JP2008150598A - Resin molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin molded product excellent in surface hardness, appearance and durability. <P>SOLUTION: The resin molded product is a member for water-related areas and is made of a resin composition obtained by compounding 100 pts.wt. thermoplastic polyester resin (A) with 1-200 pts.wt. acrylic resin (B). The resin molded product preferably further comprises a compatibilizer (C) and more preferably further comprises an inorganic filler (D). More preferably, the component (A) contains polybutylene terephthalate and, particularly preferably, the component (B) is a methacrylic resin essentially comprising methyl methacrylate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention is a resin molded product which is a water-borne member comprising a resin composition obtained by blending a thermoplastic polyester resin (A) and an acrylic resin (B), and is excellent in surface hardness, appearance and durability. The present invention relates to a resin molded product.

  Conventionally, various containers such as tableware and flowerpots, wash bowls, hand-washing counters, bathtubs, toilet components such as toilet bowls, mainly inorganic materials such as ceramics, resin compositions mainly composed of vinyl chloride, Artificial marble made of a thermosetting resin composition containing an inorganic filler has been used. However, in view of environmental problems in recent years, expectations for recyclable materials are increasing, and resin compositions using thermoplastic resins such as recyclable thermoplastic polyesters are drawing attention.

  Patent Document 1 discloses a resin composition and a molded body in which a fibrous filler is blended with a polytrimethylene terephthalate resin. However, although the surface hardness and appearance are improved to some extent, durability and the like are insufficient, and further improvement has been demanded.

On the other hand, Patent Document 2 discloses a resin composition and a molded product obtained by blending a thermoplastic polyester resin, a specific acrylic resin, and an inorganic reinforcing filler. However, the surface hardness is insufficient and further improvement has been demanded.
JP 2006-257158 A JP 2002-47397 A

  The present invention has been achieved as a result of examining the solution of the problems in the above-described prior art as an object. That is, an object of the present invention is to provide a resin molded product excellent in surface hardness, appearance and durability.

  The present invention employs the following means in order to solve such problems.

That is, the present invention
(1) A resin molded article that is a water-borne member comprising a resin composition comprising 100 parts by weight of a thermoplastic polyester resin (A) and 1 to 200 parts by weight of an acrylic resin (B),
(2) The resin molded product according to (1), wherein the water-circulating member is at least one member of a toilet component, a bathroom component, a toilet component, and a kitchen component,
(3) The resin composition further comprises a compatibilizer (C) that is a compound having at least one functional group selected from a glycidyl group, an acid anhydride group, and a carboxyl group (1) Or the resin molded product according to (2),
(4) The resin molded product according to any one of (1) to (3), wherein the resin composition further comprises an inorganic filler (D).
(5) The resin molded product according to any one of (1) to (4), wherein the thermoplastic polyester resin (A) contains polybutylene terephthalate,
(6) The resin molded product according to any one of (1) to (5), wherein the acrylic resin (B) is a methacrylic resin having a methyl methacrylate unit as a main component.
(7) Any of (1) to (6), wherein the inorganic filler (D) contains at least one fibrous inorganic filler selected from wollastonite, aluminum borate, and glass fiber. Or a resin molded product according to claim 1,
(8) The resin according to any one of (1) to (7), wherein the water-circulating member is a toilet component member selected from any one of a wash bowl, a hand wash bowl, a hand wash counter, and a wash storage shelf. Molding,
(9) The resin molded product according to any one of (1) to (7), wherein the water-circulating member is a bathroom constituent member selected from any one of a bathtub, a bathroom counter, a bathroom floor, and a bathroom storage shelf. ,
(10) The resin molded product according to any one of (1) to (7), wherein the water-circulating member is a toilet component selected from any one of a toilet bowl, a toilet lid, a toilet seat, and a toilet counter,
(11) The resin molded product according to any one of (1) to (7), wherein the water-circulating member is a kitchen component selected from any one of a kitchen counter, a kitchen sink, and a kitchen top plate,
It is.

  The resin molded product of the present invention can provide a resin molded product excellent in surface hardness, appearance and durability, and by taking advantage of this property, it can be used as a major housing component such as a wash bowl, bathtub, toilet bowl and kitchen counter. It can utilize for the structural member of a water circumference part.

  Hereinafter, the present invention will be described in detail.

  The thermoplastic polyester resin (A) used in the present invention comprises (a) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, (b) a hydroxycarboxylic acid or an ester-forming derivative thereof, (c) It is a polymer or copolymer obtained by polycondensation of one or more selected from lactones.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acid units such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivative thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Dioxy compounds such as 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F, and the like And La ester forming derivatives.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples thereof include ester-forming derivatives. Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one.

  Specific examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene terephthalate, polypropylene (terephthalate / isophthalate), polyethylene terephthalate, polyethylene (terephthalate / isophthalate), bisphenol A. (Terephthalate / isophthalate), polybutylene naphthalate, polybutylene (terephthalate / naphthalate), polypropylene naphthalate, polypropylene (terephthalate / naphthalate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, polycyclohexanedimethylene (terephthalate / isophthalate) Phthalate), poly (cyclohexanedimethine / ethylene) terephthalate , Aromatic polyesters such as poly (cyclohexanedimethylene / ethylene) (terephthalate / isophthalate), polybutylene (terephthalate / isophthalate) / bisphenol A, polyethylene (terephthalate / isophthalate) / bisphenol A, and polybutylene (terephthalate / succinate) , Polypropylene (terephthalate / succinate), polyethylene (terephthalate / succinate), polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / sulfoisophthalate / adipate), polyethylene (terephthalate) / Sulfoisophthalate / succinate), polypropylene (te Phthalate / sulfoisophthalate / succinate), polybutylene (terephthalate / sebate), polypropylene (terephthalate / sebate), polyethylene (terephthalate / sebate), polybutylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polyethylene terephthalate / polyethylene glycol, poly Butylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene) Oxide) glycol Polybutylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, polypropylene terephthalate / poly (propylene oxide / ethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (propylene oxide / ethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / Copolymer obtained by copolymerizing polyether or aliphatic polyester such as poly (propylene oxide / ethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polybutylene terephthalate / poly-ε-caprolactone with aromatic polyester Polyethylene oxalate, polypropylene oxalate, poly Butylene oxalate, polyneopentyl glycol oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polybutylene adipate, polypropylene adipate, polyethylene adipate, polybutylene (succinate / adipate), polypropylene (succinate / adipate), polyethylene ( Succinate / adipate), polyhydroxyalkanoates such as polyhydroxybutyric acid and copolymers of β-hydroxybutyric acid and β-hydroxyvaleric acid, aliphatic polyesters such as polycaprolactone, polyglycolic acid, polylactic acid, polybutylene succinate / carbonate Aliphatic polyester carbonates such as p-oxybenzoic acid / polyethylene terephthalate, p-oxybenzoic acid Examples thereof include liquid crystalline polyesters such as copolyesters such as acid / 6-oxy-2-naphthoic acid. “/” Indicates copolymerization.

  Among these, a polymer obtained by polycondensation of aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol or its ester-forming derivative as main components is preferable. Specifically, polybutylene terephthalate, polypropylene terephthalate , Polyethylene terephthalate, poly (cyclohexanedimethylene / ethylene) terephthalate, polypropylene naphthalate, polybutylene naphthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene (terephthalate / isophthalate), polybutylene terephthalate / Polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polyethylene terephthalate / polyethylene glycol Polybutylene terephthalate / poly (tetramethylene oxide) glycol, polypropylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, Polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate / adipate), polypropylene (terephthalate / adipate), polyethylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polypropylene (terephthalate / succinate) , Polyethylene (terephthalate / succinate It can be mentioned preferably.

  Ratio of aromatic dicarboxylic acid or ester-forming derivative thereof to total dicarboxylic acid in a polymer obtained by polycondensation of aromatic dicarboxylic acid or ester-forming derivative thereof and aliphatic diol or ester-forming derivative thereof as main components Is more preferably 30 mol% or more, and further preferably 40 mol% or more.

  Among these, a polymer obtained by polycondensation of terephthalic acid or an ester-forming derivative thereof and an aliphatic diol selected from ethylene glycol, propylene glycol, or butanediol or an ester-forming derivative thereof as a main component is more preferable. Specifically, polypropylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polypropylene (terephthalate / isophthalate), polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / Poly (tetramethylene oxide) glycol, polypropylene terephthalate / Poly (teto Methylene oxide) glycol, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polyethylene terephthalate / isophthalate / poly (tetramethylene oxide) glycol, polypropylene (terephthalate / isophthalate) / poly (tetramethylene oxide) glycol, polybutylene (terephthalate) / Isophthalate) / poly (tetramethylene oxide) glycol, polyethylene (terephthalate / succinate), polyethylene (terephthalate / adipate), polypropylene (terephthalate / succinate), polypropylene (terephthalate / adipate), polybutylene (terephthalate / succinate), polybutylene ( Terephthalate / adipate), polybutylene (terephthalate) Over DOO / sebacate), polybutylene (terephthalate / decane dicarboxylate), it may be mentioned poly (cyclohexane dimethylene terephthalate / isophthalate).

  The ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer obtained by polycondensation of terephthalic acid or its ester-forming derivative and butanediol or its ester-forming derivative as a main component is 30 mol% or more. It is more preferable that it is 40 mol% or more.

  Further preferred examples of the thermoplastic polyester resin (A) in the present invention include polyethylene terephthalate, polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polyethylene (terephthalate / succinate), polybutylene (terephthalate). / Succinate), polyester elastomer, polypropylene terephthalate, polybutylene terephthalate / poly (tetramethylene oxide) glycol, polybutylene succinate, and particularly preferred examples include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, poly Butylene terephthalate / poly (tetramethylene oxide) glyco Le, polybutylene (terephthalate / isophthalate) can include at least one selected from, most preferably those containing polybutylene terephthalate.

  In the present invention, it is useful from the viewpoint of surface appearance, glossiness, and rigidity to use two or more kinds of thermoplastic polyester resins as the component (A). For example, when two types of thermoplastic polyester resins are used as the component (A), a resin having a high crystallization rate is a thermoplastic polyester resin (1), and a resin having a low crystallization rate is a thermoplastic polyester resin (2). These blending ratios are preferably 20 to 90% by weight of the thermoplastic polyester resin (1) and 10 to 80% by weight of the thermoplastic polyester resin (2), (1) 30 to 80% by weight, (2) More preferably, it is 20 to 70% by weight, (1) 50 to 80% by weight, and (2) 20 to 50% by weight. Specific combinations of the thermoplastic polyester resin (1) and the thermoplastic polyester resin (2) include polybutylene terephthalate and polyethylene terephthalate, polybutylene terephthalate and polypropylene terephthalate, polypropylene terephthalate and polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, Examples include combinations of polypropylene terephthalate and polyethylene naphthalate.

  The viscosity of the thermoplastic polyester (A) used in the present invention is not particularly limited as long as it can be melt-kneaded. Usually, the intrinsic viscosity when an o-chlorophenol solution is measured at 25 ° C. is 0.36 to It is preferably 1.60 dl / g. In terms of moldability, those in the range of 0.42 to 1.25 dl / g are more preferred, and 0.50 to 1.10 dl / g are even more preferred.

  The melting point of the thermoplastic polyester resin (A) used in the present invention is not particularly limited, but is preferably 120 ° C or higher, more preferably 150 ° C or higher, from the viewpoint of heat resistance, and 180 ° C. More preferably, it is more preferably 220 ° C. or higher. The upper limit is 350 ° C. In the present invention, the melting point of the thermoplastic polyester resin (A) is a value measured with a differential scanning calorimeter (DSC) at a temperature elevation rate of 20 ° C./min.

  The vinyl terminal group amount of the thermoplastic polyester resin (A) used in the present invention is not particularly limited, but is preferably 15 eq / t or less, more preferably 10 eq / t or less in terms of hue and appearance. Preferably, it is 5 eq / t or less. The lower limit is 0 eq / t. In the present invention, the amount of vinyl end groups is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The amount of hydroxyl terminal groups of the thermoplastic polyester resin (A) used in the present invention is not particularly limited, but is preferably 50 eq / t or more and 80 eq / t or more in terms of appearance and durability. More preferably, it is more preferably 100 eq / t or more, and particularly preferably 120 eq / t or more. The upper limit is not particularly limited, but is 180 eq / t. In the present invention, the amount of hydroxyl end groups is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The amount of carboxyl end groups (COOH amount) of the thermoplastic polyester resin (A) used in the present invention is not particularly limited, but is preferably 50 eq / t or less in terms of appearance and durability, and is durable. Is more preferably 30 eq / t or less, more preferably 20 eq / t or less, particularly preferably 15 eq / t or less, and most preferably 10 eq / t or less. preferable. The lower limit is 0 eq / t.

  In the present invention, the COOH amount is a value measured by dissolving the thermoplastic polyester (A) in an o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  As the thermoplastic polyester resin (A) used in the present invention, the amount of terminal groups such as the amount of COOH can be controlled by appropriately selecting conditions such as raw materials, catalyst, polymerization method, temperature and pressure. For example, as a catalyst, any one or more selected from an aluminum-based catalyst, a titanium-based catalyst, a tin-based catalyst, a germanium-based catalyst, and the like, and as a polymerization method, by selecting either a continuous type or a batch type, etc. A thermoplastic polyester resin (A) having an end group amount such as the desired COOH amount can be obtained.

  The method for producing the thermoplastic polyester resin (A) used in the present invention is not particularly limited, and can be produced by a known polycondensation method or ring-opening polymerization method. Any of them may be used, and any of transesterification reaction and direct polymerization reaction can be applied. However, continuous polymerization is preferable in terms of greatly improving appearance and durability, and direct polymerization in terms of cost. Is preferred.

  As the acrylic resin (B) used in the present invention, methacrylic acid, acrylic acid, methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-propyl methacrylate, n-propyl acrylate, n-butyl methacrylate, n-butyl acrylate , T-butyl methacrylate, t-butyl acrylate, n-hexyl methacrylate, n-hexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, chloromethyl methacrylate, chloromethyl acrylate, 2-chloroethyl methacrylate, 2-chloroethyl acrylate, 2-hydroxy Ethyl methacrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl methacrylate, 3-hydroxypropyl Acrylate, 2,3,4,5,6-pentahydroxyhexyl methacrylate, 2,3,4,5,6-pentahydroxyhexyl acrylate, 2,3,4,5-tetrahydroxypentyl methacrylate, allyl methacrylate or 2, Examples include homopolymers or copolymers (copolymers) of monomers such as 3,4,5-tetrahydroxypentyl acrylate.

  The acrylic resin (B) used in the present invention is preferably a methacrylic resin mainly composed of a methyl methacrylate unit in terms of surface hardness, appearance, glossiness and durability, and the methyl methacrylate unit is 50 wt. It is more preferably a methacrylic resin obtained by polymerizing at least 70% by weight, more preferably a methacrylic resin obtained by polymerizing 70% by weight or more of methyl methacrylate units, and a methacrylic resin obtained by polymerizing 90% by weight or more of methyl methacrylate units. Is particularly preferred. It is also preferable to copolymerize at least one copolymerizable monomer other than a methyl methacrylate unit, and it is more preferable that the copolymer is a copolymer obtained by copolymerizing 1 to 50% by weight of a copolymerizable monomer. Preferably, the copolymer is a copolymer obtained by copolymerizing 1 to 30% by weight of a copolymerizable monomer, and is a copolymer obtained by copolymerizing 1 to 10% by weight of a copolymerizable monomer. Is particularly preferred.

  In addition, as a copolymerizable monomer other than the methyl methacrylate unit, a styrene monomer or the like may be included in addition to the above monomer.

  Preferable specific examples of the acrylic resin (B) used in the present invention include polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid), poly (methyl methacrylate / acrylic acid), poly (methyl methacrylate / ethyl methacrylate), poly (methyl methacrylate). Methacrylate / ethyl acrylate), poly (methyl methacrylate / n-propyl methacrylate), poly (methyl methacrylate / n-propyl acrylate), poly (methyl methacrylate / t-butyl methacrylate), poly (methyl methacrylate / t-butyl acrylate), Poly (methyl methacrylate / n-hexyl methacrylate), poly (methyl methacrylate / n-hexyl acrylate), poly (methyl methacrylate / cyclohexyl methacrylate) , Poly (methyl methacrylate / cyclohexyl acrylate), poly (methyl methacrylate / chloromethyl methacrylate), poly (methyl methacrylate / chloromethyl acrylate), poly (methyl methacrylate / 2-chloroethyl methacrylate), poly (methyl methacrylate / 2-chloro Ethyl acrylate), poly (methyl methacrylate / 2-hydroxyethyl methyl methacrylate), poly (methyl methacrylate / 2-hydroxyethyl methyl acrylate), poly (methyl methacrylate / 2-hydroxyethyl ethyl acrylate), poly (methyl methacrylate / poly 3 -Hydroxypropyl methacrylate), poly (methyl methacrylate / poly-3-hydroxypropyl acrylate), poly (methyl methacrylate) Acrylate / 2,3,4,5,6-pentahydroxyhexyl methacrylate), poly (methyl methacrylate / 2,3,4,5,6-pentahydroxyhexyl acrylate), poly (methyl methacrylate / 2,3,4, 5-tetrahydroxypentyl methacrylate), poly (methyl methacrylate / 2,3,4,5-tetrahydroxypentyl acrylate), poly (methyl methacrylate / methacrylamide), poly (methyl methacrylate / acrylamide), poly (methyl methacrylate / methacrylate) Nitrile), poly (methyl methacrylate / acrylonitrile), poly (methyl methacrylate / styrene), poly (methyl methacrylate / α-methyl styrene), poly (methyl methacrylate / monochlorostyrene), poly (Methyl methacrylate / allyl methacrylate), poly (methyl methacrylate / acrylic acid / allyl methacrylate), poly (methyl methacrylate / N-phenylmaleimide), poly (methyl methacrylate / N-phenylmaleimide / styrene), poly (methyl methacrylate / methacrylic) Acid) and poly (methyl methacrylate / 2-hydroxyethylethyl acrylate) and other methacrylic resins containing a ring structure, and methyl methacrylate in terms of surface hardness, appearance, durability, and heat resistance. Polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid), poly (methyl methacrylate / acrylic acid), poly (methyl methacrylate / 2-hydroxyethyl ethyl acrylate) whose unit is the main component ), Poly (methyl methacrylate / allyl methacrylate), poly (methyl methacrylate / acrylic acid / allyl methacrylate), poly (methyl methacrylate / N-phenylmaleimide), poly (methyl methacrylate / 2-hydroxyethylethyl acrylate) The lactone ring-containing methacrylic resin is preferable, and in terms of appearance, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid), and poly (methyl methacrylate / acrylic acid) are more preferable, and in terms of heat resistance, poly ( More preferred are methyl methacrylate / allyl methacrylate) and poly (methyl methacrylate / acrylic acid / allyl methacrylate). These acrylic resins can be used alone or in combination of two or more.

  The acrylic resin (B) used in the present invention preferably has a melt flow rate (MFR) of less than 3 g / 10 minutes in terms of surface hardness, appearance, durability, and glossiness. A range of 2.5 g / 10 min is more preferable, and a range of 0.5-2 g / 10 min is more preferable. The lower limit is 0.05 g / 10 minutes. When the MFR of the acrylic resin (B) of the present invention is in the above range, a resin-shaped product particularly excellent in surface hardness, appearance and durability can be obtained. In the present invention, the MFR of the acrylic resin (B) is a value measured at 230 ° C. and 37.3 N according to JIS K7210.

  The acrylic resin (B) used in the present invention preferably has a glass transition temperature in the range of 80 to 150 ° C. and 110 to 150 ° C. in terms of surface hardness, appearance, durability and heat resistance. It is more preferable. When the glass transition temperature is in the above range, a resin molded article having excellent surface hardness and heat resistance can be obtained. In the present invention, the glass transition temperature of the acrylic resin (B) is a value measured with a differential scanning calorimeter (DSC) at a heating rate of 20 ° C./min.

  As a manufacturing method of acrylic resin (B) used by this invention, well-known polymerization methods, such as block polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, can be used. By appropriately selecting conditions such as raw material composition, temperature, pressure, and time as conditions during production, characteristics such as MFR and glass transition temperature can be controlled, and acrylic resin (B) having desired characteristics Can be obtained. For example, the temperature condition during the polymerization is preferably 100 ° C. or lower, more preferably 70 ° C. or lower, further preferably 30 ° C. or lower, and particularly preferably −10 ° C. or lower in terms of heat resistance.

  The present invention is a resin molded product comprising a resin composition comprising 100 parts by weight of a thermoplastic polyester resin (A) and 1 to 200 parts by weight of an acrylic resin (B).

  The blending amount of the acrylic resin (B) is preferably 10 to 150 parts by weight and more preferably 10 to 100 parts by weight in terms of surface hardness, appearance, durability, glossiness and heat resistance. It is preferably 20 to 70 parts by weight, more preferably 25 to 60 parts by weight.

  In the present invention, the phase is a compound having at least one functional group selected from a glycidyl group, an acid anhydride group, and a carboxyl group in terms of surface hardness, appearance, durability, glossiness, and heat resistance. It is preferable to add a solubilizer (C).

  As such a compatibilizing agent (C), for example, a modified acrylic in which at least one functional group selected from a glycidyl group, an acid anhydride group, and a carboxyl group is introduced into the main chain or side chain in the molecule. And a graft copolymer of a vinyl polymer, a vinyl polymer, or an acrylic polymer and a vinyl polymer. At this time, as long as any one or more of a glycidyl group, an acid anhydride, and a carboxyl group are included, other functional groups may be included. Specific examples of other functional groups include oxazoline group, acid hydride group, acid amide group, carboxylic acid ester group, acid azide group, sulfone group, nitrile group, cyano group, isocyanate group, amino group, imide group, Examples thereof include a hydroxyl group, a thiol group, and a carbodiimide group.

  As a preferable example of the compatibilizer (C), in the glycidyl group-containing compatibilizer, poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate, glycidyl group-containing acrylic polymer, glycidyl group-containing acrylic / styrene polymer, acid anhydride Group-containing compatibilizers include poly (ethylene / ethyl acrylate / maleic anhydride) -g-polymethyl methacrylate, poly (ethylene / ethyl acrylate / maleic anhydride) -g-poly (acrylonitrile / styrene), poly (methyl methacrylate). / (Maleic anhydride) and carboxyl group-containing compatibilizers include poly (ethylene / methacrylic acid), ionomer resins in which poly (ethylene / methacrylic acid) molecules are crosslinked with metal ions. Among them, the dispersion form of the component (B) in the component (A) can be controlled, and the surface hardness, appearance, and durability can be greatly improved. It is preferably a physical group-containing compatibilizing agent, and more preferably a glycidyl group-containing compatibilizing agent. In the glycidyl group-containing compatibilizer, a glycidyl group-containing acrylic polymer or a glycidyl group-containing acrylic / styrene polymer is particularly preferably used.

  In the present invention, when the compatibilizing agent (C) is a glycidyl group-containing compatibilizing agent, the glycidyl group content is not particularly limited, but in terms of surface hardness, appearance, and durability, an epoxy value of 1 to 10 meq / g is preferable, 2-7 meq / g is more preferable, and 3-5 meq / g is further more preferable. Here, the epoxy value is a value measured by a hydrochloric acid-dioxane method.

  In the present invention, when the compatibilizer (C) is a glycidyl group-containing acrylic polymer or a glycidyl group-containing acrylic / styrene polymer, it is a polymer having a weight average molecular weight of 1,000 to 300,000 in that bleeding out can be suppressed. The weight average molecular weight is more preferably 5,000 to 250,000.

  In the present invention, when the compatibilizer (C) is a glycidyl group-containing acrylic polymer or a glycidyl group-containing acrylic / styrene polymer, the glass transition temperature is not particularly limited, but it is excellent in handling properties. The temperature is preferably in the range of 30 to 100 ° C, more preferably in the range of 40 to 70 ° C, and most preferably in the range of 50 to 65 ° C. The method for measuring the glass transition temperature is not particularly limited, and either a method using a differential scanning calorimeter or a method using a dynamic viscoelasticity test can be used. A method of measuring with a scanning calorimeter is preferred. In addition, the glass transition temperature of the polymer containing a glycidyl group-containing vinyl-based unit can be controlled by adjusting the composition of the copolymerization component. The glass transition temperature can usually be increased by copolymerizing aromatic vinyl units such as styrene, and can be decreased by copolymerizing acrylic ester units such as butyl acrylate.

  In the present invention, when the compatibilizer (C) is a glycidyl group-containing acrylic polymer or a glycidyl group-containing acrylic / styrene polymer, a sulfur compound is used as a chain transfer agent (molecular weight modifier) in order to obtain a low molecular weight product. In that case, the polymer usually contains sulfur. Here, although sulfur content is not specifically limited, From the viewpoint of suppressing unpleasant odor, it is preferable that the sulfur content is small. Specifically, the sulfur atom is preferably 1000 ppm or less, more preferably 100 ppm or less, further preferably 10 ppm or less, and most preferably 1 ppm or less. In the present invention, whether or not the sulfur content is in the above range can also be detected from the resin molded body.

  The melt viscosity of the compatibilizer (C) used in the present invention is not particularly limited, but the MFR may be 0.5 to 300 g / 10 minutes in terms of surface hardness, appearance, durability, and heat resistance. In terms of surface hardness and rigidity, it is more preferably 5 to 300 g / 10 minutes, and further preferably 100 to 300 g / 10 minutes. Here, the MFR of the compatibilizing agent (C) is a value measured under conditions of 190 ° C., 3.2 N, or 21.2 N. In addition, when it is difficult to measure under the conditions of 190 ° C. and 21.2N, it is a value measured under the conditions of 190 ° C. and 3.2N.

  In the present invention, the blending amount of the compatibilizing agent (C) is preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) component in terms of compatibility and surface hardness. 0.1 to 70 parts by weight, more preferably 0.5 to 50 parts by weight, particularly preferably 0.7 to 30 parts by weight, and 0.9 to 10 parts by weight. Most preferably.

  In the present invention, it is preferable to further blend an inorganic filler (D) in terms of surface hardness.

  As the inorganic filler (D) used in the present invention, any of fibrous, plate-like, granular, and powdery materials can be used. Specifically, asbestos fibers, carbon fibers, graphite fibers, metal fibers , Potassium titanate whisker, Aluminum borate whisker, Magnesium whisker, Silicon whisker, Wollastonite, Sepiolite, Asbestos, Slag fiber, Zonolite, Elestadite, Gypsum fiber, Silica fiber, Silica / alumina fiber, Zirconia fiber, Boron nitride Fibrous inorganic fillers such as fibers, silicon nitride fibers, glass fibers and boron fibers, glass flakes, non-swelling mica, graphite, metal foil, ceramic beads, talc, clay, mica, sericite, zeolite, bentonite, dolomite, Kaolin, finely divided silicic acid, feldspar powder, Plates such as potassium titanate, shirasu balloon, calcium carbonate, magnesium carbonate, barium sulfate, calcium oxide, aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, zirconium silicate, aluminum silicate, silicon oxide, gypsum, novaculite, dosonite and clay And inorganic fillers in the form of particles may be used, or one kind or two or more kinds may be used in combination. Among these, it is preferable that it contains a fibrous inorganic filler in terms of surface hardness, and at least one fibrous inorganic filler selected from wollastonite, aluminum borate and glass fiber. It is preferable to contain Wollastonite and / or glass fiber, and it is more preferable to contain Wollastonite. Further, in terms of appearance, it is preferable to contain a plate-like or particulate inorganic filler, and at least one selected from glass flakes, calcium carbonate, barium sulfate, aluminum oxide, titanium oxide and zirconium silicate. It is preferable to contain the above plate-like or particulate inorganic filler, more preferably at least one selected from barium sulfate, aluminum oxide and zirconium silicate, barium sulfate and More preferably, it contains zirconium silicate. By containing barium sulfate and / or zirconium silicate, a resin molded product excellent in appearance, gloss, weight and texture can be obtained.

  In the present invention, when a fibrous inorganic filler and a particulate inorganic filler are used in combination, a resin molded product excellent in surface hardness, appearance, durability and heat resistance can be obtained. It is preferable to use a combination of rustonite and barium sulfate and / or zirconium silicate because a resin molded product having a texture like ceramics can be obtained in addition to the above characteristics.

  The average particle diameter of the inorganic filler (D) used in the present invention is preferably 0.01 to 50 μm, more preferably 0.1 to 30 μm, and 1 to 25 μm in terms of surface hardness. More preferably, it is more preferably 0.5 to 5 μm from the viewpoint of appearance. When the average particle size is in the above range, a resin molded product excellent in surface hardness, appearance and durability can be obtained. Here, the average particle diameter is a value measured by a laser diffraction / scattering apparatus. In particular, when the inorganic filler (D) contains barium sulfate and / or zirconium silicate, it is possible to obtain a resin molded product excellent in appearance, gloss and impact resistance. The average particle diameter of barium is preferably 0.1 to 1.0 μm, more preferably 0.4 to 0.8 μm, and the average particle diameter of zirconium silicate is 0.1 to 20 μm. Is preferable, 0.1 to 5.0 μm is more preferable, 0.1 to 1.0 μm is further preferable, and 0.1 to 0.8 μm is particularly preferable.

  In the present invention, when the inorganic filler (D) contains a fibrous inorganic filler, the aspect ratio indicating the ratio of the fiber length to the fiber diameter is 1 to 50 in terms of surface hardness and rigidity. It is preferably in the range, more preferably in the range of 3-40, still more preferably in the range of 5-30, and particularly preferably in the range of 10-25. Here, the aspect ratio of the fibrous inorganic filler is a value that can be measured by observing the resin molded product with an electron microscope.

  The inorganic filler (D) used in the present invention may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, such as aminosilane or epoxysilane. It may be treated with a coupling agent or the like, and is preferably aminosilane-treated or epoxysilane-treated in terms of surface hardness, appearance, strength, rigidity, moist heat resistance and surface glossiness, and in terms of moist heat resistance. More preferably, it is treated with epoxy silane.

  The amount of the inorganic filler (D) used in the present invention is 0.1 to 200 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) in terms of surface hardness, appearance, durability and heat resistance. Is preferable, 1-150 weight part is more preferable, and 20-120 weight part is further more preferable.

  In the present invention, the addition of a hydrolysis inhibitor can improve the moist heat resistance and durability. Such a hydrolysis inhibitor is not particularly limited as long as it is a compound capable of blocking the carboxyl end group of the thermoplastic polyester resin (A) used in the present invention. As a so-called carboxyl group-reactive end blocker, Those commonly used can be used. As such a carboxyl group-reactive end-blocking agent, it is preferable to use at least one compound selected from an epoxy compound, an oxazoline compound, an oxazine compound, a carbodiimide compound, and an isocyanate compound. In addition, in this invention, the epoxy compound used as a hydrolysis inhibiting agent is a compound which does not express the effect as a compatibilizer (C) used by this invention.

  In the present invention, glycidyl ether compounds, glycidyl ester compounds, glycidyl amine compounds, glycidyl imide compounds, and alicyclic epoxy compounds can be preferably used as the epoxy compound that can be used as a carboxyl group-reactive end-blocking agent.

  Examples of glycidyl ether compounds include butyl glycidyl ether, stearyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, o-phenylphenyl glycidyl ether, ethylene oxide lauryl alcohol glycidyl ether, ethylene oxide phenol glycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol Diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, polytetramethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, glycerol triglycidyl ether, trimethylolpropane trig Bisphenols such as cidyl ether, pentaerythritol polyglycidyl ether, 2,2-bis- (4-hydroxyphenyl) propane, 2,2-bis- (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) sulfone Examples thereof include a bisphenol A diglycidyl ether type epoxy resin, a bisphenol F diglycidyl ether type epoxy resin, a bisphenol S diglycidyl ether type epoxy resin obtained from a condensation reaction with epichlorohydrin. Among these, bisphenol A diglycidyl ether type epoxy resin is preferable.

  Examples of glycidyl ester compounds include benzoic acid glycidyl ester, p-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester, palmitic acid glycidyl ester, versatic acid glycidyl ester, oleic acid glycidyl ester Ester, linoleic acid glycidyl ester, linolenic acid glycidyl ester, terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, phthalic acid diglycidyl ester, naphthalene dicarboxylic acid diglycidyl ester, benzoic acid diglycidyl ester, methyl terephthalic acid diglycidyl ester, Hexahydrophthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, cyclo Xanthenedicarboxylic acid diglycidyl ester, adipic acid diglycidyl ester, succinic acid diglycidyl ester, sebacic acid diglycidyl ester, dodecanedioic acid diglycidyl ester, octadecanedicarboxylic acid diglycidyl ester, trimellitic acid triglycidyl ester, pyromellitic acid tetra A glycidyl ester etc. can be mentioned. Among these, benzoic acid glycidyl ester and versatic acid glycidyl ester are preferable.

  Examples of glycidylamine compounds include tetraglycidylaminodiphenylmethane, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidylaniline, diglycidyltoluidine, tetraglycidylmetaxylenediamine, diglycidyltribromoaniline, tetra Examples thereof include glycidyl bisaminomethylcyclohexane, triglycidyl cyanurate, and triglycidyl isocyanurate.

  Examples of glycidylimide compounds include N-glycidylphthalimide, N-glycidyl-4-methylphthalimide, N-glycidyl-4,5-dimethylphthalimide, N-glycidyl-3-methylphthalimide, N-glycidyl-3,6- Dimethylphthalimide, N-glycidyl-4-ethoxyphthalimide, N-glycidyl-4-chlorophthalimide, N-glycidyl-4,5-dichlorophthalimide, N-glycidyl-3,4,5,6-tetrabromophthalimide, N -Glycidyl-4-n-butyl-5-bromophthalimide, N-glycidyl succinimide, N-glycidyl hexahydrophthalimide, N-glycidyl-1,2,3,6-tetrahydrophthalimide, N-glycidyl maleimide, N- Glycidyl-α, β-dimethyl Succinimide, N-glycidyl-α-ethylsuccinimide, N-glycidyl-α-propylsuccinimide, N-glycidylbenzamide, N-glycidyl-p-methylbenzamide, N-glycidylnaphthamide, N-glycidylsteramide, etc. be able to. Of these, N-glycidylphthalimide is preferable.

  Examples of alicyclic epoxy compounds include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexylcarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene diepoxide, N-methyl-4, 5-epoxycyclohexane-1,2-dicarboxylic imide, N-ethyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-phenyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide N-naphthyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, N-tolyl-3-methyl-4,5-epoxycyclohexane-1,2-dicarboxylic imide, and the like.

  Further, as other epoxy compounds, epoxy-modified fatty acid glycerides such as epoxidized soybean oil, epoxidized linseed oil, and epoxidized whale oil, phenol novolac type epoxy resins, cresol nozolac type epoxy resins and the like can be used.

  Examples of the oxazoline compound that can be used as a carboxyl group-reactive end-blocking agent used in the present invention include 2-methoxy-2-oxazoline, 2-ethoxy-2-oxazoline, 2-propoxy-2-oxazoline, 2-butoxy 2-oxazoline, 2-pentyloxy-2-oxazoline, 2-hexyloxy-2-oxazoline, 2-heptyloxy-2-oxazoline, 2-octyloxy-2-oxazoline, 2-nonyloxy-2-oxazoline, 2 -Decyloxy-2-oxazoline, 2-cyclopentyloxy-2-oxazoline, 2-cyclohexyloxy-2-oxazoline, 2-allyloxy-2-oxazoline, 2-methallyloxy-2-oxazoline, 2-crotyloxy-2-oxazoline , 2-pheno Ci-2-oxazoline, 2-cresyl-2-oxazoline, 2-o-ethylphenoxy-2-oxazoline, 2-o-propylphenoxy-2-oxazoline, 2-o-phenylphenoxy-2-oxazoline, 2-m -Ethylphenoxy-2-oxazoline, 2-m-propylphenoxy-2-oxazoline, 2-p-phenylphenoxy-2-oxazoline, 2-methyl-2-oxazoline, 2-ethyl-2-oxazoline, 2-propyl- 2-oxazoline, 2-butyl-2-oxazoline, 2-pentyl-2-oxazoline, 2-hexyl-2-oxazoline, 2-heptyl-2-oxazoline, 2-octyl-2-oxazoline, 2-nonyl-2- Oxazoline, 2-decyl-2-oxazoline, 2-cyclopentyl-2-oxy Zolin, 2-cyclohexyl-2-oxazoline, 2-allyl-2-oxazoline, 2-methallyl-2-oxazoline, 2-crotyl-2-oxazoline, 2-phenyl-2-oxazoline, 2-o-ethylphenyl-2 -Oxazoline, 2-o-propylphenyl-2-oxazoline, 2-o-phenylphenyl-2-oxazoline, 2-m-ethylphenyl-2-oxazoline, 2-m-propylphenyl-2-oxazoline, 2-p -Phenylphenyl-2-oxazoline, 2,2'-bis (2-oxazoline), 2,2'-bis (4-methyl-2-oxazoline), 2,2'-bis (4,4'-dimethyl- 2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4′-diethyl-2-oxy) Sazoline), 2,2′-bis (4-propyl-2-oxazoline), 2,2′-bis (4-butyl-2-oxazoline), 2,2′-bis (4-hexyl-2-oxazoline) 2,2′-bis (4-phenyl-2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2 , 2'-p-phenylenebis (2-oxazoline), 2,2'-m-phenylenebis (2-oxazoline), 2,2'-o-phenylenebis (2-oxazoline), 2,2'-p -Phenylenebis (4-methyl-2-oxazoline), 2,2'-p-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-m-phenylenebis (4-methyl-2) -Oxazoline), 2, 2 -M-phenylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-ethylenebis (2-oxazoline), 2,2'-tetramethylenebis (2-oxazoline), 2,2'- Hexamethylene bis (2-oxazoline), 2,2′-octamethylene bis (2-oxazoline), 2,2′-decamethylene bis (2-oxazoline), 2,2′-ethylene bis (4-methyl-2) -Oxazoline), 2,2'-tetramethylenebis (4,4'-dimethyl-2-oxazoline), 2,2'-9,9'-diphenoxyethanebis (2-oxazoline), 2,2'- Examples include cyclohexylenebis (2-oxazoline) and 2,2′-diphenylenebis (2-oxazoline).

  Furthermore, the polyoxazoline compound etc. which contain the above-mentioned compound as a monomer unit can be mentioned.

  Examples of oxazine compounds as carboxyl group-reactive endblockers that can be used in the present invention include 2-methoxy-5,6-dihydro-4H-1,3-oxazine, 2-ethoxy-5,6-dihydro. -4H-1,3-oxazine, 2-propoxy-5,6-dihydro-4H-1,3-oxazine, 2-butoxy-5,6-dihydro-4H-1,3-oxazine, 2-pentyloxy- 5,6-dihydro-4H-1,3-oxazine, 2-hexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-heptyloxy-5,6-dihydro-4H-1,3- Oxazine, 2-octyloxy-5,6-dihydro-4H-1,3-oxazine, 2-nonyloxy-5,6-dihydro-4H-1,3-oxazine, 2-decyloxy-5 6-dihydro-4H-1,3-oxazine, 2-cyclopentyloxy-5,6-dihydro-4H-1,3-oxazine, 2-cyclohexyloxy-5,6-dihydro-4H-1,3-oxazine, 2-allyloxy-5,6-dihydro-4H-1,3-oxazine, 2-methallyloxy-5,6-dihydro-4H-1,3-oxazine, 2-crotyloxy-5,6-dihydro-4H- 1,3-oxazine, and the like. Furthermore, 2,2′-bis (5,6-dihydro-4H-1,3-oxazine), 2,2′-methylenebis (5,6-dihydro-4H— 1,3-oxazine), 2,2′-ethylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-propylenebis (5,6-dihydro-4H-1,3- Oxazi ), 2,2′-butylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-hexamethylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2′-p-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2,2′-m-phenylenebis (5,6-dihydro-4H-1,3-oxazine), 2, 2'-naphthylene bis (5,6-dihydro-4H-1,3-oxazine), 2,2'-P, P'-diphenylene bis (5,6-dihydro-4H-1,3-oxazine), etc. Can be mentioned. Furthermore, the polyoxazine compound etc. which contain an above-described compound as a monomer unit are mentioned.

  Among the oxazoline compounds and oxazine compounds, 2,2'-m-phenylenebis (2-oxazoline) and 2,2'-p-phenylenebis (2-oxazoline) are preferable.

  The carbodiimide compound that can be used as a carboxyl group-reactive end-blocking agent in the present invention is a compound having at least one carbodiimide group represented by (—N═C═N—) in the molecule. The organic isocyanate can be heated in the presence of a simple catalyst and produced by a decarboxylation reaction.

  Examples of carbodiimide compounds include diphenylcarbodiimide, di-cyclohexylcarbodiimide, di-2,6-dimethylphenylcarbodiimide, diisopropylcarbodiimide, dioctyldecylcarbodiimide, di-o-toluylcarbodiimide, di-p-toluylcarbodiimide, di-p- Nitrophenylcarbodiimide, di-p-aminophenylcarbodiimide, di-p-hydroxyphenylcarbodiimide, di-p-chlorophenylcarbodiimide, di-o-chlorophenylcarbodiimide, di-3,4-dichlorophenylcarbodiimide, di-2 , 5-dichlorophenylcarbodiimide, p-phenylene-bis-o-toluylcarbodiimide, p-phenylene-bis-dicyclohexylcarbodiimide, p-phenylene- Su-di-p-chlorophenylcarbodiimide, 2,6,2 ', 6'-tetraisopropyldiphenylcarbodiimide, hexamethylene-bis-cyclohexylcarbodiimide, ethylene-bis-diphenylcarbodiimide, ethylene-bis-dicyclohexylcarbodiimide, N , N′-di-o-triylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-di-2,6-dimethylphenylcarbodiimide, N-triyl-N ′ -Cyclohexylcarbodiimide, N, N'-di-2,6-diisopropylphenylcarbodiimide, N, N'-di-2,6-di-t-butylphenylcarbodiimide, N-toluyl-N'-phenylcarbodiimide, N, N'-di-p-nitrof Nylcarbodiimide, N, N′-di-p-aminophenylcarbodiimide, N, N′-di-p-hydroxyphenylcarbodiimide, N, N′-di-cyclohexylcarbodiimide, N, N′-di-p-tolylcarbodiimide N, N′-benzylcarbodiimide, N-octadecyl-N′-phenylcarbodiimide, N-benzyl-N′-phenylcarbodiimide, N-octadecyl-N′-tolylcarbodiimide, N-cyclohexyl-N′-tolylcarbodiimide, N -Phenyl-N'-tolylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N, N'-di-o-ethylphenylcarbodiimide, N, N'-di-p-ethylphenylcarbodiimide, N, N'- Di-o-isopropylphenylcarbodiimide, N, N '-Di-p-isopropylphenylcarbodiimide, N, N'-di-o-isobutylphenylcarbodiimide, N, N'-di-p-isobutylphenylcarbodiimide, N, N'-di-2,6-diethylphenylcarbodiimide N, N′-di-2-ethyl-6-isopropylphenylcarbodiimide, N, N′-di-2-isobutyl-6-isopropylphenylcarbodiimide, N, N′-di-2,4,6-trimethylphenyl Mono- or dicarbodiimide compounds such as carbodiimide, N, N′-di-2,4,6-triisopropylphenylcarbodiimide, N, N′-di-2,4,6-triisobutylphenylcarbodiimide, poly (1,6 -Hexamethylenecarbodiimide), poly (4,4'-methylenebiscyclohexylcarbodi) ), Poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide), poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-) Diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylenecarbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly ( And polycarbodiimides such as triethylphenylenecarbodiimide) and poly (triisopropylphenylenecarbodiimide). Of these, N, N′-di-2,6-diisopropylphenylcarbodiimide and 2,6,2 ′, 6′-tetraisopropyldiphenylcarbodiimide are preferable, and polycarbodiimide is preferable.

  As the carboxyl group-reactive end-blocking agent, one or more compounds can be arbitrarily selected and used.

  In the present invention, the blending amount of the hydrolysis inhibitor is preferably 0.1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A) in terms of moisture and heat resistance, bleed out and mold deposit suppression. More preferred is 2-3 parts by weight.

  In the present invention, the flowability and appearance can be improved by adding a fluidity improver. Examples of fluidity improvers include branched polymers, liquid crystal polymers, low molecular weight linear polyesters, low molecular weight linear polycarbonates, aromatic low molecular compounds, acrylic compounds, and compounds having three or more functional groups. Can be mentioned.

  In the present invention, a stabilizer such as a crystal nucleating agent, a plasticizer, an ultraviolet absorber, an antibacterial agent, an antioxidant and a metal deactivator, a release agent, a pigment and a dye are added within a range not impairing the effects of the present invention. One or more various additives such as a coloring agent, a lubricant and an antistatic agent can be added.

  Although the manufacturing method of the resin composition used by this invention is not specifically limited as long as the requirements prescribed | regulated by this invention are satisfy | filled, For example, a thermoplastic polyester resin (A) and acrylic resin (B), as needed The other compatibilizing agent (C) and the inorganic filler (D) are previously blended and then melted and kneaded uniformly with a single or twin screw extruder above the melting point, or mixed in a solution. A method of removing the solvent later can be preferably used, but a method of melt kneading with a twin screw extruder is preferred in terms of surface hardness, appearance, durability, heat resistance, rigidity, and surface gloss. In addition, when the inorganic filler (D) is blended, the thermoplastic polyester resin (A) and the acrylic resin (A) and the acrylic resin (A) can be obtained particularly in that a resin molded product having excellent surface hardness, appearance and rigidity can be obtained. It is preferable to feed into a twin screw extruder using a side feeder from an inlet different from the hopper into which B) is introduced.

  110-360 degreeC is preferable, as for the melt kneading | mixing temperature at the time of manufacturing the resin composition used by this invention, 210-280 degreeC is more preferable, and 240-270 degreeC is more preferable.

  In the resin molded product of the present invention, one of the thermoplastic polyester resin (A) and the acrylic resin (B) forms a matrix phase and the other forms a dispersed phase, but the thermoplastic polyester resin (A ) Form a matrix phase, and the acrylic resin (B) preferably forms a dispersed phase. In the present invention, the dispersion form of the thermoplastic polyester resin (A) and the acrylic resin (B) is preferably such that the dispersion diameter of the acrylic resin (B) is 20 μm or less in terms of surface hardness. More preferably, it is 10 μm or less, further preferably 1 μm or less, and particularly preferably 0.5 μm or less. When the dispersion diameter of the acrylic resin (B) is in the above range, a resin molded product particularly excellent in surface hardness can be obtained.

  As for the surface hardness of the resin molded product of the present invention, the pencil hardness is preferably HB or more, more preferably H or more, further preferably 2H or more, and particularly preferably 3H or more. In the present invention, the pencil hardness is a hardness that does not leave a scratch mark even when the resin is rubbed with a pencil having a specific pencil hardness, and can be measured according to JIS K-5600. It is preferable to use the pencil hardness used for the hardness test as an index.

  Pencil hardness is soft in the order of 9H, 8H, 7H, 6H, 5H, 4H, 3H, 2H, H, F, HB, 2B, 3B, 4B, 5B, 6B, the hardest is 9H, and the softest Is 6B.

  The carboxyl end group amount (COOH amount) of the resin molded product of the present invention is not particularly limited, but is preferably 50 eq / t or less in terms of appearance and durability, and 20 eq / t in terms of durability. More preferably, it is more preferably 10 eq / t or less, particularly preferably 7 eq / t or less, and most preferably 5 eq / t or less. The lower limit is 0 eq / t. In the present invention, the COOH amount is a value measured by dissolving a resin molded product with an o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide. In the resin molded product of the present invention, a thermoplastic polyester resin (A) is selected, an additive is blended as necessary, and a kneading condition and a molding condition are selected, whereby a resin molded product having a desired amount of COOH is obtained. Obtainable.

  In the present invention, the resin molded product can be produced by various molding methods using the resin composition used in the present invention. Examples of the molding method include injection molding, extrusion molding, press molding, blow molding, and the like. Among these, injection molding is preferable in that it has excellent shape flexibility and can reduce costs.

  In the present invention, when the resin molded product is produced, the processing temperature is preferably 110 to 300 ° C, more preferably 210 to 280 ° C as a temperature range in which the resin can be melted and deterioration can be suppressed. 240-270 degreeC is further more preferable. When the molding method is an injection molding method, the mold temperature is preferably 30 to 150 ° C., more preferably 50 to 120 ° C. in terms of appearance and fluidity, 55 More preferably, it is -100 degreeC, and it is especially preferable that it is 60-90 degreeC.

  The resin molded product of the present invention is a water-related member, and is used around water in a member used in various industries such as a housing-related member, a horticultural-related member, an automobile-related member, and an electric / electronic component-related member. Includes all members.

  The resin molded product of the present invention can be suitably used as at least one member of a toilet component, a bathroom component, a toilet component, and a kitchen component, among water-repellent members.

  In the present invention, when the resin molded product is a lavatory component, specifically, a wash bowl (wash basin), a hand wash bowl (hand basin), a wash counter, a hand wash counter, a storage case, a storage shelf, a mirror frame , Faucet members, floors and walls, and the like. Among them, any one of a wash bowl, a hand wash bowl, a hand wash counter and a wash storage shelf is preferable.

  In the present invention, when the resin molded product is a bathroom component, specifically, a bathtub, a bath lid, a bathroom washing place, a bathroom wall, a bathroom counter, a bathroom floor, a waterproof pan, a bathroom storage shelf, a bathroom ceiling, a washing bowl Bathroom constituent members such as shower faucet members, washing chairs and handrails can be mentioned, and among them, any one of a bathtub, a bathroom counter, a bathroom floor and a bathroom storage shelf is preferable.

  In the present invention, when the resin molded product is a toilet component, specifically, a toilet component such as a toilet bowl, toilet bowl lid, toilet seat, toilet counter, washing nozzle, toilet storage shelf, etc. It is preferably one of a toilet bowl, toilet bowl lid, toilet seat and toilet counter.

  In the present invention, when the resin molded product is a kitchen component, specific examples include kitchen components such as a kitchen counter, a kitchen sink, a kitchen bag, a kitchen top plate, a storage shelf, and a storage shelf door. Of these, any one of a kitchen counter, a kitchen sink, and a kitchen top plate is preferable.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, these do not limit this invention.

  The abbreviations and the contents of main raw materials used in Examples and the like are summarized below.

(A) Thermoplastic polyester A-1: Polybutylene terephthalate resin: Inherent viscosity 0.86 dl / g, COOH amount 45 eq / t
A-2: Polybutylene terephthalate resin: intrinsic viscosity 0.86 dl / g, COOH amount 21 eq / t
A-3: Polybutylene terephthalate resin: intrinsic viscosity 0.86 dl / g, COOH amount 12 eq / t
A-4: Polybutylene terephthalate resin: Intrinsic viscosity 1.20 dl / g, COOH amount 12 eq / t
A-5: Polyethylene terephthalate resin: intrinsic viscosity 0.70 dl / g
A-6: Polypropylene terephthalate resin: Intrinsic viscosity 0.90 dl / g.

(B) Acrylic resin B-1: Methacrylic resin (HT121 manufactured by Atofina): Methyl methacrylate content 90% by weight or more, MFR 2 g / 10 min, glass transition temperature 118 ° C.
B-2: Methacrylic resin (“SUMIPEX” LG35 manufactured by Sumitomo Chemical Co., Ltd.): Methyl methacrylate content 90% by weight or more, MFR 36 g / 10 min, glass transition temperature 95 ° C.

(C) Compatibilizer C-1: Glycidyl group-containing acrylic / styrene-based polymer (“ARUFON” UG4040 manufactured by Toa Gosei): MFR 255 g / 10 min (3.2 N), epoxy value 2.1 meq / g
C-2: Glycidyl group-containing acrylic / styrene polymer ("Joncrill" ADR-4368 manufactured by BASF): MFR 270 g / 10 min (3.2 N), epoxy value 3.5 meq /
g
C-3: Glycidyl group-containing acrylic polymer (“Mafproof” CP-50M manufactured by NOF Corporation): MFR 265 g / 10 min (3.2 N), epoxy value 2.9 meq / g
C-4: Poly (ethylene / glycidyl methacrylate) -g-polymethyl methacrylate (“MODIPA” A4200 manufactured by NOF Corporation): MFR 0.6 g / 10 min (21.2 N)
C-5: Poly (ethylene / ethyl acrylate / maleic anhydride) -g-polymethyl methacrylate (“MODIPA” A8200 manufactured by NOF Corporation): MFR 1.3 g / 10 min (21.2 N).

(D) Inorganic filler D-1: Wollastonite (KAP350 manufactured by Kansai Matec): Average particle size 5.01 μm
D-2: Wollastonite (FH-90 epoxy silane-treated product manufactured by Kinsei Matec): average particle size 23 μm, aspect ratio 25
D-3: Wollastonite (“NYGLOS” 8 manufactured by NYCO): average particle size 12 μm, aspect ratio 17
D-4: Wollastonite (manufactured by NYCO “NYGLOS” 8 epoxy silane treated product): average particle size 12 μm, aspect ratio 17
D-5: Aluminum borate whisker (“Arbolex” YS3A manufactured by Shikoku Chemicals)
D-6: Glass fiber (manufactured by Nittobo 3J948): Fiber diameter 13 μm
D-7: Barium sulfate (B-55, Sakai Chemical Industry): Average particle size 0.66 μm
D-8: Calcium carbonate (KS-1200 manufactured by Calfine): Average particle size 2 μm
D-9: Silica (SQP-14 manufactured by Kinsei Matec): Average particle size of 15 μm
D-10: Silica (F-HD05 manufactured by Kinsei Matec): Average particle size of 5 μm
D-11: Zirconium silicate (manufactured by Kinsei Matec # 400): average particle size 10 μm
D-12: Zirconium silicate (A-PAX45M manufactured by Kinsei Matec): Average particle size 1 μm
D-13: Zirconium silicate (“Micropax” SS manufactured by Hakusui Tech Co., Ltd.): Average particle size 0.6 μm.

(E) Carboxyl group-reactive end-capping agent E-1: Epoxy compound (Japan Epoxy Resin “Cardura” E10P): Epoxy value 4.1 meq / g
E-2: Epoxy compound (“Epicoat” 819 manufactured by Japan Epoxy Resin): epoxy value of 5 meq / g.

  Moreover, the evaluation method used in an Example etc. is summarized below.

(1) Surface hardness The pencil hardness of the surface of the molded product was measured according to JIS K5600. In addition, the pencil of the standard JIS S6006 was used.

(2) Appearance The glossiness at an incident angle of 20 ° was measured using a handy gloss meter IG320 manufactured by Horiba.

(3) Durability and heat resistance (moisture heat resistance)
Using a thermostatic chamber, the temperature was 90 ° C., the relative humidity was 95%, and the surface was treated for 500 hours, and the deformation and the surface appearance were determined according to the following criteria.
◎: No deformation, gloss retention of 95% or more ○: Deformation is slightly observed, or gloss retention of 70% or more and less than 95% ×: Deformation is remarkable, or gloss retention is 70% Less than.

(4) Scratch resistance A sponge containing a neutral detergent stock solution was rubbed 200 times with a load of 1 kg, washed with water, and the surface condition was determined according to the following criteria.
A: Glossiness retention is 95% or more. B: Glossiness retention is 70% or more and less than 95%. X: Glossiness retention is less than 70%.

(5) Carboxyl end group amount (COOH amount)
1 g was cut out from the resin molded article, dissolved in 100 mL of o-cresol / chloroform solvent, and titrated with ethanolic potassium hydroxide.

(6) Chemical resistance A neutral detergent stock solution for bathroom was applied to the inner surface of the molded article, left standing for 12 hours, washed with water, and the deformation and surface appearance were determined according to the following criteria.
◎: No deformation, gloss retention of 95% or more ○: Deformation is slightly observed, or gloss retention of 70% or more and less than 95% ×: Deformation is remarkable, or gloss retention is 70% Less than.

(7) Boiling test Place the molded product on a horizontal floor, fill the molded product with water to a depth of 80%, adjust the temperature to 80 ° C with a throwing heater, hold it for 8 hours, drain it, and then temperature the surface of the molded product Let stand until 30 ° C. This was performed for 12 cycles, and the surface condition was determined according to the following criteria.
○: No cracks, discoloration, and deformation are observed at all. ×: Any one or more of cracks, discoloration, and deformation is observed.

[Examples 1-44, Comparative Examples 1-3]
The above raw materials were mixed in the proportions shown in Table 1, Table 2 and Table 3, and melt kneaded with a 44 mm diameter twin screw extruder under conditions of a cylinder temperature of 260 ° C. and a rotation speed of 200 rpm to obtain a resin composition. . The obtained resin composition was dried with a hot air dryer at 120 ° C. for 5 hours, and then washed with a wash bowl (outside dimensions) using an injection molding machine with a clamping force of 13000 kN at a cylinder temperature of 260 ° C. and a mold temperature of 90 ° C. A width 530 mm, a depth 530 mm, a wash surface depth 105 mm, a drain port φ = 43 mm, and a flush fitting mounting hole φ = 34 mm) were injection molded. Various evaluation was performed using the obtained molded article. The results are shown in Table 1, Table 2 and Table 3.

  From this result, it can be seen that the resin molded product of the present invention has practically good surface hardness, appearance, durability, heat resistance and scratch resistance.

[Examples 45 to 88]
The raw materials were mixed at the ratios shown in Tables 4 and 5, and melt kneaded with a 30 mm diameter twin-screw extruder under the conditions of a cylinder temperature of 260 ° C. and a rotation speed of 150 rpm to obtain a resin composition. The obtained resin composition was dried with a hot air dryer at 120 ° C. for 5 hours, and then washed with a wash bowl (outside dimensions) using an injection molding machine with a clamping force of 13000 kN at a cylinder temperature of 260 ° C. and a mold temperature of 90 ° C. 530mm in width, 530mm in depth, 105mm in depth of wash surface, drain port φ = 43mm, flush fitting mounting hole φ = 34mm), injection molding, cylinder temperature 260 ° C, mold temperature 80 ° C, bathtub model (external width 300mm) , Depth 150 mm, depth 100 mm, average thickness 5 mm). Various evaluation was performed using the obtained molded article. The results are shown in Tables 4 and 5.

  From this result, it can be seen that the resin molded article of the present invention has practically good surface hardness, appearance, durability, heat resistance, scratch resistance and chemical resistance.

Claims (11)

  A resin molded article which is a water-borne member comprising a resin composition comprising 100 parts by weight of a thermoplastic polyester resin (A) and 1 to 200 parts by weight of an acrylic resin (B). The resin molded article according to claim 1, wherein the water-circulating member is at least one member of a toilet component, a bathroom component, a toilet component, and a kitchen component. The resin composition further comprises a compatibilizer (C), which is a compound having at least one functional group selected from a glycidyl group, an acid anhydride group, and a carboxyl group. The resin molded product described. The resin molded product according to any one of claims 1 to 3, wherein the resin composition further comprises an inorganic filler (D). The resin molded product according to any one of claims 1 to 4, wherein the thermoplastic polyester resin (A) contains polybutylene terephthalate. The resin molded product according to any one of claims 1 to 5, wherein the acrylic resin (B) is a methacrylic resin having a methyl methacrylate unit as a main component. The inorganic filler (D) contains at least one fibrous inorganic filler selected from wollastonite, aluminum borate, and glass fiber. Resin molded products. The resin molded product according to any one of claims 1 to 7, wherein the water-circulating member is a toilet building component selected from any one of a wash bowl, a hand wash bowl, a hand wash counter, and a wash storage shelf. The resin molded product according to any one of claims 1 to 7, wherein the water-circulating member is a bathroom constituent member selected from any one of a bathtub, a bathroom counter, a bathroom floor, and a bathroom storage shelf. The resin-molded article according to any one of claims 1 to 7, wherein the water-circulating member is a toilet component selected from any one of a toilet bowl, a toilet lid, a toilet seat, and a toilet counter. The resin molded product according to any one of claims 1 to 7, wherein the water-circulating member is a kitchen component selected from any one of a kitchen counter, a kitchen sink, and a kitchen top plate.