JP2017222747A - Polybutylene terephthalate-based resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polybutylene terephthalate-based resin composition which is excellent in water repellency and scratch resistance, is excellent in the appearance and dimensional stability of a molded article, and is also excellent in lightweight properties and the like in molding.SOLUTION: The polybutylene terephthalate-based resin composition contains 0.2 to 12 pts.mass of a polyolefin-based resin or styrenic resin (B), 0.5 to 10 pts.mass of a silicone compound (C), and 0.5 to 10 pts.mass of an inorganic filler (D) with respect to 100 pts.mass of a polybutylene terephthalate resin (A) having a melting point of 215°C or more.SELECTED DRAWING: None

Description

  The present invention relates to a polybutylene terephthalate resin composition, and particularly relates to a polybutylene terephthalate resin composition that is particularly excellent in water repellency and scratch resistance.

  Thermoplastic polyester resins represented by polybutylene terephthalate are excellent in mechanical strength, chemical resistance, electrical insulation, etc., and have excellent heat resistance, moldability, and recyclability. It is also used for automobile parts, electrical and electronic equipment parts, other precision equipment parts, and sanitary equipment such as toilet seats, washstands, hand basins, and basin bowls.

  The present applicant previously described in Patent Document 1 that a polyester resin composition in which zirconium silicate having a specific particle diameter is blended with a polyester resin is a polyester resin composition having a ceramic-like high-quality material feeling, but is flexible. Proposed excellent properties (tensile elongation and impact resistance), appearance of molded products (surface gloss), hydrolysis resistance, moldability (residual heat stability), but especially in terms of water repellency and scratch resistance. It was not enough.

JP 2009-30029 JP

  An object (problem) of the present invention is to provide a polybutylene terephthalate-based resin composition that is excellent in water repellency and scratch resistance and that is also suitable as a member of sanitary equipment.

The inventors of the present invention provide a polybutylene terephthalate resin composition comprising a polybutylene terephthalate resin having a melting point equal to or higher than a specific temperature, a polyolefin resin or a styrene resin, a silicone compound, and an inorganic filler in specific amounts. However, the present inventors have found that the above problems can be solved and completed the present invention.
The present invention relates to the following polybutylene terephthalate resin composition, molded article, and method for producing the resin composition.

[1] For 100 parts by mass of polybutylene terephthalate resin (A) having a melting point of 215 ° C. or higher, 0.2 to 12 parts by mass of polyolefin-based resin or styrene-based resin (B) and 0.5% of silicone compound (C) A polybutylene terephthalate-based resin composition containing 10 to 10 parts by mass and 0.5 to 10 parts by mass of an inorganic filler (D).
[2] The polybutylene terephthalate resin composition according to the above [1], wherein the total content of the polyolefin resin and the styrene resin (B) and the silicone compound (C) is 1 to 15 parts by mass.
[3] The above [1] or [2], wherein the mass ratio (B) / (C) of the polyolefin resin and styrene resin (B) to the silicone compound (C) is 25/75 to 60/40 The polybutylene terephthalate resin composition described in 1.
[4] The polybutylene terephthalate resin composition according to any one of [1] to [3], wherein the inorganic filler (D) is selected from titanium oxide, zinc sulfide, and zinc oxide.
[5] A molded article for sanitary equipment comprising the polybutylene terephthalate resin composition according to any one of [1] to [4].
[6] The polybutylene terephthalate resin composition according to [1], wherein the polybutylene terephthalate resin (A) is blended as a mixture of a polyolefin resin or a styrene resin (B) and a silicone compound (C) in advance. Manufacturing method.

The polybutylene terephthalate resin composition of the present invention has a high water droplet contact angle, high antifouling properties and water repellency, excellent scratch resistance, and good appearance, surface gloss, and dimensional stability. Excellent, and also excellent in measuring properties during molding.
For this reason, the molded article of the polybutylene terephthalate resin composition of the present invention can be suitably used for sanitary equipment such as a toilet seat, a wash basin, a hand basin, and a basin bowl.

[Summary of Invention]
The polybutylene terephthalate resin composition of the present invention has a melting point of 215 ° C. or more of polybutylene terephthalate resin (A) 100 parts by mass, polyolefin resin or styrene resin (B) 0.2 to 12 parts by mass, It contains 0.5 to 10 parts by mass of the silicone compound (C) and 0.5 to 10 parts by mass of the inorganic filler (D).

Hereinafter, the contents of the present invention will be described in detail.
The description of each constituent element described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is interpreted to be limited to such embodiments and specific examples. It is not a thing. In the specification of the present application, “to” is used in the sense of including the numerical values described before and after it as the lower limit value and the upper limit value.

[Polybutylene terephthalate resin (A)]
The polybutylene terephthalate resin (A) used in the present invention is essentially a polybutylene terephthalate resin mainly composed of a polybutylene terephthalate resin and having a melting point of 215 ° C. or higher, preferably 220 ° C. or higher, more preferably 222 ° C. or higher. By using a polybutylene terephthalate resin having a melting point of 215 ° C. or higher, a resin composition having high surface hardness and excellent scratch resistance can be obtained. When the melting point is lower than 215 ° C., the surface hardness is low, and scratch resistance of the resulting molded product is deteriorated.
The melting point of the polybutylene terephthalate resin (A) is usually 250 ° C. or lower, preferably 240 ° C. or lower, more preferably 230 ° C. or lower.

  In the present invention, the melting point of the polyester resin containing the polybutylene terephthalate resin (A) is the melting point of the resin (Tm) measured at a temperature increase rate of 20 ° C./min by differential thermal analysis (DSC) based on JIS K7121. It is.

  The polybutylene terephthalate resin (A) used in the present invention may be a polybutylene terephthalate homopolymer or copolymer as long as the melting point is 215 ° C. or higher, but terephthalic acid is the only dicarboxylic acid unit. Polybutylene terephthalate homopolymers having 1,4-butanediol as the only diol unit are preferred. The dicarboxylic acid unit may be a polybutylene terephthalate copolymer containing at least one dicarboxylic acid other than terephthalic acid and / or at least one diol other than 1,4-butanediol as the diol unit. The proportion of terephthalic acid in the unit is preferably more than 90 mol%, more preferably more than 95 mol%, still more preferably more than 98 mol%, and the proportion of 1,4-butanediol in the diol unit However, it is preferably more than 90 mol%, more preferably more than 95 mol%, still more preferably more than 98 mol%

  Specific examples of dicarboxylic acids other than terephthalic acid include isophthalic acid, orthophthalic acid, 1,5-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, biphenyl-2,2 ′. -Dicarboxylic acid, biphenyl-3,3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, bis (4,4'-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, etc. Aromatic dicarboxylic acids, 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as 4,4'-dicyclohexyldicarboxylic acid, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, and dimer acid Etc.

Specific examples of diol units other than 1,4-butanediol include aliphatic or alicyclic diols having 2 to 20 carbon atoms, bisphenol derivatives, and the like. Specific examples include ethylene glycol, propylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, decamethylene glycol, cyclohexanedimethanol, 4,4′-dicyclohexylhydroxymethane, 4 4,4'-dicyclohexylhydroxypropane, bisphenol A ethylene oxide addition diol, and the like.
In addition to the above-mentioned bifunctional monomers, trifunctional monomers such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure, and fatty acids are used for molecular weight control. A monofunctional compound can also be used in a small amount, and the amount is preferably less than 1 mol%, for example.

The polybutylene terephthalate resin (A) can be produced by melt-polymerizing the above-described dicarboxylic acid component or ester derivative thereof and the above-described diol component in a batch or continuous manner. After the polybutylene terephthalate resin is produced, the melting point can be increased by further solid-phase polymerization under a nitrogen stream or under reduced pressure.
The polybutylene terephthalate resin is preferably obtained by a continuous melt polycondensation of a dicarboxylic acid component containing terephthalic acid as a main component and a diol component containing 1,4-butanediol as a main component.

  The catalyst used in performing the esterification reaction may be a conventionally known catalyst, and examples thereof include a titanium compound, a tin compound, a magnesium compound, and a calcium compound. Of these, titanium compounds are particularly preferred. Specific examples of the titanium compound as the esterification catalyst include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate.

[Polyolefin resin or styrene resin (B)]
The polybutylene terephthalate resin composition of the present invention contains a polyolefin resin or a styrene resin (B).

[Polyolefin resin (B1)]
As the polyolefin resin (B1) used in the present invention, various polyolefin resins can be used. Among them, ethylene or a homopolymer of propylene, ethylene and ethylene of propylene, butene, hexene, octene, or vinyl acetate. Preferable examples include polyethylene resins such as a copolymer, and polypropylene resins such as a propylene copolymer of propylene and butene, hexene, or octene. Preferred examples include polyethylene resins and polypropylene resins. Specific examples of the polyethylene resin include high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ethylene-vinyl acetate copolymer (EVA). Preferable examples of the polypropylene resin include polypropylene and propylene-ethylene copolymer.

  There are no restrictions on the production method and polymerization catalyst of the polyolefin resin (B1), and various known production methods such as solution method, bulk method, gas phase, high pressure method, radical initiator, Ziegler catalyst, chromium catalyst, metallocene Any of a catalyst or the like may be used.

  The polyolefin resin (B1) may be used alone or in combination of two or more.

  Content of polyolefin-type resin (B1) is 0.2-12 mass parts with respect to 100 mass parts of polybutylene terephthalate resin (A). When the content of the polyolefin resin (B1) is less than 0.2 parts by mass, the water repellency is lowered, and when the content is more than 12 parts by mass, the surface appearance, heat resistance and strength are lowered. The content of the polyolefin resin (B1) is preferably 10 parts by mass or less, more preferably 7 parts by mass or less, particularly preferably 5 parts by mass or less, preferably 0.5 parts by mass or more, more preferably 1 part by mass. Part or more, more preferably 1.5 parts by weight or more, and particularly preferably 2 parts by weight or more.

[Styrene resin (B2)]
The styrene resin (B2) used in the present invention is preferably a homopolymer of a styrene monomer or a copolymer of a styrene monomer and another copolymerizable monomer. Can be mentioned.
Specific examples of the styrene resin (B2) include polystyrene (PS), high impact polystyrene (HIPS), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-butadiene-styrene copolymer (MBS resin). , Methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), acrylonitrile-acrylic rubber-styrene copolymer (AAS resin), acrylonitrile-ethylenepropylene rubber-styrene copolymer (AES resin) and the like are preferable. It is done. Among these, polystyrene (PS), impact-resistant polystyrene (HIPS), and acrylonitrile-butadiene-styrene copolymer (ABS resin) are particularly preferable.

  The styrene resin (B2) may be used alone or in combination of two or more.

  The mass average molecular weight of the styrene resin (B2) is usually 50000 or more, preferably 100,000 or more, more preferably 150,000 or more, and the upper limit is usually 500,000 or less, preferably 400,000 or less. And more preferably 300,000 or less. The number average molecular weight is usually 10,000 or more, preferably 30000 or more, more preferably 50000 or more, and the upper limit is usually 300000 or less, preferably 200000 or less, more preferably Is 150,000 or less. It is preferable to use the styrene resin (B2) having such a mass average molecular weight because strength is improved.

  The melt flow rate (MFR) of the styrene resin (B2) measured in accordance with JIS K7210 (temperature 200 ° C., load 5 kgf) is preferably 0.1 to 30 g / 10 minutes, 0.5 More preferably, it is ˜25 g / 10 minutes. If the MFR is less than 0.1 g / 10 minutes, the fluidity may be lowered, and if it exceeds 30 g / 10 minutes, the impact resistance tends to be lowered, which is not preferable.

  Examples of the method for producing the styrene resin (B2) include known methods such as an emulsion polymerization method, a solution polymerization method, a suspension polymerization method, and a bulk polymerization method.

  The content of the styrene resin (B2) is 0.2 to 12 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). When the content of the styrenic resin (B2) is less than 0.2 parts by mass, the water repellency is lowered, and when the content is more than 12 parts by mass, the surface appearance, heat resistance and strength are lowered. The content of the styrenic resin (B2) is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, further preferably 1.5 parts by mass or more, and particularly preferably 2 parts by mass or more. Preferably it is 10 mass parts or less, More preferably, it is 7 mass parts or less, Most preferably, it is 5 mass parts or less.

  Moreover, it is also preferable to contain both polyolefin resin (B1) and styrene resin (B2). In that case, the total content of polyolefin resin (B1) and styrene resin (B2) is polybutylene terephthalate. It is preferable that it is 0.2-12 mass parts with respect to 100 mass parts of resin (A), More preferably, it is preferable that it is 0.5-10 mass parts.

[Silicone compound (C)]
The silicone compound (C) used in the present invention is an organosilicon compound having a siloxane bond as a skeleton and an organic group or the like directly bonded to the silicon. As the organic group directly bonded to silicon, a methyl group, an ethyl group, a phenyl group, a vinyl group, a trifluoropropyl group, and a combination thereof are known, and these known silicone compounds can be used without any particular limitation. In addition, a substituent in which a part of the organic group has an epoxy group, an amino group, a fluorine-containing group, a polyether group, a carboxyl group, a mercapto group, an ester group, a chloroalkyl group, an alkyl group having 3 or more carbon atoms, a hydroxyl group, or the like Silicones substituted with can also be used.
The silicone compound (C) is preferably an organopolysiloxane such as dimethylpolysiloxane produced by hydrolysis and polycondensation of dimethyldichlorosilane and trimethylchlorosilane, methylphenylpolysiloxane, methylhydropolyenepolysiloxane, Examples thereof include silicone oils such as oxyalkylene dimethylpolysiloxane, modified silicone oils such as alkyl-modified, amino-modified, carboxyl-modified, alkylaralkyl-modified, and epoxy-modified. Of these, dimethylpolysiloxane is particularly preferred.

  The silicone compound (C) used in the present invention preferably has a high viscosity at 25 ° C. of 1,000,000 cSt or more. Those having a viscosity of less than 1,000,000 cSt are not preferable in terms of measurement stability and long-term retention of water repellency.

  Content of a silicone compound (C) is 0.5-10 mass parts with respect to 100 mass parts of polybutylene terephthalate resins (A). When the content of the silicone compound (C) is less than 0.5 parts by mass, the water repellency is lowered, and when the content is more than 10 parts by mass, surface layer peeling tends to occur. The content of the silicone compound (C) is preferably 1 part by mass or more, more preferably 1.5 parts by mass or more, further preferably 2 parts by mass or more, preferably 9 parts by mass or less, more preferably 8 parts by mass. Hereinafter, it is more preferably 7 parts by mass or less.

The total content of the polyolefin resin (B1) and the styrene resin (B2) (both components together (B)) and the silicone compound (C) is 1 to 15 parts by mass. From the viewpoint of aqueousness, it is preferably 1 part by mass or more, more preferably 2 parts by mass or more, particularly preferably 4 parts by mass or more, more preferably 13 parts by mass or less, still more preferably 10 parts by mass or less, particularly preferably. Is 5 parts by mass or less.
The mass ratio (B) / (C) of the polyolefin resin and styrene resin (B) to the silicone compound (C) is 25/75 to 60/40 from the viewpoint of appearance and water repellency. Preferably, it is 40/60 to 60/40.

In the present invention, the silicone compound (C) is blended as a mixture in the form of a masterbatch previously mixed with the above-described polyolefin resin (B1) or styrene resin (B2), thereby improving the dispersibility of the silicone and water repellency. It is preferable because it is easy to improve. In this case, the mass ratio (B) / (C) of the polyolefin resin and styrene resin (B) to the silicone compound (C) is preferably 25/75 to 60/40 from the viewpoint of workability. More preferably, it is 40/60-60/40.
Use of a polyolefin resin (B1) or styrene resin (B2) obtained by graft polymerization of a silicone compound is not preferable from the viewpoint of water repellency and appearance.

[Inorganic filler (D)]
As the inorganic filler (D) contained in the polybutylene terephthalate resin composition of the present invention, various inorganic fillers can be used. Among them, white inorganic particles are preferable, for example, titanium oxide, barium sulfate, zinc sulfide. , Zinc oxide, silica, calcium carbonate, aluminum silicate, calcium phosphate, alumina, magnesium carbonate, zinc carbonate, antimony oxide, cerium oxide, zirconium oxide, tin oxide, lanthanum oxide, magnesium oxide, barium carbonate, zinc carbonate, basic lead carbonate , Calcium sulfate, lead sulfate, mica, talc, clay, kaolin, lithium fluoride and calcium fluoride can be used, among which titanium oxide, barium sulfate, zinc sulfide, zinc oxide and zinc sulfate are preferable, More preferred are titanium oxide, zinc sulfide or zinc oxide. Ku, in particular titanium oxide are preferable.
The titanium oxide may be either anatase type or rutile type. In addition, the particle surface may be subjected to an inorganic treatment such as alumina or silica, or may be subjected to an organic treatment such as silicone or alcohol.

  In addition, the inorganic filler (D) may be used after its surface is treated with a silane coupling agent or a titanium coupling agent. For example, a surface treated with a silane compound such as vinyltriethoxysilane, 3-aminopropyltriethoxysilane, or 3-glycidoxypropyltriethoxysilane can be used.

  Content of an inorganic filler (D) is 0.5-10 mass parts with respect to 100 mass parts of polybutylene terephthalate resin (A), Preferably it is 1 mass part or more, More preferably, it is 1.5 mass part or more. Preferably, it is 5 parts by mass or less, more preferably 4 parts by mass or less, and further preferably 3 parts by mass or less. When the content is 0.5 parts by mass or more, the whiteness of the resulting resin composition can be improved, and by 10 parts by mass or less, high strength and surface smoothness can be obtained. Become.

[Flame Retardant (E)]
The polybutylene terephthalate resin composition of the present invention preferably contains a flame retardant, particularly preferably a bromine flame retardant.

  Brominated flame retardants include brominated polycarbonate resin, brominated epoxy compound, brominated phenoxy resin, brominated polyphenylene ether resin, brominated polycarbonate oligomer, brominated polystyrene resin, brominated bisphenol A, glycidyl brominated bisphenol A, penta Various bromine compounds such as bromobenzyl polyacrylate and brominated imide (brominated phthalimide and the like) can be mentioned, but brominated polystyrene, brominated epoxy compounds and brominated aromatic polycarbonate oligomers are preferable.

Examples of the brominated polystyrene include brominated polystyrene containing a repeating unit represented by the following general formula (1).
(In formula (1), t is an integer of 1 to 5, and n is the number of repeating units.)

Brominated polystyrene may be either brominated polystyrene or produced by polymerizing brominated styrene monomers, but the polymerized brominated styrene is free bromine (atom) This is preferable because the amount is small.
In the general formula (1), the CH group to which brominated benzene is bonded may be substituted with a methyl group. The brominated polystyrene may be a copolymer obtained by copolymerizing another vinyl monomer. Examples of the vinyl monomer in this case include styrene, α-methylstyrene, acrylonitrile, methyl acrylate, butadiene, and vinyl acetate. Moreover, brominated polystyrene may be used as a single substance or a mixture of two or more different structures, and may contain units derived from styrene monomers having different numbers of bromines in a single molecular chain.

  Specific examples of brominated polystyrene include, for example, poly (4-bromostyrene), poly (2-bromostyrene), poly (3-bromostyrene), poly (2,4-dibromostyrene), poly (2,6 -Dibromostyrene), poly (2,5-dibromostyrene), poly (3,5-dibromostyrene), poly (2,4,6-tribromostyrene), poly (2,4,5-tribromostyrene) , Poly (2,3,5-tribromostyrene), poly (4-bromo-α-methylstyrene), poly (2,4-dibromo-α-methylstyrene), poly (2,5-dibromo-α- Methyl (styrene), poly (2,4,6-tribromo-α-methylstyrene), poly (2,4,5-tribromo-α-methylstyrene) and the like, and poly (2,4,6-tribromostyrene). And poly (2,4,5-tribromostyrene) and polydibromostyrene and polytribromostyrene containing an average of 2 to 3 bromine groups in the benzene ring are particularly preferably used.

In the brominated polystyrene, the number n (average polymerization degree) of the repeating units in the general formula (1) is preferably 30 to 1,500, more preferably 150 to 1,000, particularly 300 to 800. Is preferred. If the average degree of polymerization is less than 30, blooming tends to occur. On the other hand, if it exceeds 1,500, poor dispersion tends to occur and the mechanical properties tend to deteriorate. The mass average molecular weight (Mw) of brominated polystyrene is preferably 5,000 to 500,000, more preferably 10,000 to 500,000, and 10,000 to 300,000. More preferably, it is particularly preferably 30,000 to 80,000.
In particular, in the case of the brominated product of polystyrene described above, the mass average molecular weight (Mw) is preferably 50,000 to 70,000, and in the case of brominated polystyrene by a polymerization method, the mass average molecular weight (Mw) is 10 It is preferable that it is about 3,000-30,000. In addition, a mass average molecular weight (Mw) can be calculated | required as a value of standard polystyrene conversion by a gel permeation chromatography (GPC) measurement.

Moreover, as a brominated epoxy compound, the bisphenol A brominated epoxy compound represented by tetrabromobisphenol A epoxy is mentioned, for example.
The molecular weight of the brominated epoxy compound is not particularly limited. An oligomer may be used in combination as the brominated epoxy compound. When an oligomer is used in combination as the brominated epoxy compound, for example, by using about 0 to 50% by mass of an oligomer having a molecular weight of 5000 or less, flame retardancy, releasability and fluidity can be satisfied.

As the brominated aromatic polycarbonate oligomer, particularly brominated aromatic polycarbonate oligomer obtained by reacting (condensation polymerization) tetrabromobisphenol A with phosgene or carbonic acid diester using an appropriate molecular weight regulator is particularly preferable. preferable. Further, it may be a copolymer type in which a part of tetrabromobisphenol A is substituted with another dihydric phenol, and the dihydric phenol described in the above aromatic polycarbonate resin is used as the other dihydric phenol. Furthermore, bisphenol A is preferable from the viewpoints of yield during synthesis, ease of solidification, and high versatility (price).
When such a brominated aromatic polycarbonate oligomer has a degree of polymerization of 1, it tends to bleed out from the molded product at the time of molding, and on the other hand, when the degree of polymerization increases, it becomes difficult to obtain satisfactory fluidity. The preferred degree of polymerization is 2-15.

  The bromine flame retardant preferably has a bromine concentration of 52 to 75% by mass, more preferably 56 to 73% by mass, and even more preferably 57 to 72% by mass. By setting the bromine concentration in such a range, it is easy to keep good flame retardancy.

The flame retardant (E) may be used alone or in combination of two or more.
It is preferable that content of a flame retardant (E) is 1-30 mass parts with respect to 100 mass parts of polybutylene terephthalate resins. When the content is less than 1 part by mass, it is difficult to obtain a sufficient flame retardant effect, and when it exceeds 30 parts by mass, the mechanical strength tends to decrease. The preferable content of the flame retardant (E) is more preferably 3 parts by mass or more, further preferably 4 parts by mass or more, and particularly preferably 5 parts by mass or more with respect to 100 parts by mass of the polybutylene terephthalate resin. More preferably, it is 25 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less.

[Antimony flame retardant aid (F)]
The polybutylene terephthalate resin composition of the present invention preferably contains an antimony flame retardant aid (F), and includes antimony trioxide (Sb ₂ O ₃ ), antimony pentoxide (Sb ₂ O ₅ ), and antimonic acid. Sodium and the like can be mentioned, but antimony pentoxide tends to cause a drop in impact resistance, and antimony trioxide is particularly preferable.
The content of the antimony flame retardant auxiliary (F) is preferably 1 to 15 parts by mass, more preferably 2 parts by mass or more, and further 3 parts by mass with respect to 100 parts by mass of the polybutylene terephthalate resin (A). It is above, More preferably, it is 13 mass parts or less, More preferably, it is 10 mass parts or less. If the content is less than 1 part by mass, the flame retardancy tends to decrease, and if it exceeds 15 parts by mass, mechanical properties such as impact resistance tend to decrease.

  The mass concentration of the bromine atom derived from the brominated flame retardant and the antimony atom derived from the antimony flame retardant auxiliary compound (F) in the polybutylene terephthalate resin composition of the present invention is usually 3 to 25 mass in total. %, More preferably 4 to 22% by mass, still more preferably 5 to 16% by mass, and particularly preferably 6 to 15% by mass. If it is less than 3% by mass, the flame retardancy tends to decrease, and if it exceeds 25% by mass, the mechanical strength and tracking resistance may decrease. The mass ratio (Br / Sb) of bromine atoms and antimony atoms is preferably 0.3 to 5, and more preferably 0.3 to 4.

[Stabilizer]
It is preferable that the polybutylene terephthalate-based resin composition of the present invention further contains a stabilizer because it has effects of improving thermal stability and preventing deterioration of mechanical strength, transparency, and hue. As the stabilizer, a phosphorus stabilizer, a phenol stabilizer, and a thioether stabilizer are preferable.

  As a phosphorus stabilizer, an organic phosphate compound, an organic phosphite compound, or an organic phosphonite compound is preferable.

The organic phosphate compound is preferably the following general formula:
(R ¹ O) _3-n P (═O) OH _n
(In the formula, R ¹ is an alkyl group or an aryl group, and may be the same or different. N represents an integer of 0 to 2.)
It is a compound represented by these. More preferably, R ¹ is a long-chain alkyl acid phosphate compound having 8 to 30 carbon atoms. Specific examples of the alkyl group having 8 to 30 carbon atoms include octyl group, 2-ethylhexyl group, isooctyl group, nonyl group, isononyl group, decyl group, isodecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group, A hexadecyl group, an octadecyl group, an eicosyl group, a triacontyl group, etc. are mentioned.

  Examples of the long chain alkyl acid phosphate include octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, lauryl acid phosphate, octadecyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate Acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid phosphate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, geo Chill acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phosphate, diphenyl acid phosphate, and a bis-nonylphenyl acid phosphate, or the like.

As the organic phosphite compound, preferably, the following general formula:
^{R 2 O-P (OR 3} ) (OR 4)
Wherein R ² , R ³ and R ⁴ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and at least one of R ² , R ³ and R ⁴ One is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphite compound include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris (tridecyl). ) Phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite Hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite), tetra (tridecyl) 4,4′-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, di Lauryl pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite Phytopolymer, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite Phosphite, 2,2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

The organic phosphonite compound is preferably the following general formula:
R ⁵ -P (OR ⁶ ) (OR ⁷ )
(Wherein R ⁵ , R ⁶ and R ⁷ are each a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and at least one of R ⁵ , R ⁶ and R ⁷ ) One is an aryl group having 6 to 30 carbon atoms.)
The compound represented by these is mentioned.

  Examples of the organic phosphonite compound include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2, -Di-tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, and tetrakis (2,6- And di-tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  Examples of the phenol-based stabilizer include pentaerythritol tetrakis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), octadecyl-3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate, thiodiethylenebis (3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate), pentaerythritol tetrakis (3- (3,5-di-neopentyl-4-hydroxyphenyl) ) Propionate) and the like.

  Examples of the thioether stabilizer include didodecyl thiodipropionate, ditetradecyl thiodipropionate, dioctadecyl thiodipropionate, pentaerythritol tetrakis (3-dodecyl thiopropionate), pentaerythritol tetrakis (3- Lauryl thiopropionate), thiobis (N-phenyl-β-naphthylamine), 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, tetramethylthiuram monosulfide, tetramethylthiuram disulfide, nickel dibutyldithiocarbamate, nickel isopropylxanthane Tate, trilauryl trithiophosphite and the like can be mentioned.

  One type of stabilizer may be contained, or two or more types may be contained in any combination and ratio.

  Content of a stabilizer is 0.001-1 mass part normally with respect to 100 mass parts of polybutylene terephthalate resins (A). When the content of the stabilizer is less than 0.001 part by mass, it is difficult to expect an improvement in the thermal stability of the resin composition, and when the amount exceeds 1 part by mass, a decrease in molecular weight or a deterioration in hue tends to occur. There is a tendency that the amount of silver becomes excessive and the occurrence of silver and the deterioration of hue are more likely to occur. The content of the stabilizer is more preferably 0.001 to 0.7 parts by mass, and still more preferably 0.005 to 0.5 parts by mass.

[Release agent]
The polybutylene terephthalate resin composition of the present invention preferably further contains a release agent. As the release agent, known release agents usually used for polybutylene terephthalate resins can be used, and among them, polyolefin compounds and fatty acid ester compounds are particularly preferable.

  Examples of the polyolefin compound include paraffin wax, polyethylene wax, and oxidized polyethylene wax. Among them, those having a mass average molecular weight of 700 to 10,000, more preferably 900 to 8,000 are preferable.

  Examples of the fatty acid ester compounds include fatty acid esters such as glycerin fatty acid esters and sorbitan fatty acid esters, and partially saponified products thereof. Preferred are mono- or di-fatty acid esters. Specifically, glycerol monostearate, glycerol monobehenate, glycerol dibehenate, glycerol-12-hydroxy monostearate, sorbitan monobehenate, etc. are mentioned.

  It is preferable that content of a mold release agent is 0.05-2 mass parts with respect to 100 mass parts of polybutylene terephthalate resin (A). If the amount is less than 0.05 parts by mass, the surface property tends to be lowered due to defective mold release at the time of melt molding. The surface of the product may be cloudy. The content of the release agent is preferably 0.07 to 1.5 parts by mass, more preferably 0.1 to 1.0 parts by mass.

[Other ingredients]
The polybutylene terephthalate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Such additives include anti-dripping agents, UV absorbers, dyes and pigments, carbon black, fluorescent brighteners, antistatic agents, antifogging agents, lubricants, antiblocking agents, fluidity improvers, plasticizers, dispersions Agents, antibacterial agents and the like.

  In addition, the polybutylene terephthalate resin composition in the present invention can contain other thermoplastic resins other than the polybutylene terephthalate resin in a range that does not significantly impair the effects of the present invention. Specific examples of other thermoplastic resins include polycarbonate resins, polyacetal resins, polyamide resins, polyphenylene oxide resins, polyphenylene sulfide resins, polysulfone resins, polyether sulfone resins, polyetherimide resins, polyether ketone resins, and the like. Is mentioned.

[Method for Producing Resin Composition]
As a manufacturing method of the polybutylene terephthalate-type resin composition of this invention, it can carry out in accordance with the conventional method of polybutylene terephthalate-type resin composition preparation. Usually, the components and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Also, the resin composition of the present invention can be prepared by mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Furthermore, a masterbatch is prepared by melting and kneading a part of the polybutylene terephthalate resin with a part of the other ingredients, and then blending the remaining polybutylene terephthalate resin and other ingredients to the melt. You may knead. In particular, as described above, the silicone compound (C) is preferably blended as a mixture in the form of a masterbatch previously mixed with the polyolefin resin (B1) or the styrene resin (B2).

  The heating temperature at the time of melt kneading can be appropriately selected from the range of usually 220 to 300 ° C. If the temperature is too high, decomposition gas is likely to be generated, which may cause opacity. Therefore, it is desirable to select a screw configuration in consideration of shear heat generation. In order to suppress decomposition during kneading or molding in the subsequent process, it is desirable to use an antioxidant or a heat stabilizer.

[Molded body]
The polybutylene terephthalate resin composition of the present invention is used after being molded into various molded articles.
The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the polybutylene terephthalate type-resin composition can be employ | adopted arbitrarily. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, Examples thereof include a blow molding method. Among these, it is preferable to use an injection molding method.
In particular, the polybutylene terephthalate resin composition of the present invention is characterized by excellent meterability during molding.

The polybutylene terephthalate resin composition of the present invention has a high water droplet contact angle, high antifouling properties and water repellency, excellent scratch resistance, and excellent appearance, surface gloss and dimensional stability of the molded product. In addition, it is excellent in measuring properties at the time of molding.
The polybutylene terephthalate resin composition of the present invention has a high degree of water repellency, and the contact angle between the flat plate and water droplets when 0.5 μl of pure water is dropped on the surface of the flat plate-shaped product is preferably 85 ° or more. Can be achieved. In addition, the polybutylene terephthalate resin composition of the present invention enables a high degree of flame retardancy by containing a flame retardant. In the combustion test UL-94 test, the test piece has a thickness of 1.6 mm and a V-2 level. Can be achieved.
The molded article of the polybutylene terephthalate resin composition of the present invention can be suitably used for members for sanitary equipment such as a toilet seat, a wash basin, a hand basin, and a basin bowl.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not construed as being limited to the following examples.
In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.
In the following Examples, Reference Examples and Comparative Examples, the components used are as shown in Table 1 below.

(Examples 1-4, Reference Example 1, Comparative Examples 1-7)
Each component described in Table 1 is blended so as to have a blending ratio (part by mass) described in Table 2, and a twin screw extruder (“TEX-30α” manufactured by Nippon Steel Works, L / D = 52) is used. Then, pellets of the extruded resin composition were produced at a barrel set temperature of 250 ° C. and a rotation speed of 200 rpm. The characteristics of the obtained pellets were evaluated for test pieces that were injection molded at a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (Nex80-9E manufactured by Nissei Plastic Industry Co., Ltd.). In molding, the resin composition was dried at 120 ° C. for 6 to 8 hours until immediately before the molding.

<Evaluation method>
Each evaluation method is as follows.
(1) Water repellency On the surface of a plate-shaped molded product having a size of 100 × 100 × 3 mm, using an Elmer Goniometer manufactured by Elmer, based on ASTM D-5725, under conditions of a relative humidity of 65% and a temperature of 23 ° C. The contact angle (unit: °) between the flat plate and water droplets when 0.5 μl of pure water was dropped was measured.
The contact angle was determined as “◎” when the contact angle was 93 ° or more, “◯” when 91 ° or more and less than 93 °, “Δ” when 88 ° or more and less than 91 °, and “×” when less than 88 °.

(2) Appearance The presence or absence of peeling of the above-mentioned size 100 × 100 × 3 mm flat molded product was visually observed and evaluated according to the following criteria.
○: No peeling, Δ: There is a small amount of peeling, ×: The peeling is conspicuous In addition, for the above plate-shaped molded product, a spectrocolorimeter (CM-3600d manufactured by Konica Minolta) is used and regular reflection at a wavelength of 550 nm The rate (unit:%) was measured. A specular reflectance of 90% or more is acceptable.
In Table 2, the criteria for appearance determination are as follows.
×: Evaluation of peeling is x or Regular reflection rate is less than 90% ○: Regular reflection rate is 90% or more and peeling evaluation is Δ ◎: Regular reflection rate is 90% or more and peeling evaluation Are the ones

(3) Meterability After the pellets obtained above were dried at 120 ° C. for 5 hours, using an injection molding machine (“J85AD” manufactured by Nippon Steel Co., Ltd.), weighing 65 mm, screw rotation speed 100 rpm, back pressure Measure the measurement time (unit: seconds) required from the start of measurement to completion when injection molding an ISO test piece under the conditions of 5 MPa, cylinder temperature 250 ° C., mold temperature 80 ° C. did.
○: Weighing time 15 seconds or less △: Weighing time more than 15 seconds to less than 20 seconds ×: Weighing time 20 seconds or more

(4) Secondary shrinkage evaluation The above-mentioned flat molded product having a size of 100 × 100 × 3 mm is left in a hot air oven at a temperature of 150 ° C. for 3 hours, and the dimensional change (unit:%) before and after is measured. A change of less than 0.1% was judged as a good “◯”, and a change of 0.1% or more was judged as a defective “×”.

(5) Flame retardancy (UL-94)
Combustion test piece of size 125 x 12.5 mm x 1.6 mmt is molded and left for 48 hours or longer at 23 ° C ± 2 ° C and humidity 50% ± 5%, then difficult to comply with UL-94 standard Flammability was evaluated.

(6) Scratch resistance The surface of the above-mentioned flat molded product having a size of 100 × 100 × 3 mm is scratched by applying a load of 150 g with a needle-shaped molded product having a tip of 1 mmφ molded from bisphenol A-type polycarbonate, Observe visually, the following criteria:
Evaluation was made with “◯” for scars, “Δ” for scars, and “x” for scars.
The above evaluation results are shown in Table 2 below.

  The polybutylene terephthalate resin composition of the present invention has a high water droplet contact angle, high antifouling properties and water repellency, and excellent appearance and dimensional stability of the molded product. Since it can be suitably used as a member for sanitary equipment such as a bowl, the industrial utility is very high.

Claims (6)

  With respect to 100 parts by mass of the polybutylene terephthalate resin (A) having a melting point of 215 ° C. or more, 0.2 to 12 parts by mass of the polyolefin resin or styrene resin (B) and 0.5 to 10 mass of the silicone compound (C). And 0.5 to 10 parts by mass of the inorganic filler (D), and a polybutylene terephthalate resin composition.   The polybutylene terephthalate resin composition according to claim 1, wherein the total content of the polyolefin resin and the styrene resin (B) and the silicone compound (C) is 1 to 15 parts by mass.   The polybutylene terephthalate according to claim 1 or 2, wherein the mass ratio (B) / (C) of the polyolefin resin and styrene resin (B) to the silicone compound (C) is 25/75 to 60/40. -Based resin composition.   The polybutylene terephthalate resin composition according to any one of claims 1 to 3, wherein the inorganic filler (D) is selected from titanium oxide, zinc sulfide, and zinc oxide.   A molded article for sanitary equipment comprising the polybutylene terephthalate resin composition according to any one of claims 1 to 4.   The method for producing a polybutylene terephthalate resin composition according to claim 1, wherein the polybutylene terephthalate resin (A) is blended as a mixture of a polyolefin resin or a styrene resin (B) and a silicone compound (C) in advance.