Liquid masterbatch, resin molding material, and resin molded article

Abstract

To provide a liquid master batch which has such storage stability that separation and precipitation of solid particles in long-term storage are suppressed, and such moldability that liquid bubbles are not generated on the surface of the molding when being mixed with a resin and molded, a resin molding material using the liquid master batch, and a molding.SOLUTION: A liquid master batch is used for molding a polyethylene terephthalate resin, a polybutylene terephthalate resin or a polycarbonate resin, and contains a fatty acid ester that is liquid at normal temperature, solid particles and a surface active agent, wherein the fatty acid ester contains diacetylmonoacyl glycerol having a fatty acid and / or a diacetylmonoacyl glycerol derivative having a fatty acid, the surface active agent contains at least one selected from a fatty acid amide-based surface active agent, a metallic soap and a cured castor oil, and the solid particles (B) are solid particles excluding a pigment and a dye.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid masterbatch of resin, a resin molding material, and a resin molded article. [Background technology]

[0002] In recent years, resin molded products using thermoplastic resins have been used in a wide range of fields, including containers, electrical and electronic components, and automotive parts, due to their ease of molding and processing. These resin molded products are manufactured by mixing additives into the resin to enhance their functionality according to their intended use.

[0003] In the processing of resin molded products such as extrusion molding, injection molding, and blow molding, the mixing of additives to modify the resin, and the coloring with pigments and dyes, are performed by preparing highly concentrated additive concentrates or colorant concentrates in advance and diluting them with resin pellets or resin powder immediately before molding. Examples of such additive concentrates and colorant concentrates include masterbatches formed by kneading resin and additives or colorant dyes into pellets, colored pellets in which colorant dyes or additives are attached to the surface of resin pellets, dry colors formed by mixing metal soap with colorant dyes or additives into a paste, and liquid masterbatches in which additives or colorant dyes are dispersed in oil.

[0004] In particular, liquid masterbatches, unlike other concentrates, are in a liquid state, making them easy to mix uniformly even in small amounts when diluted with resin pellets or resin powders. This uniform mixing improves physical properties, and they have been used in applications requiring high dispersion, such as coloring translucent molded products.

[0005] However, because liquid masterbatches are in a (low-viscosity) liquid state, additives, pigments, and dyes tend to separate and settle at the bottom of the liquid during long-term storage, requiring re-stirring before reuse.

[0006] Patent Document 1 describes a liquid colorant for ABS resin, which includes a liquid polyester obtained by reacting a pigment or dye with an aliphatic dicarboxylic acid and a dihydric alcohol, and states that it can produce molded articles that do not undergo thermal deformation at high temperatures or bleed onto the surface. However, as mentioned above, because it is a liquid, the pigments and dyes settle during long-term storage. When a dispersant is added to the liquid masterbatch to prevent this settling, the compatibility between the liquid polyester, dispersant, and resin is poor, and liquid bubbles originating from the liquid polyester sometimes occur on the surface of molded products produced in multiple batches.

[0007] Furthermore, Patent Document 2 describes a metal oxide particle dispersion containing metal oxide particles, a plasticizer, and a dispersant, with the haze difference when a specific molded article is formed being used as a parameter. It states that by selecting a fatty acid polyester resin obtained by the reaction of a polycarboxylic acid and a polyhydric alcohol, a polyalkylene glycol resin, a polyether ester resin, and tributyl acetylcitrate as the liquid plasticizer, and using a phosphate ester compound as the dispersant, a highly dispersed, transparent molded article can be obtained without a decrease in physical properties, even when nano-sized metal oxide particles are used, and a stable dispersion can be produced.

[0008] Furthermore, Patent Document 3 describes a method for producing a resin coloring masterbatch by kneading a resin with a liquid coloring agent containing a vegetable oil with an iodine value of 90 or more, and adding a surfactant to either the resin or the liquid coloring agent that exhibits a specific value when measured by the felt natural sedimentation method. This method yields a resin coloring masterbatch with good pigment dispersibility and even coloring without color unevenness.

[0009] However, Patent Document 2 is an invention that addresses problems specific to nanoparticles, and does not describe the sedimentation of the dispersion or the state of the surface of the molded body when multiple batches of molded bodies are produced. Furthermore, Patent Document 3 does not address the sedimentation of the liquid colorant because it is mixed with the resin after the liquid colorant is prepared, and it does not address problems in the molded body, as the example shows that a thin film is made using a hot plate. [Prior art documents] [Patent Documents]

[0010] [Patent Document 1] Japanese Patent Application Publication No. 61-9453 [Patent Document 2] Japanese Patent Publication No. 2019-206655 [Patent Document 3] Japanese Patent Publication No. 2018-188577 [Overview of the project] [Problems that the invention aims to solve]

[0011] The present invention provides a liquid masterbatch that exhibits storage stability with suppressed separation and sedimentation of solid particles during long-term storage, and moldability that prevents the formation of liquid bubbles on the surface of molded articles even when molded in large batches after mixing with a resin; and a resin molding material and molded articles using the liquid masterbatch. [Means for solving the problem]

[0012] The present inventors have provided a liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin, The liquid masterbatch comprises a liquid fatty acid ester (A) at room temperature, solid particles (B), and a surfactant (C), wherein the fatty acid ester (A) comprises diacetyl monoacylglycerol having a fatty acid and / or a diacetyl monoacylglycerol derivative having a fatty acid, the surfactant (C) is at least one selected from fatty acid amide surfactants, metal soaps, and hydrogenated castor oil, and the solid particles (B), excluding pigments and dyes, have an average particle size of 0.5 to 800 μm and a true specific gravity of 1 to 7 g / cm³. 3 We discovered that the above objective can be achieved by providing a liquid masterbatch characterized by being solid particles of a resin modifier, and thus completed the present invention.

[0013] That is, the present invention is (1) A liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin, The liquid masterbatch contains a fatty acid ester (A) that is liquid at room temperature, solid particles (B), and a surfactant (C), The fatty acid ester (A) contains diacetyl monoacyl glycerol having a fatty acid and / or a derivative of diacetyl monoacyl glycerol having a fatty acid, and the surfactant (C) is at least one selected from fatty acid amide surfactants, metal soaps, and hydrogenated castor oil. The solid particles (B) are resin modifiers excluding pigments and dyes, having an average particle size of 0.5 to 800 μm and a true specific gravity of 1 to 7 g / cm 3 of solid particles, and the surfactant (C) is contained in an amount of 0.2 to 10 parts by weight, and the solid particles (B) are contained in an amount of 0.5 to 85 parts by weight based on 100 parts by weight of the liquid masterbatch. A liquid masterbatch characterized by this, (2) The liquid masterbatch according to (1) and a resin molding material containing a thermoplastic resin, (3) A resin molded body containing the liquid masterbatch according to (1), (4) A resin molded body obtained by molding the resin molding material according to (2), is.

Effects of the Invention

[0014] According to the present invention, a liquid masterbatch having storage stability in which separation and sedimentation of solid particles are suppressed during long-term storage, and moldability in which no bubbles occur on the surface of the molded body even in the molding of a large number of lots when molding is performed after mixing with the resin, a resin molding material using the liquid masterbatch, and a molded body can be provided.

Modes for Carrying Out the Invention

[0015] <00Hereinafter, embodiments for carrying out the present invention will be described in detail. Note that this embodiment is merely one form for carrying out the present invention, and the present invention is not limited by this embodiment, and various changes and embodiments are possible without departing from the gist of the present invention. Also, in this specification, the notation "a~b" in the description of the numerical range represents a or more and b or less, unless otherwise specified. For example, "1~5 parts by weight" means "1 part by weight or more and 5 parts by weight or less".

[0016] The liquid masterbatch of the present invention is a liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin. The liquid masterbatch contains a fatty acid ester (A) that is liquid at room temperature, solid particles (B), and a surfactant (C). The fatty acid ester (A) contains diacetyl monoacyl glycerol having a fatty acid and / or a derivative of diacetyl monoacyl glycerol having a fatty acid. The surfactant (C) is at least one selected from fatty acid amide surfactants, metal soaps, and hydrogenated castor oil. The solid particles (B) are solid particles of a resin modifier having an average particle size of 0.5~800 μm and a true specific gravity of 3 3 1~7 g / cm³, excluding pigments and dyes, and is a liquid masterbatch characterized by this.

[0017] By using the fatty acid ester and the surfactant in combination, the liquid masterbatch exhibits structural viscosity, has storage stability in which sedimentation of solid particles is suppressed during long-term storage, and can provide a liquid masterbatch having moldability in which no bubbles occur on the surface of the molded body when molding a plurality of lots after mixing with the resin. Since the liquid masterbatch does not cause unevenness of solid particles due to sedimentation, it can also be used as a liquid masterbatch having excellent dispersibility when mixed with the resin.

[0018] The composition contained in the liquid masterbatch will be described below.

[0019] [Fatty Acid Ester] In the present invention, the fatty acid ester is liquid at room temperature and is used as a solvent. The fatty acid ester used is diacetylmonocylglycerol having a fatty acid, and / or a diacetylmonocylglycerol derivative having a fatty acid. Furthermore, in the present invention, room temperature means 25°C.

[0020] The aforementioned diacetylmonoacylglycerol has a monovalent acyl group and two acetyl groups. The aforementioned diacetylmonoacylglycerol can be obtained by known methods such as (i) esterification reaction with glycerol, acetic acid, and a fatty acid having one carboxyl group, or (ii) transesterification reaction of a fatty acid alkyl ester having one ester bond with glycerol or a triglyceride such as oil or fat, followed by acetylation. However, the method of synthesis is not particularly limited. The number of carbon atoms in the monovalent acyl group is preferably 6 to 36, and more preferably 8 to 24.

[0021] The diacetylmonoacylglycerol derivative has two acetyl groups and a hydroxyl group derivative of a fatty acid, and the hydroxyl group derivative of the fatty acid may be a fatty acid having a hydroxyl group, or an ester of a fatty acid having a hydroxyl group and a fatty acid having a monovalent carboxyl group. Diacetylmonoacylglycerol derivatives having the hydroxyl group derivative and a hydroxyl group derivative having an ester of the monovalent carboxyl group fatty acid, respectively, can be used in combination. The number of carbon atoms in the hydroxyl group-containing fatty acid is preferably 6 to 36, and more preferably 8 to 24. The aforementioned diacetylmonoacylglycerol derivative can be obtained by known methods, such as esterifying a monoglyceride obtained by distilling castor oil and excess glycerol with acetic acid, but the synthesis method is not particularly limited.

[0022] The aforementioned fatty acid ester, when used as a solvent for a liquid masterbatch, suppresses the sedimentation of solid particles during long-term storage of the liquid masterbatch, and also allows for the production of a molded article without liquid bubbles on the surface of the molded article when the resin and liquid masterbatch are molded together. However, other solvents such as vegetable oil, polyethylene glycol, polypropylene glycol, higher alcohols, and liquid paraffin may be added, as long as they do not impair the effects of the present invention.

[0023] The fatty acid ester is preferably in an amount of 5 to 98.8 parts by weight, and more preferably in an amount of 10 to 98.5 parts by weight, per 100 parts by weight of liquid masterbatch.

[0024] The surfactant used in this invention is at least one selected from fatty acid amide surfactants, metal soaps, and hydrogenated castor oil. By using the surfactant, the sedimentation of solid particles is suppressed during long-term storage of the liquid masterbatch, and a molded article can be obtained in which no liquid bubbles are formed on the surface of the molded article when the resin and liquid masterbatch are molded together. The surfactant is preferably in an amount of 0.2 to 15 parts by weight, and more preferably 0.5 to 10 parts by weight, per 100 parts by weight of liquid masterbatch. An amount of 0.2 parts by weight or more suppresses the sedimentation of solid particles during long-term storage of the liquid masterbatch, while an amount of 15 parts by weight or less allows for the production of a molded article without the formation of liquid bubbles.

[0025] [Fatty acid amide surfactants] The fatty acid amide surfactant is preferably stearate amide, oleate amide, erucate amide, ethylenebisstearate amide, methylenebisstearate amide, ethylenebisoleate amide, or behenamide, with ethylenebisstearate amide being more preferred.

[0026] [Metal soaps] The aforementioned metal soap is preferably an alkali metal salt of a fatty acid in which the fatty acid is lauric acid, myristic acid, montanic acid, behenic acid, or palmitic acid, and the alkali metal is magnesium, calcium, sodium, potassium, zinc, barium, or aluminum, with magnesium stearate being particularly preferred.

[0027] [Hydrogenated castor oil] The aforementioned hardened castor oil is a triglyceride of 12-hydroxystearic acid obtained by completely hardening castor oil through a hydrogenation reaction, and commercially available products such as K-3 wax and Kawastar CR (both manufactured by Kawaken Fine Chemical Co., Ltd.) are available.

[0028] The liquid masterbatch of the present invention may contain other surfactants in combination with the surfactant, provided that the effects of the present invention are not impaired and the liquid masterbatch does not swell. Examples of other interfacial surfactants include nonionic surfactants such as sorbitan-based surfactants, higher alcohol-based surfactants, or alkylphenol-based surfactants, as well as anionic surfactants, cationic surfactants, or amphoteric surfactants.

[0029] Examples of the sorbitan-based surfactants include sorbitan fatty acid esters and polyoxyethylene sorbitan fatty acid esters. Specific examples include sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, and polyoxyethylene sorbitan triisostearate.

[0030] [Solid particles] The solid particles used in the present invention are solid and dispersed in the fatty acid ester of the present invention at 25°C, and include solid particles used as a resin modifier.

[0031] The solid particles preferably have an average particle size of 0.5 μm or more and 800 μm or less, and more preferably 0.6 μm or more and 500 μm or less. By being 800 μm or less, a liquid masterbatch with suppressed sedimentation of solid particles during long-term storage can be obtained while maintaining a stable supply flow by a pump, and by being 0.5 μm or more, a liquid masterbatch excellent in resin modification can be obtained. In addition, the "particle size" described in this specification is the volume-average median diameter. The particle size of the solid particles can be calculated, for example, by measuring and analyzing a solvent in which the solid particles are dispersed using a laser diffraction particle size analyzer.

[0032] The solid particles preferably have a true specific gravity of 1 g / cm 3 or more and 7 g / cm 3 or less, and more preferably 1.02 g / cm 3 or more and 6 g / cm 3 or less. By being 1 g / cm 3 or more and 7 g / cm 3 or less, a liquid masterbatch with suppressed sedimentation of solid particles during long-term storage can be obtained. The true specific gravity can be determined by measurement using the pycnometer method (liquid phase replacement method) or the gas phase replacement method. Examples of the measuring instrument include Ultrapyc5000 of AntonPaar and UltraPycnometer1000 of QUANTACHROME.

[0033] Examples of the solid particles include inorganic particles and organic particles such as nucleating agents, antiblocking agents, ultraviolet absorbers, light stabilizers, flame retardants, antibacterial agents, antifungal agents, deodorants, antioxidants, heat insulating agents, strength improvers, surface modifiers, conductivity improvers, thermal conductivity improvers, optical property control agents, polymerization terminating / neutralizing agents, etc., which are used as resin modifiers.

[0034] Examples of inorganic particles include kaolin, aluminum silicate, clay, talc, mica, silica, alumina, calcium silicate, bentonite, kaolinite, wollastonite, zeolite, magnesium silicate, aluminum borate, hydrotalcite, calcium carbonate, magnesium carbonate, barium carbonate, calcium sulfate, calcium sulfite, barium sulfate, aluminum sulfate, calcium phosphate, potassium titanate, barium titanate, magnesium oxide, antimony trioxide, antimony pentoxide, diatomaceous earth, zinc oxide, magnesium hydroxide, aluminum hydroxide, iron hydroxide, zirconia, zirconium, silicon carbide, silicon nitride, boron nitride, aluminum nitride, antimond-doped tin oxide, graphite, glass fiber, etc. Surface-treated inorganic particles can also be used.

[0035] Examples of the aforementioned organic particles include the following: As nucleating agents, carboxylate metal salts such as sodium benzoate, 4-tert-butylbenzoate aluminum salt, sodium adipate and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate, phosphate ester metal salts such as sodium bis(4-tert-butylphenyl) phosphate, sodium-2,2'-methylenebis(4,6-ditert-butylphenyl) phosphate and lithium-2,2'-methylenebis(4,6-ditert-butylphenyl) phosphate, dibenzylidenesorbitol, bis( Examples include polyhydric alcohol derivatives such as methylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and bis(dimethylbenzylidene)sorbitol, and amide compounds such as N,N',N''-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N''-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexyl-naphthalenedicarboxamide, and 1,3,5-tri(dimethylisopropoylamino)benzene.

[0036] Examples of antiblocking agents include organic fine particles such as polystyrene, polyether, polyacrylic, polyamide, epoxy resin, polyphenylene sulfide, and thermoplastic elastomer.

[0037] Examples of UV absorbers include benzotriazole-based, triazine-based, and benzophenone-based UV absorbers. The aforementioned benzotriazole-based UV absorbers include, for example, 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dimethylphenyl)benzotriazole, 2-(2-methyl-4-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-3-methyl-5-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-amylphenyl)benzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)benzotriazole, 2-(2-hydroxy-3,5-dimethylphenyl)-5-methoxybenzotriazole, 2-(2-n-octadecyloxy-3,5-dimethylphenyl)-5-methylbenzotriazole, 2-(2-hydroxy-5-methoxyphenyl)-5-methylbenzotriazole, 2-(2-hydroxy-3-t-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-( 2-hydroxy-5-t-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-phenylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-dichlorophenylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-5-methylphenyl)-5,6-dichlorobenzotriazole, 2-(2-hydroxy-3,5-di-t-butylphenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-4,5-dichloro Examples include (lophenyl)-5-chlorobenzotriazole, 2-(2-hydroxy-3-methylphenyl)-5-butoxycarbonylbenzotriazole, 2-(2-acetoxy-5-methylphenyl)benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, and 2-(2H-benzotriazol-2-yl)-4-methyl-6-(3,4,5,6-tetrahydrophthalimidylmethyl)phenol.

[0038] Furthermore, examples of the triazole-based ultraviolet absorber include 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine.

[0039] Examples of the aforementioned light stabilizers include hindered amine-based light stabilizers, such as 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, and tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate. Diethyl tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-diter-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycellulose Compound, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane / 2,4-dichloro-6-tertiaryoctylamino-s-triazine polycondensate, 1,5,8,12-tetrakis[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetrakis[2, 4-Bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]-1,5,8-12-tetraazadodecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-Tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazine-6-yl]aminoundecane, bis{4-(1-octyloxy-2,Examples include 2,6,6-tetramethyl)piperidyl}decandionate and bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl)carbonate.

[0040] Furthermore, examples of flame retardants include aromatic phosphate esters such as triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-xylenyl phosphate, and resorcinol bis(diphenyl phosphate); phosphonic acid esters such as divinyl phenylphosphonate, diallyl phenylphosphonate, and phenylphosphonic acid (1-butenyl); phosphinic acid esters such as phenyl diphenylphosphinate, methyl diphenylphosphinate, and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives; phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine polyphosphate, ammonium polyphosphate, and phosphorus-containing vinylben Examples include organophosphorus flame retardants such as zyl compounds, brominated bisphenol A type epoxy resins, brominated phenol novolac type epoxy resins, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromopenyne), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ethers, brominated polystyrene and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A type dimethacrylate, pentabromobenzyl acrylate, and organobrominated flame retardants such as brominated styrene.

[0041] Other antibacterial agents include methyl parahydroxybenzoate, ethyl parahydroxybenzoate, and bis(2-pyridylthio-1-oxide)zinc.

[0042] Furthermore, examples of antioxidants include phenolic antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenolic antioxidants include 2,2-methylenebis(4-methyl-6-t-butylphenol), 4,4-methylenebis(2,6-di-t-butylphenol), 2,2-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 4,4-butylidenebis(6-t-butyl-m-cresol), 2,2-ethylidenebis(4-sec-butyl-6-t-butylphenol), 2,2-ethylidenebis(4,6-di-t-butylphenol), 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, 4,4-thiobis(6-t-butyl-m-cresol), and tocopherol.

[0043] Examples of the phosphorus-based antioxidants include tris(2-t-butyl-4-methylphenyl) phosphite, tris(nonylphenyl) phosphite, tris(dinonylphenyl) phosphite, tris(cyclohexylphenyl) phosphite, 2,2-methylenebis(4,6-di-t-butylphenyl)octyl phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-decyloxy-9,10-dihydro-9-oxide. Examples include monophosphite compounds such as xa-10-phosphaphenanthrene, and diphosphite compounds such as 4,4'-butylidene-bis(3-methyl-6-t-butylphenyl-di-tridecyl phosphite), 4,4'-isopropylidene-bis(phenyl-di-alkyl(C12~C15) phosphite), 4,4'-isopropylidene-bis(diphenylmonoalkyl(C12~C15) phosphite), 1,1,3-tris(2-methyl-4-di-tridecyl phosphite-5-t-butylphenyl)butane and tetrakis(2,4-di-t-butylphenyl)-4,4'-biphenylene phosphite.

[0044] Examples of the aforementioned sulfur-based antioxidants include lauryl stearyl-3,3'-thiodipropionate, dioctadecyl sulfide, and pentaerythryl-tetra(β-lauryl-thiopropionate) ester.

[0045] The amount of solid particles used in this invention is preferably 0.5 to 85 parts by weight, and more preferably 1 to 80 parts by weight, per 100 parts by weight of liquid masterbatch. If the amount is less than 0.5 parts by weight, sufficient improvement in physical properties cannot be obtained, and if it is greater than 85 parts by weight, the liquid masterbatch will not blend well with the resin when mixed with the resin.

[0046] The solid particles can be used individually or in combination of two or more types. When two or more types of solid particles are used in combination, it is preferable that the total weight of all solid particles relative to 100 parts by weight of liquid masterbatch is within the range of the weight of the solid particles.

[0047] The liquid masterbatch of the present invention may contain a thickening agent. Examples of thickening agents include phosphate ester salts, fine silica particles, curable vegetable oils, curable animal fats, etc., and one or more of these can be used.

[0048] The aforementioned fine silica particles include hydrophilic fine silica particles and hydrophobic fine silica particles. Preferred commercially available hydrophilic silica products include AEROSIL-300 and AEROSIL-380 (manufactured by Nippon Aerosil Co., Ltd.), while preferred commercially available hydrophobic silica products include AEROSIL-974D and AEROSIL-972 (manufactured by Nippon Aerosil Co., Ltd.), Silohobic 200 and Silohobic 326 (manufactured by Fuji Silicia Co., Ltd.).

[0049] Examples of the aforementioned curable vegetable oils include curable vegetable oils and animal oils with a melting point of 30 degrees or higher. Examples of vegetable oils include curable rapeseed oil, curable soybean oil, curable palm oil, curable coconut oil, curable rice oil, or curable jojoba oil. Examples of curable animal fats include curable beef tallow, curable pork tallow, or curable horse oil.

[0050] The amount of the thickening agent is preferably 0.1 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the liquid masterbatch.

[0051] [Method for manufacturing liquid masterbatch] The method for producing a liquid masterbatch in the present invention is not particularly limited. For example, a liquid masterbatch can be obtained by adding a liquid fatty acid ester (A), solid particles (B), a surfactant (C), and various additives as needed, mixing them in a Henschel mixer, tumbler, disperser, etc., and then dispersing them using a mixer, bead mill, and paint shaker. In addition to the above, any other dispersion apparatus such as a kneader, roll mill, ball mill, sand mill, etc. can be used.

[0052] [Resin molding materials] The resin molding material of the present invention is a resin molding material for forming a molded article containing the liquid masterbatch and a thermoplastic resin. Examples of the resin molding material include a mixture of thermoplastic resin pellets and liquid masterbatch, or a compound in the form of pellets, powder, granules, or beads obtained by pre-kneading the thermoplastic resin and liquid masterbatch.

[0053] The aforementioned resin molding material can be formed by directly melt-kneading a mixture of a liquid masterbatch and a thermoplastic resin, and then molding a molded body. Alternatively, a resin molding material that has been pre-formed into pellets or the like can be further diluted by melt-kneading it with a thermoplastic resin, and then molded body is formed.

[0054] [Thermoplastic resin] The thermoplastic resin contained in the resin molding material or molded article of the present invention is a resin that serves as the main component of the molded article to which a liquid masterbatch is added, and polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin is preferably used.

[0055] [Polyethylene terephthalate resin] The aforementioned polyethylene terephthalate mainly consists of terephthalic acid and ethylene glycol. The polyethylene terephthalate may be copolymerized with, to the extent that its properties are not impaired, other acid components besides terephthalic acid, such as aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfisoisophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and diphenylsulfondicarboxylic acid; aromatic polycarboxylic acids such as trimellitic acid and pyromellitic acid and their acid anhydrides; and aliphatic dicarboxylic acids such as oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and decanedicarboxylic acid. Furthermore, the polyethylene terephthalate may be copolymerized with, to the extent that its properties are not impaired, alcohol components other than ethylene glycol, such as aliphatic diols such as propylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, 1,5-pentanediol, neopentyl glycol, triethylene glycol, and polyethylene glycol; aliphatic polyhydric alcohols such as trimethylolpropane and pentaerythritol; alicyclic diols such as 1,4-cyclohexanedimethanol and 1,4-cyclohexanediethanol; aromatic diols such as ethylene oxide adducts of bisphenol A and bisphenol S; and hydroxycarboxylic acids such as 4-hydroxybenzoic acid and ε-caprolactone.

[0056] [Polybutylene terephthalate resin] The aforementioned polybutylene terephthalate resin mainly consists of terephthalic acid or its ester-forming derivative and 1,4-butanediol or its ester-forming derivative. The polybutylene terephthalate resin may contain other copolymer components as long as their properties are not impaired. Preferred examples of these polymers and copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sevacate), polybutylene (terephthalate / decanedicarboxylate), polybutylene (terephthalate / naphthalate), and poly(butylene / ethylene) terephthalate, which may be used individually or in combination of two or more.

[0057] [Polycarbonate resin] The aforementioned polycarbonate resin can be easily produced by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or diester carbonate. The reaction can be carried out using known reactions, for example, by an interfacial method when using phosgene, or by a transesterification method in which the reaction is carried out in a molten state when using diester carbonate.

[0058] Examples of the above aromatic dihydroxy compounds include bis(hydroxyaryl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, as well as 1,1-bis(4-hydroxy( Examples include bis(hydroxyaryl)cycloalkanes such as cyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane, dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. These are used individually or in combination of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcinol, and 4,4'-dihydroxydiphenyl compounds may be used in combination. Furthermore, branched aromatic polycarbonate resins incorporating polyfunctional compounds such as phloroglucin can also be used.

[0059] Examples of carbonate precursors to be reacted with the aromatic dihydroxy compound include phosgene, diaryl carbonates such as diphenyl carbonate and ditril carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0060] The mixing ratio of the thermoplastic resin and liquid masterbatch in the aforementioned resin molding material is preferably such that the liquid fatty acid ester in the liquid masterbatch is 0.05 to 10 parts by weight per 100 parts by weight of thermoplastic resin, and more preferably 0.1 to 5 parts by weight. If the amount is greater than 10 parts by weight, liquid bubbles may form on the surface of the molded article when the fatty acid ester is molded, and the material may slip in the mixer used during mixing. If the amount is less than 0.05 parts by weight, sufficient improvement in physical properties cannot be obtained.

[0061] The aforementioned resin molding material may contain additives such as other surfactants, antioxidants, ultraviolet absorbers, hindered amine-based weather stabilizers, various stabilizers including antistatic agents, flame retardants, and antiblocking agents, to the extent that they do not impair the effects of the present invention. Furthermore, these additives may be added as a masterbatch pre-mixed into the thermoplastic resin.

[0062] [Molded body] The molded article of the present invention is formed from a resin molding material containing the liquid masterbatch and the thermoplastic resin. The molded article of the present invention may contain the liquid masterbatch and the thermoplastic resin, and specific methods for forming the article include, for example, (a) a method of obtaining a molded article by mixing the liquid masterbatch and pellets of thermoplastic resin, etc., and then melt-kneading them together as a resin molding material; (b) a method of obtaining a molded article by using a resin molding material that has been previously melt-kneaded the liquid masterbatch and thermoplastic resin to form a pellet-shaped masterbatch, and then further melt-kneading it together with pellets of thermoplastic resin, etc.; and (c) a method of obtaining a molded article by melt-kneading the liquid masterbatch and the resin molding material that has been melt-kneaded the thermoplastic resin to form pellets, etc., as is.

[0063] The liquid masterbatch content in the molded article is preferably such that the liquid fatty acid ester in the liquid masterbatch is 0.05 to 10 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the molded article. If the amount is greater than 10 parts by weight, whitening may occur due to the solvent in the liquid masterbatch, and the material may slip in the extrusion screw of the molding machine. If the amount is less than 0.05 parts by weight, sufficient improvement in physical properties cannot be obtained.

[0064] The molding method for obtaining a molded body using a liquid masterbatch is not particularly limited, and known methods such as injection molding, blow molding, extrusion molding, film molding, and compression molding can be used.

[0065] The molded article may be a mixture of thermoplastic resin and liquid masterbatch. During molding, the thermoplastic resin may be put into the hopper of the molding machine, the liquid masterbatch may be added and mixed using a known pump or the like, and then the molded article may be obtained by melt-kneading. Alternatively, the resin molding material may be put into the molding machine in the form of pellets, powder, granules, or beads beforehand. [Examples]

[0066] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these. In the examples and comparative examples, "parts" refers to parts by weight, and "%" refers to weight percent.

[0067] Table 1 shows the materials used in the examples and comparative examples, and Tables 2 and 3 show the compositions of the liquid masterbatches.

[0068] [Table 1]

[0069] <Preparation of liquid masterbatch> For Examples 1-20 and Comparative Examples 1-12, the materials were mixed and stirred according to the formulations described in Tables 2 and 3, and then dispersed in a paint shaker for 2 hours to prepare a liquid masterbatch. The values ​​in Tables 2 and 3 are in weight percent.

[0070] [Table 2]

[0071] [Table 3]

[0072] <Manufacturing of resin molding materials and molded products> A resin molding material was prepared by weighing and mixing 0.2 parts by weight of the obtained liquid masterbatch with 100 parts by weight of the thermoplastic resin pellets listed in Tables 2 and 3. The following thermoplastic resins were used. Polyethylene terephthalate resin (PET): PIFG8 (manufactured by Bell Polyester Products Co., Ltd.) Polycarbonate resin (PC): Yupiron S-1000 (manufactured by Mitsubishi Engineering Plastics Corporation) Polybutylene terephthalate resin (PBT): Novaduran 5020 (manufactured by Mitsubishi Engineering Plastics Corporation) The resins used in Examples 1-20 and Comparative Examples 1-12 are listed in Tables 2 and 3.

[0073] Furthermore, after the resin molding material was fed into the hopper of an injection blow molding machine (manufactured by Nissei ASB Co., Ltd., model number: ASB-12N, screw diameter: 44 mm), a bottle-shaped molded body was produced under the following molding temperature and mold temperature conditions of 15-20°C. • Polyethylene terephthalate resin: 290℃ • Polybutylene terephthalate resin: 260℃ • Polycarbonate resin: 290℃ The molded body produced had a height of 160 mm, a diameter of 61 mm, and a wall thickness of 0.5 mm.

[0074] The sedimentation properties of the liquid masterbatches in Examples 1-20 and Comparative Examples 1-12 were evaluated, and the liquid foaming properties of the molded products were evaluated. The evaluation results are shown in Tables 4 and 5. For the overall evaluation, products that received a "○" in all evaluations were considered good products.

[0075] <Settlement Assessment> The liquid masterbatch described above was prepared, stored in a glass bottle, and its sedimentation was evaluated by visually checking its settling state after 7 days. Sedimentation was evaluated on a two-point scale: ○: no settling observed, ×: settling observed.

[0076] <Liquid foam evaluation> Fifty shots of the aforementioned bottle-shaped molded bodies were produced, and the surface of all molded bodies was observed to evaluate the presence or absence of liquid bubbles with a diameter of 1 mm or more. Liquid bubbles were evaluated in two stages: ○: No liquid bubbles were observed on the surface of any of the molded bodies, ×: Liquid bubbles were observed on the surface of one or more molded bodies.

[0077] [Table 4]

[0078] [Table 5]

Claims

1. A liquid masterbatch used for molding polyethylene terephthalate resin, polybutylene terephthalate resin, or polycarbonate resin, The liquid masterbatch comprises a liquid fatty acid ester (A) at room temperature, solid particles (B), and a surfactant (C). The fatty acid ester (A) comprises diacetyl monoacylglycerol having a fatty acid and / or a diacetyl monoacylglycerol derivative having a fatty acid, and the surfactant (C) is at least one selected from fatty acid amide surfactants, metal soaps, and hydrogenated castor oil. The solid particles (B) consist of, excluding pigments and dyes. Average particle size 0.5-800μm , and true specific gravity 1-7 g / cm³ These are solid particles of the resin modifier, The surfactant (C) is present in an amount of 0.2 to 10 parts by weight per 100 parts by weight of the liquid masterbatch. The solid particles (B) are present in an amount of 0.5 to 85 parts by weight per 100 parts by weight of liquid masterbatch. A liquid masterbatch characterized by the following features.

2. A resin molding material comprising the liquid masterbatch according to claim 1 and a thermoplastic resin.

3. A resin molded article comprising the liquid masterbatch described in claim 1.

4. A resin molded article obtained by molding the resin molding material described in claim 2.

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