TW202409201A - Aromatic polysulfone composition, molded article, and molded article manufacturing method - Google Patents

Abstract

An aromatic polysulfone composition containing an aromatic polysulfone, a liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives, wherein the fatty acid derivative may be a fatty acid amide.

Description

Aromatic polysulfone composition, formed body, and method for producing the formed body

The present invention relates to an aromatic polysulfide composition, a molded body, and a method for producing the molded body. This case claims priority based on Special Application No. 2022-113183 filed in Japan on July 14, 2022, and its contents are cited herein.

Aromatic polyethylene has excellent heat resistance, mechanical properties, electrical properties, and hot water resistance. Therefore, aromatic polystyrene compositions are used as molding materials for various applications such as electronics, machinery, automobiles, aircraft, and the medical and food industries.

In addition, aromatic polyester is sometimes used together with other resins. For example, Patent Document 1 discloses a composition including aromatic polystyrene resin having a specific melt viscosity, liquid crystal polyester having a specific flow temperature, and glass fibers having a specific average fiber diameter. [Prior technical documents] [Patent documents]

[Patent Document 1] Japanese Patent Publication No. 2002-20621

[The problem the invention is trying to solve]

When the aromatic polysulfone composition is used as a molding material to produce a body, the composition can be easily filled into the fine structure part in the mold by improving the fluidity of the aromatic polysulfone composition, which is suitable for producing a molded body with a fine structure.

The aromatic polyester composition containing liquid crystal polyester can improve the fluidity of the composition by containing liquid crystal polyester. However, since the resin composition shown in Patent Document 1 contains liquid crystal polyester, the strength of the produced molded article decreases.

The present invention has been accomplished in order to solve the above-mentioned problems, and its object is to provide an aromatic polyurethane composition excellent in balance between fluidity and strength. [Technical means to solve problems]

The inventors of the present invention have made great efforts to study and solve the above problems. As a result, they have found that by containing at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives, the strength reduction of the molded body can be suppressed and the fluidity of the composition can be improved, thereby completing the present invention. That is, the present invention has the following aspects.

<1> An aromatic polystyrene composition containing an aromatic polystyrene, a liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives. <2> The aromatic polystyrene composition according to the above <1>, wherein the mass ratio of the contents of the above-mentioned aromatic polystyrene and the above-mentioned liquid crystal polyester is the above-mentioned aromatic polystyrene/the above-mentioned liquid crystal polyester=95/5～ 70/30. <3> The aromatic polystyrene composition according to the above <1> or <2>, wherein the content of the fatty acid compound is 0.1 parts by mass relative to 100 parts by mass of the total mass of the aromatic polysene and the liquid crystal polyester. More than 1 part by mass and less than 1 part by mass. <4> The aromatic polysene composition according to any one of the above <1> to <3>, which contains 30 mass % or more 95% with respect to 100 mass % of the total mass of the aromatic polysene composition. Mass % or less of the above-mentioned aromatic polyester. <5> The aromatic polystyrene composition according to any one of the above <1> to <4>, which contains the above-mentioned fatty acid derivative, and the above-mentioned fatty acid derivative contains a fatty amide. <6> The aromatic polystyrene composition according to any one of the above <1> to <5>, wherein the aromatic polystyrene is an aromatic polyether having a repeating unit represented by the following formula (S1) Qi. (S1)-Ph ¹ -SO ₂ -Ph ² -O- [In the formula, Ph ¹ and Ph ² each independently represent a phenylene group. The hydrogen atoms on the above-mentioned phenylene groups may be independently substituted with alkyl groups, aryl groups or halogen atoms] <7> The aromatic polysulfone composition as described in any one of the above <1> to <6>, The liquid crystal polyester has a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit ((3) represented by the following formula). 3) Liquid crystal polyester. (1)-O-Ar ¹ -CO- (2)-CO-Ar ² -CO- (3)-X-Ar ³ -Y- [In the formula, Ar ¹ represents a phenyl group, a naphthyl group or an ylene group phenyl. Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylene group, or a group represented by the following formula (4). X and Y each independently represent an oxygen atom or an imine group (-NH-). The hydrogen atom on the above-mentioned group represented by Ar ¹ , Ar ² or Ar ³ may be independently substituted with a halogen atom, an alkyl group or an aryl group] (4)-Ar ⁴ -Z-Ar ⁵ - [wherein, Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group] <8> The aromatic polystyrene composition according to any one of the above <1> to <7>, further containing a fibrous filler . <9> A molded article containing the aromatic polyurethane composition according to any one of the above <1> to <8>. <10> A method of manufacturing a molded article, which includes injection molding the aromatic polystyrene composition according to any one of the above <1> to <8>. [Effects of the invention]

According to the present invention, it is possible to provide an aromatic polyurethane composition having an excellent balance between fluidity and strength.

The following describes the implementation of the aromatic polysulfone composition, the molded body, and the method for producing the molded body of the present invention.

≪Aromatic polystyrene composition≫ The aromatic polystyrene composition of the embodiment contains aromatic polystyrene, liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives ( Hereinafter, sometimes referred to as "fatty acid compound").

The aromatic polysulfone composition of the embodiment can significantly improve the fluidity of the composition by including both a liquid crystal polyester and a fatty acid compound. In addition, by containing a fatty acid compound, the decrease in strength can be suppressed and the fluidity of the aromatic polysulfone composition can be improved. The strength of the aromatic polysulfone composition of the embodiment is evaluated by the welding bending strength measured on the following test piece (molded body). The fluidity of the aromatic polysulfone composition of the embodiment is evaluated by the flow length of the molded body obtained by injection molding the above-mentioned aromatic polysulfone composition under specified conditions using a mold having a specific spiral flow path in accordance with the description of [Evaluation of Fluidity] below.

The following describes the various components of the aromatic polysulfone, liquid crystal polyester, and fatty acid compound formulated in the aromatic polysulfone composition of the embodiment, as well as any component that can be formulated in the aromatic polysulfone composition of the embodiment as needed. The total content of the aromatic polysulfone, the liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives can be from 50 to 100 parts by mass, or from 55 to 100 parts by mass, relative to 100 parts by mass of the total mass of the aromatic polysulfone composition.

<Aromatic Polysulfone> Aromatic polysulfone is typically a resin having repeating units including a divalent aromatic group (a residue formed by removing two hydrogen atoms bonded to the aromatic ring of an aromatic compound) and a sulfonyl group (-SO ₂ -).

The aromatic polystyrene used in this embodiment is preferably a so-called aromatic polyether styrene having repeating units including a divalent aromatic group, a sulfonyl group, and an ether bond.

In terms of heat resistance or chemical resistance, the aromatic polystyrene preferably has a repeating unit represented by the following formula (S1) (hereinafter, may be referred to as "repeating unit (S1)"). The aromatic polypropylene may further have one or more repeating units represented by the following formula (S2) (hereinafter, sometimes referred to as "repeating units (S2)"), or repeating units represented by the following formula (S3) unit (hereinafter, sometimes referred to as "repeating unit (S3)") and other repeating units.

(S1)-Ph ¹ -SO ₂ -Ph ² -O- [wherein Ph ¹ and Ph ² each independently represent a phenylene group. The hydrogen atom on the phenylene group may be independently substituted with an alkyl group, an aryl group or a halogen atom]

(S2)-Ph ³ -R-Ph ⁴ -O- [In the formula, Ph ³ and Ph ⁴ each independently represent a phenylene group. The hydrogen atoms on the above-mentioned phenylene groups may be independently substituted by alkyl groups, aryl groups or halogen atoms. R represents an alkylene group, oxygen atom or sulfur atom]

(S3)-(Ph ⁵ ) _n -O- [wherein, Ph ⁵ represents a phenylene group. The hydrogen atoms on the phenylene group may be independently substituted with alkyl groups, aryl groups or halogen atoms. n represents an integer of 1 to 3. When n is 2 or more, the plural Ph ⁵ groups may be the same or different from each other]

The phenylene group represented by any one of Ph ¹ to Ph ⁵ may be a p-phenylene group, a m-phenylene group, or an o-phenylene group, and is preferably a p-phenylene group.

In the alkyl group that can substitute the hydrogen atom on the above-mentioned phenylene group, the number of carbon atoms is preferably from 1 to 10. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, 2-ethylhexyl, n- Octyl, n-decyl, etc.

The aryl group which may substitute the hydrogen atom on the phenylene group preferably has a carbon number of 6 or more and 20 or less. Specific examples thereof include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, 2-naphthyl and the like.

Examples of the halogen atom that can replace the hydrogen atom on the phenylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

When the hydrogen atoms on the above-mentioned phenyl groups are substituted with the above-mentioned groups, the number thereof is preferably 2 or less, and more preferably 1, independently on each of the above-mentioned phenyl groups.   In the above, the hydrogen atoms on the above-mentioned phenyl groups are preferably unsubstituted.

The carbon number of the alkylene group represented by R is preferably 1 to 5. Specific examples thereof include methylene, ethylene, isopropylene, and 1-butylene.

The aromatic polyethylene preferably has 50% or more of repeating units (S1) based on the total number of total repeating units (100%), more preferably 80% or more, and still more preferably has substantially only repeating units (S1). S1) as a repeating unit. The term "substantially" here means that it contains more than 98% and less than 100% of the repeating units (S1) relative to the total number of repeating units (100%), which means that it may also contain a small amount derived from the raw material monomers. The structure of impurities, etc. Furthermore, the aromatic polyester may independently have two or more types of repeating units (S1) to (S3).

The relative viscosity of the aromatic polysulphate may be 0.18 dL/g or more, 0.25 dL/g or more and 0.50 dL/g or less, or 0.30 dL/g or more and 0.42 dL/g or less. The higher the relative viscosity of the aromatic polysulphate, the easier it is to improve the heat resistance, strength and rigidity. On the other hand, if the relative viscosity of the aromatic polysulphate is too high, the melting temperature or melt viscosity is likely to increase, and the fluidity is likely to decrease. That is, if the relative viscosity of the aromatic polysulphate is within the above range, the heat resistance, strength and rigidity are likely to increase, and the melting temperature or melt viscosity is unlikely to increase, and the fluidity is unlikely to decrease.

In this specification, the concentrated viscosity (dL/g) of the aromatic polysulfate refers to the value obtained by the following method. First, approximately 1 g of the aromatic polysulfate is accurately weighed and dissolved in N,N-dimethylformamide, and the volume thereof is set to 1 dL. Then, the viscosity (η) of the solution and the viscosity (η ₀ ) of N,N-dimethylformamide as a solvent are measured at 25°C using an Oswald-type viscometer. Then, the concentrated viscosity of the aromatic polysulfate is obtained by dividing the specific viscosity ((η－η ₀ )/η ₀ ) obtained from the measured value by the concentration of the above solution (approximately 1 g/dL).

The aromatic polysulfone composition of the embodiment may contain 30% by mass or more of the aromatic polysulfone, 30% by mass or more and 95% by mass or less, 40% by mass or more and 90% by mass or less, 45% by mass or more and 85% by mass or less, 50% by mass or more and 85% by mass or less, 50% by mass or more and 75% by mass or less, or 60% by mass or more and 75% by mass or less, relative to the total mass (100% by mass) of the aromatic polysulfone composition.

[Production method of aromatic polyester] Aromatic polyester can be produced by condensing a dihalogen compound and a dihydroxy compound corresponding to the repeating units constituting it.

For example, a resin having a repeating unit (S1) can be produced by condensing a compound represented by the following formula (S4) as a dihalogenated sulfone compound (hereinafter also referred to as "compound (S4)") and a compound represented by the following formula (S5) as a dihydroxy compound.

Moreover, the resin having the repeating unit (S1) and the repeating unit (S2) can be produced by polycondensing the compound (S4) which is the dihalogen compound and the compound represented by the following formula (S6) which is the dihydroxy compound. .

Moreover, the resin having the repeating unit (S1) and the repeating unit (S3) can be produced by polycondensing the compound (S4) which is the dihalogenated triane compound and the compound represented by the following formula (S7) which is the dihydroxy compound. .

(S4)X ¹ -Ph ¹ -SO ₂ -Ph ² -X ² [wherein X ¹ and X ² each independently represent a halogen atom. Ph ¹ and Ph ² have the same meanings as above]

(S5) HO-Ph ¹ -SO ₂ -Ph ² -OH [wherein Ph ¹ and Ph ² have the same meanings as above]

(S6) HO-Ph ³ -R-Ph ⁴ -OH [wherein Ph ³ , Ph ⁴ and R have the same meanings as above]

(S7)HO-(Ph ⁵ ) _n -OH [wherein Ph ⁵ and n have the same meanings as above]

The condensation of aromatic polysulfuric acid is preferably carried out using an alkali metal salt of carbonate in a solvent. The alkali metal salt of carbonate may be a carbonate as a normal salt, a bicarbonate (bicarbonate) as an acidic salt, or a mixture of the two. As the carbonate, sodium carbonate or potassium carbonate may be preferably used, and as the bicarbonate, sodium bicarbonate or potassium bicarbonate may be preferably used.

As the solvent for polycondensation, organic polar solvents are preferably used. Specific examples include: dimethylstyrene, 1-methyl-2-pyrrolidinone, cyclotetrahydrofuran (also known as 1,1-dioxotetrahydrofuran), 1,3-dimethyl-2 -Imidazolidinone, 1,3-diethyl-2-imidazolidinone, dimethyl sulfate, diethyl sulfide, diisopropyl sulfate, diphenyl sulfide, or mixed solvents thereof, etc.

<Liquid crystal polyester> The liquid crystal polyester contained in the aromatic polyester composition of this embodiment is not particularly limited as long as it is a polyester resin that is liquid crystalline in a molten state. Furthermore, the liquid crystal polyester may also be liquid crystal polyester amide, liquid crystal polyester ether, liquid crystal polyester carbonate, or liquid crystal polyester amide.

The flow starting temperature of the liquid crystal polyester is preferably 250°C or higher, more preferably 270°C or higher, and further preferably 280°C or higher. Furthermore, the flow starting temperature of the liquid crystal polyester is preferably 400°C or lower, more preferably 360°C or lower, and further preferably 340°C or lower.

For example, the flow initiation temperature of the liquid crystal polyester is preferably 250° C. to 400° C., more preferably 270° C. to 360° C., and further preferably 280° C. to 340° C.

In this specification, the flow starting temperature is also called flow temperature or flow temperature, which is the temperature that becomes the standard for the molecular weight of liquid crystal polyester (refer to the editor of Nao Koide, "Liquid Crystal Polymer-Synthesis, Forming, Application-", CMC Co., Ltd., June 5, 1987, p. 95).

As a method for determining the flow initiation temperature of liquid crystal polyester, specifically, a flow tester is used to melt the liquid crystal polyester while heating it at a rate of 4°C/min under a load of 9.8 MPa (100 kg/cm ² ). When the liquid crystal polyester is extruded from a nozzle with an inner diameter of 1 mm and a length of 10 mm, the temperature at which it shows a viscosity of 4800 Pa･s (48000 poise) is the flow initiation temperature of the liquid crystal polyester.

The liquid crystal polyester is preferably a fully aromatic liquid crystal polyester having only repeating units derived from aromatic compounds as raw material monomers.

Typical examples of the liquid crystal polyester include aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, and at least one selected from the group consisting of aromatic diol, aromatic hydroxylamine, and aromatic diamine. A polymer formed by polymerizing (polycondensing) a plurality of aromatic hydroxycarboxylic acids; a polymer formed by polymerizing an aromatic dicarboxylic acid and a compound selected from aromatic diols, aromatic hydroxylamines and aromatic A polymer formed by polymerizing at least one compound in the group consisting of diamines; a polymer formed by polymerizing polyesters such as polyethylene terephthalate and aromatic hydroxycarboxylic acid. Here, aromatic hydroxycarboxylic acid, aromatic dicarboxylic acid, aromatic diol, aromatic hydroxylamine and aromatic diamine can also be independently polymerized derivatives thereof to replace part or all of them. .

Examples of polymerizable derivatives of compounds having carboxyl groups such as aromatic hydroxycarboxylic acids and aromatic dicarboxylic acids include those obtained by converting a carboxyl group into an alkoxycarbonyl group or an aryloxycarbonyl group (i.e., ester); those formed by converting a carboxyl group into a haloformyl group (i.e., acyl halide); those formed by converting a carboxyl group into a hydroxyl carbonyl group (i.e., acid anhydride), etc.

Examples of polymerizable derivatives of compounds having a hydroxyl group such as aromatic hydroxycarboxylic acids, aromatic diols, and aromatic hydroxylamines include those obtained by acylation of the hydroxyl group to an acyl alkyloxy group (i.e., acylation). Examples of polymerizable derivatives of compounds having an amino group such as aromatic hydroxylamines and aromatic diamines include those obtained by acylation of the amino group to an amide group (i.e., acylation).

The liquid crystal polyester preferably has a repeating unit represented by the following formula (1) (hereinafter also referred to as "repeating unit (1)"). The liquid crystal polyester more preferably has a repeating unit (1), a repeating unit represented by the following formula (2) (hereinafter also referred to as "repeating unit (2)"), and a repeating unit represented by the following formula (3) (Hereinafter also referred to as "repeating unit (3)").

(1)-O-Ar ¹ -CO- (2)-CO-Ar ² -CO- (3)-X-Ar ³ -Y- [In the formula, Ar ¹ represents a phenyl group, a naphthyl group or an ylene group phenyl. Ar ² and Ar ³ each independently represent a phenylene group, a naphthylene group, a biphenylene group, or a group represented by the following formula (4). X and Y each independently represent an oxygen atom or an imine group (-NH-). The hydrogen atom on the above-mentioned group represented by Ar ¹ , Ar ² or Ar ³ may be independently substituted with a halogen atom, an alkyl group or an aryl group]

(4)-Ar ⁴ -Z-Ar ⁵ - [In the formula, Ar ⁴ and Ar ⁵ each independently represent a phenylene group or a naphthylene group. Z represents oxygen atom, sulfur atom, carbonyl group, sulfonyl group or alkylene group]

Examples of the halogen atom that can substitute for one or more hydrogen atoms in the above group represented by Ar ¹ , Ar ² or Ar ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group that can substitute one or more hydrogen atoms in the above-mentioned group represented by Ar ¹ , Ar ² or Ar ³ is preferably an alkyl group with a carbon number of 1 to 10, and examples thereof include: methyl, ethyl base, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-hexyl, 2-ethylhexyl, n-octyl, or n-decyl, etc.

The aryl group which may substitute for one or more hydrogen atoms in the above groups represented by Ar ¹ , Ar ² or Ar ³ is preferably an aryl group having 6 to 20 carbon atoms, and examples thereof include phenyl, o-tolyl, m-tolyl, p-tolyl, 1-naphthyl, and 2-naphthyl.

When the hydrogen atom in the above-mentioned group represented by Ar ¹ , Ar ² or Ar ³ is substituted by the above-mentioned group, the number of substitutions is preferably 1 or 2, more preferably 1.

The alkylene group in Z in formula (4) is preferably an alkylene group with a carbon number of 1 to 10 and less. Examples include: methylene, ethylene, isopropylene, n-butylene, Or 2-ethylhexylene, etc.

The liquid crystal polyester preferably has a repeating unit (3) in which X and Y are oxygen atoms, that is, a repeating unit derived from an aromatic diol, because the melt viscosity is easily lowered. More preferably, the liquid crystal polyester has only a repeating unit (3) in which X and Y are oxygen atoms.

The liquid crystal polyester having the repeating units (1) to (3) is more preferably a repeating unit represented by the following formula (1-1), a repeating unit represented by the following formula (2-1), and a repeating unit represented by the following formula (3-1). (1-1)-O-Ar ^1-1 -CO- (2-1)-CO-Ar ^2-1 -CO- (3-1)-O-Ar ^3-1 -O- Ar ^1-1 represents a 2,6-naphthylene group, a 1,4-phenylene group, or a 4,4'-biphenylene group. Ar ^2-1 and Ar ^3-1 each independently represent a 2,6-naphthylene group, a 2,7-naphthylene group, a 1,4-phenylene group, a 1,3-phenylene group, or a 4,4'-biphenylene group. The hydrogen atom in the above groups represented by Ar ^1-1 , Ar ^2-1 or Ar ^3-1 may be independently substituted with a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

The repeating unit (1) is a repeating unit derived from an aromatic hydroxycarboxylic acid. As the repeating unit (1), preferably, Ar ¹ is a 1,4-phenylene group (e.g., a repeating unit derived from p-hydroxybenzoic acid) or Ar ¹ is a 2,6-naphthylene group (e.g., a repeating unit derived from 6-hydroxy-2-naphthoic acid).

In this specification, "derived from" means that due to the polymerization of the raw material monomers, the chemical structure of the functional group that contributes to the polymerization changes, while other structures do not change. The origin system here also includes the concept of using polymerizable derivatives of raw material monomers as sources.

The repeating unit (2) is a repeating unit derived from an aromatic dicarboxylic acid. As the repeating unit (2), preferably, Ar ² is a 1,4-phenylene group (e.g., a repeating unit derived from terephthalic acid), Ar ² is a 1,3-phenylene group (e.g., a repeating unit derived from isophthalic acid), Ar ² is a 2,6-naphthylene group (e.g., a repeating unit derived from 2,6-naphthalenedicarboxylic acid), or Ar ² is a diphenyl ether-4,4'-diyl group (e.g., a repeating unit derived from diphenyl ether-4,4'-dicarboxylic acid), and more preferably, Ar ² is a 1,4-phenylene group, Ar ² is a 1,3-phenylene group, or Ar ² is a 2,6-naphthylene group.

The repeating unit (3) is a repeating unit derived from an aromatic diol, an aromatic hydroxylamine or an aromatic diamine. As the repeating unit (3), preferably, Ar ³ is a 1,4-phenylene group (e.g., a repeating unit derived from hydroquinone, p-aminophenol or p-phenylenediamine), or Ar ³ is a 4,4'-biphenylene group (e.g., a repeating unit derived from 4,4'-dihydroxybiphenyl, 4-amino-4'-hydroxybiphenyl or 4,4'-diaminobiphenyl).

The number of repeating units (1) is preferably not less than 30% and not more than 80%, more preferably not less than 40% and not more than 70%, and still more preferably not more than 45% relative to the total number (100%) of the total number of repeating units constituting the liquid crystal polyester. Above 70% below.

The number of repeating units (2) is preferably 35% or less, more preferably 10% or more and 35% or less, and still more preferably 15% or more and 30% with respect to the total number of repeating units (100%) constituting the liquid crystal polyester. the following.

The number of repeating units (3) is preferably 35% or less, more preferably 10% or more and 35% or less, and still more preferably 15% or more and 30% with respect to the total number of repeating units (100%) constituting the liquid crystal polyester. the following.

The ratio of the number of repeating units (2) to the number of repeating units (3) is expressed as [the number of repeating units (2)]/[the number of repeating units (3)], and is preferably 0.9/1 to 1/0.9, more preferably 0.95/1 to 1/0.95, and further preferably 0.98/1 to 1/0.98.

Furthermore, the liquid crystal polyester may each have two or more types of repeating units (1) to (3). In addition, the liquid crystal polyester may have repeating units other than the repeating units (1) to (3). The number is preferably 10% or less, more preferably 5% or less based on the total number of the total repeating units (100%). .

In this specification, the number of each repeating unit (the degree of polymerization of each repeating unit) can be determined by the analysis method described in Japanese Patent Application Laid-Open No. 2000-19168. Specifically, the liquid crystalline polyester is reacted with a lower alcohol (alcohol having 1 to 3 carbon atoms) in a supercritical state, and the liquid crystalline polyester is depolymerized until it becomes a monomer that induces its repeating unit, and the liquid crystalline polyester is depolymerized by liquid chromatography. The number of each repeating unit can be calculated by quantifying the monomers obtained as depolymerization products that induce each repeating unit. For example, when the liquid crystal polyester contains repeating units (1) to (3), the number of repeating units (1) can be determined as follows: Calculate the respective induced repeating units (1) to ((1) through liquid chromatography). The molar concentration of the monomer in 3) is calculated by calculating the monomer that induces the repeating unit (1) when the total molar concentration of the monomers that induce the repeating units (1) to (3) is 100%. The ratio of molar concentration can be obtained.

One type of liquid crystal polyester may be used alone, or two or more types may be used in combination.

[Production method of liquid crystal polyester] Liquid crystal polyester can be produced by melt polymerizing raw material monomers corresponding to the structural units that constitute it. For example, it can be produced according to the method described in Japanese Patent No. 6439027.

<Fatty acid compound> The fatty acid compound contained in the aromatic polysulfate composition of the present embodiment is at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives.

As the fatty acid, a fatty acid having a carbon number of 12 or more is preferred, a fatty acid having a carbon number of 12 or more and 28 or less is preferred, and a fatty acid having a carbon number of 12 or more and 20 or less is more preferred. The above-mentioned fatty acids may be saturated fatty acids or unsaturated fatty acids.

Specific examples of the fatty acid having 12 or more carbon atoms include lauric acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, palmitic acid, pearlic acid, stearic acid, oleic acid, nonadecanoic acid, eicosanoic acid, heneicosanoic acid, behenic acid, and montanic acid.

As the fatty acid salt, a fatty acid metal salt is preferred. Examples of the metal of the fatty acid metal salt include calcium, lithium, barium, aluminum, potassium, or sodium.

Examples of the fatty acid in the fatty acid salt include the fatty acids having 12 or more carbon atoms exemplified above, preferably fatty acid salts of fatty acids having 12 or more and 28 or less carbon atoms, and more preferably fatty acid salts of fatty acids having 12 or more and 20 or less carbon atoms.

If stearate is taken as a preferred specific example of the fatty acid salt, calcium stearate, lithium stearate, barium stearate, aluminum stearate, potassium stearate, or sodium stearate may be cited.

Examples of fatty acid derivatives include fatty acid esters and fatty amide. From the viewpoint of improving the fluidity of the composition and suppressing the decrease in strength of the molded article, the fatty acid derivative preferably contains a fatty amide, and may be substantially composed only of a fatty amide. The term "substantially" here means containing 98% to 100% of fatty acid amide relative to the total mass of the fatty acid derivatives.

Examples of the fatty acid among the fatty acid derivatives include fatty acids with 12 or more carbon atoms as exemplified above, preferably fatty acid derivatives with 12 or more carbon atoms and 28 or less carbon atoms, more preferably 12 or more carbon atoms and 20 or less carbon atoms. Fatty acid derivatives of fatty acids.

Specific examples of the fatty amides having 12 or more carbon atoms include lauryl amide, tridecyl amide, tetradecyl amide, pentadecyl amide, palmityl amide, pearlyl amide, octadecyl amide, oleyl amide, nonadecyl amide, eicosyl amide, heneicosyl amide, behenyl amide, and montanyl amide.

In this specification, fatty acid amide includes the concept of fatty acid bisamide. Fatty acid amide is preferably fatty acid bisamide.

If stearic acid derivatives are taken as examples as preferred specific examples of fatty acid diamides, ethylene distearylamide, ethylene dihydroxystearylamide, and the like can be cited.

Fatty amide and fatty acid bisamide may have any structure as long as they have the structure of fatty amide (R ⁰ -CO-NH-. R ⁰ represents an optionally substituted hydrocarbon chain derived from fatty acid) in the molecule. substituents or structures.

<Optional Ingredients> The aromatic polystyrene composition of this embodiment may contain optional ingredients such as one or more fillers, resins other than the above-mentioned aromatic polysene and the above-mentioned liquid crystal polyester, additives, etc., if necessary.

The aromatic polystyrene composition of this embodiment can be composed of the above-mentioned aromatic polystyrene, liquid crystal polyester, fatty acid compound, and any optional components used as needed, and their contents (mass %) in the aromatic polystyrene composition are The total amount is prepared so that the total mass (100 mass%) of the aromatic polysene composition of the embodiment does not exceed 100 mass%.

Furthermore, when the aromatic polysulfone described above as the formulation components of the aromatic polysulfone composition, the liquid crystal polyester, the fatty acid compound, and any other optional components are obtained and the reactants produced by the mutual reaction of these components are also included in the aromatic polysulfone composition of the present invention.

(Filler) The aromatic polystyrene composition of this embodiment may further contain a filler. The filler can be fibrous filler, plate filler, granular filler, etc. Moreover, the filler may be an inorganic filler or an organic filler.

The aromatic polysulfone composition of this embodiment preferably further comprises a fibrous filler.

The above-mentioned fibrous filler may be a fibrous inorganic filler or a fibrous organic filler.

Examples of the fibrous inorganic filler include glass fiber; carbon fiber; ceramic fiber such as silica fiber, alumina fiber, or silica aluminum fiber; and metal fiber such as iron, gold, copper, aluminum, brass, or stainless steel. ; Silicon carbide fiber; or boron fiber, etc. Furthermore, examples of fibrous inorganic fillers include potassium titanate whiskers, barium titanate whiskers, wollastonite whiskers, aluminum borate whiskers, silicon nitride whiskers, and silicon carbide whiskers. crystal.

Examples of the fibrous organic filler include polyester fiber, para- or meta-aromatic polyamide fiber, or PBO fiber.

As the fibrous filler in this embodiment, among the above, glass fiber or carbon fiber is preferred, and glass fiber is more preferred.

・Glass fiber The type of glass fiber is not particularly limited, and publicly known ones can be used. Examples of glass fibers include those produced by various methods, such as chopped glass fibers and ground glass fibers. Also, examples include: E glass (i.e., alkali-free glass), C glass (i.e., glass suitable for acid-resistant purposes), AR glass (i.e., glass suitable for alkali-resistant purposes), S glass or T glass, etc.

Glass fiber can be either without surface treatment or with surface treatment. Glass fiber can be treated with modifiers, silane coupling agents, or boron compounds. Examples of the modifier include aromatic polyurethane modifiers, aliphatic polyurethane modifiers, acrylic modifiers, and the like.

As the glass fiber, among the above, E glass is preferred.

The preferred fiber diameter (single fiber diameter) of the glass fiber can be specified according to the raw materials used in the method for producing the aromatic polysulfide composition described below. The fiber diameter (single fiber diameter) of the glass fiber is preferably 5 μm or more and 20 μm or less. Compared with the case where the fiber diameter is less than 5 μm, when the fiber diameter of the glass fiber is 5 μm or more, it is easier to use and can improve production efficiency. The fiber diameter of the glass fiber is more preferably 5.5 μm or more, further preferably 6 μm or more, more preferably more than 8 μm, and particularly preferably 10 μm or more. Furthermore, compared to the case where the fiber diameter exceeds 20 μm, when the fiber diameter of the glass fiber is 20 μm or less, the fluidity of the aromatic polysulfone composition is improved, and thus the effect of the glass fiber as a reinforcing material for the molded body is further improved. The fiber diameter of the glass fiber is preferably 17 μm or less, and more preferably 15 μm or less. As an example of the numerical range of the fiber diameter (single fiber diameter) of the above-mentioned glass fiber, it is preferably 5 μm to 20 μm, more preferably 5.5 μm to 17 μm, further preferably 6 μm to 15 μm, particularly preferably 8 μm to 15 μm, and particularly preferably 10 μm to 15 μm.

Furthermore, regarding the diameter of the glass fiber, there is no substantial change after melt mixing during melt forming.

In addition, unless otherwise specified, the "fiber diameter of glass fiber as a raw material" is a value measured by "Method A" of the methods described in JIS R3420 "7.6 Single fiber diameter".

The number average fiber length of the glass fibers used as the raw material is preferably 20 μm or more, more preferably 1000 μm or more, and further preferably 2000 μm or more. The number average fiber length of the glass fibers is preferably 6000 μm or less, more preferably 5000 μm or less, further preferably 4500 μm or less. As an example of the numerical range of the number average fiber length of the above-mentioned glass fibers, it is preferably from 20 μm to 6000 μm, more preferably from 1000 μm to 5000 μm, and further preferably from 2000 μm to 4500 μm.

In addition, in this specification, the "number average fiber length of the glass fiber used as the raw material" is a value measured using the method described in JIS R3420 "7.8 Strand length" unless otherwise specified.

・Carbon fiber  The type of carbon fiber is not particularly limited, and known carbon fibers can be used, such as PAN-based, asphalt-based, rayon-based, phenol-based, or lignin-based carbon fibers.  In addition, for the purpose of imparting conductivity, carbon fibers coated with metals such as nickel, copper, or iron can also be used.

The content of the fibrous filler in the aromatic polyester composition is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and still more preferably 100 parts by mass of the total mass of the aromatic polyurethane and liquid crystal polyester. It is 15 parts by mass or more. Moreover, the content of the fibrous filler is preferably 100 parts by mass or less, more preferably 85 parts by mass or less, and still more preferably 50 parts by mass or less based on 100 parts by mass of the total mass of the aromatic polyester and the liquid crystal polyester. The upper limit value and the lower limit value mentioned above can be combined arbitrarily. As an example of the numerical range of the content of the fibrous filler in the aromatic polystyrene composition of the embodiment, it is preferably 1 part by mass or more per 100 parts by mass relative to 100 parts by mass of the total mass of the aromatic polysene and the liquid crystal polyester. parts by mass or less, more preferably not less than 10 parts by mass and not more than 85 parts by mass, still more preferably not less than 15 parts by mass and not more than 50 parts by mass.

By making the content of the fibrous filler within the above preferred range, the mechanical strength of the molded body can be further improved.

As resins other than the above-mentioned aromatic polyesters and liquid crystal polyesters, there can be cited: thermoplastic resins such as polypropylene, polyamide, polyesters other than liquid crystal polyesters, polyphenylene sulfide, polyether sulfide, polyether ketone, polycarbonate, polyphenylene ether, or polyether imide; or thermosetting resins such as phenol resins, epoxy resins, polyimide resins, or cyanate resins. The aromatic polyester composition may include fluororesins such as polytetrafluoroethylene (PTFE). "Fluororesin" refers to a resin containing fluorine atoms in the molecule, and examples thereof include polymers having structural units containing fluorine atoms.

Examples of the additives include release agents, colorants (pigments, dyes, carbon black, etc.).

The mass ratio of the content of aromatic polystyrene and liquid crystal polyester in the aromatic polystyrene composition is preferably aromatic polystyrene/liquid crystal polyester = 95/5~65/35, more preferably 95/5~70/30 , more preferably 95/5～75/25, particularly preferably 90/10～80/20. By containing aromatic polyester and liquid crystal polyester within the above mass ratio range, it is possible to easily provide an aromatic polyester composition with excellent balance between fluidity and strength (for example, welding bending strength described below).

The content of at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives in the above-mentioned aromatic polysulfide composition is preferably from 0.05 mass parts to 5 mass parts, more preferably from 0.1 mass parts to 1 mass part, and further preferably from 0.1 mass parts to 0.5 mass parts, relative to 100 mass parts of the total mass of the above-mentioned aromatic polysulfide and the above-mentioned liquid crystal polyester. By containing fatty acid compounds within the above-mentioned mass ratio range, an aromatic polysulfide composition having an excellent balance between fluidity and heat resistance can be easily provided.

Similarly, when the above-mentioned aromatic polysulfone composition further contains other resins besides the aromatic polysulfone and the liquid crystal polyester, the content of at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives in the above-mentioned aromatic polysulfone composition is preferably from 0.05 to 5 parts by mass, more preferably from 0.1 to 1 part by mass, and further preferably from 0.1 to 0.5 parts by mass, relative to 100 parts by mass of the total mass of the above-mentioned aromatic polysulfone, the above-mentioned liquid crystal polyester, and other resins.

On the other hand, the aromatic polysulfone composition as an embodiment, for example, relative to the total mass (100 mass %) of the aromatic polysulfone composition of the embodiment, it is preferred that the content ratio of the aromatic polysulfone is 40 mass % to 90 mass %, the content ratio of the liquid crystal polyester is 3 mass % to 40 mass %, the content ratio of the fatty acid compound is 0.01 mass % to 1 mass %, and the content ratio of the fibrous filler is 1 mass % to 50 mass %. It is more preferred that the content ratio of the aromatic polysulfone is 45 mass % to 85 mass %, the content ratio of the liquid crystal polyester is 5 mass % to 35 mass %, the content ratio of the fatty acid compound is 0.05 mass % to 0.8 mass %, and the fibrous filler is The present invention relates to a composition in which the content ratio of the aromatic polysulfide is from 5 mass % to 30 mass %, more preferably, the content ratio of the aromatic polysulfide is from 50 mass % to 75 mass %, the content ratio of the liquid crystal polyester is from 5 mass % to 30 mass %, the content ratio of the fatty acid compound is from 0.05 mass % to 0.8 mass %, and the content ratio of the fibrous filler is from 15 mass % to 25 mass %. Further preferably, the composition in which the content ratio of the aromatic polysulfide is from 60 mass % to 75 mass %, the content ratio of the liquid crystal polyester is from 5 mass % to 20 mass %, the content ratio of the fatty acid compound is from 0.05 mass % to 0.8 mass %, and the content ratio of the fibrous filler is from 15 mass % to 25 mass %.

As explained above, the fluidity of the aromatic polystyrene composition of the embodiment including both the liquid crystal polyester and the fatty acid compound is significantly improved.

The mechanism by which the fluidity of an aromatic polysulfone composition is significantly improved by including both a liquid crystal polyester and a fatty acid compound is still unclear. However, aromatic polysulfones and liquid crystal polyesters are generally considered to be incompatible. It is speculated that the friction generated at the interface between the aromatic polysulfone phase and the liquid crystal polyester phase during the flow of the composition can be reduced by the action of the fatty acid compound, and the fluidity of the composition containing an aromatic polysulfone and a liquid crystal polyester can be effectively improved.

In addition, the strength of the composition is not easily reduced when the fatty acid compound is contained. The aromatic polysulfone composition of the embodiment containing the fatty acid compound is a very useful composition with an excellent balance between fluidity and strength.

The aromatic polysene composition according to the embodiment has an excellent balance between fluidity in a flowing state and strength and heat resistance in a hardened state. Therefore, the aromatic polystyrene composition of the embodiment can be suitably used as a molding material for melt molding, and particularly can be suitably used as a molding material for injection molding.

[Manufacturing method of aromatic polysulfone composition] The aromatic polysulfone composition of the implementation method can be obtained by mixing the above-mentioned aromatic polysulfone, liquid crystal polyester, at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives, and any optional components used together or in an appropriate order.

According to the method for producing the aromatic polysulfone composition of the embodiment, the aromatic polysulfone composition of the embodiment can be produced.

Examples of the aromatic polyester, liquid crystal polyester, fatty acid compound, optional components, and blending ratios thereof are those described in the above «Aromatic polyester composition».

An example of a method of producing an aromatic polystyrene composition according to an embodiment is a method of producing an aromatic polystyrene including a step of mixing an aromatic polystyrene, a liquid crystal polyester, and a fatty acid compound.

In the above-mentioned manufacturing method, the mass ratio of the blending amount of the above-mentioned aromatic polysulfone and the above-mentioned liquid crystal polyester is preferably the above-mentioned aromatic polysulfone/the above-mentioned liquid crystal polyester = 95/5 to 65/35, more preferably 95/5 to 70/30, and further preferably 90/10 to 80/20.

In the above-mentioned manufacturing method, the compounding amount of at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives is greater than 100 parts by mass of the total mass of the above-mentioned aromatic polyester and the above-mentioned liquid crystal polyester. Preferably it is not less than 0.05 parts by mass and not more than 5 parts by mass, more preferably not less than 0.1 parts by mass and not more than 1 part by mass, still more preferably not less than 0.1 parts by mass and not more than 0.5 parts by mass.

The above-mentioned mixing is preferably melt kneading. The aromatic polysulfate composition of this embodiment can be provided in the form of granules by melt kneading the above-mentioned aromatic polysulfate, liquid crystal polyester, fatty acid compound, and optional components used as needed using an extruder.

In addition, optional components other than the aromatic polyester and liquid crystal polyester (for example, fatty acid compounds, additives, etc.) may be added to the pellets obtained by melt-kneading the aromatic polyester and the liquid crystal polyester using an extruder. ingredients, etc.), is provided in the form of an aromatic polyester composition in a state attached to the particle surface.

The aromatic polyurethane composition obtained in this way, especially the particles of the aromatic polyurethane composition, can be suitably used as a molding material for the following molded articles.

≪Molded body≫ The molding system of the embodiment includes a molded body of the aromatic polystyrene composition according to one embodiment of the present invention.

Examples of the molded article of this embodiment include a molded article containing aromatic polyester, liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives. As the molded article of this embodiment, a molded article containing the aromatic polystyrene composition of the embodiment can be exemplified.

The molded article of the embodiment can be produced using the aromatic polystyrene composition of the above embodiment which is excellent in fluidity. Therefore, it is possible to provide a molded article having a fine structure and excellent balance with strength and heat resistance.

In addition, the strength of the aromatic polystyrene composition of the embodiment can be evaluated by measuring the welding bending strength and tensile strength on the following test pieces (molded articles).

[Welding bending strength] Using an injection molding machine (e.g., manufactured by Sumitomo Heavy Industries, Ltd., trade name "SE100EV-A"), the test object composition is used as the molding material, and a mold having a gate portion at both ends and a shape of a Type A multifunctional test piece (thickness 3 mm) specified in ISO 3167:93 is used to injection mold a test piece (molded body) for welding test having a weld in the center, at a barrel temperature of 380°C, a mold temperature of 150°C, and an injection speed of 50 mm/sec. For the obtained test piece (molded body), a bending test is performed in accordance with ISO 178 at 23°C, a test speed of 2 mm/min, a fulcrum distance of 64 mm, a ram width of 1 mm, and a ram front end radius of 5 mm. The flexural strength value was calculated using the average value of the results of three test pieces.

The welding bending strength of the above-mentioned test piece of the aromatic polysulfone composition obtained by the measuring method is preferably 30 MPa or more, more preferably 35 MPa or more, and further preferably 40 MPa or more.   The upper limit value of the welding bending strength of the above-mentioned test piece is not particularly limited. As an example, it may be less than 200 MPa, less than 150 MPa, or less than 100 MPa.   As an example of the numerical range of the welding bending strength of the above-mentioned test piece, it may be more than 30 MPa and less than 200 MPa, more than 35 MPa and less than 150 MPa, or more than 40 MPa and less than 100 MPa.

[Tensile strength]  Use an injection molding machine (e.g. manufactured by Nissei Resin Industrial Co., Ltd., trade name "NEX50IV-5EG"), use the test object composition as the molding material, and injection mold an ASTM No. 4 dumbbell-shaped test piece under the conditions of a barrel temperature of 380°C, a mold temperature of 150°C, and an injection speed of 50 mm/sec.  For the obtained test piece (molded body), the tensile strength is measured in accordance with ASTM D638 at a tensile speed of 10 mm/min at an environment of 23°C. For the value of tensile strength, the average value of the results of 5 test pieces is adopted.

The tensile strength of the above-mentioned test piece of the aromatic polysene composition obtained by this measurement method is preferably 100 MPa or more, more preferably 110 MPa or more, and still more preferably 120 MPa or more. The upper limit of the tensile strength of the above-mentioned test piece is not particularly limited. As an example, it may be 200 MPa or less, 175 MPa or less, or 150 MPa or less. As an example of the numerical range of the tensile strength of the above-mentioned test piece, it may be 100 MPa or more and 200 MPa or less, it may be 110 MPa or more and 175 MPa or less, or it may be 120 MPa or more and 150 MPa or less.

When the above-mentioned fatty acid amide or fatty acid bisamide is contained, the tensile strength is less likely to decrease compared to the case where the fatty acid, fatty acid metal salt, or fatty acid ester is contained.

The heat resistance of the aromatic polystyrene composition of the embodiment can be evaluated by measuring the heat deformation temperature under load on the following test piece (molded article).

[Thermal deformation temperature under load]  Use an injection molding machine (e.g. manufactured by Nissei Resin Industrial Co., Ltd., trade name "NEX50IV-5EG"), use the composition of the test object as the molding material, and manufacture a rod-shaped test piece (molded body) with a width of 12.7 mm, a length of 127 mm, and a thickness of 6.4 mm at a barrel temperature of 380°C, a mold temperature of 150°C, and an injection speed of 50 mm/sec.  For the obtained test piece (molded body), the heat deformation temperature under load (DTUL) is measured in accordance with ASTM D648 under the conditions of a load of 1.82 MPa and a heating rate of 2°C/min.

The thermal deformation temperature under load of the above-mentioned test piece of the aromatic polystyrene composition obtained by this measurement method is preferably 180°C or higher, more preferably 190°C or higher, and still more preferably 200°C or higher. The upper limit of the heat deformation temperature under load of the above-mentioned test piece is not particularly limited. As an example, it may be 250°C or lower, 240°C or lower, or 230°C or lower. As an example of the numerical range of the heat deformation temperature under load of the above-mentioned test piece, it may be 180°C or more and 250°C or less, it may be 190°C or more and 240°C or less, or it may be 200°C or more and 230°C or less.

The molded article of this embodiment is generally applicable to all uses to which the resin composition is applicable. Examples of the molded body of this embodiment include connectors, sockets, IC (Integrated Circuit) sockets, pre-fired sockets, relay parts, bobbins, optical pickups, oscillators, and printed wiring boards. , circuit substrates, semiconductor packages, or computer-related parts and other electrical and electronic parts; IC trays or wafer carriers and other semiconductor process-related parts; VTR (video tape recorder, video recorder), televisions, irons, air conditioners, stereo equipment , vacuum cleaners, refrigerators, electric cookers, or lighting fixtures and other household electrical product parts; reflector lamps or lamp holders and other lighting fixture parts; optical discs, laser disks (registered trademarks), or speakers and other audio product parts; optical cable ferrules, Telephone parts, fax machine parts, or communication equipment parts such as data machines; parts related to photocopiers or printing machines such as separation claws or heater brackets; mechanical parts such as impellers, fan gears, gears, bearings, motor parts, or casings; for automobiles Automobile parts such as mechanical parts, engine parts, engine room parts, electrical parts, or interior parts; cooking utensils such as microwave cooking pots or heat-resistant tableware; heat or sound insulation materials such as flooring or wall materials, beams or columns, etc. Support materials, building materials such as roofing materials, or materials for civil construction; parts for aircraft, spacecraft, or space machines; components of radiation facilities such as nuclear reactors; components of marine facilities, cleaning jigs, optical machine parts, and valves , tubes, nozzles, filters, membranes, medical machine parts or medical materials, sensor parts, sanitary products, sporting goods, entertainment products, or cable ties, etc.

≪Production method of molded article≫ As a method of producing a formed article, examples include a method including molding the aromatic polystyrene composition of the embodiment into a desired shape. As this manufacturing method, a molding method corresponding to the shape of the desired molded article, etc. can be selected for the aromatic polysene composition of the embodiment. As the molding method, melt molding is preferred.

The method for producing the aromatic polysulfone composition of an embodiment may include melt-forming the aromatic polysulfone composition of an embodiment of the present invention.

Examples of the melt molding method include injection molding, blow molding, vacuum molding, and press molding, among which injection molding is preferred.

The method for manufacturing the aromatic polysulfone composition of an embodiment may include injection molding the aromatic polysulfone composition of an embodiment of the present invention.

For example, when the above-mentioned aromatic polysulfone composition particles are used as molding materials and are molded by injection molding, a known injection molding machine can be used to melt the aromatic polysulfone composition particles, and the melted aromatic polysulfone composition particles are injected into a mold to form the particles. Examples of known injection molding machines include: "NEX50IV-5EG" manufactured by Nissei Resin Industries Co., Ltd., "SE100EV-A" manufactured by Sumitomo Heavy Industries Co., Ltd., etc.

The temperature conditions for injection molding can be appropriately determined depending on the type of aromatic polyester and liquid crystal polyester resin. As other injection conditions, the mold temperature, screw rotation speed, back pressure, injection speed, holding pressure, or holding pressure time can be appropriately adjusted.

According to the method for manufacturing a molded body of the embodiment, the aromatic polysulfone composition of the embodiment is used to manufacture a molded body, so that a molded body with a fine structure can be manufactured, and the strength and heat resistance of the manufactured molded body are well balanced. [Example]

Next, the present invention will be described in further detail by showing embodiments, but the present invention is not limited to the following embodiments.

<Production of Liquid Crystal Polyester> Into a reactor equipped with a stirring device, a torque meter, a nitrogen inlet tube, a thermometer and a reflux condenser were added 6-hydroxy-2-naphthoic acid (1034.99 g, 5.5 mol), 2,6-naphthalene dicarboxylic acid (378.33 g, 1.75 mol), terephthalic acid (83.07 g, 0.5 mol), hydroquinone (272.52 g, 2.475 mol, 0.225 mol excess relative to the total molar amount of 2,6-naphthalene dicarboxylic acid and terephthalic acid), acetic anhydride (1226.87 g, 12 mol), and 1-methylimidazole (0.17 g) as a catalyst. After replacing the gas in the reactor with nitrogen, under a nitrogen flow, the temperature was raised from room temperature to 145°C over 15 minutes while stirring, and refluxed at 145°C for 1 hour. Then, while distilling off by-product acetic acid and unreacted acetic anhydride, the temperature was raised from 145°C to 310°C over 3 hours and 30 minutes. After maintaining at 310°C for 3 hours, the solid prepolymer (reaction mixture) was taken out and cooled to room temperature. Then, the cooled prepolymer was crushed using a grinder to a particle size of about 0.1 mm to 1 mm. The obtained pulverized product was heated from room temperature to 250°C over 1 hour, then from 250°C to 302°C over 8 hours and 40 minutes, and kept at 302°C for 5 hours under a nitrogen atmosphere to perform solid phase polymerization. The solid phase polymer was cooled to obtain a liquid crystal polyester in powder form. The flow starting temperature of the obtained liquid crystal polyester was 320°C.

＜Manufacturing of resin composition＞  (Materials)  ・Aromatic polyether sulphate:  "Sumikaexcel (registered trademark) PES 3600P" manufactured by Sumitomo Chemical Co., Ltd., polyether sulphate, specific viscosity 0.36 dL/g  ・Liquid crystal polyester:  The one manufactured above  ・Aliphatic amide additive:  "light amide WH-510K" manufactured by Kyoeisha Chemical Co., Ltd.  ・Glass fiber:  "CS3J260S" manufactured by Nitto Bosho Co., Ltd., fiber diameter 11 μm, number average fiber length 3.0 mm

[Reference Examples 1-7, Implementation Examples 1-9] Aromatic polyether sulphate, liquid crystal polyester, fatty amide additive and glass fiber were mixed in the amounts (parts by mass) shown in Table 1 and fed into a double-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30), and granulated at a barrel temperature of 340°C to obtain the resin composition (granules) of each example.

<Manufacturing of molded bodies>  [Evaluation of fluidity]  Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name "SE100EV-A"), a mold having a spiral flow path with a width of 8 mm and a thickness of 1 mm as the shape inside the mold was used to evaluate the flow length (refer to Figure 3 for the shape of the flow path). In Figure 3, G represents a gate connected to the flow path, and when the composition flows into the gate, a direct gate method is adopted. The resin composition of each example was used as a molding material and injection molding was performed. Under the conditions of barrel temperature of 380°C, mold temperature of 150°C, injection speed of 50 mm/sec, and measurement position of 25 mm in the above molding machine, pressure control was switched to when the injection pressure reached 150 MPa, and a molded body was obtained by continuously applying 150 MPa within 2 seconds of injection time. The distances from the flow end of the molded body were measured at 10 points, and the average value was taken as the flow length.

(Manufacture of test pieces for heat resistance and tensile strength tests) Using an injection molding machine (manufactured by Nissei Plastics Industry Co., Ltd., trade name "NEX50IV-5EG"), the resin compositions of each example were used as molding materials. Under the conditions of cylinder temperature 380°C, mold temperature 150°C, and injection speed 50 mm/second, ASTM No. 4 dumbbell-shaped test pieces and rod-shaped test pieces with a width of 12.7 mm, a length of 127 mm, and a thickness of 6.4 mm were manufactured respectively.

(Manufacture of test pieces for welding bending strength test) Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name "SE100EV-A"), the resin composition of each example was used as the molding material. Under the conditions of barrel temperature of 380°C, mold temperature of 150°C, and injection speed of 50 mm/sec, a mold in the shape of a type A multifunctional test piece specified in ISO 3167:93 (with a thickness of 3 mm) having gate parts at both ends was used to manufacture a test piece for welding test having a weld in the center.

[Determination of welding bending strength] Regarding the test pieces for welding test made of the resin composition of each example, the bending test was carried out in accordance with ISO 178 at 23°C, a test speed of 2 mm/min, a support distance of 64 mm, a press head width of 1 mm, and a radius of 5 mm at the front end of the press head. The value of the bending strength was the average value of the results of the three test pieces.

[Measurement of tensile strength] Regarding ASTM No. 4 dumbbell-shaped test pieces produced using the resin compositions of each example, the tensile strength was measured in accordance with ASTM D638 at a tensile speed of 10 mm/min in an environment of 23°C. As for the value of tensile strength, the average value of the results of five test pieces is used.

[Measurement of heat deformation temperature (°C) under load] Regarding the rod-shaped test pieces produced using the resin compositions of each example, the load was measured under the conditions of a load of 1.82 MPa and a temperature rise rate of 2°C/min in accordance with ASTM D648. Thermal distortion temperature (DTUL).

The above measurement results are shown in Table 1 and Figures 1 and 2. Figure 1 is a graph showing the relationship between spiral flow length and bending strength.

[Table 1] Allocation Measurement Polyether sulfide Liquid crystal polyester Fatty amide additives Glass fiber Spiral flow length Flow length elongation ※ Welding bending strength Strength retention rate ※ Tensile strength Thermal deformation temperature under load 3600P WH-510K CS3J260S ASTM D638 ASTM D648 Quality Quality Quality Quality mm % MPa % MPa ℃ Reference Example 1 100 0 0 25 125 - 95 - 129 221 Reference Example 2 90 10 0 25 185 - 78 - 124 218 Reference Example 3 80 20 0 25 271 - 58 - 131 218 Reference Example 4 70 30 0 25 310 - 43 - 135 217 Reference Example 5 100 0 0.1 25 129 103 99 105 127 218 Embodiment 1 90 10 0.1 25 193 105 78 100 137 218 Embodiment 2 80 20 0.1 25 296 109 58 100 126 217 Embodiment 3 70 30 0.1 25 348 112 43 100 133 216 Reference Example 6 100 0 0.5 25 135 108 99 105 126 214 Embodiment 4 90 10 0.5 25 213 115 79 101 134 213 Embodiment 5 80 20 0.5 25 315 116 62 106 128 213 Embodiment 6 70 30 0.5 25 405 131 41 95 131 210 Reference Example 7 100 0 1 25 151 120 94 99 120 209 Embodiment 7 90 10 1 25 255 138 79 101 126 208 Embodiment 8 80 20 1 25 384 142 61 106 126 207 Embodiment 9 70 30 1 25 456 147 41 96 126 204 ※ Strength retention and flow elongation are based on the same liquid crystal polyester blending ratio in Reference Examples 1 to 4 (%)

According to the results of Reference Examples 1 to 4, as the amount of the liquid crystal polyester is increased, the fluidity of the resin composition can be improved. However, as the amount of the liquid crystal polyester is increased, it is confirmed that the welding bending strength decreases.

Therefore, in the compositions of Reference Examples 1 to 4, it can be seen that if a certain degree of reduction in welding bending strength is not allowed, it is not expected that the fluidity of the resin composition can be improved by blending liquid crystal polyester.

Therefore, as shown in Examples 1 to 9, when a fatty amide additive is further formulated, no significant decrease in welding bending strength occurs, and the fluidity of the resin composition can be improved.

For example, when the welding bending strength of Reference Example 4 is 43 MPa, the flowability (the value of the spiral flow length) is 310 mm. In contrast, in Example 3 in which 0.1 parts by mass of the fatty amide additive was blended, the value of the spiral flow length increased to 343 mm when the welding bending strength was 43 MPa (see Table 1 and Figure 1).

When comparing resin compositions with desired fluidity, it can be said that the weld bending strength is improved by the formulation of fatty amide additives. For example, the weld bending strength value of Reference Example 4 at the fluidity (the value of the spiral flow length is 310 mm) is 43 MPa. In contrast, the weld bending strength value of Example 2, which is formulated with 0.1 parts by mass of fatty amide additives, is increased to 58 MPa when showing the same fluidity (the spiral flow length is 296 mm) (see Table 1, Figure 1).

FIG. 2 is a graph showing the relationship between the flow length elongation value shown in Table 1 and the compounding amounts of liquid crystal polyester and fatty amide additives. Even when focusing only on the effect of improving fluidity, compared with Reference Examples 5 to 7 in which no fatty amide additive was blended, it can be seen that Example 1 in which both the liquid crystal polyester and the fatty amide additive were blended was The fluidity of the resin composition of ~9 is significantly improved.

When attention is also paid to the heat resistance evaluated by the heat deformation temperature (° C.) under load, Examples 1 to 9 all exhibit good heat resistance (Table 1).

<Research on types of additives> [Reference Examples 8 to 15] As additives, the following types of additives were studied.・Barium stearate (manufactured by Sakai Chemical Industry Co., Ltd.) ・Stearic acid (manufactured by New Nippon Rika Co., Ltd., stearic acid 5000) ・Polyhydric alcohol fatty acid ester (manufactured by Emery Oleochemicals Japan Co., Ltd., LOXIOL G15)・Fatty amide based additive (manufactured by Kyoeisha Chemical Co., Ltd., light amide WH-510K) ・Fatty amide based additive (manufactured by Kyoeisha Chemical Co., Ltd., light amide WH-255) ・Stearylamide (MCC TRADING Co., Ltd. Manufactured by the company, AMIDE AP-1) ・ Ethylene distearamide (manufactured by MCC TRADING Co., Ltd., Slipacks E)

The same operation as in Reference Example 1 or Reference Example 5 was performed to prepare aromatic polyether sulphate PES 3600P (100 parts by mass), the additives shown in Table 2 (0 parts by mass or 0.3 parts by mass), and glass fiber (20 parts by mass), and the mixture was fed into a double-screw extruder (manufactured by Ikegai Co., Ltd., PCM-30), and granulated at a barrel temperature of 340° C. to obtain the resin composition (granules) of each example.

Table 2 shows the above measurement results.

[Table 2] Additive Type Addition amount Spiral flow length Tensile strength Thermal deformation temperature under load ASTM D638 ASTM D648 Quality mm MPa ℃ Reference Example 8 without 0 125 129 221 Reference Example 9 Ba stearate 0.3 130 112 218 Reference Example 10 Stearic acid 0.3 136 101 215 Reference Example 11 Polyol fatty acid esters LOXIOL G15 0.3 136 109 215 Reference Example 12 Fatty amide additives WH-510K 0.3 135 127 217 Reference Example 13 Fatty amide additives WH-255 0.3 145 130 216 Reference Example 14 Stearylamide Amide AP-1 0.3 140 127 214 Reference Example 15 Ethylene bis(stearylamide) SLIPACKS E 0.3 143 131 216

Based on the results shown in Table 2, it is considered that when any additive among fatty acids, fatty acid salts, and fatty acid derivatives is blended (Reference Examples 9 to 15), compared to the case where no additive is blended (Reference Example 8), It has the effect of improving liquidity. When fatty acid amide additives equivalent to fatty acid amide or fatty acid diamide are formulated among these fatty acids, fatty acid salts, and fatty acid derivatives (Reference Examples 12 to 15), the fluidity-improving effect is further improved, showing that A better tensile strength value was obtained.

According to the above results, it is shown that an aromatic polystyrene combination containing an aromatic polystyrene, a liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives is suitable for embodiments of the present invention. The evaluation result shows that the material achieves an excellent balance between fluidity, various strengths and heat resistance, and is an extremely useful composition suitable for use as a molding material for injection molding.

Each structure in each embodiment and the combination thereof are examples, and additions, omissions, substitutions, and other changes in the structure may be made without departing from the scope of the invention. In addition, the present invention is not limited to each embodiment but is limited to the scope of the claims (claimed scope). [Industrial availability]

According to the present invention, it is possible to provide an aromatic polyurethane composition having an excellent balance between fluidity and strength.

G: gate

Figure 1 is a graph showing the relationship between the spiral flow length and the welding bending strength of the compositions of the embodiments and reference examples. Figure 2 is a graph showing the relationship between the flow length elongation value of the compositions of the embodiments and reference examples and the formulation amounts of liquid crystal polyester and fatty amide additives. Figure 3 is a schematic diagram illustrating the flow path shape of the mold used to evaluate fluidity in the embodiments.

Claims (10)

An aromatic polyester composition, which contains aromatic polyester, liquid crystal polyester, and at least one fatty acid compound selected from the group consisting of fatty acids, fatty acid salts, and fatty acid derivatives. The aromatic polysulfone composition of claim 1, wherein the mass ratio of the aromatic polysulfone to the liquid crystal polyester is the aromatic polysulfone/the liquid crystal polyester = 95/5 to 70/30. The aromatic polystyrene composition of claim 1 or 2, wherein the content of the fatty acid compound is 0.1 to 1 part by mass relative to 100 parts by mass of the total mass of the aromatic polystyrene and the liquid crystal polyester. The aromatic polysulfone composition of claim 1 or 2 contains the aromatic polysulfone in an amount of 30 mass % to 95 mass % relative to 100 mass % of the total mass of the aromatic polysulfone composition. The aromatic polystyrene composition of Claim 1 or 2, which contains the above-mentioned fatty acid derivative, and the above-mentioned fatty acid derivative contains fatty amide. An aromatic polysulfone composition as claimed in claim 1 or 2, wherein the aromatic polysulfone is an aromatic polyether sulfone having repeating units represented by the following formula (S1): (S1) -Ph ¹ -SO ₂ -Ph ² -O- [wherein Ph ¹ and Ph ² each independently represent a phenylene group; the hydrogen atom on the phenylene group may each independently be substituted with an alkyl group, an aryl group or a halogen atom]. The aromatic polysulfone composition of claim 1 or 2, wherein the liquid crystal polyester is a liquid crystal polyester having a repeating unit (1) represented by the following formula (1), a repeating unit (2) represented by the following formula (2), and a repeating unit (3) represented by the following formula (3): (1) -O-Ar ¹ -CO- (2) -CO-Ar ² -CO- (3) -X-Ar ³ -Y- [wherein Ar ^{1 represents a phenylene group, a naphthylene group or a biphenylene group; Ar 2 and Ar 3 each independently represent a phenylene group, a naphthylene group, a biphenylene group or a group represented by the following formula (4); X and Y each independently represent an oxygen atom or an imino group (-NH-); the hydrogen atom in the above group represented by Ar 1 , Ar 2 or Ar 3 may be independently substituted by a halogen atom, an alkyl group or an aryl group] (4) -Ar 4 -Z-Ar 5 - [wherein Ar 4 and Ar 3 each independently represent a phenylene group, a naphthylene group or a biphenylene group; X and Y each independently represent an oxygen atom or an imino group (-NH-); the hydrogen atom in the above group represented by Ar 1 , Ar 2 or Ar 3} may be independently substituted by a halogen atom, an alkyl group or ^an aryl group] ⁵ each independently represents a phenylene group or a naphthylene group; Z represents an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group or an alkylene group]. The aromatic polysulfone composition of claim 1 or 2 further contains a fibrous filler. A shaped body comprising the aromatic polysulfone composition of claim 1 or 2. A method for manufacturing a molded body, comprising injection molding the aromatic polysulfone composition as claimed in claim 1 or 2.