Molded article, method for manufacturing molded article, and method for improving flowability of thermoplastic resin

Abstract

To provide a molding composed of thermoplastic resin which exhibits highly versatile superplasticizing properties while maintaining mechanical properties.SOLUTION: A molding comprises a resin composition comprising at least a thermoplastic resin A, which is at least one selected from a polyester resin, a polyamide resin, and a polyarylene sulfide resin, inorganic filler B, a thermoplastic resin C excluding the thermoplastic resin A, and a high superplasticizing agent D. The inorganic filler B is covered with the thermoplastic resin C.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a molded article obtained by reducing the melt viscosity to increase fluidity and improve processability, a method for producing a molded article, and a method for improving the fluidity of a thermoplastic resin. [Background technology]

[0002] Molded products made from thermoplastic resins are widely used in a variety of applications, including automotive parts, electrical and electronic parts, and industrial machinery parts, due to their excellent mechanical properties, electrical properties, heat resistance, weather resistance, water resistance, chemical resistance, and solvent resistance.

[0003] In particular, as electronic devices become smaller and lighter, there is an increasing demand for thin-wall flowability. In thin-walled, plate-like or box-shaped molded products, such as microswitch cases, small coil bobbins, thin-walled connectors, and housings for next-generation communication devices, problems such as molding defects (insufficient filling of molded product) due to reduced flowability and increased warpage due to uneven resin flow have been present, so a material with improved thin-wall flowability has been desired.

[0004] The current trend in technology is to manufacture parts with complex, intricate designs that have a narrow flow cross-sectional area and a thickness of 2 mm or less. In this manufacturing process, conventional thermoplastic resin compositions do not have sufficient fluidity and transferability to molds.

[0005] For example, Patent Document 1 proposes a resin composition in which a specific compound having multiple hydroxyl groups is contained in a polyester resin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Special Publication No. 2009-506191 Summary of the Invention [Problem to be solved by the invention]

[0007] However, although this technique has been shown to be effective to a certain extent with polyester resins, it is not versatile enough and further improvements are required.

[0008] An object of the present invention is to provide a molded article made of a thermoplastic resin that exhibits versatile high fluidity while maintaining mechanical properties. [Means for solving the problem]

[0009] The object of the present invention has been achieved by the following. 1. A molded article made of a resin composition containing at least one thermoplastic resin A, which is at least one selected from polyester resins, polyamide resins, and polyarylene sulfide resins; inorganic filler B; thermoplastic resin C other than thermoplastic resin A that has affinity with inorganic filler B; and superplasticizer D, wherein inorganic filler B is coated with thermoplastic resin C. 2. The molded article according to 1 above, wherein the superplasticizer D is at least one selected from the group consisting of a compound H having three or more functional groups, a cyclic oligomer J, a glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less, and a hyperbranched polymer W. 3. The molded product according to 1 or 2 above, wherein the molded product has a thin-walled portion of 2 mm or less. 4. A method for producing a molded product having improved fluidity from a resin composition containing at least one thermoplastic resin A selected from the group consisting of polyester resins, polyamide resins, and polyarylene sulfide resins, inorganic filler B, a thermoplastic resin C other than thermoplastic resin A, and a superfluidizer D, the method comprising melt-kneading inorganic filler B and thermoplastic resin C in advance to coat inorganic filler B with thermoplastic resin C, and then melt-kneading the thermoplastic resin A and superfluidizer D together. 5. A method for improving the fluidity of a resin composition containing at least one thermoplastic resin A selected from the group consisting of polyester resins, polyamide resins, and polyarylene sulfide resins, an inorganic filler B, a thermoplastic resin C other than the thermoplastic resin A, and a superfluidizer D, the method comprising melt-kneading the inorganic filler B and the thermoplastic resin C in advance to coat the inorganic filler B with the thermoplastic resin C, and then melt-kneading the thermoplastic resin A and the superfluidizer D. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a molded article having better resistance to elution than ever before. [Brief explanation of the drawings]

[0011] [Figure 1] 1 is an electron microscope (×20,000 magnification) photograph of a cross section of a molded article of Example 2 of the present invention. [Figure 2] 1 is an electron microscope (×20,000 magnification) photograph of a cross section of a molded article containing an inorganic filler that is not surface-coated, which is one embodiment of the present invention. [Figure 3] 1 is an electron microscope (×20,000 magnification) photograph of a cross section of a molded article of Comparative Example 2. [Figure 4] 1 is a schematic view of an extruder according to one embodiment of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0012] The molded article of the present invention is a molded article made of a resin composition containing at least a thermoplastic resin A, an inorganic filler B, a thermoplastic resin C other than the thermoplastic resin A, and a superplasticizer D, and is characterized in that the inorganic filler B is coated with the thermoplastic resin C.

[0013] <Thermoplastic resin A> The thermoplastic resin A of the present invention is at least one selected from polyester-based resins, polyamide-based resins, and polyarylene sulfide-based resins.

[0014] Specific examples include polybutylene terephthalate resin (PBT), polyethylene terephthalate resin (PET), polytrimethylene terephthalate resin (PTT), polyphenylene sulfide resin (PPS), polyamide resin (PA), etc. The thermoplastic resin A of the present invention can be produced by a conventional method.

[0015] <Polyester resin> The polyester resin is a polyester resin obtained by reacting a dicarboxylic acid component mainly composed of a dicarboxylic acid compound and / or its ester-forming derivative with a diol component mainly composed of a diol compound and / or its ester-forming derivative, and at least one of the dicarboxylic acid component and the diol component contains an aromatic compound.

[0016] Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (e.g., about C4-40 dicarboxylic acids, preferably about C4-14 dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid, and dimer acid), alicyclic dicarboxylic acids (e.g., about C4-40 dicarboxylic acids, preferably about C8-12 dicarboxylic acids, such as hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, and hymic acid), and aromatic dicarboxylic acids. Examples of the dicarboxylic acid include dicarboxylic acids (for example, phthalic acid, isophthalic acid, terephthalic acid, methyl isophthalic acid, methyl terephthalic acid, naphthalenedicarboxylic acids such as 2,6-naphthalenedicarboxylic acid, and dicarboxylic acids having about C8 to C16, such as 4,4'-biphenyldicarboxylic acid, 4,4'-diphenoxyetherdicarboxylic acid, 4,4'-dioxybenzoic acid, 4,4'-diphenylmethanedicarboxylic acid, and 4,4'-diphenylketonedicarboxylic acid), and derivatives thereof (for example, derivatives capable of forming esters such as lower alkyl esters, aryl esters, and acid anhydrides).

[0017] These dicarboxylic acid components can be used alone or in combination. Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid (particularly terephthalic acid and 2,6-naphthalenedicarboxylic acid). The dicarboxylic acid component preferably contains, for example, 50 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more of aromatic dicarboxylic acids. Furthermore, if necessary, polycarboxylic acids such as trimellitic acid and pyromellitic acid or their ester-forming derivatives (alcohol esters, etc.) may be used in combination. The use of such polyfunctional compounds in combination also makes it possible to obtain a branched polyester resin.

[0018] Examples of diol components include aliphatic alkanediols (e.g., C2-C12 aliphatic diols such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, and decanediol, preferably C2-C10 aliphatic diols), polyoxyalkylene glycols (glycols having an alkylene group of C2-C4 and multiple oxyalkylene units, such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, and polytetramethylene glycol), and alicyclic diols (e.g., 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and hydrogenated bisphenol A). Aromatic diols such as hydroquinone, resorcinol, bisphenol, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis-(4-(2-hydroxyethoxy)phenyl)propane, and xylylene glycol may also be used in combination. These diol components can be used alone or in combination. Preferred diol components include C2-10 alkylene glycols (straight-chain alkylene glycols such as ethylene glycol, trimethylene glycol, propylene glycol, and 1,4-butanediol). The diol component preferably contains, for example, 50 mol% or more, preferably 80 mol% or more, and more preferably 90 mol% or more of C2-10 alkylene glycol. Furthermore, polyols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol, or their ester-forming derivatives, may also be used in combination, as necessary. The use of such polyfunctional compounds in combination also makes it possible to obtain a branched polyester resin.

[0019] As the polyester-based resin, a copolyester that combines two or more of the above-mentioned dicarboxylic acid components and diol components, or a copolyester that further combines an oxycarboxylic acid component, a lactone component, etc. as another copolymerizable monomer (hereinafter sometimes referred to as a copolymerizable monomer) can also be used.

[0020] Examples of the hydroxycarboxylic acid (or hydroxycarboxylic acid component or hydroxycarboxylic acids) include hydroxycarboxylic acids such as hydroxybenzoic acid, hydroxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, and hydroxycaproic acid, as well as derivatives thereof. Examples of the lactone include C3-12 lactones such as propiolactone, butyrolactone, valerolactone, and caprolactone (e.g., ε-caprolactone).

[0021] In the copolyester, the proportion of the copolymerizable monomer can be selected, for example, from the range of about 0.01 mol% to about 30 mol%, and is usually about 1 mol% to about 30 mol%, preferably about 3 mol% to about 25 mol%, and more preferably about 5 mol% to about 20 mol%.

[0022] Furthermore, when a homopolyester and a copolyester are used in combination, the ratio of the homopolyester to the copolyester is such that the proportion of the copolymerizable monomer relative to the total monomers is in the range of 0.1 mol% to 30 mol% (preferably approximately 1 mol% to 25 mol%, and more preferably approximately 5 mol% to 25 mol%), and can usually be selected within the range of homopolyester / copolyester = 99 / 1 to 1 / 99 (mass ratio), preferably 95 / 5 to 5 / 95 (mass ratio), and more preferably approximately 90 / 10 to 10 / 90 (mass ratio).

[0023] Preferred polyester resins include homopolyesters or copolyesters containing alkylene arylate units such as alkylene terephthalate or alkylene naphthalate as the main component (e.g., about 50 to 100 mol %, preferably about 75 to 100 mol %) [e.g., homopolyesters such as polyalkylene terephthalate (e.g., polyC2-4 alkylene terephthalates such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT)), 1,4-cyclohexanedimethylene terephthalate (PCT), polyalkylene naphthalate (e.g., polyC2-4 alkylene naphthalates such as polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate); and copolyesters containing alkylene terephthalate and / or alkylene naphthalate units as the main component (e.g., 50 mol % or more)], and these can be used alone or in combination of two or more.

[0024] Particularly preferred polyester resins are homopolyester resins or copolyester resins containing 80 mol % or more (particularly 90 mol % or more) of C2-4 alkylene arylate units such as ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and tetramethylene-2,6-naphthalate (e.g., polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polytetramethylene-2,6-naphthalenedicarboxylate resin, etc.).

[0025] Of these, polyethylene terephthalate resin and polybutylene terephthalate resin are preferred, with polybutylene terephthalate resin being particularly preferred.

[0026] The intrinsic viscosity IV of the polyester resin of the present invention is 1.2 dL / g or less, preferably 0.6 dL / g or more, preferably 0.7 to 1.0 dL / g, and more preferably 0.7 to 0.9. If the intrinsic viscosity is lower than 0.6, the strength and toughness will decrease significantly due to hydrolysis, and if it exceeds 1.2 dL / g, the thermoplastic resin C may peel off from the inorganic filler B coated with the thermoplastic resin C during kneading, resulting in a loss of effectiveness. The intrinsic viscosity can also be adjusted by blending polyester resins with different intrinsic viscosities.

[0027] For example, a polyester resin with an intrinsic viscosity of 0.9 dL / g can be prepared by blending a polyester resin with an intrinsic viscosity of 1.0 dL / g with a polyester resin with an intrinsic viscosity of 0.7 dL / g. The intrinsic viscosity (IV) of the polyester resin can be measured in o-chlorophenol at 35°C.

[0028] The carboxylic acid terminal concentration of the polyester resin is preferably 0.5 to 30 meq / kg, more preferably 0.5 to 25 meq / kg, and even more preferably 0.5 to 12 meq / kg. To achieve this range of carboxylic acid terminal concentration, a high molecular weight polymer with fewer terminal groups may be used as the polyester resin, or a melt polymerized product with an intrinsic viscosity IV of about 0.1 to 0.8 dL / g may be polymerized by solid-state polymerization.

[0029] When solid-state polymerization is used, it is desirable to treat at a low temperature for a long time because a high treatment temperature increases the number of terminal carboxyl groups. This can usually be adjusted to, for example, 120 to 220°C, preferably 140 to 200°C, and more preferably 150 to 190°C under reduced pressure or in an inert gas atmosphere.

[0030] The carboxylic acid terminal concentration was determined by dissolving a pulverized sample of polyester resin pellets obtained by polymerization in benzyl alcohol at 215° C. for 10 minutes, and then titrating it with a 0.01 N aqueous sodium hydroxide solution.

[0031] <Polyamide resin> Polyamide resins include polyamides derived from diamines and dicarboxylic acids, polyamides obtained by using aminocarboxylic acids, optionally in combination with diamines and / or dicarboxylic acids, and polyamides derived from lactams, optionally in combination with diamines and / or dicarboxylic acids. Polyamides also include copolyamides formed from at least two different polyamide-forming components.

[0032] Examples of diamines include aliphatic diamines such as trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2,2,4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, and octamethylenediamine; aromatic diamines such as phenylenediamine and metaxylylenediamine; and alicyclic diamines such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane. These diamines can be used alone or in combination.

[0033] Examples of dicarboxylic acids include aromatic dicarboxylic acids such as phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, and naphthalenecarboxylic acid; alicyclic dicarboxylic acids such as cyclohexane-1,4-dicarboxylic acid and cyclohexane-1,3-dicarboxylic acid; C4-20 aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and octadecanedioic acid; and dimerized fatty acids (dimer acids).

[0034] Examples of aminocarboxylic acids include C4-20 aminocarboxylic acids such as aminoheptanoic acid, aminononanoic acid, and aminoundecanoic acid. Examples of lactams that can be used alone or in combination with aminocarboxylic acids include C4-20 lactams such as butyrolactam, pivalolactam, caprolactam, capryllactam, enantholactam, undecanolactam, and dodecalactam. These lactams can also be used alone or in combination.

[0035] Examples of polyamide resins include aliphatic polyamides such as nylon 46, nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, and nylon 12; polyamides obtained from aromatic dicarboxylic acids (e.g., terephthalic acid and / or isophthalic acid) and aliphatic diamines (e.g., hexamethylenediamine); polyamides obtained from aliphatic dicarboxylic acids (e.g., adipic acid) and aromatic diamines (e.g., metaxylylenediamine); and polyamides obtained from aromatic and aliphatic dicarboxylic acids (e.g., terephthalic acid and adipic acid) and aliphatic diamines (e.g., hexamethylenediamine).

[0036] These polyamide resins can be used alone or in combination. Preferred polyamides include nylon 6, nylon 66, nylon 610, nylon 612, nylon 11, nylon 12, and polyamides in which at least one of the diamine component and the dicarboxylic acid component is an aromatic compound.

[0037] <Polyarylene sulfide resin> Polyarylene sulfide resins are polymeric compounds mainly composed of repeating units of -(Ar-S)- (where Ar is an arylene group), and in this embodiment, polyarylene sulfide resins with a generally known molecular structure can be used.

[0038] Examples of the arylene group include p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p,p'-diphenylene sulfone, p,p'-biphenylene, p,p'-diphenylene ether, p,p'-diphenylene carbonyl, and naphthalene. The PAS resin may be a homopolymer consisting of the above repeating units, or a copolymer containing the following different repeating units may be preferable in terms of processability, etc.

[0039] As a homopolymer, a polyphenylene sulfide resin (also called a PAS resin) having a p-phenylene sulfide group as a repeating unit, in which a p-phenylene group is used as the arylene group, is preferably used. Furthermore, as a copolymer, a combination of two or more different arylene sulfide groups consisting of the above-mentioned arylene groups can be used, and a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferred. Among these, a copolymer containing 70 mol % or more, preferably 80 mol % or more of p-phenylene sulfide groups is suitable from the viewpoint of physical properties such as heat resistance, moldability, and mechanical properties.

[0040] Among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization of a monomer mainly composed of a bifunctional halogenated aromatic compound is particularly preferred. The polyarylene sulfide resin used in this embodiment may be a mixture of two or more polyphenylene sulfide resins having different molecular weights.

[0041] In addition to the linear polyphenylene sulfide resin, examples of the polymer include a polymer in which a partially branched structure or a crosslinked structure is formed by using a small amount of a monomer such as a polyhaloaromatic compound having three or more halogen substituents during condensation polymerization, and a polymer in which the melt viscosity is increased by oxidative crosslinking or thermal crosslinking by heating a low-molecular-weight linear polymer at a high temperature in the presence of oxygen or the like, thereby improving moldability.

[0042] <Inorganic filler B> Examples of the inorganic filler B to be contained in the molded article of the present invention include a fibrous filler, a plate-like filler, and a granular filler.

[0043] Examples of fibrous fillers include inorganic fibers such as glass fibers, asbestos fibers, carbon fibers, silica fibers, alumina fibers, silica-alumina fibers, aluminum silicate fibers, zirconia fibers, potassium titanate fibers, silicon carbide fibers, and whiskers (whiskers of silicon carbide, alumina, silicon nitride, etc.).

[0044] Examples of the plate-like filler include talc, mica, glass flakes, graphite, etc. Examples of the powdery filler include glass beads, glass powder, milled fiber (e.g., milled glass fiber), wollastonite, etc.

[0045] The average diameter of the fibrous filler may be, for example, about 1 μm to 30 μm (preferably 5 μm to 20 μm, more preferably 10 to 15 μm), and the average length may be, for example, about 100 μm to 5 mm (preferably 300 μm to 4 mm, more preferably 500 μm to 3.5 mm).

[0046] The average primary particle size of the plate-like or granular filler can be, for example, about 0.1 μm to 500 μm, and preferably about 1 μm to 100 μm. These inorganic fillers can be used alone or in combination of two or more.

[0047] The average diameter and length of the fibrous filler and the average primary particle diameter of the plate-like or granular filler are values ​​calculated by analyzing images of the fibrous filler, plate-like or granular filler before being blended into the resin composition, taken with a CCD camera, and calculating the weighted average. These values ​​can be calculated, for example, using a dynamic image analysis / particle (state) analyzer PITA-3 manufactured by Seishin Enterprise Co., Ltd. The aspect ratio of the plate-like or granular filler is not particularly limited and can be, for example, 1 or more and 10 or less.

[0048] <Thermoplastic resin C> The thermoplastic resin C of the present invention is not particularly limited as long as it is other than the thermoplastic resin A and is capable of coating the inorganic filler B. Examples thereof include polyolefin resins such as polypropylene resin, polyethylene resin, poly(1-)butene resin, and polypentene resin, polystyrene resin, acrylonitrile-butadiene-styrene (ABS) resin, polyvinyl acetal resin, ethylene-vinyl acetate copolymer (EVA) resin, polyvinyl alcohol resin, polyphenylene ether resin, acrylic resin, polyamide resin, polyvinyl chloride resin (PVC), novolac resin, polyurethane resin, polyisobutylene, elastomer, and the like.

[0049] Examples of the elastomer include olefin-based elastomers, styrene-based elastomers, silicone-based elastomers, polyester-based elastomers, polyamide-based elastomers, and urethane-based elastomers.

[0050] The olefin-based elastomer is a copolymer containing ethylene and / or propylene as a component, and specific examples thereof include ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer, ethylene-propylene-butene copolymer, ethylene-propylene-diene copolymer, ethylene-ethyl acrylate copolymer, ethylene-vinyl acetate copolymer, ethylene-glycidyl methacrylate copolymer, etc., but are not limited to these. Most preferred are epoxy group-containing olefin-based copolymers that have groups reactive with inorganic fillers.

[0051] Furthermore, among olefin-based elastomers, graft copolymers can also be used in which one or more polymers or copolymers composed of repeating units represented by the following general formula (1) are chemically bonded in a branched or crosslinked structure to an ethylene-unsaturated carboxylic acid alkyl ester copolymer or an olefin-based copolymer composed of an α-olefin and a glycidyl ester of an α,β-unsaturated acid.

[0052] [ka] (wherein R represents hydrogen or a lower alkyl group, and X represents one or more groups selected from -COOCH3, -COOC2H5, -COOC4H9, -COOCH2CH(C2H5)C4H9, -C6H5, and -CN)

[0053] As the α-olefin, a C2-4 olefin such as ethylene or propylene can be used, with ethylene or propylene being preferred. As the α,β-unsaturated acid glycidyl ester, glycidyl acrylate or glycidyl methacrylate is preferred. In addition, a third component such as a C1-12 (meth)acrylic acid ester or vinyl acetate may be copolymerized.

[0054] The olefin and glycidyl ester can be contained in the copolymer in a range of 30 to 90 mol % or 70 to 10 mol %, respectively, and the third component can be contained in a range of 0 to 30 mol %.

[0055] In the present invention, ethylene-glycidyl methacrylate copolymer (hereinafter also referred to as EGMA) is particularly preferred. The ratio of glycidyl methacrylate to ethylene is not particularly limited, but the ratio is preferably in the range of 1 to 30 parts by mass, preferably 3 to 20 parts by mass, and more preferably 8 to 15 parts by mass, based on 100 parts by mass of the copolymer, when the modified sites of the copolymer are converted into the mass of each monomer.

[0056] Examples of styrene-based elastomers include block or graft copolymers (or hydrogenated products thereof) of hard segments composed of a homopolymer or copolymer of an aromatic vinyl monomer such as styrene, α-methylstyrene, or vinyltoluene, and soft segments composed of a homopolymer or copolymer of at least one monomer selected from α-olefins (α-C2-12 olefins such as ethylene, propylene, 1-butene, 1-hexene, and 1-octene) and diene monomers (butadiene, isoprene, etc.).

[0057] The styrene-based elastomer may also be an elastomer having a reactive functional group, such as an acid-modified elastomer modified with an acid or acid anhydride, such as (meth)acrylic acid or maleic anhydride, or an epoxy-modified elastomer obtained by using a copolymerizable monomer having a glycidyl group or an epoxy group (such as glycidyl (meth)acrylate) or by epoxidizing the unsaturated bond of an elastomer.

[0058] Representative styrene-based elastomers include styrene-diene-styrene block copolymers [styrene-butadiene-styrene block copolymer (SBS), styrene-isoprene-styrene block copolymer (SIS), etc.], hydrogenated block copolymers [styrene-ethylene-butylene-styrene block copolymer (or hydrogenated (styrene-butadiene-styrene block copolymer)) (SEBS), styrene-ethylene-propylene-styrene block copolymer (or hydrogenated (styrene-isoprene-styrene block copolymer)) (SEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer (SEEPS), hydrogenated polymers of random styrene-butadiene copolymers, etc.], and modified copolymers in which functional groups (epoxy groups, carboxyl groups, acid anhydride groups, etc.) have been introduced into these copolymers [epoxidized styrene-diene copolymers in which the unsaturated bonds of the diene have been epoxidized (epoxidized styrene-diene-styrene block copolymers or their hydrogenated polymers, etc.)].

[0059] Silicone elastomers are elastomers containing organopolysiloxane as the main component, and are divided into polydimethylsiloxane, polymethylphenylsiloxane, and polydiphenylsiloxane. A portion of the organopolysiloxane may be modified with a vinyl group, an alkoxy group, or the like. Specific examples of silicone elastomers include silicone rubber (poly(dimethylsiloxane) and poly(dimethylsiloxane-co-methylvinylsiloxane)).

[0060] Commercially available silicone elastomers include the KE series (manufactured by Shin-Etsu Chemical Co., Ltd.), SE series, CY series, and SH series (all manufactured by Toray Dow Corning Silicone Co., Ltd.).

[0061] Examples of polyester-based elastomers include, but are not limited to, block copolymers having an aromatic polyester such as polyethylene terephthalate or polybutylene terephthalate as a hard segment and a polyether such as polyethylene glycol or polytetramethylene glycol, or an aliphatic polyester such as polyethylene adipate, polybutylene adipate, or polycaprolactone as a soft segment.

[0062] Examples of polyamide elastomers include, but are not limited to, block copolymers having nylon 6, nylon 66, nylon 11, nylon 12, or the like as hard segments and polyether or aliphatic polyester as soft segments.

[0063] Examples of urethane-based elastomers include, but are not limited to, block copolymers having a polyurethane as a hard segment obtained by reacting a diisocyanate such as 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tolylene diisocyanate, or hexamethylene diisocyanate with a glycol such as ethylene glycol or tetramethylene glycol, and a polyether such as polyethylene glycol, polypropylene glycol, or polytetramethylene glycol, or an aliphatic polyester such as polyethylene adipate, polybutylene adipate, or polycaprolactone as a soft segment.

[0064] The inorganic filler B of the present invention is characterized in that its surface is coated with a thermoplastic resin C. Whether or not it is coated can be determined by observing the cross section of a molded article with an SEM or by the following method (hereinafter also referred to as coating B).

[0065] Inorganic filler B coated with thermoplastic resin C can be produced by a coating process in which thermoplastic resin C and inorganic filler B are melt-kneaded. This inorganic filler B, whose surface is coated with thermoplastic resin C, is melt-kneaded with thermoplastic resin A. The thermoplastic resin A not involved in the coating and excess thermoplastic resin C are removed using a solvent that can dissolve both thermoplastic resin A and thermoplastic resin C. The coated inorganic filler B is then measured by FT-IR.

[0066] When absorption due to thermoplastic resin C is observed in FT-IR compared with an inorganic filler that has not been coated, it is clear that inorganic filler B is coated with thermoplastic resin C.

[0067] The resin composition for molded articles can be produced by going through a production step in which the surface of inorganic filler is coated with thermoplastic resin C, then adding thermoplastic resin A, and further melt-kneading the mixture.

[0068] For example, inorganic filler B and thermoplastic resin C may first be melt-kneaded in an extruder, pelletized to form a masterbatch, and then polyester thermoplastic resin A and the masterbatch may be melt-kneaded again to form pellets, which may then be produced in an injection molding machine. Alternatively, the masterbatch and thermoplastic resin A may be blended in any ratio, and then directly charged into an injection molding machine to produce the masterbatch.

[0069] Alternatively, a method that does not involve masterbatching may be used, for example, by feeding inorganic filler B and thermoplastic resin C into an extruder and melt-kneading them, then feeding thermoplastic resin A and melt-kneading them, pelletizing them, and then injection molding them. In this case, kneading may be performed using a so-called tandem extruder. Tandem extruders allow for precise control of the number of screws used in each barrel, the kneading pattern, the kneading temperature, and the like. Using this method, a molded product can be obtained in which inorganic filler B coated with thermoplastic resin C is dispersed in thermoplastic resin A.

[0070] The thermoplastic resin C may be added to the coated thermoplastic resin C during melt-kneading with the thermoplastic resin A.

[0071] In the present invention, the inorganic filler B is contained in an amount of preferably 20 to 200 parts by mass, more preferably 30 to 160 parts by mass, per 100 parts by mass of the thermoplastic resin A.

[0072] In the present invention, inorganic filler BN, which is not surface-coated, can also be blended in addition to inorganic filler B, the surface of which is coated with thermoplastic resin C. The blending amount is appropriately selected depending on the desired mechanical properties, but it is preferably contained in an amount of 0 to 200 parts by mass per 100 parts by mass of thermoplastic resin A.

[0073] In the present invention, it is preferable that the thermoplastic resin C has affinity with the inorganic filler B. Here, affinity refers to the degree to which the thermoplastic resin C does not peel off from the surface of the inorganic filler B during melt-kneading, such as molding, of the resin composition.

[0074] For example, the thermoplastic resin C may contain a functional group reactive with the inorganic filler B, or the inorganic filler B may be treated with a surface treatment agent to reduce the hydrophobicity of the inorganic filler B or to promote reaction or hydrogen bonding with the functional group of the thermoplastic resin C. Alternatively, a thermoplastic resin C having a higher viscosity than the thermoplastic resin A may be selected to reduce shear deformation of the thermoplastic resin C during melt-kneading with the thermoplastic resin A.

[0075] <High flow agent D> The superplasticizer D of the present invention is not limited as long as it is a material that can superplasticize a thermoplastic resin composition, but is preferably at least one selected from a compound H having three or more functional groups, a cyclic oligomer J, a glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less, and a hyperbranched polymer W.

[0076] <Compound H having three or more functional groups> The compound H having three or more functional groups (hereinafter also referred to as compound H) used in the present invention is a component necessary for improving the fluidity of the thermoplastic resin of the present invention. Compound H is not limited as long as it is a polyfunctional compound having three or more functional groups in the molecule, and may be a low molecular weight compound or a high molecular weight polymer.

[0077] The functional group of such compound H is preferably at least one selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, a glycidyl group, an isocyanate group, an ester group, and an amide group, and compound H preferably has three or more of these functional groups, which may be the same or different.

[0078] Furthermore, compound H may be any compound having three or more functional groups, such as a trifunctional compound, a tetrafunctional compound, or a pentafunctional compound, but is more preferably a trifunctional compound or a tetrafunctional compound in terms of excellent fluidity and mechanical properties.

[0079] Preferred examples of the compound H having three or more functional groups, when the functional group is a hydroxyl group, include polyhydric alcohols having 3 to 24 carbon atoms such as 1,2,4-butanetriol, 1,2,5-pentanetriol, 1,2,6-hexanetriol, 1,2,3,6-hexanetetrol, glycerin, diglycerin, triglycerin, tetraglycerin, pentaglycerin, hexaglycerin, triethanolamine, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tritrimethylolpropane, 2-methylpropanetriol, 2-methyl-1,2,4-butanetriol, pentaerythritol, dipentaerythritol, tripentaerythritol, methyl glucoside, sorbitol, mannitol, sucrose, 1,3,5-trihydroxybenzene, and 1,2,4-trihydroxybenzene, and polymers such as polyvinyl alcohol.

[0080] Among these, glycerin, diglycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol, which have a branched structure, are preferred in terms of fluidity and mechanical properties.

[0081] Preferred examples of the compound H having three or more functional groups, when the functional group is a carboxyl group, include polycarboxylic acids such as propane-1,2,3-tricarboxylic acid, 2-methylpropane-1,2,3-triscarboxylic acid, butane-1,2,4-tricarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid, trimesic acid, hemimellitic acid, pyromellitic acid, benzenepentacarboxylic acid, cyclohexane-1,2,4-tricarboxylic acid, cyclohexane-1,3,5-tricarboxylic acid, cyclohexane-1,2,4,5-tetracarboxylic acid, naphthalene-1,2,4-tricarboxylic acid, naphthalene-2,5,7-tricarboxylic acid, pyridine-2,4,6-tricarboxylic acid, naphthalene-1,2,7,8-tetracarboxylic acid, and naphthalene-1,4,5,8-tetracarboxylic acid, as well as polymers of acrylic acid and methacrylic acid, and acid anhydrides thereof can also be used.

[0082] Among these, propane-1,2,3-tricarboxylic acid, trimellitic acid, trimesic acid and acid anhydrides thereof, which have a branched structure, are preferred in terms of fluidity.

[0083] When the functional group of compound H having three or more functional groups is an amino group, it is preferable that at least one of the three or more substituents is a primary or secondary amine, more preferably that all of them are primary or secondary amines, and particularly preferably that all of them are primary amines.

[0084] Preferred examples of the compound H having three or more functional groups, when the functional group is an amino group, include 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2,4-triaminobutane, 1,2,3,4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetraminobenzene, 1,2,4-triaminonaphthalene, 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, and 1,4,5,8-tetraminonaphthalene. Among these, 1,2,3-triaminopropane, 1,3,5-triaminocyclohexane, and 1,3,5-triaminobenzene, which have a branched structure, are preferred in terms of flowability.

[0085] Preferred examples of the compound H having three or more functional groups, when the functional group is a glycidyl group, include monomers such as triglycidyl triazolidine-3,5-dione and triglycidyl isocyanurate, and polymers such as poly(ethylene / glycidyl methacrylate)-g-polymethyl methacrylate, glycidyl group-containing acrylic polymers, and glycidyl group-containing acrylic / styrene polymers.

[0086] Preferred examples of the compound H having three or more functional groups, when the functional groups are isocyanate groups, include nonane triisocyanate (for example, 4-isocyanatomethyl-1,8-octane diisocyanate (TIN)), decane triisocyanate, undecane triisocyanate, and dodecane triisocyanate.

[0087] Preferred examples of the compound H having three or more functional groups, when the functional group is an ester group, include aliphatic acid esters or aromatic acid esters of the compound having three or more hydroxyl groups, and ester derivatives of the compound having three or more carboxyl groups.

[0088] Preferred examples of the compound H having three or more functional groups include, when the functional groups are amide groups, amide derivatives of the above-mentioned compound having three or more carboxyl groups.

[0089] From the viewpoint of fluidity and mechanical properties, it is preferable that the compound H having three or more functional groups contains one or more alkylene oxide units. Preferred examples of the alkylene oxide unit include aliphatic alkylene oxide units having 1 to 4 carbon atoms, and specific examples include methylene oxide units, ethylene oxide units, trimethylene oxide units, propylene oxide units, tetramethylene oxide units, 1,2-butylene oxide units, 2,3-butylene oxide units, and isobutylene oxide units.

[0090] In the present invention, it is preferable to use a compound containing an ethylene oxide unit or a propylene oxide unit as an alkylene oxide unit in view of excellent flowability, mechanical properties, recyclability, or productivity, and it is particularly preferable to use a compound containing a propylene oxide unit in view of excellent hydrolysis resistance and bleed-out resistance.

[0091] The number of alkylene oxide units contained in the compound H having three or more functional groups used in the present invention is preferably 0.1 to 20, more preferably 0.5 to 10, and even more preferably 1 to 5, alkylene oxide units per functional group.

[0092] Preferred examples of the compound H having three or more functional groups containing one or more alkylene oxide units, when the functional group is a hydroxyl group, include (poly)oxymethylene glycerin, (poly)oxyethylene glycerin, (poly)oxytrimethylene glycerin, (poly)oxypropylene glycerin, (poly)oxyethylene-(poly)oxypropylene glycerin, (poly)oxytetramethylene glycerin, (poly)oxymethylene diglycerin, (poly)oxyethylene diglycerin, (poly)oxytetramethylene glycerin, (poly)oxymethylene diglycerin, (poly)oxyethylene diglycerin, and (poly)oxytetramethylene glycerin. Trimethylene diglycerin, (poly)oxypropylene diglycerin, (poly)oxymethylene trimethylolpropane, (poly)oxyethylene trimethylolpropane, (poly)oxytrimethylene trimethylolpropane, (poly)oxypropylene trimethylolpropane, (poly)oxyethylene-(poly)oxypropylene trimethylolpropane, (poly)oxytetramethylene trimethylolpropane, (poly)oxymethylene ditrimethylolpropane, (poly)oxyethylene Examples of the olefin copolymer include ditrimethylolpropane, (poly)oxytrimethylene ditrimethylolpropane, (poly)oxypropylene ditrimethylolpropane, (poly)oxymethylene pentaerythritol, (poly)oxyethylene pentaerythritol, (poly)oxytrimethylene pentaerythritol, (poly)oxypropylene pentaerythritol, (poly)oxyethylene-(poly)oxypropylene pentaerythritol, (poly)oxytetramethylene pentaerythritol, (poly)oxymethylene dipentaerythritol, (poly)oxyethylene dipentaerythritol, (poly)oxytrimethylene dipentaerythritol, (poly)oxypropylene dipentaerythritol, (poly)oxymethylene glucose, (poly)oxyethylene glucose, (poly)oxytrimethylene glucose, (poly)oxypropylene glucose, (poly)oxyethylene-(poly)oxypropylene glucose, and (poly)oxytetramethylene glucose.

[0093] When the functional group is a carboxylic acid, examples thereof include propane-1,2,3-tricarboxylic acid containing a (poly)methylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly)ethylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly)trimethylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly)propylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly)tetramethylene oxide unit, 2-methylpropane-1,2,3-triscarboxylic acid containing a (poly)methylene oxide unit, 2-methylpropane-1,2,3-triscarboxylic acid containing a (poly)ethylene oxide unit, 2-methylpropane-1,2,3-triscarboxylic acid containing a (poly)trimethylene oxide unit, 2-methylpropane-1,2,3-triscarboxylic acid containing a (poly)propylene oxide unit, and 2-methylpropane-1,2,3-triscarboxylic acid containing a (poly)tetramethylene oxide unit. 2-Methylpropane-1,2,3-tricarboxylic acid, butane-1,2,4-tricarboxylic acid containing (poly)methylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly)ethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly)trimethylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly)propylene oxide units, butane-1,2,4-tricarboxylic acid containing (poly)tetramethylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly)methylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly)ethylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly)trimethylene oxide units, butane-1,2,3,4-tetracarboxylic acid containing (poly)propylene oxide units, butane-1,2,3,4-tetracarboxylic acid, trimellitic acid containing (poly)methylene oxide units, trimellitic acid containing (poly)ethylene oxide units, trimellitic acid containing (poly)trimethylene oxide units, trimellitic acid containing (poly)propylene oxide units, trimellitic acid containing (poly)tetramethylene oxide units, trimesic acid containing (poly)methylene oxide units, trimesic acid containing (poly)ethylene oxide units, trimesic acid containing (poly)trimethylene oxide units, trimesic acid containing (poly)propylene oxide units, trimesic acid containing (poly)tetramethylene oxide units, hemimellitic acid containing (poly)methylene oxide units, hemimellitic acid containing (poly)ethylene oxide units, hemimellitic acid containing (poly)trimethylene oxide units, hemimellitic acid containing (poly)propylene oxide units, Examples of such an acid include hemimellitic acid containing (poly)tetramethylene oxide units, pyromellitic acid containing (poly)methylene oxide units, pyromellitic acid containing (poly)ethylene oxide units, pyromellitic acid containing (poly)trimethylene oxide units, pyromellitic acid containing (poly)propylene oxide units, pyromellitic acid containing (poly)tetramethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly)methylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly)ethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly)trimethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly)propylene oxide units, and cyclohexane-1,3,5-tricarboxylic acid containing (poly)tetramethylene oxide units.

[0094] When the functional group is an amino group, 1,2,3-triaminopropane containing (poly)methylene oxide units, 1,2,3-triaminopropane containing (poly)ethylene oxide units, 1,2,3-triaminopropane containing (poly)trimethylene oxide units, 1,2,3-triaminopropane containing (poly)propylene oxide units, 1,2,3-triaminopropane containing (poly)tetramethylene oxide units, 1,2,3-triaminopropane containing (poly)methylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly)ethylene oxide units, 1,2 ,3-triamino-2-methylpropane, 1,2,3-triamino-2-methylpropane containing (poly)trimethylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly)propylene oxide units, 1,2,3-triamino-2-methylpropane containing (poly)tetramethylene oxide units, 1,2,4-triaminobutane containing (poly)methylene oxide units, 1,2,4-triaminobutane containing (poly)ethylene oxide units, 1,2,4-triaminobutane containing (poly)trimethylene oxide units, (poly i) 1,2,4-triaminobutane containing propylene oxide units, 1,2,4-triaminobutane containing (poly)tetramethylene oxide units, 1,2,3,4-tetraminobutane containing (poly)methylene oxide units, 1,2,3,4-tetraminobutane containing (poly)ethylene oxide units, 1,2,3,4-tetraminobutane containing (poly)trimethylene oxide units, 1,2,3,4-tetraminobutane containing (poly)propylene oxide units, 1,2,3,4-tetraminobutane containing (poly)tetramethylene oxide units, 1,3,5-triaminocyclohexane containing (poly)methylene oxide units, 1,3,5-triaminocyclohexane containing (poly)ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly)trimethylene oxide units, 1,3,5-triaminocyclohexane containing (poly)propylene oxide units, 1,3,5-triaminocyclohexane containing (poly)tetramethylene oxide units, 1,2,4-triaminocyclohexane containing (poly)methylene oxide units, 1,2,4-Triaminocyclohexane, 1,2,4-triaminocyclohexane containing (poly)trimethylene oxide units, 1,2,4-triaminocyclohexane containing (poly)propylene oxide units, 1,2,4-triaminocyclohexane containing (poly)tetramethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly)methylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly)ethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly)trimethylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly)propylene oxide units, 1,2,4,5-tetraminocyclohexane containing (poly)tetramethylene oxide units, 1,3,5-triaminobenzene containing (poly)methylene oxide units, (poly Examples of the amino groups include 1,3,5-triaminobenzene containing ethylene oxide units, 1,3,5-triaminobenzene containing (poly)trimethylene oxide units, 1,3,5-triaminobenzene containing (poly)propylene oxide units, 1,3,5-triaminobenzene containing (poly)tetramethylene oxide units, 1,2,4-triaminobenzene containing (poly)methylene oxide units, 1,2,4-triaminobenzene containing (poly)ethylene oxide units, 1,2,4-triaminobenzene containing (poly)trimethylene oxide units, 1,2,4-triaminobenzene containing (poly)propylene oxide units, and 1,2,4-triaminobenzene containing (poly)tetramethylene oxide units. Trimethylolpropane tris[poly(propylene glycol)amine] ether is also suitable.

[0095] When the functional group is an ester group, examples thereof include aliphatic acid esters or aromatic acid esters of the above-mentioned alkylene oxide unit-containing compound having three or more hydroxyl groups, and ester derivatives of the above-mentioned alkylene oxide unit-containing compound having three or more carboxyl groups.

[0096] When the functional group is an amide group, examples include amide derivatives of the above-mentioned compounds containing alkylene oxide units and having three or more carboxyl groups.

[0097] Particularly preferred examples of the compound H having three or more functional groups containing one or more alkylene oxide units from the viewpoint of fluidity include (poly)oxymethylene glycerin, (poly)oxypropylene glycerin, (poly)oxyethylene diglycerin, (poly)oxyethylene trimethylolpropane, (poly)oxypropylene trimethylolpropane, (poly)oxyethylene ditrimethylolpropane, (poly)oxypropylene ditrimethylolpropane, (poly)oxyethylene pentaerythritol, (poly)oxypropylene pentaerythritol, (poly)oxyethylene dipentaerythritol, and (poly)oxypropylene dipentaerythritol when the functional group is a carboxylic acid; and include propane-1,2,3-tricarboxylic acid containing a (poly)ethylene oxide unit, propane-1,2,3-tricarboxylic acid containing a (poly)propylene oxide unit, and trimellitic acid containing a (poly)ethylene oxide unit. , trimellitic acid containing (poly)propylene oxide units, trimesic acid containing (poly)ethylene oxide units, trimesic acid containing (poly)propylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly)ethylene oxide units, cyclohexane-1,3,5-tricarboxylic acid containing (poly)propylene oxide units, and when the functional group is an amino group, examples thereof include 1,2,3-triaminopropane containing (poly)ethylene oxide units, 1,2,3-triaminopropane containing (poly)propylene oxide units, 1,3,5-triaminocyclohexane containing (poly)ethylene oxide units, 1,3,5-triaminocyclohexane containing (poly)propylene oxide units, 1,3,5-triaminobenzene containing (poly)ethylene oxide units, 1,3,5-triaminobenzene containing (poly)propylene oxide units, and trimethylolpropane tris[poly(propylene glycol)amine] ether.

[0098] The viscosity of the compound H having three or more functional groups used in the present invention is preferably 15,000 m·Pa or less at 25°C, more preferably 5,000 m·Pa or less from the standpoint of fluidity and mechanical properties, and particularly preferably 2,000 m·Pa or less.

[0099] The molecular weight or weight average molecular weight (Mw) of the compound H having three or more functional groups used in the present invention is preferably in the range of 50 to 10,000, more preferably in the range of 150 to 8,000, and even more preferably in the range of 200 to 3,000, from the viewpoint of fluidity.

[0100] In the present invention, the Mw of the compound H having three or more functional groups is a value calculated as polymethyl methacrylate (PMMA) measured by size exclusion chromatography (SEC) using hexafluoroisopropanol as a solvent.

[0101] The water content of the compound H having three or more functional groups used in the present invention is preferably 1% or less. More preferably, the water content is 0.5% or less, and even more preferably, 0.1% or less. There is no particular lower limit for the water content of the compound H. A water content higher than 1% is not preferred because it causes a decrease in mechanical properties.

[0102] The compound H having three or more functional groups used in the present invention may contain a metal component, for example, a catalyst containing an alkali metal or alkaline earth metal used to introduce an alkylene oxide unit.

[0103] In the present invention, the blending amount of compound H having three or more functional groups is preferably in the range of 0.01 to 5 parts by mass of compound H per 100 parts by mass of thermoplastic resin A in terms of flowability, mechanical properties, hydrolysis resistance, and bleed-out resistance; from the viewpoints of flowability and mechanical properties, a blending amount in the range of 0.01 to 3 parts by mass is more preferable, a blending amount in the range of 0.01 to 1 part by mass is even more preferable, and a blending amount in the range of 0.1 to 1 part by mass is particularly preferable.

[0104] In the present invention, it is preferable from the viewpoint of fluidity that compound H having three or more functional groups has at least one hydroxyl group or one carboxyl group, more preferably compound H has three or more hydroxyl groups, carboxyl groups, or amino groups, and even more preferably compound H has three or more hydroxyl groups.

[0105] <Cyclic Oligomer J> The cyclic oligomer J of the present invention may include a cyclic polyester oligomer.

[0106] The cyclic polyester oligomer (hereinafter also referred to as cyclic polyester or cyclic ester oligomer) may be a cyclic polymer having a polyester skeleton. The polyester skeleton (or the polyester constituting the polyester skeleton) may be any of aromatic polyester, alicyclic polyester, aliphatic polyester, etc. The polyester skeleton may usually be an aromatic polyester.

[0107] Representative cyclic polyester oligomers include compounds (particularly cyclic aromatic polyester oligomers) having structural units represented by the following formula:

[0108] [ka]

[0109] (wherein R represents an alkylene group or a divalent alicyclic group, (A) represents a divalent aromatic group or an alicyclic group, and n represents an integer of 1 or greater).

[0110] In the above formula, examples of the alkylene group R include alkylene groups having 2 to 12 carbon atoms such as ethylene, propylene, trimethylene, tetramethylene, and hexamethylene (particularly linear alkylene groups having 2 to 12 carbon atoms), preferably alkylene groups having 2 to 8 carbon atoms, and more preferably alkylene groups having 2 to 4 carbon atoms.

[0111] In the above formula, examples of the divalent alicyclic group R include a cycloalkylene group R (for example, a cycloalkylene group having 5 to 10 carbon atoms such as a 1,4-cyclohexylene group), and a cycloalkanedialkylene group (for example, a cycloalkane-dialkylene group having 1 to 4 carbon atoms such as a 1,4-cyclohexanedimethylene group).

[0112] Furthermore, n may be 1 or more, for example, 1 to 10, preferably 1 to 5, more preferably 1 to 3, and particularly 1. When n is 2 or more, multiple Rs may be the same or different alkylene groups or cycloalkylene groups.

[0113] In the above formula, examples of the aromatic group (A) include arylene groups having 6 to 12 carbon atoms, such as phenylene groups (e.g., m-phenylene groups, p-phenylene groups, etc.) and naphthylene groups (e.g., 2,6-naphthylene groups, etc.), preferably arylene groups having 6 to 10 carbon atoms, more preferably arylene groups having 6 to 8 carbon atoms, etc. Examples of the alicyclic group (A) include cycloalkylene groups (e.g., cycloalkylene groups having 5 to 10 carbon atoms, such as 1,4-cyclohexylene groups, etc.).

[0114] Preferred cyclic polyester oligomers include cyclic polyalkylene arylates, for example, cyclic polyalkylene terephthalates having 2 to 6 carbon atoms, such as cyclic polyethylene terephthalate oligomer, cyclic polypropylene terephthalate oligomer, and cyclic polybutylene terephthalate (polytetramethylene terephthalate) oligomer; and cyclic polycyclohexanedimethylene terephthalate. In particular, cyclic polyalkylene terephthalate oligomers, particularly cyclic polyalkylene terephthalates having 2 to 4 carbon atoms, such as cyclic polybutylene terephthalate, are preferred.

[0115] The average degree of polymerization of the cyclic polyester oligomer may be, for example, about 2 to 30, preferably about 3 to 25, more preferably about 5 to 20 (for example, about 6 to 18), and usually about 8 to 15.

[0116] In particular, the cyclic polyester oligomer may be a mixture of cyclic oligomers having various degrees of polymerization, with the majority (e.g., the region showing a peak in size exclusion chromatography) being oligomers having a degree of polymerization of up to 12.

[0117] The melting point of the cyclic polyester oligomer may be, for example, about 100 to 250°C, preferably about 110 to 220°C, and more preferably about 120 to 210°C (for example, about 130 to 200°C).

[0118] The cyclic oligomer J may be produced by a known method, such as a method of condensing a corresponding diol and a dicarboxylic acid halide (such as terephthaloyl chloride) in the presence of a sterically unhindered amine; the method described in JP-A-8-225633 (a method of contacting a bis-hydroxyalkyl-terminated diester or oligomer with a high-boiling solvent and esterification); the method described in JP-A-8-19962 (Patent No. 3426064); the method described in JP-A-2004-507599; or the method described in JP-A-2002-317041, or a commercially available product may also be used.

[0119] For example, cyclic polyester oligomer (cyclic polybutylene terephthalate oligomer) is available from Cyclics Corporation under the trade name CBT.

[0120] The amount of cyclic oligomer J added is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0.1 to 12 parts by mass, and usually about 0.01 to 10 parts by mass, per 100 parts by mass of thermoplastic resin A.

[0121] <Glycerin fatty acid ester K with a hydroxyl value of 200 to 600> The glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less (hereinafter also referred to as glycerin fatty acid ester K) of the present invention is an ester composed of glycerin and / or a dehydration condensate thereof and a fatty acid having 12 or more carbon atoms.

[0122] Examples of fatty acids having 12 or more carbon atoms that constitute the ester include lauric acid, oleic acid, palmitic acid, stearic acid, behenic acid, and montanic acid. Fatty acids having 12 to 32 carbon atoms are preferred, and fatty acids having 12 to 22 carbon atoms are particularly preferred, with lauric acid, stearic acid, and behenic acid being particularly preferred.

[0123] The glycerin fatty acid ester K used in the present invention can be produced by a method known per se. The glycerin fatty acid ester K used in the present invention is one whose esterification has been adjusted so that the hydroxyl value measured by the method described below is 200 or more, and preferably has a hydroxyl value of 250 or more. A hydroxyl value of less than 200 is not preferred because it has little effect in improving fluidity.

[0124] Examples of preferred esters include glycerin monostearate, glycerin monobehenate, diglycerin monostearate, triglycerin monostearate, tetraglycerin stearic acid partial ester, and decaglycerin lauric acid partial ester.

[0125] The blending amount of glycerin fatty acid ester K is 0.05 to 10 parts by mass, preferably 0.5 to 5 parts by mass, per 100 parts by mass of thermoplastic resin A.

[0126] The hydroxyl value was measured according to Japan Oil Chemists' Society 2.3.6.2-1996 Hydroxyl Value (Pyridine-Acetic Anhydride Method).

[0127] <Hyperbranched Polymer W> The hyperbranched polymer W includes a hyperbranched polyester. The hyperbranched polymer in the present invention is a non-crosslinked polymer having hydroxyl and carboxyl groups, which starts from a central molecule similar to a dendrimer, but the chain lengths of the branches may be of different lengths.

[0128] On the other hand, they may have a linear structure and functional side groups, or they may combine the two extremes and have linear and branched molecular parts. For definitions of dendrimers and hyperbranched polymers, reference may also be made to P.J. Flory, J.Am.Chem.Soc. 1952, 74, 2718 and H.Frey et al., Chem.Eur.J. 2000, 6, No. 14, 2499.

[0129] The hyperbranched polymer W preferably has a number average molecular weight Mn of 300 to 30,000, especially 400 to 25,000, and especially 500 to 20,000 g / mol, as measured by size exclusion chromatography (SEC) with PMMA standards and dimethylacetamide as the developing agent.

[0130] The hydroxyl number is 0 to 600, preferably 1 to 500, and in particular 20 to 500 mg KOH / g polymer according to DIN 53240. The acid number is preferably 0 to 600, preferably 1 to 500, and in particular 2 to 500 mg KOH / g polymer.

[0131] The Tg is advantageously between −50° C. and 140° C., and in particular between −50 and 100° C. (using DSC according to DIN 53765).

[0132] Particularly advantageous are hyperbranched polymers W having an OH or COOH number greater than 0, preferably greater than 0.1 and in particular greater than 0.5.

[0133] The hyperbranched polymer W according to the present invention can be obtained by the method described in WO2006 / 018127.

[0134] The blending amount of the hyperbranched polymer W is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, more preferably 0.1 to 12 parts by mass, and usually 0.01 to 10 parts by mass, per 100 parts by mass of the thermoplastic resin A.

[0135] <Other ingredients> In the present invention, in addition to the above-mentioned components, known additives generally added to thermoplastic resins and thermosetting resins, namely, burr inhibitors, release agents, lubricants, plasticizers, flame retardants, colorants such as dyes and pigments, crystallization accelerators, crystal nucleating agents, various antioxidants, heat stabilizers, weather resistance stabilizers, corrosion inhibitors, etc. may also be blended within the scope of not impairing the effects of the present invention.

[0136] <Molded products> The molded article of the present invention is obtained by molding the resin composition for molded articles described above. The method for producing the molded article of the present invention is not particularly limited, and any known method can be used. For example, the molded article can be produced by feeding the resin composition described above into an extruder, melt-kneading it, and pelletizing it, and then feeding the pellets into an injection molding machine equipped with a predetermined mold and injection molding it.

[0137] This is particularly useful from the viewpoint of transferability to the mold when molding a molded product having a thin-walled portion of 2 mm or less. The thin-walled portion is preferably 0.1 mm or more. [Example]

[0138] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these. Evaluations were carried out in an atmosphere of 23°C and 50% RH unless otherwise specified.

[0139] <Material> Evaluation samples were prepared using the following materials. The amounts used (parts by mass) are shown in Tables 1 and 2. A1 Polybutylene terephthalate resin (PBT, intrinsic viscosity 0.69 dL / g, carbon Acid terminal concentration 23 meq / k): Polyplastics Co., Ltd. B1 Mica: Micalet 21PU manufactured by Yamaguchi Mica Kogyosho C1 Ethylene-glycidyl methacrylate copolymer: Bondfast 7L manufactured by Sumitomo Chemical Co., Ltd. B 1MC11 After blending B1:C1 = 10:10 (parts by mass), the mixture was melt-kneaded and made into a masterbatch. BN1 Glass fiber: Nippon Electric Glass T187 (diameter 13 μm, length 3.0 mm) D Glycerin mono-12-hydroxystearate (hydroxyl value 420, Riken Vitamin Co., Ltd. "Rikemal HC-100") P Antioxidant: BASF Japan Irganox 1010 Q Lubricant: Sanwax 161-P manufactured by Sanyo Chemical Industries, Ltd.

[0140] <Production of Resin Composition> The master batch was prepared by melt-kneading B and C in the amounts shown in Table 1 at a cylinder temperature of 190°C, followed by pelletizing. In Example 1, thermoplastic resin A1, pelletized masterbatch, and other ingredients, antioxidant P, lubricant Q, and superplasticizer D, were charged from a hopper, and glass fiber BN1 was charged from a side feed. The mixture was mixed at a cylinder temperature of 260°C and then injection molded to produce an ISO multipurpose test piece Type-1A according to ISO3167. By the above coating confirmation method, it was confirmed that the inorganic filler B1 was coated with the thermoplastic resin C1.

[0141] In Comparative Example 1, thermoplastic resin A1, pelletized masterbatch, and other ingredients such as antioxidant P and lubricant Q were added from a hopper, and glass fiber BN1 was added from a side feed. The mixture was mixed at a cylinder temperature of 260°C and then injection molded to produce an ISO multipurpose test piece Type-1A according to ISO3167. By the above coating confirmation method, it was confirmed that the inorganic filler B1 was coated with the thermoplastic resin C1.

[0142] In Comparative Example 2, thermoplastic resin A1, thermoplastic resin C1, inorganic filler B1, and other components such as antioxidant P and lubricant Q were charged from a hopper, and glass fiber BN1 was charged from a side feed. The mixture was mixed at a cylinder temperature of 260°C and then injection molded to produce an ISO multipurpose test piece Type-1A according to ISO3167.

[0143] In Comparative Example 3, thermoplastic resin A1, inorganic filler B1, and other components such as antioxidant P and lubricant Q were added from a hopper, and thermoplastic resin C1 and glass fiber BN1 were added from a side feed. The mixture was kneaded at a cylinder temperature of 260°C and then injection molded to produce an ISO multipurpose test piece Type-1A according to ISO3167.

[0144] <Evaluation> <Melt viscosity> The melt viscosity of the resin composition was measured using a Capillograph 1B model manufactured by Toyo Seiki Seisakusho Co., Ltd. at 260°C with an orifice having an inner diameter of 1 mm and a length of 20 mm at a shear rate of 1000 / sec in accordance with ISO11443. <Mechanical properties> Using ISO multipurpose test specimen Type-1A conforming to ISO3167, the tensile strength and tensile breaking strain were measured in accordance with ISO527-1, 2 using an Orientec universal testing machine, Tensilon RTC-1325A. The results are shown in Table 1. <Evaluation results>

[0145] [Table 1]

[0146] [Table 2]

[0147] As shown in Tables 1 and 2, the present invention provides a molded article that can reduce the melt viscosity while maintaining mechanical properties. The present invention can provide a method for producing a molded article with improved fluidity and a method for improving the fluidity of a thermoplastic resin. [Explanation of symbols]

[0148] A Thermoplastic resin B. Inorganic filler BN: Inorganic filler (glass fiber) without surface coating C coated thermoplastic resin X CO Feed Y Side Feed 1 Hopper 2 motors 3 screws 4 cylinders 5 Strand Bus 6 cutter Pelet

Claims

1. A molded article made of a resin composition containing a thermoplastic resin A, an inorganic filler B, a thermoplastic resin C other than the thermoplastic resin A, and a glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less, the thermoplastic resin A is polybutylene terephthalate, The inorganic filler B includes a plate-like filler and a fibrous filler, the plate-like filler is mica, the thermoplastic resin C is an ethylene-glycidyl methacrylate copolymer, The glycerin fatty acid ester K is glycerin mono-12-hydroxystearate, A molded article in which the plate-like filler is coated with the thermoplastic resin C.

2. The molded article according to claim 1, wherein the molded article has a thin-walled portion of 2 mm or less.

3. A method for producing a molded product having improved fluidity from a resin composition comprising a thermoplastic resin A, an inorganic filler B, a thermoplastic resin C other than the thermoplastic resin A, and a glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less, the method comprising: the thermoplastic resin A is polybutylene terephthalate, The inorganic filler B includes a plate-like filler and a fibrous filler, the plate-like filler is mica, the thermoplastic resin C is an ethylene-glycidyl methacrylate copolymer, The glycerin fatty acid ester K is glycerin mono-12-hydroxystearate, The method for producing a molded product with improved fluidity includes melt-kneading the plate-like filler and the thermoplastic resin C in advance, coating the plate-like filler with the thermoplastic resin C, and then melt-kneading the plate-like filler with the thermoplastic resin A and the glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less.

4. A method for improving fluidity of a resin composition comprising a thermoplastic resin A, an inorganic filler B, a thermoplastic resin C other than the thermoplastic resin A, and a glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less, the method comprising: the thermoplastic resin A is polybutylene terephthalate, The inorganic filler B includes a plate-like filler and a fibrous filler, the plate-like filler is mica, the thermoplastic resin C is an ethylene-glycidyl methacrylate copolymer, The glycerin fatty acid ester K is glycerin mono-12-hydroxystearate, A method for improving fluidity, comprising melt-kneading the plate-like filler and the thermoplastic resin C in advance to coat the plate-like filler with the thermoplastic resin C, and then melt-kneading the plate-like filler with the thermoplastic resin A and the glycerin fatty acid ester K having a hydroxyl value of 200 or more and 600 or less.

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