JP2006137867A - Alkali resistant and surface property favorable thermoplastic resin composition and molded article therefrom - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a thermoplastic resin composition which is excellent in rigidity, deflection temperature under load, and surface appearance, and is favorable in alkali resistance; and to provide a molded article from the same. <P>SOLUTION: The thermoplastic resin composition comprises an inorganic filler, wherein the inorganic filler comprises one inorganic filler having a particle size of 1-100 μm and another inorganic filler having that of less than 1 μm, and the inorganic filler having the particle size of less than 1 μm satisfies at least one of conditions (a) and (b) in respect of an equivalent circular area diameter (D) and at least one of conditions (c) and (d) in respect of a layer thickness (T), and the thermoplastic resin is a polybutylene terephthalate base resin used alone or an alloy with the other polybutylene terephthalate base resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition used for molding a product that requires smoothness and surface property, and an injection-molded article (particularly, a tableware article) molded using the resin composition.

  As tableware items such as trays used for transporting tableware and tableware, etc., tableware items using thermosetting resin and molded by the SMC method have been used. In the midst of increasing demand, there is an increasing demand for tableware using thermoplastic resins.

  In general, tableware using a polypropylene resin has a problem in heat resistance, and a tableware using a polycarbonate resin has a problem of elution of environmental hormones typified by bisphenol A. Under such circumstances, a tableware using a thermoplastic polyester resin (particularly, polyethylene terephthalate) reinforced with an inorganic filler has been studied.

  For the purpose of increasing the rigidity and heat resistance of the thermoplastic resin, various inorganic fillers such as glass fibers, carbon fibers, fibrous inorganic materials such as potassium titanate whiskers, glass flakes, glass beads, talc, mica, kaolin, etc. Compounding of particulate inorganic substances is performed. However, when incinerating a molded product using a glass material such as glass fiber or glass beads, there has been a problem in disposal processing, such as glass being fused in an incinerator. Furthermore, when using a fibrous inorganic material, there is a problem that the molded body is warped because anisotropy occurs due to the fibrous inorganic material orientation during injection molding, and the surface appearance is impaired by adding a large amount of the fibrous inorganic material. is there. In addition, when a general particulate inorganic material is used, a large amount of addition is required as compared with the fibrous inorganic material when trying to obtain a predetermined rigidity although the occurrence of warping due to anisotropy is reduced. Compared to the addition of fibrous inorganic substances, there are problems such as an increase in mechanical strength and deflection temperature under load, and an increase in specific gravity. The disadvantages in blending such particulate inorganic substances are considered to be caused by poor dispersion and too large dispersed particle size, and various techniques for finely dispersing particulate inorganic substances in thermoplastic resins have been investigated. Yes.

  Among the particulate inorganic materials, as an attempt to finely disperse layered silicate in a thermoplastic resin, a layered inorganic filler having a layer charge of 0.2 to 1.0 and a bottom surface space expanded to 5 times or more of the initial value. And a resin composition containing a thermoplastic polyester resin (for example, Patent Document 1), and a resin composition in which a layered silicate is dispersed as a molecular nucleus in a crystalline thermoplastic resin with an aspect ratio of 20 or more Invention (for example, patent document 2), invention (for example, patent document 3) related to a resin composition in which a layered silicate having an average layer thickness of 25 to 1000 mm and an aspect ratio of 20 to 300 is dispersed in a thermoplastic resin. It is disclosed.

  However, even in the above technology, although the amount of addition of inorganic substances can be reduced by improving the warpage due to the orientation of the inorganic filler and increasing the efficiency of the rigidity, the product is uneconomical and usable because of the costs associated with fine dispersion. There was still the problem of being limited.

Further, among the thermoplastic polyester resins, polyethylene terephthalate has a problem that it cannot be used when alkali resistance is high because hydrolysis is accelerated by an alkaline solution.
JP-A-7-26123 JP-A-9-183910 JP-A-9-1224836

  The object of the present invention is to improve such conventional problems, to easily disperse inorganic substances in the granulation process by an extruder, to achieve high rigidity and high heat resistance, and to improve the surface appearance. An object of the present invention is to provide a thermoplastic resin composition that is good and has improved alkali resistance, and an injection-molded article of tableware that is molded using the resin composition.

  As a result of intensive studies to achieve the above object, the present inventors have found that a particle size of 1 μm is contained in a polybutylene terephthalate resin or an alloyed thermoplastic resin composition of a polybutylene terephthalate resin and another thermoplastic resin. The present inventors have found that the above-mentioned problems can be solved by mixing less than ultrafine inorganic particles and relatively large inorganic particles having a particle diameter of 1 to 100 μm.

That is, the first of the present invention is
A thermoplastic resin composition comprising an inorganic filler,
The inorganic filler is composed of those having a particle size of 1 to 100 μm and those having a particle size of less than 1 μm, and the inorganic filler having a particle size of less than 1 μm satisfies at least one of the following (a) and (b): ) And (d)
Further, the present invention relates to a thermoplastic resin composition, wherein the thermoplastic resin is a polybutylene terephthalate resin or an alloy of a polybutylene terephthalate resin and another thermoplastic resin.
(A) The ratio of the inorganic filler whose equivalent area circular diameter [D] is 300 nm or less is 20% or more.
(B) The average value of the equivalent area circle diameter [D] is 500 nm or less.
(C) Layer thickness [T] is 200 nm or less.
(D) The average value of the layer thickness [T] is 50 nm or less.

As a preferred embodiment,
(1) The thermoplastic resin is an alloy of a polybutylene terephthalate resin and another thermoplastic resin, and the mixing ratio of the polybutylene terephthalate resin is 60 wt% or more as a weight ratio,
(2) The thermoplastic resin is an alloy of polybutylene terephthalate and polytrimethylene terephthalate,
(3) The thermoplastic resin is an alloy of polybutylene terephthalate and polyethylene terephthalate,
(4) The inorganic filler having a particle size of less than 1 μm is one or more layered silicates selected from smectite clay and swellable mica,
(5) The layered silicate is a polyether-treated clay,
The present invention relates to the thermoplastic resin composition described above.

  A second aspect of the present invention relates to an injection molded product using the thermoplastic resin composition described above. As a preferred embodiment, a tableware article using the thermoplastic resin composition described above, more preferably a tableware and tableware using the thermoplastic resin composition described above. It is related to a tray.

  The thermoplastic resin composition of the present invention can efficiently increase the flexural modulus and the deflection temperature under load as compared with a general combination of only inorganic fillers.

  As a result, high rigidity and heat resistance can be obtained without using fibrous fillers and in a smaller amount than conventional inorganic fillers, and dimensionality, warp deformation and surface appearance are good. In addition, a molded article having improved alkali solution resistance can be obtained.

  Embodiments of the present invention will be described below.

  The thermoplastic resin of the present invention is a polybutylene terephthalate resin alone or an alloy of another thermoplastic resin with the polybutylene terephthalate resin.

  In the present invention, durability against alkali solution can be improved by using a polybutylene terephthalate resin alone as a thermoplastic resin. Alternatively, by using a polybutylene terephthalate resin obtained by alloying another thermoplastic resin, high surface glossiness can be obtained while maintaining durability against the alkali solution property.

  Specific examples of other thermoplastic resins to be alloyed in the present invention include, for example, an amorphous resin such as an ABS resin, a polycarbonate resin, and a cyclopolyolefin resin, and a crystalline resin such as a polyester resin, Examples thereof include polyamide resin, polyolefin resin, and polyether sasphone resin. Among these, as the other thermoplastic resin to be alloyed in the present invention, it is preferable to use a thermoplastic polyester resin other than the polybutylene terephthalate resin.

  The polybutylene terephthalate resin used in the present invention is selected in consideration of the molding fluidity in the molding process and various physical properties of the final product, and the molecular weight is not preferably too low or too high, and an appropriate molecular weight is set. There is a need. That is, the molecular weight of the polybutylene terephthalate resin has a logarithmic viscosity of 0.3 to 2.0 (dl / g) measured at 25 ° C. using a phenol / tetrachloroethane (5/5 weight ratio) mixed solvent. Preferably it is 0.35-1.9 (dl / g), More preferably, it is 0.4-1.8 (dl / g). When the logarithmic viscosity is less than 0.3 (dl / g), the strength of the resulting resin molded product tends to be low. May cause problems.

  If necessary, the polybutylene terephthalate resin used in the present invention is preferably 20% by weight or less, particularly preferably 10% by weight or less when the polybutylene terephthalate is 100% by weight. Can be polymerized. As a copolymerization component, a known acid component, alcohol component and / or phenol component, or derivatives thereof having ester forming ability can be used.

  Examples of the copolymerizable acid component include a divalent or higher aromatic carboxylic acid having 8 to 22 carbon atoms, a divalent or higher aliphatic carbonic acid having 4 to 12 carbon atoms, and a divalent or higher carbon number. Examples thereof include 8 to 15 alicyclic carboxylic acids and derivatives thereof having ester forming ability. Specific examples of the copolymerizable acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carbodiphenyl) methaneanthracene dicarboxylic acid, 4-4′-diphenylcarboxylic acid, 1,2-bis. (Phenoxy) ethane-4,4′-dicarboxylic acid, 5-sodium sulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, maleic acid, trimesic acid, trimellitic acid, pyromellitic acid, 1,3 -Cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and derivatives thereof having ester forming ability. These may be used alone or in combination of two or more. Of these, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid are preferred because the resulting resin is excellent in physical properties, handleability, and ease of reaction.

  Examples of the copolymerizable alcohol and / or phenol component include dihydric or higher aliphatic alcohols having 2 to 15 carbon atoms, dihydric or higher alicyclic alcohols having 6 to 20 carbon atoms, and 6 to 40 carbon atoms. Examples thereof include aromatic alcohols having a valence of 2 or more, phenols, and derivatives thereof having an ester forming ability. Specific examples of the copolymerizable alcohol and / or phenol component include ethylene glycol, propanediol, hexanediol, decanediol, neopentyl glycol, cyclohexanedimethanol, cyclohexanediol, and 2,2′-bis (4-hydroxyphenyl). ), Propane, 2,2′-bis (4-hydroxycyclohexyl) propane, hydroquinone, glycerin, pentaerythritol, and the like, derivatives thereof having ester forming ability, and cyclic esters such as ε-caprolactone. Among these, ethylene glycol and butanediol are preferable because they are excellent in physical properties, handleability, and reaction ease.

  Furthermore, some polyalkylene glycol units may be copolymerized. Specific examples of the polyoxyalkylene glycol include, for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random or block copolymers thereof, alkylene glycols of bisphenol compounds (polyethylene glycol, polypropylene glycol, polytetramethylene glycol) , And random or block copolymers thereof) modified polyoxyalkylene glycols such as adducts. Among these, bisphenol A having a molecular weight of 500 to 2,000 is preferable because the heat stability during copolymerization is good and the heat resistance of the molded product obtained from the resin composition of the present invention is hardly lowered. Polyethylene glycol adducts are preferred.

  The thermoplastic polyester resin other than the polybutylene terephthalate resin used in the present invention is an acid component mainly composed of a dicarboxylic acid compound and / or an ester-forming derivative of a dicarboxylic acid, and a diol compound and / or an ester formation of a diol compound. It is a conventionally well-known arbitrary thermoplastic polyester resin obtained by reaction with the diol component which has a functional derivative as a main component.

  With the said main component, the ratio which occupies in an acid component or a diol component intends that it is 80% or more, Furthermore, 90% or more, and an upper limit is 100%.

  Specific examples of thermoplastic polyester resins other than polybutylene terephthalate resins include polyethylene terephthalate, polypropylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, neopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, poly Examples include butylene naphthalate, polyhexamethylene naphthalate, and polytrimethylene terephthalate. Moreover, the copolyester manufactured using 2 or more types of the acid component and / or diol component which are used for manufacture of these resin is mentioned.

  Among the thermoplastic polyester resins other than the polybutylene terephthalate resin, polytrimethylene terephthalate and polyethylene terephthalate are preferable from the viewpoint of strength, elastic modulus, cost, surface property, and the like. Furthermore, polytrimethylene terephthalate is preferable from the viewpoint of improving the surface gloss.

  Moreover, in this invention, the recycled resin composition material after shaping | molding / use other than a virgin resin material can be used. That is, for example, in addition to a virgin resin material of polyethylene terephthalate, a recovered used PET bottle pulverized can be used alone or in combination.

  In the present invention, when the thermoplastic resin is an alloy of polybutylene terephthalate and another thermoplastic resin, the lower limit of the amount of the other thermoplastic resin mixed is 100 parts by weight of polybutylene terephthalate. The amount is preferably 10 parts by weight, more preferably 20 parts by weight, and particularly preferably 25 parts by weight. The upper limit of the amount is typically 50 parts by weight, preferably 40 parts by weight, more preferably 35% by weight, and still more preferably 33% by weight. When the blending amount of other thermoplastic resins is less than 20 parts by weight, the alkali solution resistance is good, but the surface gloss may be slightly insufficient. On the other hand, when the mixing amount of the other thermoplastic resin exceeds 50 parts by weight, the alkali solution resistance tends to be lowered.

  A method for obtaining a resin obtained by alloying polybutylene terephthalate and other thermoplastic resin is not particularly limited, and examples thereof include a method of melt kneading using various general kneaders. Examples of the kneader include a single screw extruder, a twin screw extruder, a roll, a Banbury mixer, a kneader, and the like, and a kneader with high shear efficiency is particularly preferable.

  The thermoplastic resin composition of the present invention comprises an inorganic filler.

  The inorganic filler in the present invention is not particularly limited as long as the particle size is 100 μm or less. Kaolin, clay, wollastonite, montmorillonite, bentonite, sepiolite, imogolite, sericite, silica balun, diatomaceous earth, titanium oxide, calcium oxide, magnesium oxide, iron oxide, tin oxide, antimony oxide, calcium carbonate, magnesium carbonate, zinc carbonate, Barium carbonate, dawsonite, hydrotalcite, calcium sulfate, barium sulfate, aluminum nitride, boron nitride, silicon nitride, magnesia, carbon fiber, sericite, various metal foils, graphite, silica, quartz, etc. Can also be synthesized . Of these, layered silicates such as smectite group clay and swelling mica, talc and mica are preferred.

  The particle size of the inorganic filler used in the present invention is 100 μm or less, preferably 50 μm or less, more preferably 40 μm or less. When the particle size of the inorganic filler exceeds 100 μm, the toughness tends to decrease. In addition, in this invention, a particle size is a particle size calculated | required by the laser diffraction method.

  The inorganic filler of the present invention satisfies a particle size of 100 μm or less, and further comprises a particle size of 1 to 100 μm and a particle size of less than 1 μm.

  In the present invention, the inorganic filler is composed of one having a particle diameter of 1 to 100 μm and one having a particle diameter of less than 1 μm. ), Rigidity and good surface properties, and suppression of hydrolysis with respect to alkali solution properties.

  As the inorganic filler having a particle size of less than 1 μm (hereinafter sometimes referred to as “ultrafine inorganic filler”), among the inorganic fillers, a layered silicate is preferable from the viewpoint of cleavage of aggregated particles.

  The layered silicate is formed mainly from a tetrahedral sheet of silicon oxide and an octahedral sheet of a metal hydroxide, and examples thereof include smectite group clay and swellable mica.

The smectite clay is represented by the following general formula (1):
X _0.2 to _0.6 Y ₂ to ₃ Z ₄ O ₁₀ (OH) ₂ .nH ₂ O (1)
(However, X is at least one selected from the group consisting of K, Na, 1 / 2Ca, and 1 / 2Mg, and Y is a group consisting of Mg, Fe, Mn, Ni, Zn, Li, Al, and Cr. And Z is at least one selected from the group consisting of Si and Al, where H ₂ O represents a water molecule bonded to an interlayer ion, and n is an interlayer ion. And fluctuates significantly depending on relative humidity)
It is expressed by natural or synthetic.

  Specific examples of the smectite group clay include, for example, montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite, bentonite, or the like, or a substitution product, derivative thereof, or a mixture thereof. . The bottom surface spacing in the initial aggregated state of the smectite group clay is about 1 to 1.7 nm, and the average particle size of the smectite group clay in the aggregated state is about 100 to 100,000 nm.

The swelling mica is represented by the following general formula (2):
X _0.5 to _1.0 Y ₂ to ₃ (Z ₄ O ₁₀ ) (F, OH) ₂ (2)
(However, X is at least one selected from the group consisting of Li, Na, K, Rb, Ca, Ba, and Sr, and Y is selected from the group consisting of Mg, Fe, Ni, Mn, Al, and Li) Z is at least one selected from the group consisting of Si, Ge, Al, Fe, and B.)
It is expressed by natural or synthetic.

  These are water, a polar solvent that is compatible with water at an arbitrary ratio, and a material that swells in a mixed solvent of water and the polar solvent. For example, lithium-type teniolite, sodium-type teniolite, lithium-type four Examples thereof include silicon mica and sodium-type tetrasilicon mica, or substituted products, derivatives, or mixtures thereof. The bottom face spacing in the initial aggregated state of the swellable mica is approximately 1 to 1.7 nm, and the average particle size of the swellable mica in the aggregated state is approximately 100 to 100,000 nm.

Some of the above swellable mica have a structure similar to that of vermiculites, and such vermiculite equivalents can also be used. The vermiculite-equivalent products include three octahedron type and two octahedron type, and the following general formula (3):
_{(Mg, Fe, Al) 2} ~ 3 (Si 4-x Al x) O 10 (OH) 2 · (M +, M 2+ 1/2) x · nH 2 O (3)
(Wherein M is an exchangeable cation of an alkali or alkaline earth metal such as Na and Mg, x = 0.6 to 0.9, and n = 3.5 to 5)
The thing represented by is mentioned. The bottom surface interval in the initial aggregated state of the vermiculite equivalent is approximately 1 to 1.7 nm, and the average particle size in the aggregated state is approximately 100 to 500,000 nm.

  The crystal structure of the layered silicate is preferably high in purity, which is regularly stacked in the c-axis direction, but so-called mixed layer minerals in which the crystal period is disturbed and a plurality of types of crystal structures are mixed can also be used. As layered silicates, montmorillonite, bentonite, hectorite and swellable mica having sodium ions between layers are readily available, dispersibility in the resulting thermoplastic resin composition and improved physical properties of the thermoplastic resin composition It is preferable in terms of effect. A layered silicate may be used independently and may be used in combination of 2 or more type.

  In the present invention, in order to enhance dispersibility in the thermoplastic resin, it is preferable to use the layered silicate after pretreatment.

  As a pretreatment method, a layered inorganic filler having a layer charge of 0.2 to 1.0 described in JP-A-7-26123 is swelled with glycols, and then a polyester resin is interposed between the layers of the layered inorganic filler. And a method of dispersing an inorganic compound obtained by heat-treating a mixture of a specific ratio of talc and alkali fluorosilicate described in JP-A-7-268188 to improve dispersibility. There is no particular limitation as long as it can be performed.

  However, it is preferable to use a polyether-treated layered silicate obtained by treating the layered silicate with a polyether compound from the viewpoint of dispersibility. Examples of the polyether-treated layered silicate include a silicate single-layer structure or a delaminated body produced by treating the layered silicate with a polyether compound.

  The polyether compound is intended to be a compound whose main chain is polyoxyalkylene such as polyoxyethylene or polyoxyethylene-polyoxypropylene copolymer, and is intended to have about 2 to 100 repeating units. To do.

  The polyether compound may have an arbitrary substituent in the side chain and / or main chain as long as it does not adversely affect the thermoplastic polyester resin or the layered compound. Examples of the substituent include a hydrocarbon group, a group bonded by an ester bond, an epoxy group, an amino group, a carboxyl group, a group having a carbonyl group at the terminal, an amide group, a mercapto group, and a sulfonyl bond. Groups containing sulfinyl bonds, nitro groups, nitroso groups, nitrile groups, alkoxysilyl groups, silanol groups, Si-containing atom functional groups that can form Si-O- bonds, halogen atoms, hydroxyl groups, etc. Can be mentioned. One of these may be substituted, or two or more may be substituted.

  The hydrocarbon group is a linear or branched (that is, having a side chain) saturated or unsaturated monovalent or polyvalent aliphatic hydrocarbon group, aromatic hydrocarbon group, or alicyclic hydrocarbon group. Meaning, for example, alkyl group, alkenyl group, alkynyl group, phenyl group, naphthyl group, cycloalkyl group and the like. In the present specification, the term “alkyl group” is intended to include a polyvalent hydrocarbon group such as an “alkylene group” unless otherwise specified. Similarly, the alkenyl group, alkynyl group, phenyl group, naphthyl group, and cycloalkyl group include an alkenylene group, an alkynylene group, a phenylene group, a naphthylene group, a cycloalkylene group, and the like, respectively.

  The composition ratio of the substituents in the polyether compound is not particularly limited, but it is desirable that the polyether compound is soluble in water or a polar solvent containing water. Specifically, for example, the solubility in 100 g of water at room temperature is 1 g or more, preferably 2 g or more, more preferably 5 g or more, still more preferably 10 g or more, and particularly preferably 20 g or more. . Examples of the polar solvent include alcohols such as methanol, ethanol, and isopropanol, glycols such as ethylene glycol, propylene glycol, and 1,4-butanediol, ketones such as acetone and methyl ethyl ketone, diethyl ether, and tetrahydrofuran. Examples of ethers, amide compounds such as N, N-dimethylformamide and N, N-dimethylacetamide, and other solvents include pyridine, dimethyl sulfoxide and N-methylpyrrolidone. Carbonic acid diesters such as dimethyl carbonate and diethyl carbonate can also be used. These polar solvents may be used alone or in combination of two or more.

  Specific examples of the polyether compound used in the present invention include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol-polypropylene glycol, polyethylene glycol-polytetramethylene glycol, polyethylene glycol monomethyl ether, polyethylene glycol dimethyl ether, polyethylene glycol. Monoethyl ether, polyethylene glycol diethyl ether, polyethylene glycol monoallyl ether, polyethylene glycol diallyl ether, polyethylene glycol monophenyl ether, polyethylene glycol diphenyl ether, polyethylene glycol octylphenyl ether, polyethylene glycol methyl ethyl ether, poly Tylene glycol methyl allyl ether, polyethylene glycol glyceryl ether, polyethylene glycol monomethacrylate, polyethylene glycol monoacrylate, polypropylene glycol monomethacrylate, polypropylene glycol monoacrylate, polyethylene glycol-polypropylene glycol monomethacrylate, polyethylene glycol-polypropylene glycol monoacrylate, polyethylene glycol- Polytetramethylene glycol monomethacrylate, polyethylene glycol-polytetramethylene glycol monoacrylate, methoxypolyethylene glycol monomethacrylate, methoxypolyethylene glycol monoacrylate, octoxypolyethylene glycol-polypropylene Lenglycol monomethacrylate, octoxypolyethyleneglycol-polypropyleneglycolmonoacrylate, lauroxypolyethyleneglycolmonomethacrylate, lauroxypolyethyleneglycolmonoacrylate, stearoxypolyethyleneglycolmonomethacrylate, stearoxypolyethyleneglycolmonoacrylate, allyloxypolyethyleneglycolmonomethacrylate, Allyloxy polyethylene glycol monoacrylate, nonylphenoxy polyethylene glycol monomethacrylate, nonylphenoxy polyethylene glycol monoacrylate, polyethylene glycol dimethacrylate, polyethylene glycol diacrylate, polyethylene glycol-polytetramethylene glycol di Methacrylate, polyethylene glycol-polytetramethylene glycol diacrylate, bis (polyethylene glycol) butylamine, bis (polyethylene glycol) octylamine, polyethylene glycol bisphenol A ether, polyethylene glycol-polypropylene glycol bisphenol A ether, ethylene oxide modified bisphenol A dimethacrylate, Ethylene oxide modified bisphenol A diacrylate, ethylene oxide-propylene oxide modified bisphenol A dimethacrylate, polyethylene glycol diglycidyl ether, polyethylene glycol ureidopropyl ether, polyethylene glycol mercaptopropyl ether, polyethylene glycol phenylsulfonyl Ropirueteru, polyethylene glycol phenylsulfinyl propyl ether, polyethylene glycol nitro propyl ether, polyethylene glycol nitroso propyl ether, polyethylene glycol cyanoethyl ethers, polyethylene glycol cyanoethyl ether. These polyether compounds may be used alone or in combination of two or more. Among the polyether compounds of the present invention, those having a cyclic hydrocarbon group such as an aromatic hydrocarbon group or an alicyclic hydrocarbon group are preferred, and among them, the following general formula (4)

（式中、−Ａ−は、−Ｏ−、−Ｓ−、−ＳＯ−、−ＳＯ₂-、−ＣＯ−、炭素数１〜２０のアルキレン基、または炭素数６〜２０のアルキリデン基であり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、およびＲ⁸は、いずれも水素原子、ハロゲン原子、または炭素数１〜５の１価の炭化水素基であり、Ｒ⁹、Ｒ¹⁰はいずれも炭素数１〜５の２価の炭化水素基であり、Ｒ¹¹、Ｒ¹²はいずれも水素原子、炭素数１〜２０の１価の炭化水素基であり、それらはそれぞれ同一であっても異なっていても良い。ｍおよびｎはオキシアルキレン単位の繰り返し単位数を示し、２≦ｍ＋ｎ≦５０である。）
で表されるものが、層状珪酸塩の分散性および熱安定性の点から好ましい。

(Wherein, -A- is, -O -, - S -, - SO -, - SO 2 -, - CO-, an alkylene group or alkylidene group having 6 to 20 carbon atoms, having 1 to 20 carbon atoms , R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are all hydrogen atoms, halogen atoms, or monovalent hydrocarbon groups having 1 to 5 carbon atoms. , R ⁹ and R ¹⁰ are all divalent hydrocarbon groups having 1 to 5 carbon atoms, R ¹¹ and R ¹² are both hydrogen atoms and monovalent hydrocarbon groups having 1 to 20 carbon atoms, They may be the same or different, and m and n represent the number of repeating units of oxyalkylene units, and 2 ≦ m + n ≦ 50.
Is preferable from the viewpoint of the dispersibility and thermal stability of the layered silicate.

  In the present invention, the lower limit of the blending amount of the inorganic filler in the thermoplastic resin composition is typically 1% by weight, preferably 3% by weight, more preferably 5% by weight, More preferably, it is 10 weight%, Most preferably, it is 15 weight%. The upper limit of the blending amount of the inorganic filler is typically 60% by weight, preferably 50% by weight, more preferably 40% by weight, and further preferably 35% by weight. The If the lower limit of the blending amount of the inorganic filler is less than 1% by weight, the effect of improving mechanical properties, deflection temperature under load, dimensional stability and releasability may be insufficient, and the upper limit is 60%. When it exceeds%, the appearance of the molded product and the fluidity during molding tend to be impaired.

  In the present invention, the amount of the inorganic filler (ultrafine inorganic filler) having a particle size of less than 1 μm is 1 to 40% by weight, preferably 3 to 35% by weight in the thermoplastic resin composition. More preferably, the content is 3 to 15% by weight. If the amount of the ultrafine inorganic filler is less than 1% by weight, the effect of improving the mechanical properties and the deflection temperature under load tends to be insufficient. There is a tendency to be damaged.

  Most of the ultrafine inorganic fillers dispersed in the thermoplastic resin composition of the present invention are subdivided independently of each other with the layers cleaved. The dispersion state of the ultrafine inorganic filler can be expressed by an equivalent area circle diameter [D] or a film thickness [T] described below.

  The ultra-small inorganic filler in the present invention has (a) a ratio of the inorganic filler having an equivalent area circle diameter [D] of 300 nm or less of 20% or more, and (b) an average of equivalent area circle diameter [D]. It satisfies any one or more of the values being 500 nm or less.

  In the present invention, the equivalent area circle diameter [D] is the diameter of a circle having an area equal to the area of each inorganic filler dispersed in various shapes in an image obtained by an electron microscope or the like. Is defined as

  In the present invention, the ratio of the number of inorganic fillers having an equivalent area circle diameter [D] of 300 nm or less among the ultrafine inorganic fillers dispersed in the thermoplastic resin composition is 20% or more, preferably 35. % Or more, more preferably 50% or more, and particularly preferably 65% or more. If the ratio of the equivalent area circle diameter [D] is 300 nm or less is less than 20%, the effect of improving the mechanical properties, the deflection temperature under load, the dimensional stability or the moldability of the thermoplastic resin composition tends to be insufficient. .

  The average value of the equivalent area circular diameter [D] of the ultrafine inorganic filler in the thermoplastic resin composition in the present invention is 500 nm or less, preferably 450 nm or less, more preferably 400 nm or less, particularly preferably. Is 350 nm or less. When the average value of the equivalent area circle diameter [D] is larger than 500 nm, the effect of improving the mechanical properties and load deflection temperature of the thermoplastic resin composition is not sufficient, and the surface property tends to be impaired. There is no particular lower limit of the average value of the equivalent area circle diameter [D], but the effect is almost the same if it is less than about 10 nm.

  The equivalent area circle diameter [D] is measured by selecting an arbitrary region including 100 or more layers of ultra-fine inorganic filler on an image taken using a microscope or the like, and using an image processing apparatus or the like. Can be quantified by computerization and computer processing.

  In the present invention, in addition to the definition of the equivalent area circular diameter [D], the ultrafine inorganic filler has (c) a layer thickness [T] of 200 nm or less, and (d) an average value of the layer thickness [T]. Satisfy | fills any one or more of being 50 nm or less.

  In the present invention, the layer thickness [T] of the ultrafine inorganic filler refers to a width positioned so as to be orthogonal to the longitudinal direction in the shape observed on the earthworm. In the present invention, the average layer thickness is defined as the number average value of the layer thickness [T] of the ultrafine inorganic filler dispersed in a thin plate shape.

  In the present invention, the upper limit value of the average layer thickness of the ultrafine inorganic filler in the thermoplastic resin composition is 50 nm or less, preferably 45 nm or less, more preferably 40 nm or less. When the average layer thickness is larger than 50 nm, there may be a case where the effect of improving the mechanical properties, the deflection temperature under load, and the dimensional stability of the obtained thermoplastic resin composition cannot be sufficiently obtained. The lower limit of the average layer thickness is not particularly limited, but is preferably larger than 1 nm.

  In the present invention, when the maximum layer thickness is defined as the maximum value of the layer thickness [T] of the ultrafine inorganic filler dispersed in the thermoplastic resin composition, the upper limit value of the maximum layer thickness of the ultrafine inorganic filler Is 200 nm or less, preferably 180 nm or less, and more preferably 150 nm or less. If the maximum layer thickness is greater than 200 nm, the surface properties of the resulting thermoplastic resin composition may be impaired. The lower limit value of the maximum layer thickness of the ultrafine inorganic filler is not particularly limited, but is preferably larger than 1 nm.

  The ultra-fine inorganic filler layer thickness in the thermoplastic resin composition is obtained by heat-melting the thermoplastic resin composition and then hot-press molding or stretch molding, and injection molding the molten resin. A thin molded article or the like can be obtained from an image photographed using an electron microscope or the like.

  In other words, it is assumed that a thin plate-like injection-molded test piece of the film prepared by the above method or a thickness of about 0.5 to 2 mm is placed on the XY plane. The film or test piece is cut into an ultrathin section having a thickness of about 50 μm to 100 μm in a plane parallel to the XZ plane or the YZ plane, and the section is cut into about 10,000 to 1 million using a transmission electron microscope or the like. It can be obtained by observing at a high magnification of twice or more. For the measurement, on the transmission electron microscope image obtained by the above method, an arbitrary region containing 100 or more ultrafine inorganic fillers is selected, imaged by an image processing apparatus, etc., and subjected to computer processing, etc. Can be quantified. Alternatively, it can be obtained by measurement using a ruler or the like.

  In the present invention, additives such as pigments and dyes, heat stabilizers, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers, flame retardants, and antistatic agents are added depending on the purpose. can do. The thermoplastic resin composition obtained in the present invention may be molded by injection molding or hot press molding, and can also be used for blow molding. Among these, it is particularly suitable for injection molding from the viewpoint of good response to complex shape and high surface property requirements, and good productivity.

  The method for producing the thermoplastic resin composition of the present invention is not particularly limited, and can be produced as follows. For example, a method of melt-kneading a thermoplastic resin, an inorganic filler having a particle diameter of less than 1 μm (very fine inorganic filler) and an inorganic filler having a particle diameter of 1 to 100 μm using various general kneaders is exemplified. be able to. Examples of the kneader include a uniaxial kneader, a biaxial kneader, a roll, a Banbury mixer, and a kneader, and a kneader with high shear efficiency is particularly preferable. The order of addition of the thermoplastic resin, the inorganic filler having a particle size of less than 1 μm (ultra-fine inorganic filler) and the inorganic filler having a particle size of 1 to 100 μm is, for example, (Ii) A thermoplastic resin and an inorganic filler having a particle diameter of less than 1 μm or an inorganic filler having a particle diameter of 1 to 100 μm are charged together, melt-kneaded, and then filled with an inorganic filler having a particle diameter of 1 to 100 μm. An agent or an inorganic filler having a particle size of less than 1 μm may be separately added and melt-kneaded, or (iii) an inorganic filler having a particle size of less than 1 μm and a particle size of 1 are added to a thermoplastic resin previously melted. ˜100 μm inorganic filler may be added and melt kneaded.

  The production method for obtaining a molded product from the thermoplastic resin composition in the present invention is not particularly limited. For example, a special function is added to commonly used injection molding or general injection molding. There are injection molding methods such as injection compression and gas assisted injection molding, and hot melt molding methods such as extrusion molding and blow molding, among which injection molding methods are preferred.

  The molded product of the present invention thus obtained has excellent appearance, excellent mechanical properties, heat distortion resistance, etc., and good resistance to alkaline aqueous solution. For example, tableware such as tableware, coasters, tableware trays, etc. It can be used suitably for articles, and among tableware articles, it can be suitably used for tableware trays.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

  As the thermoplastic resin, polybutylene terephthalate alone, a mixture of polybutylene terephthalate and polyethylene terephthalate, or a mixture of polybutylene terephthalate and polytrimethylene terephthalate was used.

  As polybutylene terephthalate, polybutylene terephthalate KP210 (hereinafter referred to as PBT) manufactured by KOLON was used. As the polyethylene terephthalate, Kanebo Co., Ltd. polyethylene terephthalate EFG70 (hereinafter referred to as PET) was used. As the polytrimethylene terephthalate, polytrimethylene terephthalate-Corterra CP509201 (hereinafter referred to as PTT) manufactured by Shell Chemicals Japan Co., Ltd. was used.

  As an inorganic filler of less than 1 μm, a swellable mica (trade name: Somasif ME100, manufactured by Co-op Chemical Co., Ltd.) is subjected to a polyether treatment and then pulverized (hereinafter referred to as “polyether-treated layered layer”). Sometimes referred to as “silicate”). First, swellable mica and ion exchange water were mixed. Next, polyethylene glycol (manufactured by Toho Chemical Co., Ltd., trade name: Bisol 18EN) was added as a treating agent, and the treatment was continued for 15 to 60 minutes. Next, the powdered product was used.

  As an inorganic filler of 1 to 100 μm, mica (manufactured by Yamaguchi Mica, A-21S; particle size 19 to 21 μm by laser diffraction method), talc (manufactured by Nippon Talc, MS-T; particle size 20 μm by laser diffraction method) Was used.

  The evaluation is as follows.

(Mechanical properties and weighted deflection temperature)
After pellets obtained by the composition shown in Table 1 were dried at 140 ° C. for 4 hours, they were molded using a 75-ton molding machine at a nozzle tip temperature of 280 ° C. and a mold temperature of 90 ° C., and ASTM D-638. A dumbbell bar specimen according to the above was molded, and mechanical properties and deflection temperature under load were evaluated.
Regarding the mechanical properties, the flexural modulus was in accordance with ASTM D-638, the tensile strength was in accordance with ASTM D-790, and the deflection temperature under load was in accordance with ASTM D-648.

(Equivalent area circle diameter [D] and layer thickness [T] with an inorganic filler of less than 1 μm)
As the equivalent area circle diameter [D] of the inorganic filler of less than 1 μm, an ultrathin section having a thickness of 50 to 100 μm collected from a 120 mm × 120 mm × 3 mm thick flat plate molded product formed by injection molding was used. Using a transmission electron microscope, the dispersion state was observed and photographed at an acceleration voltage of 80 kV and a magnification of 40,000 to 1,000,000 times. In a TEM photograph, an arbitrary region where 100 or more dispersed particles exist was selected and measured by processing using an image analyzer. The layer thickness [T] was measured as the number average value of the individual layer thicknesses.

(Surface appearance)
As for the surface appearance, a 120 mm square, 2 mm thick mirror plate-shaped molded product was molded at a mold temperature of 90 ° C., and the molded product was visually observed and evaluated.
○: Glossy (The external shape of the fluorescent lamp can be distinguished)
△: No gloss (The appearance of the fluorescent lamp is blurred)
×: No gloss (The outer diameter of the reflected fluorescent lamp cannot be grasped)
Moreover, the glossiness value in the incident angle of 60 degree | times and the reflection angle of 60 degree | times was measured for the surface glossiness using the color difference meter (Nippon Denshoku Industries make, VGS-300A).

(Alkaline solution resistance)
The alkali solution resistance was evaluated by visually observing the surface state after dipping a dumbbell test piece produced by injection molding in a 0.2 wt% sodium hydroxide aqueous solution kept at 80 ° C. for 120 hours.
○: The shape is maintained and the surface is almost smooth.
Δ: Although the shape is maintained, generation of pores is observed on the surface.
X: A shape is not hold | maintained but thinness is seen.

Example 1
A single PBT was used as the thermoplastic resin. 10% by weight of polyether-treated layered silicate, 7% by weight of mica and 5% by weight of talc are added to the total weight of the thermoplastic resin composition, and melt kneaded (resin by a twin screw extruder (manufactured by Nippon Steel, TEX44)) The temperature was 260 ° C.) to produce pellets.
Using the obtained pellets, dumbbell bar test pieces were molded by the method described above. Table 1 shows the results of the above evaluation.

(Example 2)
As a thermoplastic resin, PBT and PTT were mixed in a ratio (weight ratio) of 75:25. Pellets were produced by adding 10% by weight of polyether-treated layered silicate, 7% by weight of mica and 5% by weight of talc to the total weight of the thermoplastic resin composition, and melt-kneading with a twin screw extruder.
Using the obtained pellets, dumbbell bar test pieces were molded by the method described above. Table 1 shows the results of the above evaluation.

(Example 3)
As a thermoplastic resin, PBT and PTT were mixed at a ratio (weight ratio) of 70:30. Pellets were produced by adding 10% by weight of polyether-treated layered silicate, 7% by weight of mica and 5% by weight of talc to the total weight of the thermoplastic resin composition, and melt-kneading with a twin screw extruder.
Using the obtained pellets, dumbbell bar test pieces were molded by the method described above. The results of the above evaluation are shown in Table 1.

Example 4
As a thermoplastic resin, PBT and PET were mixed at a ratio (weight ratio) of 75:25. Pellets were produced by adding 10% by weight of the processed layered silicate, 7% by weight of mica and 5% by weight of talc to the total weight of the thermoplastic resin composition, and melt-kneading with a twin screw extruder.
Using the obtained pellets, dumbbell bar test pieces were molded by the method described above. The results of the above evaluation are shown in Table 1.

(Example 5)
As a thermoplastic resin, PBT and PET were mixed at a ratio (weight ratio) of 70:30. Pellets were produced by adding 10% by weight of the processed layered silicate, 7% by weight of mica and 5% by weight of talc to the total weight of the thermoplastic resin composition, and melt-kneading with a twin screw extruder.
Using the obtained pellets, dumbbell bar test pieces were molded by the method described above. Table 1 shows the results of the above evaluation.

(Comparative Example 1)
As a thermoplastic resin, PBT and PET were mixed at a ratio (weight ratio) of 25:75. Pellets were produced by adding 25% by weight of mica and 5% by weight of talc to the total weight of the thermoplastic resin composition, and melt-kneading with a twin-screw extruder. Using this pellet, a dumbbell bar specimen was molded by the method described above. The results of the above evaluation are shown in Table 1.

(Comparative Example 2)
As a thermoplastic resin, PBT and PET were mixed at a ratio (weight ratio) of 25:75. 20% by weight of mica was added to the total weight of the thermoplastic resin composition, and melt-kneaded by a twin screw extruder to produce pellets. Using this pellet, a dumbbell bar specimen was molded by the method described above. The results of the above evaluation are shown in Table 1.

上記結果に見られるように、樹脂組成物総樹脂量に対し、ＰＥＴ樹脂の含有量が５０部以上と多数を占めた熱可塑性樹脂（比較例１と比較例２）に比べ、樹脂組成物総樹脂量に対し、ＰＢＴ樹脂の含有量が５０部以上と多数を占める熱可塑性樹脂組成物（実施例１〜実施例５）の方が耐アルカリ溶液性に優れることが確認された。さらには、ＰＢＴ樹脂単独（実施例１）に対し、ＰＢＴ樹脂を含む総樹脂量に対し、５０重量部以下のＰＴＴもしくはＰＥＴを混合してなる熱可塑性樹脂（実施例２〜実施例５）は耐アルカリ溶液性の低下が少なく、高い表面光沢が得ることができ、さらにはＰＥＴをブレンド（実施例４と実施例５）するのに対し、ＰＴＴをブレンド（実施例２と実施例３）することにより耐アルカリ溶液性の低下を少なく、高い表面光沢を得ることができる。

As can be seen from the above results, the resin composition total is larger than the thermoplastic resin (Comparative Example 1 and Comparative Example 2) in which the content of the PET resin occupies a large number of 50 parts or more with respect to the total resin composition. It was confirmed that the thermoplastic resin composition (Examples 1 to 5) occupying a majority of the PBT resin content of 50 parts or more with respect to the resin amount was superior in alkali solution resistance. Furthermore, with respect to the PBT resin alone (Example 1), the thermoplastic resin (Examples 2 to 5) obtained by mixing 50 parts by weight or less of PTT or PET with respect to the total resin amount including the PBT resin is as follows. There is little decrease in resistance to alkali solution, high surface gloss can be obtained, and PET is blended (Examples 4 and 5), whereas PTT is blended (Examples 2 and 3). As a result, it is possible to obtain a high surface gloss with little deterioration of the alkali solution resistance.

  As described above, in the present invention, a thermoplastic resin having high rigidity and deflection temperature under load, excellent alkali solution resistance, and high surface gloss can be obtained.

Claims (8)

A thermoplastic resin composition comprising an inorganic filler,
The inorganic filler is composed of one having a particle size of 1 to 100 μm and one having a particle size of less than 1 μm,
Furthermore, the inorganic filler having a particle size of less than 1 μm satisfies at least one of the following (a) and (b), and satisfies at least one of the following (c) and (d):
The thermoplastic resin is a polybutylene terephthalate resin alone or an alloy of a polybutylene terephthalate resin and another thermoplastic resin.
(A) The ratio of the inorganic filler whose equivalent area circular diameter [D] is 300 nm or less is 20% or more.
(B) The average value of the equivalent area circle diameter [D] is 500 nm or less.
(C) Layer thickness [T] is 200 nm or less.
(D) The average value of the layer thickness [T] is 50 nm or less.   The thermoplastic resin is an alloy of a polybutylene terephthalate resin and another thermoplastic resin, and the mixing amount of the other thermoplastic resin is 50 parts by weight or less with respect to 100 parts by weight of the polybutylene terephthalate resin. The thermoplastic resin composition according to claim 1.   The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin is an alloy of polybutylene terephthalate and polytrimethylene terephthalate.   The thermoplastic resin composition according to claim 1 or 2, wherein the thermoplastic resin is an alloy of polybutylene terephthalate and polyethylene terephthalate.   The thermoplastic resin according to any one of claims 1 to 4, wherein the inorganic filler having a particle size of less than 1 µm is one or more layered silicates selected from smectite group clay and swellable mica. Resin composition.   The thermoplastic resin composition according to claim 5, wherein the layered silicate is a polyether-treated clay.   An injection molded product using the thermoplastic resin composition according to any one of claims 1 to 6.   Tableware goods using the thermoplastic resin of any one of Claims 1-6.