JP5710864B2 - Polybutylene terephthalate resin composition and molded article - Google Patents

Description

  The present invention relates to a polybutylene terephthalate resin composition for molding a ceramic-like resin molded body, and a molded body formed by molding the resin composition.

  Resin molded products with ceramic-like luster are used in various fields such as tableware, face-washing instruments, flower pots and other containers, flooring materials, wall materials, face-washing bowls and other household equipment, and table tops, picture frames, decorative items such as dolls, etc. Widely used.

  Recently, a resin composition containing a polybutylene terephthalate resin has become mainstream as a resin composition for obtaining a ceramic-like resin molded body. As a polybutylene terephthalate-based resin composition for obtaining a ceramic-like resin molded body, for example, a resin composition comprising a thermoplastic polybutylene terephthalate resin, a polyethylene terephthalate resin, and barium sulfate is disclosed (Patent Document 1).

  According to the polybutylene terephthalate-based resin composition described in Patent Document 1, the drawbacks of the conventional resin composition for obtaining a ceramic-like resin molded article are eliminated, and the appearance, gloss, and chemical resistance are excellent while being made of resin. It is said to have sex. However, a molded body obtained by molding the resin composition described in Patent Document 1 has a problem that the surface hardness is not sufficient and is easily damaged. Therefore, from 20 to 40% by weight of thermoplastic polybutylene terephthalate resin, from 5 to 25% by weight of thermoplastic polyethylene terephthalate resin, from 5 to 25% by weight of methacrylic resin, and from 30 to 50% by weight of barium sulfate. A polybutylene terephthalate-based resin composition is disclosed (Patent Document 2).

According to the polybutylene terephthalate resin composition described in Patent Document 2, it is possible to provide a polybutylene terephthalate resin composition that constitutes a molded article having the sense of weight, texture, gloss, and surface hardness of ceramics. ing.
JP 2002-332396 A JP 2006-233066 A

  The polybutylene terephthalate-based resin composition described in Patent Document 2 is said to provide a ceramic-like resin molded body. However, there is a demand for an article having an appearance similar to that of earthenware.

  The present invention has been made in order to solve the above-mentioned problems, and its object is to provide a ceramic-like appearance having an appearance very similar to that of ceramics while maintaining the physical properties required of a ceramic-like resin molded body such as a surface hardness that is hardly damaged. An object of the present invention is to provide a polybutylene terephthalate resin composition capable of molding a resin molded body.

  The inventors of the present invention have made extensive studies to solve the above problems. As a result, (A) a thermoplastic polybutylene terephthalate resin, (B) a thermoplastic polyethylene terephthalate resin, (C) a copolymer containing a repeating unit derived from acrylonitrile and a repeating unit derived from styrene, A polybutylene terephthalate resin composition comprising a copolymer having a copolymerization ratio (acrylonitrile: styrene) in a molar ratio of 5: 5 to 7: 3, and (D) an inorganic filler having a Mohs hardness of 2.0 or more. The present inventors have found that the above-mentioned problems can be solved by using the present invention, and have completed the present invention. More specifically, the present invention provides the following.

  (1) a copolymer comprising (A) a thermoplastic polybutylene terephthalate resin, (B) a thermoplastic polyethylene terephthalate resin, (C) a repeating unit derived from acrylonitrile and a repeating unit derived from styrene, A polybutylene terephthalate resin composition comprising a copolymer having a copolymerization ratio (acrylonitrile: styrene) in a molar ratio of 5: 5 to 7: 3, and (D) an inorganic filler having a Mohs hardness of 2.0 or more. object.

  (2) The polybutylene terephthalate resin composition according to (1), wherein the component (C) is a copolymer further containing a repeating unit derived from methyl methacrylate.

  (3) The polybutylene terephthalate resin composition according to (1) or (2), wherein the content of the component (C) is 30 to 150 parts by mass with respect to 100 parts by mass of the component (A). .

  (4) The component (D) includes at least one selected from the group consisting of kaolin, wollastonite, titanium oxide, barium sulfate, calcium carbonate, and mica, according to any one of (1) to (3). Polybutylene terephthalate resin composition.

  (5) A pottery-like molded article obtained by molding the polybutylene terephthalate resin composition according to any one of (1) to (4) and having a pencil hardness of F or more.

  According to the present invention, a copolymer comprising (A) a thermoplastic polybutylene terephthalate resin, (B) a thermoplastic polyethylene terephthalate resin, (C) a repeating unit derived from acrylonitrile and a repeating unit derived from styrene. A polybutylene terephthalate system comprising a copolymer having a copolymerization ratio (acrylonitrile: styrene) of 5: 5 to 7: 3 in molar ratio and (D) an inorganic filler having a Mohs hardness of 2.0 or more By using the resin composition, it is possible to obtain a pottery-like resin molded article having an appearance very similar to that of pottery while maintaining properties such as surface hardness that are not easily damaged.

  Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within the scope of the object of the present invention. . In addition, although description may be abbreviate | omitted suitably about the location where description overlaps, the summary of invention is not limited.

  The polybutylene terephthalate resin composition of the present invention comprises (A) a thermoplastic polybutylene terephthalate resin, (B) a thermoplastic polyethylene terephthalate resin, (C) a repeating unit derived from acrylonitrile, and a repeating unit derived from styrene. A copolymer having a copolymerization ratio (acrylonitrile: styrene) in a molar ratio of 5: 5 to 7: 3, and (D) an inorganic filler having a Mohs hardness of 2.0 or more, It is characterized by including. Hereinafter, the polybutylene terephthalate resin composition of the present invention will be described.

<(A) Thermoplastic polybutylene terephthalate resin>
(A) The thermoplastic polybutylene terephthalate resin is composed of at least a polymerization component of terephthalic acid (terephthalic acid or an ester-forming derivative thereof) and alkylene glycol (1,4-butanediol) having 4 carbon atoms or an ester-forming derivative thereof. Polybutylene terephthalate resin.

  Such thermoplastic polybutylene terephthalate resin (PBT resin) is not limited to homopolybutylene terephthalate. For example, butylene terephthalate is 50% by mass or more (for example, 55% by mass to 100% by mass), preferably 60% by mass or more (for example, 65% by mass to 100% by mass), more preferably 70% by mass or more (for example, from 75% by mass). It may be a copolymer containing about 100% by mass).

  Examples of the copolymerizable monomer in the copolyester (butylene terephthalate copolymer or modified PBT resin) (hereinafter sometimes simply referred to as a copolymerizable monomer) include dicarboxylic acid components other than terephthalic acid, 1,4-butane. Examples include diols other than diols, oxycarboxylic acid components, and lactone components. The copolymerizable monomers can be used alone or in combination of two or more.

Dicarboxylic acids (or dicarboxylic acid components or dicarboxylic acids) include aliphatic dicarboxylic acids (eg, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecane dicarboxylic acids, _C 4 _{-C 40} dicarboxylic acids such as dimer acid, preferably _C 4 _{-C 14} dicarboxylic acids), alicyclic dicarboxylic acid component (e.g., hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, _C 8 _{-C 12} dicarboxylic acids such as himic acid), an aromatic dicarboxylic acid component other than terephthalic acid (e.g., phthalic acid, naphthalene dicarboxylic acids such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyl Dicarboxylic acid, 4,4'-diphe Carboxymethyl ether dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl ketone _C 8 _{-C 16} dicarboxylic acids such as dicarboxylic acids), or reactive derivatives thereof (e.g., lower alkyl esters (dimethyl phthalate and C ₁ -C ₄ alkyl esters of phthalic acid or isophthalic acid, such as dimethyl isophthalate (DMI)), acid chloride, ester formable derivatives such as acid anhydrides) and the like.

Examples of the diol include aliphatic alkylene glycols other than 1,4-butanediol (for example, ethylene glycol, trimethylene glycol, propylene glycol, neopentyl glycol, hexanediol (1,6-hexanediol, etc.), octanediol ( 1,3-octanediol, etc.), lower alkylene glycol _(C 2 _{-C 12} alkylene glycol, such as decanediol, preferably _C 2 _{-C 10,} such as alkylene glycol), a polyoxyalkylene glycol [more oxy _C 2 -C ₄ glycols having an alkylene unit, for example, diethylene glycol, dipropylene glycol, di tetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.] Alicyclic diols (e.g., 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A), aromatic diol [for example, hydroquinone, resorcinol, _C 6 _{-C 14} aromatic and naphthalene diol Diols; biphenols (4,4′-dihydroxybiphenyl and the like); bisphenols; xylylene glycol and the like] and reactive derivatives thereof (such as ester-forming derivatives such as alkyl, alkoxy or halogen-substituted products).

  The thermoplastic polybutylene terephthalate resin is preferably a homopolyester (polybutylene terephthalate) and / or a copolymer thereof (polybutylene terephthalate copolyester), and the thermoplastic polybutylene terephthalate resin is a proportion of the copolymerizable monomer (modified amount). Is usually 45 mol% or less (for example, about 0 mol% to 35 mol%), more preferably 30 mol% or less (for example, about 0 mol% to about 30 mol%) of a homo or copolyester (particularly a homopolyester). There may be.

  In the copolymer, the ratio of the copolymerizable monomer can be selected, for example, from a range of about 0.01 mol% to 30 mol%, and is usually 1 mol% to 30 mol%, preferably 3 mol% to 25 mol. %, More preferably about 5 to 20 mol% (for example, 5 to 15 mol%). In addition, when a homopolyester (polybutylene terephthalate) and a copolymer (copolyester) are used in combination, the proportion of the homopolyester and the copolyester is such that the proportion of the copolymerizable monomer is relative to the total monomers. 0.1 mol% to 25 mol%), usually the former / the latter = 99/1 to 1/99 (mass ratio), preferably 95/5 to 5/95 (mass ratio), Preferably, it can select from the range of about 90/10-10/90 (mass ratio).

  The intrinsic viscosity (IV) of the thermoplastic polybutylene terephthalate resin is preferably 1.2 dL / g or less, and more preferably 1.0 dL / g or less. By blending thermoplastic polybutylene terephthalate resins having different intrinsic viscosities, for example, blending thermoplastic polybutylene terephthalate resins having an intrinsic viscosity of 1.2 dL / g and thermoplastic polybutylene terephthalate resins having an intrinsic viscosity of 0.8 dL / g May realize an intrinsic viscosity of 1.0 dL / g or less. In addition, intrinsic viscosity (IV) can be measured on conditions with a temperature of 35 degreeC in O-chlorophonol, for example. When a thermoplastic polybutylene terephthalate resin having an intrinsic viscosity in such a range is used, it is easy to efficiently provide sufficient toughness and reduce melt viscosity. If the intrinsic viscosity is too large, the melt viscosity at the time of molding becomes high, and in some cases, there is a possibility of causing poor resin flow and poor filling in the molding die.

  Moreover, the amount of terminal carboxyl groups is not particularly limited, but is preferably 50 meq / kg or less. More preferably, it is 30 meq / kg or less. When the amount of carboxyl end groups exceeds 30 meq / kg, strength reduction due to hydrolysis in a moist heat environment may increase. The amount of terminal carboxyl groups is measured, for example, by dissolving a ground sample of polybutylene terephthalate in benzyl alcohol at 215 ° C. for 10 minutes and then titrating with a 0.01N aqueous sodium hydroxide solution.

  The thermoplastic polybutylene terephthalate resin may be a commercially available product, and terephthalic acid or a reactive derivative thereof and 1,4-butanediol can be copolymerized with 1,4-butanediol if necessary. You may use what was manufactured by copolymerization (polycondensation) by transesterification, the direct esterification method, etc.

<(B) Thermoplastic polyethylene terephthalate resin>
In the present invention, a thermoplastic polyethylene terephthalate resin (hereinafter sometimes referred to as PET resin) is an essential component for making a ceramic-like appearance. By containing a thermoplastic polyethylene terephthalate resin in the polybutylene terephthalate resin composition of the present invention, the gloss of the molded article formed by molding the resin composition of the present invention is increased, and the appearance is close to that of earthenware.

  A thermoplastic polyethylene terephthalate resin is obtained by polycondensation reaction of a dicarboxylic acid component containing at least terephthalic acid or an ester-forming derivative thereof and a glycol component containing at least C 2 alkylene glycol (ethylene glycol) or an ester-forming derivative thereof. A thermoplastic polyethylene terephthalate resin, which is not limited to a homo-PET resin, but a copolymer (copolymerized PET) resin containing 60 mol% or more (especially about 75 mol% to 95 mol%) of ethylene terephthalate units. Good.

In the copolymerized PET resin, examples of the dicarboxylic acid component (comonomer component) other than terephthalic acid and its ester-forming derivatives include, for example, aromatic dicarboxylic acid components (C ₆ such as isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, and diphenyl ether dicarboxylic acid). -C including ₁₂ aryl dicarboxylic acid), aliphatic dicarboxylic acid component (e.g., succinic acid, adipic acid, azelaic acid, C ₅ -C ₁₀ cycloalkyl dicarboxylic acid such as sebacic acid), an aromatic hydroxycarboxylic acid (hydroxy acid, Examples thereof include hydroxynaphthoic acid and the like, and ester-forming derivatives thereof. Preferred dicarboxylic acid component (comonomer component), (C ₆ -C ₁₀ aryl dicarboxylic acids, especially isophthalic acid) aromatic dicarboxylic acid component, aliphatic dicarboxylic acid component (in particular adipic acid, azelaic acid, C, such as sebacic acid It contains ₆ -C ₁₂ alkyl dicarboxylic acids.

As glycol components (comonomer components) other than ethylene glycol, aliphatic diol components [for example, alkylene glycol (propylene glycol, trimethylene glycol, 1,3-butylene glycol, hexamethylene glycol, neopentyl glycol, 1,3-octane) C ₃ -C ₁₀ alkylene glycol such as diol, polyoxy C ₂ -C ₄ alkylene glycol such as diethylene glycol, triethylene glycol, dipropylene glycol, etc.), cycloaliphatic dimethanol, alicyclic diol such as hydrogenated bisphenol A, etc.) Aromatic diol component [bisphenol A, aromatic alcohol such as 4,4′-dihydroxybiphenyl, C ₂ -C ₄ alkylene oxide adduct of bisphenol A (for example, Bisphenol A ethylene oxide 2-mole adduct, bisphenol A propylene oxide 3-mole adduct, etc.), or ester-forming derivatives thereof. These glycol components can also be used alone or in combination of two or more.

Preferred glycol component (comonomer component), an aliphatic diol component (especially C ₃ -C ₆ alkylene glycol, polyoxy C ₂ -C ₃ alkylene glycol such as diethylene glycol, alicyclic diols such as cyclohexane dimethanol), and the. The homo-PET resin and the copolymerized PET resin can be used alone or in combination of two or more.
Furthermore, the comonomer unit of the copolymerized PET resin is at least one selected from aromatic dicarboxylic acid residues (particularly at least C _{3 to} C ₁₀ alkylene glycol residues, polyoxy C _{2 to} C ₃ alkylene glycol residues). The copolymerized PET resin includes isophthalic acid copolymerized PET resin (isophthalic acid modified PET resin).

  In addition, as PET resin, the branched structure thermoplastic PET resin obtained using an aromatic polyvalent carboxylic acid component and / or a polyol component can be used similarly to the branched PBT resin.

  The content of the thermoplastic polyethylene terephthalate resin (B) contained in the polybutylene terephthalate resin composition of the present invention is preferably 20 parts by mass to 100 parts by mass, more preferably 100 parts by mass of the component (A). Is preferably about 30 to 80 parts by mass. When the component (B) is less than 20 parts by mass, the surface appearance tends to be difficult to improve, and when the component (B) exceeds 100 parts by mass, degradation due to hydrolysis tends to occur.

<(C) Copolymer containing a repeating unit derived from acrylonitrile and a repeating unit derived from styrene>
The polybutylene terephthalate resin composition of the present invention contains a copolymer containing a repeating unit derived from acrylonitrile and a repeating unit derived from styrene. By including the component (C), a sufficient surface hardness can be imparted to the resin molded body obtained by molding the composition of the present invention, and a resin molded body that is hardly damaged can be obtained.

  In particular, when the content of the repeating unit derived from acrylonitrile is large, it is possible to obtain a resin molded body that easily imparts surface hardness to the obtained molded body and is hardly damaged. However, if the content of repeating units derived from acrylonitrile is too large, the resulting resin molded product tends to be colored yellow. Therefore, in the case of an application that needs to be white, by suppressing the content of repeating units derived from acrylonitrile, or by containing titanium oxide as described later, a resin molded body that is white and hardly damaged is obtained. I can do it.

  The copolymerization ratio (acrylonitrile: styrene) of the repeating unit derived from acrylonitrile and the repeating unit derived from styrene is preferably from 5: 5 to 7: 3, more preferably from 6: 4 to 7: 3. It is. If the copolymerization ratio (acrylonitrile: styrene) of the repeating unit derived from acrylonitrile and the repeating unit derived from styrene is within the above range, the compatibility with the component (A) is good and a good appearance can be obtained. Further, the surface hardness can be improved.

  The component (C) may further contain a repeating unit derived from methyl methacrylate for imparting surface hardness and the like that are hardly damaged and for suppressing yellowing. In particular, the molar ratio of the repeating unit derived from methyl methacrylate is preferably less than 1 with respect to the molar ratio 1 of the total amount of the repeating unit derived from acrylonitrile and the repeating unit derived from styrene. By including repeating units derived from methyl methacrylate at the above copolymerization ratio, the surface hardness of the resulting resin molded body can be improved, and a resin molded body that is less likely to be damaged can be obtained. When the derived repeating component is added at a molar ratio of 1 or more, the compatibility with the component (A) is lowered, the appearance is deteriorated, and it does not become ceramic.

  The content of the component (C) is preferably 30 parts by mass to 150 parts by mass, and more preferably 75 parts by mass to 150 parts by mass with respect to 100 parts by mass of the component (A). When the content of the component (C) greatly exceeds 150 parts by mass, a ceramic-like appearance cannot be obtained, and cracking of the molded product tends to occur due to a decrease in toughness. When the amount is small, the surface hardness is not improved and the pencil hardness F or higher is not achieved.

<(D) Inorganic filler>
The inorganic filler contained in the polybutylene terephthalate-based resin composition of the present invention is an essential component for making the resulting molded article into a ceramic. Further, the type of inorganic filler also affects the surface hardness of the molded body. For this reason, the Mohs hardness of the inorganic filler needs to be 2.0 or more. In addition, as long as the conditions of the Mohs hardness are satisfied, various fillers such as fibrous and non-fibrous (powder and plate) are used as the inorganic filler depending on the purpose.

  The Mohs hardness refers to a value obtained by rubbing a standard substance with a sample substance and measuring the hardness with or without scratches. Standard substances include talc, hardness 2, gypsum, hardness 3, calcite, hardness 4, fluorite, hardness 5, olivine, hardness 6, orthoclase, hardness 7, crystal, hardness 8 9 is corundum, and hardness 10 is diamond. If the Mohs hardness of the inorganic filler is 2.0 or more, it is preferable because sufficient surface hardness can be imparted to a molded body obtained by molding the polybutylene terephthalate resin composition of the present invention.

  Among such fillers, examples of the fibrous filler include glass fiber, irregular glass, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber, boron fiber, and potassium titanate fiber. It is not limited to.

  On the other hand, as the particulate filler, metals such as silica, quartz powder, glass beads, glass powder, calcium silicate, kaolin, clay, diatomaceous earth, wollastonite, iron oxide, titanium oxide, zinc oxide, alumina Examples include, but are not limited to, oxides, carbonates of metals such as calcium carbonate and magnesium carbonate, sulfates of metals such as calcium sulfate and barium sulfate, silicon carbide, silicon nitride, boron nitride and various metal powders. is not.

  Examples of the plate-like filler include mica and glass flakes, but are not limited thereto.

  The above inorganic fillers can be used alone or in combination of two or more. Of the above inorganic fillers, kaolin, wollastonite, titanium oxide, barium sulfate, calcium carbonate, and mica are preferable.

  In many cases, a ceramic-like resin molded body is required to have a white appearance. In order to make the resin molded body white, the polybutylene terephthalate resin composition may be colored with a general white pigment or dye used for titanium oxide or resin.

  The content of (D) in the polybutylene terephthalate-based resin composition of the present invention is preferably 50 to 250 parts by mass, more preferably 70 to 200 parts by mass with respect to 100 parts by mass of component (A). Part. The surface height is improved by the component (D), but when the content exceeds 250 parts by mass, the surface is rough and does not have a ceramic appearance. When the content of the component (D) is less than 50 parts by mass, the surface hardness may be insufficient.

<Other ingredients>
The polybutylene terephthalate resin composition of the present invention is blended with additives such as other resins, pigments, antioxidants, stabilizers, lubricants, mold release agents and flame retardants, as long as the effects of the present invention are not impaired. can do.

  Examples of antioxidants and stabilizers include phenolic (such as hindered phenols), amine (such as hindered amines), phosphorus, sulfur, hydroquinone, and quinoline antioxidants.

  Inorganic stabilizers include hydrotalcite, zeolite, and alkali metal or alkaline earth metal carboxylates (carbonates, organic carboxylates, etc.) and compounds having functional groups reactive to active hydrogen atoms (reactions) Stability stabilizers).

  Examples of the mold release agent include esters or partial esters of higher fatty acids and polyhydric alcohols, and polyolefin waxes. For example, pentaerythritol stearic acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, montanic acid ester, low molecular weight polyethylene wax and the like can be mentioned.

  Examples of the flame retardant include a halogen flame retardant, a phosphorus flame retardant, a nitrogen-containing flame retardant, a sulfur-containing flame retardant, a silicon-containing flame retardant, an alcohol flame retardant, and an inorganic flame retardant. As the flame retardant aid, antimony trioxide or antimony pentoxide antimony flame retardant aid or melamine derivatives such as melamine cyanurate may be used in combination.

  In addition, the polybutylene terephthalate resin composition may be hydrolyzed by hot water or water vapor to deteriorate the resin. Therefore, a reactive stabilizer may be added. The reactive stabilizer improves moisture and heat resistance and durability, and suppresses resin degradation due to hydrolysis.

  Examples of the reactive stabilizer include compounds having at least one functional group selected from a cyclic ether group, an acid anhydride group, an isocyanate group, an oxazoline group (ring), an oxazine group (ring), a carbodiimide group, and the like. It is done.

  The compound having a cyclic ether group includes a compound having an epoxy group or an oxetane group. Examples of the compound having an epoxy group include alicyclic compounds such as vinylcyclohexene dioxide, glycidyl ester compounds such as glycidyl ester of persic acid, glycidyl ether compounds (hydroquinone diglycidyl ether, biphenol diglycidyl ether, bisphenol-A diester). Glycidyl ether, etc.), glycidyl amine compounds, epoxy group-containing vinyl copolymers (eg, epoxidized polybutadiene, epoxidized diene monomer styrene copolymer, etc.), triglycidyl isocyanurate, epoxy-modified (poly) organosiloxane, etc. It is done.

  Examples of the compound having an oxetane group include oxetanyl ester compounds such as di [1-ethyl (3-oxetanyl)] methyl ester isophthalate and di [1-ethyl (3-oxetanyl)] methyl terephthalate, and oxetanyl ether compounds. {For example, alkyl oxetanyl compounds such as di [1-ethyl (3-oxetanyl)] methyl ether and 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, etc. Aryl oxetanyl compounds, aralkyl oxetanyl ether compounds such as 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, bisphenol-A di [1-ethyl (3-oxetanyl)] methyl ether, etc. Bispheno Type oxetane resins, mono- to poly [1-ethyl (3-oxetanyl)] methyl etherified phenol novolak and mono-to-poly [1-ethyl (3-oxetanyl)] methyl etherified cresol novolak, etc.} , 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyloxetane-modified oxetane-modified (poly) organosiloxane, and derivatives having the oxetanyl unit {for example, [1-ethyl (3-oxetanyl)] Alkyl oxetanylmethyl derivative {for example, [1-methyl (3-oxetanyl)] methyl derivative} corresponding to methyl derivative}.

  Examples of the compound having an oxazoline group include 2,2 ′-(1,3-phenylene) -bis (2-oxazoline) and 2,2 ′-(1,4-phenylene) -bis (2-oxazoline). And a vinyl resin having an oxazoline group (for example, a vinyl oxazoline-modified styrene resin).

  Examples of the compound having an oxazine group include bisoxazine compounds such as 2,2′-bis (5,6-dihydro-4H-1,3-oxazine).

  Examples of the compound having a carbodiimide group include polyarylcarbodiimides such as poly (phenylcarbodiimide) and poly (naphthylcarbodiimide), poly (2-methyldiphenylcarbodiimide), poly (2,6-diethyldiphenylcarbodiimide), and poly (2 , 6-diisopropyldiphenylcarbodiimide), poly (2,4,6-triisopropyldiphenylcarbodiimide), poly (2,4,6-trit-butyldiphenylcarbodiimide), and the like, poly [4,4 ' -Methylenebis (2,6-diethylphenyl) carbodiimide], poly [4,4'-methylenebis (2-ethyl-6-methylphenyl) carbodiimide], poly [4,4'-methylenebis (2,6-diisopropylphenol) Le) carbodiimide], poly [alkylene bis (alkyl or cycloalkyl aryl) carbodiimide such as poly [4,4'-methylenebis (2-ethyl-6-methyl-phenyl) carbodiimide]] and the like.

  These reactive stabilizers can be used alone or in combination of two or more. Of these reactive stabilizers, compounds having an epoxy group and compounds having a carbodiimide group are preferred. By adding the above functional stabilizer, deterioration of the resin due to hydrolysis can be suppressed, and heat and moisture resistance, durability and the like can be improved.

  The polybutylene terephthalate resin composition of the present invention is characterized by containing the component (A) to the component (D). In addition, in order to enhance the effects of imparting to an external resin molded body such as pottery and obtaining a resin molded body that is not easily damaged, the component (C) is derived from styrene, particularly a repeating unit derived from acrylonitrile. It is necessary to have a repeating unit, a repeating unit derived from methyl methacrylate, and an inorganic filler having a Mohs hardness of 2.0 or more in the component (D).

  The polybutylene terephthalate resin composition of the present invention can be formed into a molded body by a conventionally known molding method, for example, injection molding, injection compression molding, gas assist method injection molding, extrusion molding, multilayer extrusion molding, rotational molding, heat molding. It can be formed into an injection molded body, a tube, a sheet, a film, a pipe, a bottle or the like by a method such as press molding, blow molding or foam molding.

<Molded body>
The molded article of the present invention is formed by molding the polybutylene terephthalate resin composition of the present invention by the molding method described above. The molded article of the present invention has characteristics such as high surface hardness and gloss similar to pottery.

  As for the surface hardness of the molded article of the present invention, the pencil hardness measured by the method described in the examples is preferably F or more. When the surface hardness of the molded body is not less than the pencil hardness F, the molded body is very difficult to be damaged.

  The molded product of the present invention preferably has a surface gloss of 90% to 105%. If the surface gloss is 90% or less, the surface looks dull and cannot be obtained. On the other hand, if it is 105% or more, it will be reflected like a mirror and will not be ceramic.

  Since the molded product formed by molding the resin composition of the present invention has sufficient surface hardness in addition to its excellent ceramic-like texture and gloss, it should be used as a molded product having a ceramic-like appearance. Can do. Specifically, various containers such as tableware, toiletries, flowerpots, flooring materials, wall materials, bathroom bowls, bathtubs, toilet components and other household equipment, and table tops, picture frames, decorative items such as dolls, etc. Although it can be used for a use, it is not limited to this use.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Material>
(A) Polybutylene terephthalate resin (resin A-1): manufactured by Wintech Polymer Co., Ltd. Intrinsic viscosity 0.69 dL / g
(B) Polyethylene terephthalate resin (B-1): TRF (manufactured by Teijin Fibers Limited)
(C) Copolymer (C-1): (C-1) containing a repeating unit derived from acrylonitrile and a repeating unit derived from styrene is prepared by adding acrylonitrile, styrene, A molar ratio of methyl methacrylate monomer is 6: 3: 4 (acrylonitrile: styrene ratio is 66.7: 33.3), and a mixed solution of 35 parts by mass of ethylbenzene is used as a solvent with respect to 100 parts by mass of the total amount of monomers. The polymerization is carried out at an average residence time of 2.5 hours so that the polymerization rate is 55 to 60% at a polymerization temperature of 140 to 160 ° C., and the same amount of polymer solution as the supply amount is continuously taken out. Unreacted monomer and solvent were recovered under vacuum with a deaerator to obtain a powder copolymer.
In the following (C-2) to (C-4), methacrylic acid was not used, but acrylonitrile and styrene were used, and a copolymer was obtained by the same method so that the molar ratio became a ratio described later.
A copolymer (C-2) having a copolymerization ratio (acrylonitrile: styrene) of a repeating unit derived from acrylonitrile and a repeating unit derived from styrene in a molar ratio of 6: 4.
A copolymer (C-3) having a copolymerization ratio (acrylonitrile: styrene) of a repeating unit derived from acrylonitrile and a repeating unit derived from styrene in a molar ratio of 5: 5.
A copolymer (C-4) having a copolymerization ratio (acrylonitrile: styrene) of a repeating unit derived from acrylonitrile and a repeating unit derived from styrene in a molar ratio of 4: 6.
Polystyrene resin (C-5): HF77 (manufactured by PS Japan)
Polymethyl methacrylate (PMMA) (C-6): HT-121 (manufactured by Arkema)
Kaolin (D-1): TRANSLINK 445 (manufactured by BASF Catalysts LLC) Mohs hardness 6
Wollastonite (D-2): NYGLOS 8 (manufactured by NYCO) Mohs hardness 3.5-4.5
Barium sulfate (D-3): Variace B-55 (manufactured by Sakai Chemical Industry) Mohs hardness 2.5-3.5
Titanium oxide (D-4): TITON SR-1 (manufactured by Sakai Chemical Industry) Mohs hardness 6-8
Mica (D-5): MICRON WHITE 500S (manufactured by Hayashi Kasei) Mohs hardness 1

Each resin was dry blended at a mixing ratio shown in Tables 1 and 2 and melt-kneaded at 260 ° C. using a twin-screw extruder (manufactured by Nippon Steel Co., Ltd.) having a 30 mmφ screw. Pellets were obtained.
(Extrusion conditions)
Extruder: TEX 30
CT: 250 ° C
Extrusion rate: 10 kg / h

The obtained pellets were dried at 140 ° C. for 3 hours, and then a 70 mm × 50 mm × 3 mm molded piece was molded under the following molding conditions using an injection molding machine (“EC40” manufactured by Toshiba Machine Co., Ltd.).
(Molding condition)
Cylinder temperature: 260 ° C
Mold temperature: 90 ℃

<Evaluation of pencil hardness>
The surface hardness of the molded piece was scratched when a pencil of various hardness was pressed against the surface of the molded body at an angle of 90 degrees and scratched with a weight of 1 kg based on JIS K-5400 (General paint test method 6.14 Pencil scratch test). The hardness of the pencil was measured using a scratch hardness tester (HA-301 Clemens type scratch hardness tester (manufactured by Tester Sangyo Co., Ltd.)).

<Evaluation of surface gloss>
Based on JIS Z8741, the glossiness at an incident angle of 60 ° was measured using a portable gloss meter (“HG-246” manufactured by Suga Test Instruments Co., Ltd.). The measurement results are shown in Tables 1 and 2.

<Appearance evaluation>
It was judged by visual observation whether or not the surface of the molded piece had a ceramic appearance. “○” was evaluated for those with a ceramic appearance, and “×” was evaluated for those without. The evaluation results are shown in Tables 1 and 2.

  As is clear from the results in Table 1, it was confirmed that the molded articles of Examples had sufficient surface hardness, gloss, and ceramic appearance. On the other hand, the molded body of the comparative example did not satisfy the level required for any one of surface hardness, gloss, and ceramic appearance. Accordingly, it has been confirmed that the use of the composition of the present invention makes it particularly preferable as a molded article having a ceramic appearance.

  As is clear from Examples 9 and 10 and Comparative Example 5, the use of a copolymer containing a large number of repeating units derived from acrylonitrile results in a higher surface hardness and a molded body that is less susceptible to scratching. Was confirmed.

  As apparent from Examples 1 and 3, when the copolymer contains a repeating unit derived from methyl methacrylate, the surface hardness of the resulting molded body is extremely increased, and a molded body that is not easily damaged is obtained. Can do.

Claims (4)

(A) a thermoplastic polybutylene terephthalate resin;
(B) a thermoplastic polyethylene terephthalate resin;
(C) A copolymer containing a repeating unit derived from acrylonitrile, a repeating unit derived from styrene, and a repeating unit derived from methyl methacrylate, and a copolymer of a repeating unit derived from acrylonitrile and a repeating unit derived from styrene. A copolymer having a polymerization ratio (acrylonitrile: styrene) in a molar ratio of 5: 5 to 7: 3;
(D) at least one inorganic filler selected from the group consisting of kaolin, wollastonite, titanium oxide, and calcium carbonate,
Ipoh polybutylene terephthalate resin composition containing barium sulfate. (A) a thermoplastic polybutylene terephthalate resin;
(B) a thermoplastic polyethylene terephthalate resin;
(C) A copolymer containing a repeating unit derived from acrylonitrile, a repeating unit derived from styrene, and a repeating unit derived from methyl methacrylate, and a copolymer of a repeating unit derived from acrylonitrile and a repeating unit derived from styrene. A copolymer having a polymerization ratio (acrylonitrile: styrene) in a molar ratio of 5: 5 to 7: 3;
(D ′) an inorganic filler,
The component (D ′) is a polybutylene terephthalate resin composition that is at least one selected from the group consisting of kaolin, wollastonite, titanium oxide, and calcium carbonate. 3. The polybutylene terephthalate resin composition according to claim 1, wherein the content of the component (C) is 30 to 150 parts by mass with respect to 100 parts by mass of the component (A). A pottery-like molded article obtained by molding the polybutylene terephthalate-based resin composition according to any one of claims 1 to 3 and having a pencil hardness of F or more.