On the contrary, the surface smoothness of the resin product may be lowered, and the light reflectivity and appearance may be lowered. Therefore, the thickness is usually at least 50 nm or more, preferably 50 to 500 nm, particularly preferably 100 to 300 nm.

  The resin substrate of the present invention is provided with a hard coat layer on the metal vapor deposition layer for the purpose of improving weather resistance and scratch resistance. Any conventionally known hard coat layer can be used. Usually, the hard coat layer is provided with a hard coat layer by applying a paint for forming the hard coat layer. Specific examples of such paints include acrylic, silica-containing acrylic, urethane, and silicone paints. Moreover, you may mix | blend a weather resistance improving agent in these coating materials.

  The paint thinner may be appropriately selected and determined from any conventionally known ones in consideration of adhesion of the hard coat layer and chemical resistance to the resin molded product. Specific examples include methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, xylene, and ethylbenzene. These may be used alone or in combination of two or more at any ratio.

  The hard coat layer can be formed by applying the coating material on the metal vapor deposition layer by a known method such as a dipping method, a flow coating method, or a spray method, and then drying and curing. The thickness of the hard coat layer may be appropriately selected and determined. However, if the film thickness is too thin, the durability of the hard coat layer itself is insufficient, and conversely, if it is too thick, cracks are likely to occur in the hard coat layer. . Therefore, the film thickness is usually 1 to 30 μm, preferably 3 to 15 μm.

  The resin composition of the present invention and a resin product in which a metal vapor deposition layer and a hard coat layer are provided in this order on a resin substrate formed by molding the resin composition have excellent impact resistance, chemical resistance, high cycle performance, dimensions. It has high-quality gloss, depth, and color design with a sense of stability, fluidity, and metal, so it can be used for interior parts, exterior parts, electrical / electronic / OA equipment parts, mobile phones, Suitable for a wide range of applications such as machine parts, building materials, recreational goods and miscellaneous goods.

  Specifically, for example, there are outer handles, door mirror sticks, fenders, garnishes, bumpers, roof rails, wiper arms, etc. as automotive exterior parts, and inner handles, center console, instrument panel, assist grip, seats as automotive interior parts. Examples include belt stoppers.

  Rail vehicle parts include table arms, suspension hands, and assist grips. Electric parts include shaver frames, dryers, refrigerator handles and pullers, microwave oven doors, portable MD system handles, and headphone arms. And a housing for an electric screwdriver. Examples of building material parts include door handles, crescents, and French droppings.

  The resin substrate of the present invention is preferably used particularly for vehicle / aircraft outer or inner handle applications because of its excellent appearance and productivity.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The raw materials used in Examples and Comparative Examples are as follows.

Polycarbonate resin Aromatic polycarbonate resin (1): Bisphenol A type aromatic polycarbonate produced by the interfacial polymerization method Iupilon E-2000FN, viscosity average molecular weight 28000 manufactured by Mitsubishi Engineering Plastics

  Aromatic polycarbonate resin (2): Bisphenol A type aromatic polycarbonate produced by interfacial polymerization method Iupilon S-3000FN, viscosity average molecular weight 22500, manufactured by Mitsubishi Engineering Plastics

Polyester resin Polyethylene terephthalate resin (1): Novapex GG900 manufactured by Mitsubishi Chemical Corporation (germanium atom content 28 ppm, limiting viscosity 1.10 dl / g, terminal carboxyl group concentration 9 μeq / g)

  Polybutylene terephthalate resin (1): Novaduran 5020, Mitsubishi Engineering Plastics, intrinsic viscosity 1.20 dl / g

  Polybutylene terephthalate resin (2): NOVADURAN 5008 manufactured by Mitsubishi Engineering Plastics, intrinsic viscosity 0.85 dl / g

  The intrinsic viscosity of each polyester resin described above is a value measured by dissolving in a 1 to 1 (weight ratio) mixture of phenol and tetrachloroethane at a temperature of 30 ° C. to a concentration of 1% by weight.

Thermoplastic elastomer Rubber polymer (1): Core / shell type graft copolymer consisting of polybutadiene / polystyrene copolymer (core) / alkyl acrylate / alkyl methacrylate copolymer (shell)・ Paraloid KCZ201N manufactured by Hearth Japan

  Rubber polymer (2): Core / shell type graft copolymer comprising polybutadiene (core) / alkyl acrylate / alkyl methacrylate copolymer (shell) (EXL2603, manufactured by Rohm and Haas Japan)

  Rubber polymer (3): Core / shell type graft copolymer (staphyloid MG1011 manufactured by Ganz Kasei Co., Ltd.) comprising polyalkyl acrylate (core) / acrylonitrile-styrene copolymer (shell)

Phosphorus compound (1): Chemical Formula _{O = P (OH) n ·} (OC 18 H 37) 3-n , Ltd. (n '= 1, and mixtures of 2) by Asahi Denka Kogyo STAB AX-71

  Phosphorus compound (2): Tris (2,4-di-tert-butylphenyl) phosphite Adeka Stub AS2112 manufactured by Asahi Denka Kogyo Co., Ltd.

  Polyethylene wax: manufactured by Clariant Japan Co., Ltd. Ricowax PE-520 Drop point 117-122 ° C

  Sulfur-based heat stabilizer: pentaerythritol tetrakis- (3-dodecylthiopropinate), manufactured by Cypro Kasei Co., Ltd. Sinox 412S

  Carbon black: Oil furnace carbon black # 1000 manufactured by Mitsubishi Chemical Corporation

Example 1-6 and Comparative Example 1-3:
After uniformly mixing the aromatic polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate, rubber polymer, phosphorus compound, heat stabilizer, and other components in the ratio (parts by weight) shown in Table 1, using a tumbler mixer, By using a twin screw extruder (TEX30XCT manufactured by Nippon Steel Works, L / D = 42, number of barrels 12), feeding to the extruder from barrel 1 at a cylinder temperature of 280 ° C. and a screw speed of 250 rpm, and melt-kneading The pellet of the resin composition was manufactured.

  After drying the obtained pellets at 120 ° C for 4 hours or more, using a M150AII-SJ type injection molding machine manufactured by Meiki Seisakusho, under conditions of a cylinder temperature of 280 ° C, a mold temperature of 80 ° C, and a molding cycle of 55 seconds, ASTM test pieces (normally molded products) were prepared.

(1) Impact resistance (Izod impact strength):
In accordance with ASTM D256, Izod impact strength (unit: J / m) was measured at 23 ° C. and −30 ° C. using a notched specimen having a thickness of 3.2 mm.

(2) Chemical resistance (visual):
Thinner (Fujikura Kasei Co., Ltd., dilution thinner for coating ETC5406) was applied to an ASTM 4-inch disk (thickness 3.2 mm), and chemical resistance was evaluated by visual evaluation after 72 hours at room temperature. According to the visual evaluation, “◯: There is almost no surface change and can withstand practical use as a design part”, “△: Surface roughness is recognized and cannot be used practically”, “×: Surface roughness is remarkable, and practical use is not possible at all. ”Was evaluated in three stages.

(3) Chemical resistance (handle impact test)
A resin base for an automobile outer door handle having a handshake portion at approximately the center and attachment portions to the vehicle body at both ends was molded, and a chemical resistance test was performed using this. A resin base for an automobile outer door handle was manufactured under the conditions of a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., and a molding cycle of 60 seconds using a J220EV-P type injection molding machine manufactured by Nikko Corporation as an injection molding machine.

  The obtained resin base for an automobile outer door handle was immersed in the same dilution thinner for coating as used in the evaluation in (2) for 30 minutes. After dipping, attach both ends of the resin base and the handshake part to a handle impact test jig, attach a 5 kg weight to the jig holding the handshake part, and repeatedly drop the weight freely to impact the resin base. And a destructive test was conducted.

  The destructive test was terminated when the handle was removed from the jig even at one location, and the energy required to complete the test was converted from the falling height of the weight and the number of times. The practical energy value that can be used is 9.8 J or more.

(4) Heat and humidity resistance (tensile yield stress):
An ASTM tensile test piece (thickness: 3.2 mm) was subjected to a wet heat treatment at 80 ° C./95% RH for 500 hours, and then a tensile test was performed. The heat and humidity resistance was evaluated from the strength change before and after the treatment.

(5) High Cycle Property A compression test piece for ASTM having a cylinder temperature of 280 ° C., a mold temperature of 80 ° C., a length of 50 mm, and a thickness of 12.8 mm was molded using a FANUC “α100iA type” injection molding machine. Starting from a cooling time of 15 seconds, after 5 consecutive moldings, the cooling time was shortened by 1 second.

  In the evaluation of the high cycle property, the cooling time during which continuous molding is possible and the quality of releasability at this cooling time were judged in the following four stages.

“◎: No trace of protruding pin is observed, and releasability is good”
“○: The trace of the protruding pin remains slightly, but there is no problem with the releasability”
“△: The trace of the protruding pin remains clearly, or it can be easily taken to the fixed side of the mold”
“X: The protruding pin mark is large, and the product may remain in the mold during molding.”

  As is clear from Table 1, it can be seen that the resin compositions described in Examples 1 to 7 have an excellent balance of impact resistance, chemical resistance, heat and humidity resistance, and high cycle performance. On the other hand, the resin compositions of Comparative Examples 1 to 4 in which the polyester resin and the polycarbonate resin are outside the range defined in the present invention are compared with the resin compositions described in the Examples, in terms of impact resistance, chemical resistance, and moisture resistance. It is apparent that the balance between thermal properties and high cycle properties is poor.

  The effect of the resin composition of the present invention, which is excellent in high cycle performance, is particularly remarkable when a hollow resin substrate is produced by gas injection using the resin composition. Specifically, not only can suppression of sink marks be expected, but also a characteristic of gas injection, which is a characteristic of gas injection (compared to ordinary filled resin substrates) because of low filling pressure during injection molding and subsequent holding pressure. And the effect of suppressing the generation of gas and the accompanying mold deposit is particularly remarkable.

Claims (7)

It is a polyester resin composition for resinous bases which provides a metal vapor deposition layer and a hard-coat layer in this order on the surface, and this polyester resin composition is polycarbonate resin (B) 5 to 100 parts by weight of polyester resin (A). 100 parts by weight, 0.5 to 40 parts by weight of thermoplastic elastomer (C), a sulfur-based heat stabilizer, and a compound represented by the following formula, the thermoplastic elastomer is core / shell type graft copolymer a coalescing, the core / shell type graft copolymer is a core layer of butadiene-containing rubber of a polymer, co at least one monomer component selected et or acrylic acid ester and methacrylic acid ester le therearound A polyester resin composition which is a core / shell type graft copolymer comprising a shell layer formed by polymerization.
_{O = P (OH) n ·} (OC 18 H 37) ( a mixture of n '= 1 and 2) _3-n   The polyester resin composition according to claim 1, wherein the polyester resin (A) is a polyethylene terephthalate resin and / or a polybutylene terephthalate resin.   The polyester resin (A) has a limiting viscosity of 0.4 to 2.0 dl / g when measured at 25 ° C using a phenol / tetrachloroethane mixed solvent (each 50 wt%). Item 3. The polyester resin composition according to Item 1 or 2.   The polyester resin composition according to any one of claims 1 to 3, further comprising an inorganic filler (D). By molding the resin composition according to any one of claims 1 to 4, a resin substrate provided with a metallized layer and the hard coat layer on the surface thereof in this order. 6. The resin substrate according to claim 5 , which is a hollow resin molded body. The resin substrate according to claim 5 or 6 , wherein the resin substrate is a vehicle / aircraft outer or inner handle resin substrate.