Flowability improver, composition, and molded article

Abstract

To provide a flowability improver that imparts sufficient flowability to a resin without causing deterioration of the mechanical properties of the resin.SOLUTION: A flowability improver for a thermoplastic resin comprises a polyester compound, wherein the polyester compound includes a structural unit derived from a polycarboxylic acid and a structural unit derived from an aliphatic diol having 2 to 12 carbon atoms, the structural unit derived from the polycarboxylic acid includes a structural unit derived from an aromatic polycarboxylic acid, the polyester compound has a hydroxyl value of 20 to 300 mgKOH / g, and the polyester compound has number average molecular weight of 500 to 5,000.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a fluidity improver, a composition containing the fluidity improver, and a molded article thereof.

Background Art

[0002] Engineering plastics typified by thermoplastic resins, particularly condensation polymers such as polycarbonate resins and polyester resins, are widely used in optical parts, mechanical parts, electronic and electrical parts, automotive parts, bottles, building materials, etc. because of their excellent heat resistance and mechanical properties. When manufacturing parts or the like from these engineering plastics, it is necessary to perform molding processing at a high temperature, and it is known that heat during the molding processing causes thermal oxidative degradation of the plastic, leading to a decrease in molecular weight and mechanical properties.

[0003] In recent years, demands for miniaturization and weight reduction of various products have been increasing, mainly for applications such as OA equipment and home appliances, and accordingly, thinning of resin members has been desired. When molding a resin member into a thin member, high fluidity is required when the resin melts.

[0004] In response to this demand, a technique of adding a fluidity improver to a thermoplastic resin is known. A fluidity improver is an additive that improves the melt fluidity of a thermoplastic resin, and is an additive that enables the high fluidity originally brought about by high-temperature molding processing to be obtained even at a relatively low temperature. As a result, molding processing of thermoplastic resins can be performed at a lower temperature than before, which is useful for suppressing thermal oxidative degradation and reducing energy costs.

[0005] For example, Patent Document 1 proposes a method for producing a polybutylene terephthalate resin composition containing a polyhydric hydroxyl group-containing compound. According to the same document, the fluidity of the polybutylene terephthalate resin composition can be increased by adding a polyhydric hydroxyl group-containing compound, and glycerin fatty acid ester or the like is preferably used as the polyhydric hydroxyl group-containing compound. Further, glycerin mono-12-hydroxystearate is used in the examples of the same document.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, although the low molecular weight polyhydric hydroxyl group-containing compound such as glycerin mono 12-hydroxystearate used in Patent Document 1 has an effect of improving fluidity, there is a problem of deteriorating the mechanical properties of the resin composition.

[0008] Therefore, the problem to be solved by the present invention is to provide a fluidity improver that can impart sufficient fluidity to the resin and further does not deteriorate the mechanical properties of the resin.

Means for Solving the Problems

[0009] As a result of intensive studies to solve the above problems, the present inventors have found that a fluidity improver containing a polyester compound having a specific structure can impart sufficient fluidity to the resin and further does not deteriorate the mechanical properties of the resin, and have completed the present invention.

[0010] According to the present invention, a fluidity improver for a thermoplastic resin, containing a polyester compound, the polyester compound includes a structural unit derived from a polyvalent carboxylic acid and a structural unit derived from an aliphatic diol having 2 to 12 carbon atoms, the structural unit derived from the polyvalent carboxylic acid includes a structural unit derived from an aromatic polyvalent carboxylic acid, the hydroxyl value of the polyester compound is 20 to 300 mgKOH / g, The number average molecular weight of the polyester compound is 500 to 5,000, a fluidity improver is provided.

[0011] In the fluidity improver of the present invention, the structural unit derived from the polycarboxylic acid in the polyester compound preferably contains a structural unit derived from an aromatic dicarboxylic acid.

[0012] In the fluidity improver of the present invention, the structural unit derived from the polycarboxylic acid in the polyester compound preferably contains a structural unit derived from at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.

[0013] In the fluidity improver of the present invention, the structural unit derived from the polycarboxylic acid in the polyester compound preferably contains 40 mol% or more of the structural unit derived from the aromatic polycarboxylic acid with respect to 100 mol% of the total amount of the structural units derived from the polycarboxylic acid.

[0014] In the fluidity improver of the present invention, the structural unit derived from the aliphatic diol in the polyester compound is preferably a structural unit derived from an aliphatic diol having 2 to 4 carbon atoms.

[0015] Also, according to the present invention, a composition containing a thermoplastic resin and the fluidity improver is provided.

[0016] In the composition of the present invention, the thermoplastic resin is preferably a polyester resin.

[0017] In the composition of the present invention, furthermore, it is preferable to contain glass fibers.

[0018] Also, according to the present invention, A molded article obtained from the composition is provided.

Advantages of the Invention

[0019] According to the present invention, it is possible to provide a fluidity improver that can impart sufficient fluidity to a resin and further does not reduce the mechanical properties of the resin, a composition containing the fluidity improver, and a molded article obtained from the composition.

Modes for Carrying Out the Invention

[0020] Hereinafter, embodiments of the present invention will be described in detail. <Fluidity Improver> The fluidity improver of the present invention is used for a thermoplastic resin. Examples of the thermoplastic resin include those exemplified as the thermoplastic resin contained in the composition described later.

[0021] The fluidity improver of the present invention contains a polyester compound. The polyester compound contains in its molecule a structural unit derived from a polyvalent carboxylic acid and a structural unit derived from an aliphatic diol having 2 to 12 carbon atoms.

[0022] The polyester compound can be produced by a conventionally known method. For example, a synthesis reaction of a polyvalent carboxylic acid or a polyvalent carboxylic acid derivative corresponding to the structural unit derived from the polyvalent carboxylic acid and an aliphatic diol corresponding to the structural unit derived from the aliphatic diol can be mentioned. Specifically, it can be produced by an esterification reaction of a polyvalent carboxylic acid and an aliphatic diol, a transesterification reaction of a polyvalent carboxylic acid alkyl ester and an aliphatic diol, a reaction of a polyvalent carboxylic acid halide and an aliphatic diol, a reaction of a polyvalent carboxylic acid anhydride and an aliphatic diol, etc. The production conditions such as the reaction time can be appropriately determined according to the physical properties of the desired polyester compound. The polyester compound obtained by the above methods and the like can be further separated and purified by separation and purification means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, and column chromatography, or means combining these.

[0023] Examples of the structural unit derived from the polyvalent carboxylic acid include structural units derived from aromatic polyvalent carboxylic acids, aliphatic polyvalent carboxylic acids, and the like. Examples of the structural unit derived from the aromatic polyvalent carboxylic acid include structural units derived from aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and naphthalenedicarboxylic acid; structural units derived from aromatic tricarboxylic acids such as trimellitic acid and trimesic acid; and structural units derived from tetravalent or higher aromatic carboxylic acids such as pyromellitic acid.

[0024] Examples of the structural unit derived from the aliphatic polyvalent carboxylic acid include structural units derived from aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and dimer; and structural units derived from alicyclic dicarboxylic acids such as 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanediacetic acid, 1,3-cyclohexanediacetic acid, 1,4-cyclohexanediacetic acid, and dicyclohexyl-4,4'-dicarboxylic acid.

[0025] The structural unit derived from the polyvalent carboxylic acid includes a structural unit derived from an aromatic polyvalent carboxylic acid. Among the aromatic polyvalent carboxylic acids, it is preferably a structural unit derived from an aromatic dicarboxylic acid, more preferably a structural unit derived from phthalic acid, isophthalic acid, or terephthalic acid, and even more preferably a structural unit derived from terephthalic acid. Thereby, the melting point of the polyester compound increases, and the handleability of the polyester compound is improved.

[0026] The polyester compound may contain only one kind of the structural unit derived from the polyvalent carboxylic acid, or may contain two or more kinds.

[0027] The constituent unit derived from the polycarboxylic acid in the polyester compound preferably contains 40 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more of the constituent unit derived from the aromatic polycarboxylic acid, based on 100 mol% of the total amount of the constituent units derived from the polycarboxylic acid. Thereby, the heat resistance of the polyester compound is improved. The upper limit of the content of the constituent unit derived from the aromatic polycarboxylic acid can be 100 mol% based on 100 mol% of the total amount of the constituent units derived from the polycarboxylic acid.

[0028] When the constituent unit derived from the polycarboxylic acid contains the constituent unit derived from one or more selected from phthalic acid, isophthalic acid, and terephthalic acid, it preferably contains 40 mol% or more, more preferably 60 mol% or more, and even more preferably 70 mol% or more in total of the constituent unit derived from one or more selected from phthalic acid, isophthalic acid, and terephthalic acid, based on 100 mol% of the total amount of the constituent units derived from the polycarboxylic acid. Thereby, the heat resistance of the polyester compound is improved. The upper limit of the content of the constituent unit derived from one or more selected from phthalic acid, isophthalic acid, and terephthalic acid can be 100 mol% based on 100 mol% of the total amount of the constituent units derived from the polycarboxylic acid.

[0029] The content of the constituent unit derived from the aromatic polycarboxylic acid in the constituent unit derived from the polycarboxylic acid in the polyester compound can be adjusted by adjusting the amount of the aromatic polycarboxylic acid used in the production of the polyester compound.

[0030] The content of the constituent unit derived from the aromatic polycarboxylic acid in the polyester compound is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more based on 100% by mass of the total amount of the polyester compound. Thereby, the heat resistance of the polyester compound is improved. When the polyester compound contains a structural unit derived from one or more selected from phthalic acid, isophthalic acid, and terephthalic acid, the total content of the structural units derived from phthalic acid, isophthalic acid, and terephthalic acid in the polyester compound is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more with respect to 100% by mass of the total amount of the polyester compound. Thereby, the heat resistance of the polyester compound is improved. Here, the content (% by mass) of the structural unit derived from the polyvalent carboxylic acid in the polyester compound is calculated by the molecular weight determined from the structural formula of the structural unit. The mass of the structural unit derived from the polyvalent carboxylic acid is determined from the structure of the residue obtained by deleting OH from the carboxy group COOH in the polyvalent carboxylic acid.

[0031] Examples of the structural unit derived from the aliphatic diol having 2 to 12 carbon atoms include structural units derived from linear alkanediols such as 1,2-ethanediol (ethylene glycol), 1,2-propanediol (propylene glycol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol; structural units derived from cyclic alkanediols such as 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, and cyclododecanediol; and structural units derived from dimer diol, hydrogenated dimer diol, diethylene glycol, dipropylene glycol, triethylene glycol, or polyethylene glycol, etc.

[0032] Among these, from the viewpoint of compatibility with the thermoplastic resin, the structural unit derived from the aliphatic diol is preferably a structural unit derived from an aliphatic diol having 2 to 8 carbon atoms, more preferably a structural unit derived from an aliphatic diol having 2 to 4 carbon atoms, even more preferably a structural unit derived from 1,2-ethanediol (ethylene glycol), 1,2-propanediol, 2-methyl-1,3-propanediol, or 1,4-butanediol, and particularly preferably a structural unit derived from 1,4-butanediol. Also, from the same viewpoint, the structural unit derived from the aliphatic diol is preferably a structural unit derived from a linear alkanediol or a cyclic alkanediol, and more preferably a structural unit derived from a linear alkanediol.

[0033] The polyester compound may contain one kind of structural unit derived from an aliphatic diol having 2 to 12 carbon atoms, or may contain two or more kinds.

[0034] The content of the structural unit derived from the aliphatic diol in the polyester compound is preferably 70% by mass or less, more preferably 55% by mass or less, and even more preferably 45% by mass or less, based on 100% by mass of the total amount of the polyester compound. Thereby, the heat resistance of the polyester compound is improved. Here, the content (% by mass) of the structural unit derived from the aliphatic diol in the polyester compound is calculated based on the molecular weight determined from the structural formula of the structural unit. Specifically, it is calculated based on the structure obtained by removing hydrogen atoms H from two hydroxyl groups OH of the aliphatic diol.

[0035] In addition to the structural unit derived from the aliphatic diol having 2 to 12 carbon atoms, the polyester compound may contain a structural unit derived from another diol. However, from the viewpoint of further enhancing the effects of the present invention, it is preferable that the content rate of the structural unit derived from another diol in the polyester compound is low. Specifically, among the structural units derived from diols, the proportion of the structural unit derived from the aliphatic diol having 2 to 12 carbon atoms is preferably 70 mol% or more, more preferably 80 mol% or more, even more preferably 90 mol% or more, and may be 100 mol%. Examples of the structural unit derived from another diol include a structural unit derived from an aliphatic diol having 13 or more carbon atoms.

[0036] The polyester compound has a hydroxyl value of 20 to 300 mgKOH / g. The lower limit of the hydroxyl value is preferably 35 mgKOH / g or more, more preferably 50 mgKOH / g or more, and even more preferably 60 mgKOH / g or more. Thereby, the fluidity improvement performance is improved. The upper limit of the hydroxyl value of the polyester compound is preferably 160 mgKOH / g or less, more preferably 120 mgKOH / g or less. This improves the heat resistance of the polyester compound. The hydroxyl value can be measured by the method described in JIS K 1557-1.

[0037] The molecular chain ends of the polyester compound are mainly hydroxyl groups derived from aliphatic diols having 2 to 12 carbon atoms. However, in a polyester compound obtained by the reaction of a polyvalent carboxylic acid or a polyvalent carboxylic acid derivative with an aliphatic diol, there may be a case where a part of the molecular chain ends is not a hydroxyl group derived from the aliphatic diol. Examples of the molecular chain ends other than the hydroxyl group include terminal structures of structural units derived from polyvalent carboxylic acids, such as carboxyl groups derived from polyvalent carboxylic acids or alkyl esters of carboxyl groups derived from polyvalent carboxylic acid derivatives. Among 100 mol% of all the molecular chain end groups of the polyester compound, the content ratio of the hydroxyl groups derived from aliphatic diols having 2 to 12 carbon atoms is preferably 80 mol% or more, more preferably 90 mol% or more, and even more preferably 95 mol% or more. This improves the fluidity improvement effect. The content ratio of the hydroxyl groups derived from aliphatic diols having 2 to 12 carbon atoms in all the molecular chain end groups of the polyester compound can be measured, for example, by measuring the hydroxyl value by titration as defined in JIS K 1557-1.

[0038] The hydroxyl value of the polyester compound can be made within the above range by adjusting the amount of aliphatic diol used at the time of raw material charging and the average degree of polymerization of the polyester compound in the production of the polyester compound.

[0039] The polyester compound has a number average molecular weight of 500 to 5,000. The lower limit of the number average molecular weight of the polyester compound is preferably 600 or more, more preferably 800 or more, and even more preferably 1,000 or more. This improves the heat resistance of the polyester compound. The upper limit of the number average molecular weight of the polyester compound is more preferably not more than 4,000, even more preferably not more than 3,000, and particularly preferably not more than 1,800, which enhances the effect of improving flowability.

[0040] The number average molecular weight can be measured by gel permeation chromatography (GPC) and calculated in terms of polystyrene. For example, it can be suitably measured under the following conditions. Solvent: Chloroform Solvent flow rate: 0.5 ml / min Column: SHODEX LF-804 (Resonac) Column temperature: 40℃

[0041] The number average molecular weight of the polyester compound can be adjusted to the above-mentioned range by adjusting the polymerization time, polymerization temperature, and molecular chain growth due to ester exchange between low molecular weight polyesters in the production of the polyester compound.

[0042] The flowability improver of the present invention may consist of only one type of the polyester compound, or may contain two or more types.

[0043] The flowability improver of the present invention has the effect of imparting flowability to a resin and maintaining mechanical properties. The reason for this effect is not clear, but is presumed to be as follows. That is, the polyester compound, which has a smaller molecular weight than the thermoplastic resin, is dispersed between the molecules of the thermoplastic resin, thereby weakening the intermolecular forces of the thermoplastic resin and facilitating the movement of each molecular chain, thereby providing excellent fluidity during melt processing. In addition, since the type of structural unit, hydroxyl value, and number average molecular weight of the polyester compound are within the above ranges, the effect of reducing the intermolecular forces in the thermoplastic resin at room temperature after processing is reduced, and as a result, the deterioration of the mechanical properties of the thermoplastic resin is suppressed. When the thermoplastic resin has an ester bond, in addition to the above reasons, a transesterification reaction occurs between the thermoplastic resin and the fluidity improver of the present invention, and a decrease in the molecular weight of the thermoplastic resin and an increase in the molecular weight due to crosslinking occur simultaneously. By the type, hydroxyl value, and number average molecular weight of the constituent units of the polyester compound being within the above ranges, the transesterification reaction does not proceed excessively, the fluidity during melt processing is improved, and a decrease in mechanical properties is suppressed.

[0044] <Composition> The composition of the present invention contains a thermoplastic resin and the above-described fluidity improver. The lower limit of the content of the fluidity improver is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more with respect to 100 parts by mass of the composition of the present invention. On the other hand, the upper limit of the content of the fluidity improver is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less with respect to 100 parts by mass of the composition of the present invention. Thereby, the composition of the present invention can exhibit excellent effects of fluidity and mechanical properties in a well-balanced manner.

[0045] The lower limit of the content of the fluidity improver is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin. On the other hand, the upper limit of the content of the fluidity improver is preferably 15 parts by mass or less, more preferably 12 parts by mass or less, still more preferably 8 parts by mass or less, and particularly preferably 6 parts by mass or less with respect to 100 parts by mass of the composition of the present invention. Thereby, the composition of the present invention can exhibit excellent effects of fluidity and mechanical properties in a well-balanced manner.

[0046] The lower limit of the content of the thermoplastic resin is preferably 85 parts by mass or more, more preferably 88 parts by mass or more, even more preferably 92 parts by mass or more, and particularly preferably 94 parts by mass or more with respect to 100 parts by mass of the composition of the present invention. On the other hand, the upper limit of the content of the thermoplastic resin is preferably 99.9 parts by mass or less, more preferably 99.5 parts by mass or less, even more preferably 99 parts by mass or less, and particularly preferably 98 parts by mass or less with respect to 100 parts by mass of the composition of the present invention. Thereby, the composition of the present invention can exhibit an excellent balance of fluidity and mechanical properties.

[0047] Examples of the thermoplastic resin include synthetic resins such as polyolefin resins, styrene resins, polyester resins, polycarbonate resins, polysulfide resins, polyamide resins, polyether resins, and halogen-containing resins. These may be used alone or in combination of two or more. Furthermore, examples of the thermoplastic resin include, for example, petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyurethanes, cellulose-based resins, polyimide resins, polysulfones, and liquid crystal polymers, and blends thereof. The thermoplastic resin may also be a thermoplastic elastomer such as isoprene rubber, butadiene rubber, ethylene-propylene rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, olefin-based elastomer, styrene-based elastomer, polyester-based elastomer, nitrile-based elastomer, nylon-based elastomer, vinyl chloride-based elastomer, polyamide-based elastomer, and polyurethane-based elastomer, and these may be used in combination.

[0048] Examples of the polyolefin resin include α-olefin polymers such as polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, polybutene-1, poly-3-methylpentene, poly-4-methylpentene, and ethylene / propylene block or random copolymers.

[0049] Examples of the styrenic resin include, for example, syndiotactic polystyrene and acrylonitrile-butadiene-styrene terpolymer.

[0050] Examples of the polysulfide resin include, for example, polyphenylene sulfide.

[0051] Examples of the polyamide resin include aliphatic polyamides such as polyamide 410, polyamide 6, polyamide 66, polyamide 666, polyamide 610, polyamide 612, polyamide 11, and polyamide 12; and semi-aromatic polyamides such as polyamide 4T, polyamide 6T, polyamide 9T, and polyamide 10T.

[0052] Examples of the polyester resin include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, and polycyclohexane dimethylene terephthalate; polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; and degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polyapple acid, polyglycolic acid, polydioxane, and poly(2-oxetanone).

[0053] The polycarbonate resin is a resin having a carbonate bond and is obtained, for example, by a polymerization reaction of a divalent hydroxy aromatic compound and a carbonate precursor. Examples of the divalent hydroxyaromatic compound include dihydroxybenzenes such as resorcinol and hydroquinone; bis-hydroxyaryls such as 4,4'-dihydroxydiphenyl; bis-(hydroxyaryl)alkanes such as bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenoxy)ethane, and 2,2-bis(4-hydroxyphenyl)propane; dihydroxyaryl ketones such as bis(4-hydroxyphenyl)ketone and bis(4-hydroxy-3-methylphenyl)ketone; dihydroxyaryl ethers such as 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, and 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether; dihydroxyaryl sulfur compounds such as 4,4'-thiodiphenol, bis(4-hydroxyphenyl)sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, 2,2-bis(4-hydroxyphenyl)sulfone, 4,4'-dihydroxydiphenyl sulfone, and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone, and phenolphthalein. These may be used alone or in combination of two or more kinds, and may further be used in combination with a polyvalent hydroxyaromatic compound having three or more hydroxyl groups. Preferable specific examples of the carbonate precursor include phosgene, carbonic acid diester, diphenyl carbonate, dihaloformate of divalent phenol, and mixtures thereof.

[0054] These thermoplastic resins can be used regardless of their molecular weight, degree of polymerization, polymerization method, density, softening point, ratio of insoluble matter in a solvent, degree of stereoregularity, presence or absence of catalyst residue, type and blending ratio of monomers as raw materials, type of polymerization catalyst, and the like.

[0055] The above-mentioned thermoplastic resins may be used alone or in combination of two or more kinds. Further, the thermoplastic resin may be alloyed.

[0056] Among these thermoplastic resins, polyester resins and polycarbonate resins are preferred, polyester resins are more preferred, polyalkylene terephthalates are even more preferred, and polybutylene terephthalate is particularly preferred, from the viewpoint of more effectively exhibiting the fluidity improving performance of the fluidity improver.

[0057] Other optional components may be blended in the composition of the present invention together with the fluidity improver. The timing of mixing the fluidity improver and other optional components with the thermoplastic resin is not particularly limited. For example, two or more selected from the compounding components other than the thermoplastic resin may be premixed and then compounded with the thermoplastic resin, or each component other than the thermoplastic resin may be sequentially compounded with the thermoplastic resin. When a plurality of components are premixed, each component may be pulverized and then mixed, or may be mixed and then pulverized. When the thermoplastic resin is an alloy, each component other than the thermoplastic resin may be added to the compound that is already an alloy in advance, or may be added in the alloying step. Further, as a method of mixing the fluidity improver and the thermoplastic resin, a method of mixing the fluidity improver and the entire amount of the thermoplastic resin to be mixed may be used, but a method of premixing the fluidity improver and a part of the thermoplastic resin to prepare a masterbatch and then mixing the masterbatch with the remaining thermoplastic resin may also be used. Further, the masterbatch may contain the other optional components. The content of the fluidity improver in the masterbatch can be 1 part by mass or more, and can be 10 parts by mass or more and 90 parts by mass or less, per 100 parts by mass of the masterbatch.

[0058] Hereinafter, other optional components that can be blended in the composition of the present invention will be described. It is preferable to add a phenolic antioxidant, a phosphorus antioxidant, a thioether antioxidant, an ultraviolet absorber, a hindered amine light stabilizer, etc. to the composition of the present invention as necessary to stabilize the composition.

[0059] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-di-tert-butyl-4-hydroxybenzyl thioacetate, 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionamide], 4,4'-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-m-cresol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 2,2'-ethylidenebis(4-sec-butyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 2-tert-butyl-4-methyl-6-(2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis[methyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane, thiodiethylene glycol bis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,6-hexamethylenebis[(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis[3,3-bis(4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1,3,5-tris[(3,5-Di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl] isocyanurate, 3,9-bis[1,1-dimethyl-2-{(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy}ethyl]-2,4,8,10-tetraoxaspiro[5,5]undecane, triethylene glycol bis[(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate], and the like can be mentioned. These phenolic antioxidants may be used alone or in combination of two or more. From the viewpoint of the antioxidant effect, the content of the phenolic antioxidant is preferably an amount of 0.001 to 10 parts by weight, more preferably an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin.,

[0060] Examples of the phosphorus-based antioxidant include tris(nonylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tridecyl phosphite, octyldiphenyl phosphite, didecyl monophenyl phosphite, bis(tridecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, tetrakis(tridecyl) isopropylidenediphenol diphosphite, tetrakis(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexakis(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite, tris(2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-6-yl)oxy]ethyl)amine, phosphite of 2-ethyl-2-butylpropylene glycol and 2,4,6-tri-tert-butylphenol, and the like. These phosphorus-based antioxidants may be used alone or in combination of two or more. From the viewpoint of the antioxidant effect, the content of the phosphorus-based antioxidant is preferably an amount of 0.001 to 10 parts by weight, more preferably an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin.

[0061] Examples of the thioether-based antioxidant include dialkyl thiodipropionates such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and β-alkyl mercaptopropionate esters of polyols such as pentaerythritol tetrakis(β-alkyl mercaptopropionate). These thioether-based antioxidants may be used alone or in combination of two or more. From the viewpoint of the antioxidant effect, the content of the thioether-based antioxidant is preferably an amount of 0.001 to 10 parts by weight, more preferably an amount of 0.05 to 5 parts by weight, based on 100 parts by weight of the thermoplastic resin.

[0062] Examples of the ultraviolet absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-dicumenylphenyl)benzotriazole, 2,2'-methylenebis(4-tert-octyl-6-(benzotriazolyl)phenol), and 2-(2'-hydroxy-3'-tert-butyl-5'-carboxyphenyl)benzotriazole; benzoates such as phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,4-di-tert-amylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; and triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-s-triazine, and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine. These ultraviolet absorbers may be used alone or in combination of two or more.The content of the ultraviolet absorber is preferably an amount of 0.001 to 30 parts by mass, more preferably an amount of 0.05 to 10 parts by mass, based on 100 parts by mass of the thermoplastic resin, from the viewpoint of the ultraviolet absorption effect.

[0063] Examples of the hindered amine light stabilizer include 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, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)·bis(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / succinic acid diethyl polycondensate, 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-tert-octylamino-s-triazine polycondensate, 1,5,8,12-tetrakis〔2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-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-triazin-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-triazin-6-yl〕aminoundecane, 1,6,11-tris〔2,4-bis(N-butyl-N-(1,2,2,6,(6-Pentamethyl-4-piperidyl)amino)-s-triazin-6-yl)aminoundecane, bis(2,2,6,6-tetramethyl-1-octyloxy-4-piperidyl) decanedioate, bis(2,2,6,6-tetramethyl-1-undecyloxypiperidin-4-yl) carbonate, TINUVIN NOR 371 manufactured by BASF, etc. may be mentioned. These hindered amine light stabilizers may be used alone or in combination of two or more. From the viewpoint of the light stabilizing effect, the content of the hindered amine light stabilizer is preferably an amount of 0.001 to 30 parts by weight, more preferably an amount of 0.05 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin.,

[0064] In the composition of the present invention, if necessary, further additives usually used in synthetic resins, such as crosslinking agents, antistatic agents, antifogging agents, anti-plating agents, surface treatment agents, plasticizers, lubricants, reinforcing materials, nucleating agents, flame retardants, flame retardant aids, fluorescent agents, antifungal agents, bactericides, foaming agents, metal deactivators, mold release agents, silicone oils, silane coupling agents, fillers, hydrotalcites, metal soaps, pigments, dyes, etc. can be blended within a range not impairing the effects of the present invention.

[0065] The form of the composition of the present invention is not particularly limited, but from the viewpoint of the handleability of the composition, it is preferably in the form of pellets, powder, granules or flakes, and more preferably in the form of pellets.

[0066] The composition of the present invention can be used alone or in combination with a composition, additive component other than the present invention or a mixture thereof for molding etc. Further, the composition of the present invention can be used as a masterbatch.

[0067] The composition of the present invention preferably contains glass fibers. Thereby, the rigidity and the dimensional stability at high temperature are improved. As the glass fiber, the type is not particularly limited, and any of E glass, C glass, S glass, D glass, etc. can be used. Also, the form is not particularly limited, and any glass fiber such as chopped strands, rovings, yarns, and glass wool can be used. As the glass fiber, commercially available products can be used. From the viewpoints of processability and flame retardancy, chopped strands in which single fibers are converged are preferable as the glass fiber. When using chopped strands, the cut length is preferably 0.5 mm to 10 mm, more preferably 2 mm to 5 mm, from the viewpoints of processability and fluidity. Also, the diameter of the single fiber is preferably 8 μm to 20 μm, more preferably 10 μm to 15 μm, from the viewpoints of processability and fluidity.

[0068] The glass fiber may be treated with a surface treatment agent in order to improve the wettability and adhesiveness with the thermoplastic resin. Examples of this surface treatment agent include silane-based, titanate-based, aluminum-based, chromium-based, zirconium-based, and borane-based coupling agents. Among these, silane-based coupling agents and titanate-based coupling agents are preferable, and silane-based coupling agents are particularly suitable. Examples of this silane-based coupling agent include triethoxysilane, vinyltris(β-methoxyethoxy)silane, γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, etc.

[0069] A converging agent may be used to converge the glass fiber. Examples of the converging agent include polypropylene resin, polyurethane resin, polyester resin, acrylic resin, epoxy resin, starch, vegetable oil, etc.

[0070] In the composition of the present invention, the content of the glass fiber is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass, based on 100 parts by mass of the total mass of the composition, from the viewpoints of processability and fluidity.

[0071] <Molded article> The molded article of the present invention can be obtained by molding the composition of the present invention by a known method. The molding method is not particularly limited, and examples thereof include molding methods such as extrusion molding, calender molding, injection molding, roll molding, compression molding, and blow molding. By these molding methods, molded articles of various shapes such as resin plates, sheets, films, pellets, and shaped articles can be manufactured.

[0072] The composition of the present invention and its molded articles can be used in a wide range of industrial fields such as electric, electronic, and communication, agriculture, forestry, and fisheries, mining, construction, food, fiber, clothing, medical, coal, petroleum, rubber, leather, automobile, precision equipment, wood, building materials, civil engineering, furniture, printing, musical instruments, etc. More specifically, office OA equipment such as printers, personal computers, word processors, keyboards, PDAs (small information terminals), telephones, copiers, facsimiles, ECRs (electronic cash registers), calculators, electronic notebooks, cards, holders, stationery, etc., home appliances such as washing machines, refrigerators, vacuum cleaners, microwave ovens, lighting fixtures, game machines, irons, kotatsu, etc., AV equipment such as TVs, VTRs, video cameras, radios, tape recorders, mini discs, CD players, speakers, liquid crystal displays, etc., and electric and electronic parts and communication equipment such as connectors, relays, capacitors, switches, printed circuit boards, coil bobbins, semiconductor encapsulation materials, LED encapsulation materials, electric wires, cables, transformers, deflection yokes, distribution boards, clocks, etc.

[0073] In addition, the composition of the present invention and its molded articles can also be used for optical material applications such as optical discs, CD discs, DVD discs, lenses, etc. and glass replacement applications.

[0074] Furthermore, the composition of the present invention and its molded articles are used in various applications such as seats (padding, fabric, etc.), belts, ceiling linings, convertible tops, armrests, door trims, rear package trays, carpets, mats, sun visors, foil covers, mattress covers, airbags, insulating materials, handles, handle straps, wire coatings, electrical insulating materials, paints, coating materials, upholstery materials, floor materials, partitions, carpets, wallpapers, wall finishing materials, exterior finishing materials, interior finishing materials, roofing materials, deck materials, wall materials, column materials, floorboards, materials for fences, frameworks and molds, window and door profiles, shingles, latticework, terraces, balconies, soundproofing boards, heat insulation boards, window materials, etc. for automobiles, vehicles, ships, aircraft, buildings, houses and building materials, civil engineering materials, clothing, curtains, sheets, plywood, fiberboard, rugs, entrance mats, seats, buckets, hoses, containers, glasses, bags, cases, goggles, ski boards, rackets, tents, musical instruments, etc. for daily necessities, sports goods, etc.

[0075] In the present disclosure, the following aspects are included. [1] A fluidity improver for thermoplastic resins, containing a polyester compound, wherein the polyester compound includes a structural unit derived from a polycarboxylic acid and a structural unit derived from an aliphatic diol having 2 to 12 carbon atoms, the structural unit derived from the polycarboxylic acid includes a structural unit derived from an aromatic polycarboxylic acid, the hydroxyl value of the polyester compound is 20 to 200 mgKOH / g, and the number average molecular weight of the polyester compound is 500 to 5,000. Fluidity improver. [2] The fluidity improver according to [1], wherein the structural unit derived from the polycarboxylic acid in the polyester compound includes a structural unit derived from an aromatic dicarboxylic acid. [3] The fluidity improver according to [2], wherein the structural unit derived from the polycarboxylic acid in the polyester compound includes a structural unit derived from at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid. [4] The constituent unit derived from the polyvalent carboxylic acid in the polyester compound contains 40 mol% or more of the constituent unit derived from the aromatic polyvalent carboxylic acid with respect to 100 mol% of the total amount of the constituent units derived from the polyvalent carboxylic acid. The fluidity improver according to any one of [1] to [3]. [5] The constituent unit derived from the aliphatic diol in the polyester compound is a constituent unit derived from an aliphatic diol having 2 to 4 carbon atoms. The fluidity improver according to any one of [1] to [4]. [6] A composition containing a thermoplastic resin and the fluidity improver according to any one of [1] to [5]. [7] The composition according to [6], wherein the thermoplastic resin is a polyester resin. [8] Furthermore, the composition according to [6] or [7], which contains glass fiber. [9] A molded article obtained from the composition according to any one of [6] to [8].

Examples

[0076] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited thereto in any way.

[0077] [Examples 1-1 to 1-15, Examples 2-1 to 2-28, Examples 3-1 to 3-8, Comparative Examples 2-1 to 2-7, Comparative Examples 3-1 to 3-4] <Example 1-1: Production of Fluidity Improver (A)-1> Using 155 g of dimethyl terephthalate and 151 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, an ester exchange reaction between dimethyl terephthalate and 1,4-butanediol was carried out at 200 to 230 °C under normal pressure and reduced pressure, and then the excess 1,4-butanediol was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-1.

[0078] <Example 1-2: Production of Fluidity Improver (A)-2> Using 194 g of dimethyl terephthalate and 173 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction between dimethyl terephthalate and 1,4-butanediol was carried out, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-2.

[0079] <Example 1-3: Production of Fluidity Improver (A)-3> Using 129 g of dimethyl terephthalate, 69 g of dimethyl isophthalate and 204 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction between dimethyl terephthalate and dimethyl isophthalate and 1,4-butanediol was carried out, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-3.

[0080] <Example 1-4: Production of Fluidity Improver (A)-4> Using 138 g of dimethyl terephthalate, 75 g of dimethyl isophthalate and 187 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction between dimethyl terephthalate and dimethyl isophthalate and 1,4-butanediol was carried out, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-4.

[0081] <Example 1-5: Production of Fluidity Improver (A)-5> Using 122 g of dimethyl terephthalate, 122 g of dimethyl isophthalate, and 216 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate and dimethyl isophthalate and 1,4-butanediol, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as fluidity improver (A)-5.

[0082] <Example 1-6: Production of fluidity improver (A)-6> Using 107 g of dimethyl terephthalate, 107 g of dimethyl isophthalate, and 173 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate and dimethyl isophthalate and 1,4-butanediol, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as fluidity improver (A)-6.

[0083] <Example 1-7: Production of fluidity improver (A)-7> Using 116 g of dimethyl terephthalate, 116 g of dimethyl isophthalate, and 181 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate and dimethyl isophthalate and 1,4-butanediol, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as fluidity improver (A)-7.

[0084] <Example 1-8: Production of fluidity improver (A)-8> Using 153 g of dimethyl terephthalate, 46 g of dimethyl adipate and 173 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 - 230 °C, under normal pressure and reduced pressure, the transesterification reaction of dimethyl terephthalate and dimethyl adipate with 1,4-butanediol was carried out, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-8.

[0085] <Example 1-9: Production of fluidity improver (A)-9> Using 103 g of dimethyl terephthalate, 92 g of dimethyl adipate and 182 g of 1,4-butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 - 230 °C, under normal pressure and reduced pressure, the transesterification reaction of dimethyl terephthalate and dimethyl adipate with 1,4-butanediol was carried out, and then the excess 1,4-butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-9.

[0086] <Example 1-10: Production of fluidity improver (A)-10> Using 138 g of dimethyl terephthalate, 138 g of dimethyl isophthalate and 161 g of ethylene glycol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 - 230 °C, under normal pressure and reduced pressure, the transesterification reaction of dimethyl terephthalate and dimethyl isophthalate with ethylene glycol was carried out, and then the excess ethylene glycol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as the fluidity improver (A)-10.

[0087] <Example 1-11: Production of fluidity improver (A)-11> 190 g of dimethyl terephthalate, 88 g of ethylene glycol, and 43 g of 2-methyl-1,3-propanediol were used to produce a polyester compound. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate and ethylene glycol and 2-methyl-1,3-propanediol. After that, the polyester compound was obtained by distilling off the excess ethylene glycol and 2-methyl-1,3-propanediol under reduced pressure. The obtained polyester compound was used as the fluidity improver (A)-11.

[0088] <Example 1-12: Production of Fluidity Improver (A)-14> 177 g of dimethyl terephthalate, 95 g of dimethyl isophthalate, and 188 g of 1,2-propanediol were used to produce a polyester compound. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate and dimethyl isophthalate and 1,2-propanediol. After that, the polyester compound was obtained by distilling off the excess 1,2-propanediol under reduced pressure. The obtained polyester compound was used as the fluidity improver (A)-14.

[0089] <Example 1-13: Production of Fluidity Improver (A)-15> 189 g of dimethyl terephthalate, 48 g of phthalic anhydride, and 201 g of 1,4-butanediol were used to produce a polyester compound. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 to 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate and phthalic anhydride and 1,4-butanediol. After that, the polyester compound was obtained by distilling off the excess 1,4-butanediol under reduced pressure. The obtained polyester compound was used as the fluidity improver (A)-15.

[0090] <Comparative Example 1-1: Preparation of Comparative Fluidity Improver (B)-1> Commercially available glycerin mono 12 - hydroxystearate (trade name: Rikemal HC - 100, manufacturer: Riken Vitamin) was used as Comparative Fluidity Improver (B) - 1. Comparative Fluidity Improver (B) - 1 differs from the fluidity improver of the present invention in that it does not contain a polyester compound and the hydroxyl value and molecular weight are outside the scope of the present invention.

[0091] <Comparative Example 1 - 2: Production of Comparative Fluidity Improver (B) - 2> Using 191 g of dimethyl adipate and 187 g of 1,4 - butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 - 230 °C, under normal pressure and reduced pressure, an ester exchange reaction between dimethyl adipate and 1,4 - butanediol was carried out, and then the excess 1,4 - butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as Comparative Fluidity Improver (B) - 2. Comparative Fluidity Improver (B) - 2 differs from the fluidity improver of the present invention in that it does not have a structural unit derived from an aromatic polyvalent carboxylic acid.

[0092] <Comparative Example 1 - 3: Production of Comparative Fluidity Improver (B) - 3> Using 114 g of dimethyl terephthalate, 114 g of dimethyl isophthalate and 177 g of 1,4 - butanediol, a polyester compound was produced. Specifically, using tetraisopropoxytitanium as a catalyst, at 200 - 230 °C, under normal pressure and reduced pressure, an ester exchange reaction between dimethyl terephthalate and dimethyl isophthalate and 1,4 - butanediol was carried out, and then the excess 1,4 - butanediol charged was distilled off under reduced pressure to obtain a polyester compound. The obtained polyester compound was used as Comparative Fluidity Improver (B) - 3. Comparative Fluidity Improver (B) - 3 differs from the fluidity improver of the present invention in that the number average molecular weight is outside the scope of the present invention.

[0093] <Comparative Example 1 - 4: Production of Comparative Fluidity Improver (B) - 4> Using 95 g of dimethyl terephthalate, 95 g of dimethyl isophthalate, and 151 g of 1,4-butanediol, with tetraisopropoxytitanium as a catalyst, at 200 - 230 °C, under normal pressure and reduced pressure, an ester exchange reaction was carried out between dimethyl terephthalate, dimethyl isophthalate, and 1,4-butanediol. Then, the excess 1,4-butanediol was distilled off under reduced pressure to obtain a polyester intermediate with a hydroxyl value of 35 and a number average molecular weight of 3,200. Subsequently, by reacting 200 g of the polyester intermediate with 7 g of acetic anhydride at 130 °C, a polyester compound with a hydroxyl value of 17 and a number average molecular weight of 3,300 was obtained. The obtained polyester compound was used as Comparative Flowability Improver (B)-4. Comparative Flowability Improver (B)-4 is different from the flowability improver of the present invention in that the hydroxyl value is outside the scope of the present invention.

[0094] Table 1 shows the number average molecular weight, hydroxyl value, and 5% weight loss temperature of each flowability improver used in the evaluation. Also shown is the composition of the polyvalent carboxylic acid and aliphatic diol used in the production of Flowability Improvers (A)-1 to (A)-15 and Comparative Flowability Improvers (B)-2 to (B)-4. The number average molecular weight, hydroxyl value, and 5% weight loss temperature were measured by the following <Measurement Method of Number Average Molecular Weight>, <Measurement Method of Hydroxyl Value>, and <Measurement Method of 5% Weight Loss Temperature>, respectively. For the molecular weight of Comparative Flowability Improver (B)-1, a value calculated from the structure is shown instead of the number average molecular weight.

[0095] For the polyester compounds of Flowability Improvers (A)-1 to (A)-15, among 100 mol% of all molecular chain end groups, the content ratio of hydroxyl groups derived from aliphatic diol was 95 mol% or more.

[0096] In Table 1, the numerical values shown in the column of polyvalent carboxylic acid are the usage amounts (mol%) of each polyvalent carboxylic acid with respect to 100 mol% of the total amount of polyvalent carboxylic acid used in the production, and are equal to the ratio (mol%) of the structural units derived from each polyvalent carboxylic acid with respect to 100 mol% of the total amount of structural units derived from polyvalent carboxylic acid in the produced polyester compound. In Table 1, the numerical values ​​shown in the aliphatic diol column are the amounts (mol %) of each aliphatic diol used relative to 100 mol % of the total amount of aliphatic diols used in the production, and are equal to the proportions (mol %) of the constituent units derived from each aliphatic diol relative to 100 mol % of the total amount of constituent units derived from aliphatic diols in the produced polyester compound.

[0097] <Method for measuring hydroxyl value> The hydroxyl value of the flow improver was measured in accordance with JIS K 1557-1.

[0098] <Method for measuring number average molecular weight> The number average molecular weight was measured by GPC and calculated in terms of polystyrene under the following measurement conditions: Equipment: GPC equipment manufactured by JASCO Corporation Detector: Refractive index (RI) detector Solvent: Chloroform Solvent flow rate: 0.5 ml / min Column: SHODEX LF-804 (Resonac) Column temperature: 40℃

[0099] <Method for measuring 5% weight loss temperature> Approximately 10 mg of the sample was weighed out precisely, and the weight loss rate (wt%) was measured when the sample was heated from 30°C to 400°C at a heating rate of 10°C / min under a nitrogen atmosphere using a thermogravimetric / differential thermal analyzer (Thermoplus EVO, manufactured by Rigaku). The temperature (°C) at which the sample had lost 5% by weight from the weight at the start of the measurement was determined. This temperature was defined as the 5% weight loss temperature.

[0100] [Table 1]

[0101] From Table 1, it was found that the fluidity improvers (A)-1 to (A)-15 had high weight loss temperatures and excellent heat resistance. On the other hand, the comparative fluidity improvers (B)-1 and (B)-2 had lower weight loss temperatures than the stabilizers (A)-1 to (A)-15 and were inferior in heat resistance. The above results indicate that the fluidity improver of the present invention has good heat resistance.

[0102] <Manufacture of Composition> Each component was melt-kneaded at the ratios shown in Tables 2 to 3 to obtain resin strands. The melt-kneading was carried out using a device in which a twin-screw segment extruder (device name: 2D30W2) was connected to a Laboplastomill (manufactured by Toyo Seiki Seisakusho) under the conditions of a melting temperature of 250°C and a screw speed of 40 revolutions per minute. The obtained resin strands were cut with a pelletizer to obtain a pelletized composition. The numerical values of each component in Tables 2 and 3 are in parts by mass. The details of the components in Tables 2 to 3 are as shown below.

[0103] Fluidity improver (A)-1: The fluidity improver manufactured in Example 1-1 Fluidity improver (A)-2: The fluidity improver manufactured in Example 1-2 Fluidity improver (A)-3: The fluidity improver manufactured in Example 1-3 Fluidity improver (A)-4: The fluidity improver manufactured in Example 1-4 Fluidity improver (A)-5: The fluidity improver manufactured in Example 1-5 Fluidity improver (A)-6: The fluidity improver manufactured in Example 1-6 Fluidity improver (A)-7: The fluidity improver manufactured in Example 1-7 Fluidity improver (A)-8: The fluidity improver manufactured in Example 1-8 Fluidity improver (A)-9: The fluidity improver manufactured in Example 1-9 Fluidity improver (A)-10: The fluidity improver manufactured in Example 1-10 Fluidity improver (A)-11: The fluidity improver manufactured in Example 1-11 Fluidity improver (A)-12: The fluidity improver manufactured in Example 1-12 Fluidity improver (A)-13: The fluidity improver manufactured in Example 1-13 Flow improver (A)-14: The flow improver produced in Examples 1-14 Flow improver (A)-15: The flow improver produced in Examples 1-15 Comparative flow improver (B)-1: Glyceryl mono 12-hydroxystearate (trade name: Rikemal HC-100, manufacturer: Riken Vitamin) Comparative flow improver (B)-2: The comparative flow improver produced in Comparative Example 1-2 PBT resin: Polybutylene terephthalate resin (trade name: Duranex 2002, manufacturer: Polyplastics) Glass fiber: Chopped strand (trade name: CSF3PE-957S, manufacturer: Nitto Boseki, cut length 3.0 mm, single fiber diameter 13 μm)

[0104] The fluidity and mechanical properties of the obtained compositions were evaluated by the following methods. The evaluation results are shown in Tables 2 and 3.

[0105] <Evaluation of fluidity: Melt viscosity> The melt viscosity of the composition obtained above was measured to evaluate the fluidity. The measurement was carried out using a capillary rheometer (Capilograph, manufactured by Toyo Seiki Seisakusho), in accordance with JIS K 7199, at a cylinder temperature of 250 °C and a shear rate of 1,000 s -1 under the conditions of. The lower the melt viscosity, the higher the fluidity. The results are shown in Tables 2 and 3.

[0106] <Evaluation of mechanical properties: Flexural modulus> The composition obtained above was molded by an injection molding machine (NEX80, manufactured by Nissei Plastic Industrial Co., Ltd.) under processing conditions of a resin temperature of 250 °C and a mold temperature of 60 °C to obtain a test piece (80 mm × 10 mm × 4 mm) for measuring the flexural modulus. The obtained test piece was allowed to stand in a thermo-hygrostat at 23 °C and 60% RH for 48 hours or more after molding, and then the flexural modulus (unit: MPa) was measured using a flexural testing machine (AG-1kNIS fully automatic plastic flexural testing machine, manufactured by Shimadzu Corporation) in accordance with ISO178. The results are shown in Tables 2 and 3.

[0107]

Table 2A

[0108]

Table 2B

[0109] Table 2 shows the evaluation results of the compositions (Examples 2-1 to 2-28) to which the fluidity improver of the present invention was added and the compositions (Comparative Examples 2-1 to 2-5) to which the fluidity improver of the present invention was not added, for PBT resin. The compositions (Examples 2-1 to 2-24) to which the fluidity improver of the present invention was added had improved fluidity and mechanical properties equal to or better than those of the composition (Comparative Example 2-1) to which no fluidity improver was added. On the other hand, the compositions (Comparative Examples 2-2 to 2-5) to which the comparative fluidity improver (B)-1 or (B)-2 was added had improved fluidity compared to the composition (Comparative Example 2-1) to which no fluidity improver was added, but the mechanical properties decreased. Also, the compositions (Comparative Examples 2-6 to 2-9) to which the comparative fluidity improver (B)-3 having a number average molecular weight outside the range of the present invention or the comparative fluidity improver (B)-4 having a hydroxyl value outside the range of the present invention was added did not show improved fluidity compared to the composition (Comparative Example 2-1) to which no fluidity improver was added. From this, it was found that the fluidity improver of the present invention improves the fluidity of PBT resin and does not reduce the mechanical properties.

[0110]

Table 3

[0111] Table 3 shows the evaluation results of PBT resins compounded with glass fibers. The compositions (Examples 3-1 to 3-8) to which the fluidity improver of the present invention was added had improved fluidity and equivalent or better mechanical properties compared to the composition (Comparative Example 3-1) to which no fluidity improver was added. On the other hand, the compositions (Comparative Examples 3-2 to 3-4) to which comparative fluidity improvers (B)-1 and (B)-2 were added had improved fluidity but deteriorated mechanical properties compared to the composition (Comparative Example 3-1) to which no fluidity improver was added. From this, it was found that the fluidity improver of the present invention improves the fluidity of PBT resins compounded with glass fibers and does not deteriorate the mechanical properties.

[0112] From the above results, it was shown that the fluidity improver of the present invention has an excellent fluidity improving effect on resins and does not deteriorate the mechanical properties.

Claims

1. A fluidity improver for thermoplastic resins, containing a polyester compound, wherein the polyester compound includes a structural unit derived from a polycarboxylic acid and a structural unit derived from an aliphatic diol having 2 to 12 carbon atoms, the structural unit derived from the polycarboxylic acid includes a structural unit derived from an aromatic polycarboxylic acid, the hydroxyl value of the polyester compound is 20 to 300 mgKOH / g, and the number average molecular weight of the polyester compound is 500 to 5,000. The fluidity improver.

2. The fluidity improver according to claim 1, wherein the structural unit derived from the polycarboxylic acid in the polyester compound includes a structural unit derived from an aromatic dicarboxylic acid.

3. The fluidity improver according to claim 2, wherein the structural unit derived from the polycarboxylic acid in the polyester compound includes a structural unit derived from at least one selected from the group consisting of phthalic acid, isophthalic acid, and terephthalic acid.

4. The fluidity improver according to claim 1, wherein the structural unit derived from the polycarboxylic acid in the polyester compound includes 40 mol% or more of the structural unit derived from the aromatic polycarboxylic acid with respect to 100 mol% of the total amount of the structural units derived from the polycarboxylic acid.

5. The fluidity improver according to claim 1, wherein the structural unit derived from the aliphatic diol in the polyester compound is a structural unit derived from an aliphatic diol having 2 to 4 carbon atoms.

6. A composition containing a thermoplastic resin and the fluidity improver according to any one of claims 1 to 5.

7. The composition according to claim 6, wherein the thermoplastic resin is a polyester resin.

8. The composition according to claim 6, further containing glass fibers.

9. A molded article obtained from the composition according to claim 6.

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