JP2019073591A - Liquid crystal polyester resin composition and molded article made of the same - Google Patents

Abstract

To provide a liquid crystal polyester resin composition excellent in epoxy adhesiveness and particle desorption resistance, and a molded article made of the composition.SOLUTION: The liquid crystal polyester resin composition is prepared by compounding a liquid crystal polyester resin (A) by 50 to 98 wt.%, a polyphenylene sulfide resin (B) by 1 to 45 wt.%, and an olefin-based elastomer (C) by 0.5 to 30 wt.%, where the total of (A), (B) and (C) is set 100 wt.%, in which a weight ratio (B/C) of the polyphenylene sulfide resin (B) to the olefin-based elastomer (C) is 0.30 to 6.9. In a molded article of the composition having dimensions of (12.7 mm width)×(127 mm length)×(3.2 mm thickness), a ratio (C/C) of an area ratio Cof (C) component in a surface morphology of the article observed with an electron microscope to an area ratio Cof (C) component in a center portion on a cross-section of the molded article in a thickness direction is 0.07 or more, where Cis defined by {area of (C) component on the surface of the molded article}/{total area of (A) component, (B) component and (C) component on the surface of the molded article}; and Cis defined by {area of (C) component in the center portion in a cross-section of the molded article along the thickness direction}/{total area of (A) component, (B) component and (C) component in the center portion in the cross-section of the molded article along the thickness direction}.SELECTED DRAWING: None

Description

  The present invention relates to a liquid crystal polyester resin composition and a molded article made therefrom.

  Liquid crystal polyester is excellent in heat resistance, fluidity, and dimensional stability because of its liquid crystal structure. For this reason, the demand is expanding mainly on electrical and electronic parts such as connectors and relays which require these characteristics. In these applications, particularly when bonding or sealing with an adhesive such as epoxy resin, sufficient adhesion to the adhesive is required. In addition, with the recent trend toward higher performance, higher output, smaller size, and lighter weight of equipment, particles are more likely to be generated upon impact and fall of equipment, and the generation of particles is suppressed (hereinafter referred to as resistance). Particle releasability is sometimes required). On the other hand, since liquid crystalline polyester is excellent in chemical resistance, adhesion to an epoxy resin (hereinafter sometimes abbreviated as epoxy adhesion) is low, and studies are being made to improve epoxy adhesion. For example, a compact camera module formed from a resin composition containing a liquid crystal polymer and a polyarylene sulfide (for example, see Patent Document 1), a resin composition in which an olefin copolymer is blended with a liquid crystal polyester having a predetermined end group. (For example, refer to patent document 2) is proposed. In addition, as a study to improve metal adhesion, resin compositions comprising a liquid crystalline resin, a thermoplastic resin including a polyarylene sulfide resin, and an olefin copolymer (see, for example, Patent Documents 3 to 5) ) Has been proposed.

Japanese Patent Application Publication No. 2016-535298 JP, 2017-66353, A International Publication No. 2017/110646 Japanese Patent Application Laid-Open No. 2002-38005 JP, 2013-227366, A

  However, the resin composition disclosed in Patent Document 1 is likely to generate particles at the time of impact and drop of the devices, and the epoxy adhesiveness is also insufficient. Further, the resin composition disclosed in Patent Document 2 has room for improvement although it is excellent in epoxy adhesion, and there is room for improvement in the particle detachment resistance. The resin compositions disclosed in the above Patent Documents 3 to 5 do not improve the particle releasability and the epoxy adhesion, and were insufficient for each.

  An object of the present invention is to provide a liquid crystalline polyester resin composition capable of obtaining a molded article excellent in epoxy adhesiveness and particle detachment resistance, and a molded article made thereof.

  The inventors of the present invention conducted intensive studies to solve the above problems, and as a result, a molded article comprising a liquid crystal polyester resin composition comprising a liquid crystal polyester resin, a polyphenylene sulfide resin and an olefin elastomer at a predetermined ratio is obtained. In the case of developing a specific morphology, they have been found to be extremely excellent in epoxy adhesion and particle detachment resistance, and reached the present invention.

That is, the present invention is made in order to solve at least a part of the above-mentioned subject, and can be realized as the following modes.
(1) 50 to 98% by weight of a liquid crystal polyester resin (A), 1 to 45% by weight of a polyphenylene sulfide resin (B) and an olefin elastomer (the total of 100% by weight of (A), (B) and (C) C) Liquid crystalline polyester resin composition containing 0.5 to 30% by weight and having a weight ratio (B / C) of polyphenylene sulfide resin (B) to olefin elastomer (C) of 0.30 to 6.9 An area ratio C _{1 of the} component (C) in the morphology of the 12.7 mm wide × 127 mm long × 3.2 mm thick molded article observed by an electron microscope, and the thickness direction of the molded article center of area ratio _{C 2} of the component (C) in the portion ratio of its section _(C 1 / _{C 2)} is 0.07 or more, the liquid crystal polyester resin composition.
(Here, C ₁ is {area of component (C) on the surface of the molded article) / {total area of components (A), (B) and (C) on the surface of the molded article}, and C ₂ is , {Area of component (C) at center of molded product thickness direction cross section / {total area of components (A), (B) component and (C) component at center of molded product thickness direction cross section} is there.)
(2) Melt viscosity ((A) at a melting point of + 20 ° C. of the liquid crystal polyester resin (A) and a shear rate of 1000 / sec,
The polyphenylene sulfide resin (B) is described in (1) in which the ratio (η (A) / η (B)) of melt viscosity η (B) at a shear rate of 1000 / sec at 310 ° C. is 0.25-10. Liquid crystal polyester resin composition.
(3) The total of structural units derived from p-hydroxybenzoic acid and structural units derived from terephthalic acid is 60 to 77 mol%, relative to 100 mol% of the total structural units of the liquid crystal polyester resin (A). Or the liquid-crystal polyester resin composition as described in (2).
(4) The liquid crystal polyester resin according to any one of (1) to (3), wherein the structural unit derived from hydroquinone is 2 to 20 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin (A). Composition.
(5) The filler (D) contains 10 to 200 parts by weight with respect to a total of 100 parts by weight of the liquid crystal polyester resin (A), the polyphenylene sulfide resin (B) and the olefin-based elastomer (C) Liquid crystalline polyester resin composition in any one of-(4).
(6) A molded article comprising the liquid crystal polyester resin composition according to any one of (1) to (5).
(7) The molded article according to (6), which is a molded article having a joint.
(8) The molded article according to (6) or (7), wherein the molded article is any one selected from the group consisting of a relay, a switch, a coil bobbin, a camera module, a sensor, and a connector.

  According to the liquid crystal polyester resin composition of the present invention, it is possible to obtain a molded article excellent in epoxy adhesion and particle releasability. Such a resin composition is particularly suitable for electric / electronic parts and mechanical parts having joints such as relays, switches, coil bobbins, camera modules, sensors, connectors and the like.

It is a figure showing the part which observes the morphology in the center of the surface of a molded article, and the thickness direction section. It is a figure showing the test piece which measures epoxy adhesion.

  Hereinafter, the present invention will be described in detail.

<Liquid crystal polyester resin (A)>
The liquid crystal polyester resin (A) (hereinafter sometimes simply referred to as liquid crystal polyester resin) used in the present invention is a polyester forming an anisotropic melt phase. Examples of the liquid crystalline polyester resin include polyesters composed of structural units selected to form an anisotropic melt phase from oxycarbonyl units, dioxy units, dicarbonyl units, etc. described later.

  Next, structural units constituting the liquid crystal polyester resin will be described.

  Specific examples of the oxycarbonyl unit include structural units generated from an aromatic hydroxycarboxylic acid such as p-hydroxybenzoic acid, m-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid and the like. From the viewpoint of appropriately controlling the crystallinity of the liquid crystalline polyester resin and being excellent in epoxy adhesiveness and particle detachment resistance, a structural unit generated from an aromatic hydroxycarboxylic acid is preferable, and a structural unit generated from a p-hydroxybenzoic acid is Particularly preferred.

  Specific examples of the dioxy unit include 4,4'-dihydroxybiphenyl, hydroquinone, resorcinol, t-butylhydroquinone, phenylhydroquinone, chlorohydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 3,4'- Dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxybenzophenone and the like Structural units produced from the aromatic diols of the following: aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and the like Concrete unit, 1,4-cyclohexanediol, and structural unit derived from alicyclic diol such as 1,4-cyclohexanedimethanol. From the viewpoint of appropriately controlling the crystallinity of the liquid crystalline polyester resin and being excellent in epoxy adhesion and particle detachment resistance, a structural unit formed from an aromatic diol is preferable, among which a generated unit is formed from 4,4'-dihydroxybiphenyl and hydroquinone Structural units are particularly preferred.

  Specific examples of the dicarbonyl unit include terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 3,3'-diphenyldicarboxylic acid, 2,2'-diphenyldicarboxylic acid, Aroma such as 1,2-bis (phenoxy) ethane-4,4'-dicarboxylic acid, 1,2-bis (2-chlorophenoxy) ethane-4,4'-dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid Structural units produced from aliphatic dicarboxylic acids, structural units produced from aliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, hexahydroterephthalic acid, etc. Examples include structural units generated from alicyclic dicarboxylic acids such as cyclohexanedicarboxylic acid. From the viewpoint of appropriately controlling the crystallinity of the liquid crystal polyester resin and being excellent in epoxy adhesion and particle detachment resistance, structural units generated from aromatic dicarboxylic acids are preferable, among which structural units generated from terephthalic acid and isophthalic acid are preferable. Particularly preferred.

  Further, in addition to the above structural units, structural units produced from p-aminobenzoic acid, p-aminophenol and the like can be further provided within a range that does not impair liquid crystallinity and properties.

  Specific examples of the liquid crystalline polyester resin include a structural unit generated from p-hydroxybenzoic acid, a structural unit generated from 4,4'-dihydroxybiphenyl, a structural unit generated from hydroquinone, terephthalic acid and / or isophthalic acid Liquid crystalline polyester comprising structural units, Structural unit produced from p-hydroxybenzoic acid, Structural unit produced from ethylene glycol, Structural unit produced from 4,4'-dihydroxybiphenyl, Structural unit produced from hydroquinone, terephthalic acid and / or Or a liquid crystalline polyester comprising a structural unit produced from isophthalic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from hydroquinone, a structural unit produced from 4,4'-dihydroxybiphenyl, 2,6-naphthalene Structural unit generated from carboxylic acid, liquid crystalline polyester consisting of structural unit generated from terephthalic acid, structural unit generated from p-hydroxybenzoic acid, structural unit generated from 2,6-dihydroxynaphthalene, 4,4'-dihydroxybiphenyl And liquid crystalline polyester comprising structural units produced from terephthalic acid and / or isophthalic acid.

  From the viewpoint of being able to appropriately control the crystallinity of the liquid crystalline polyester resin and being excellent in epoxy adhesiveness and particle detachment resistance, it is particularly preferable to use a structural unit generated from p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl It is a liquid crystalline polyester comprising a structural unit produced, a structural unit produced from hydroquinone, and a structural unit produced from an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid.

  Although the raw material monomer which comprises said each structural unit is not specifically limited if it is a structure which can form each structural unit, The acylation thing of the hydroxyl group of each structural unit, The esterified thing of the carboxyl group of each structural unit, an acid halide And carboxylic acid derivatives such as acid anhydrides may be used.

  The total of dioxy units constituting the liquid crystalline polyester resin and the total of dicarbonyl units are substantially equimolar. "Substantially equimolar" as used herein indicates that the structural units constituting the polymer main chain excluding the terminal are equimolar. For this reason, an aspect which is not necessarily equimolar when including the structural units constituting the end can also satisfy the “substantially equimolar” requirement.

  In the liquid crystal polyester resin used in the present invention, the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 60 to 77 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Is preferred. When the total of structural units derived from hydroxybenzoic acid and structural units derived from terephthalic acid is 60 mol% or more with respect to 100 mol% of the total structural units of the liquid crystal polyester resin, the heat resistance and rigidity of the liquid crystal polyester resin are In order to improve, it is preferable because it is excellent in anti-particle releasability. More preferably, it is 63% or more, further preferably 65% or more. On the other hand, when the total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid is 77 mol% or less with respect to 100 mol% of the total structural units of the liquid crystal polyester resin, The temperature can be appropriately controlled, and it can be set to an appropriate molding processing temperature that can suppress deterioration of the liquid crystal polyester resin composition, particularly the olefin elastomer (C) described later, and it is easy to obtain a desired morphology described later Therefore, a molded article excellent in epoxy adhesion and particle releasability can be obtained. More preferably, it is 75% or less.

  The structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid may have any one structural unit, and the other structural unit may be 0 mol%, but each is 0 mol% It is preferable to exceed.

  The liquid crystal polyester resin of the present invention preferably has 2 mol% or more of a structural unit derived from hydroquinone with respect to 100 mol% of the total amount of structural units of the liquid crystal polyester resin. By setting it as said structure, crystallinity of a liquid-crystal polyester resin can be controlled appropriately, and the molded article which is excellent in epoxy adhesiveness and particle detachment resistance is obtained. More preferably, it is 4 mol% or more, more preferably 7.5 mol% or more. On the other hand, it is preferable to have 20 mol% or less of the structural unit derived from hydroquinone. By setting it as said structure, crystallinity of a liquid-crystal polyester resin can be controlled moderately, and it is excellent in epoxy adhesiveness and particle-proof detachment property. More preferably, it is 15 mol% or less, still more preferably 12 mol% or less.

The calculation method of content of each structural unit is shown below about the liquid-crystal polyester resin of this invention. First, it was weighed liquid crystal polyester resin NMR (nuclear magnetic resonance) tube, liquid crystal polyester resin is dissolved in soluble solvents (e.g., pentafluorophenol / heavy tetrachloroethane -d ₂ solvent mixture). Next, ¹ H-NMR spectrum measurement is performed on the obtained solution, and it can be calculated from the peak area ratio derived from each structural unit.

  The melting point (Tm) of the liquid crystal polyester resin of the present invention is preferably 220 ° C. or more, more preferably 270 ° C. or more, and still more preferably 300 ° C. or more from the viewpoint of improving heat resistance. On the other hand, since the deterioration of the liquid crystal polyester resin composition, particularly the olefin elastomer (C) during molding is suppressed and it is easy to obtain the desired morphology described later, the molding is excellent in epoxy adhesion and particle detachment resistance. From the viewpoint of obtaining a product, the melting point (Tm) of the liquid crystal polyester resin is preferably 360 ° C. or less, more preferably 350 ° C. or less, and still more preferably 340 ° C. or less.

The measurement of the melting point (Tm) is performed by differential scanning calorimetry. Specifically, first, the endothermic peak temperature (Tm ₁ ) is observed by heating the polymer after completion of the polymerization from room temperature to 20 ° C./min. After observation of an endothermic peak temperature (Tm _1), holding the polymer for 5 minutes at a temperature of the endothermic peak temperature _(Tm 1) + 20 ℃. Thereafter, the polymer is cooled to room temperature under a temperature decrease condition of 20 ° C./min. Then, the endothermic peak temperature (Tm ₂ ) is observed by heating the polymer under a temperature rising condition of 20 ° C./min. The melting point (Tm) refers to the endothermic peak temperature (Tm ₂ ).

  The melt viscosity of the liquid crystal polyester resin used in the present invention is easy to control the melt viscosity ratio to the polyphenylene sulfide resin described later in a preferable range, and is easy to obtain the desired morphology described later, and thus epoxy From the viewpoint of obtaining a molded article excellent in adhesiveness and particle release resistance, 5 Pa · s or more is preferable, 8 Pa · s or more is more preferable, and 15 Pa · s or more is more preferable. On the other hand, from the viewpoint of fluidity, the melt viscosity of the liquid crystalline polyester resin is preferably 200 Pa · s or less, more preferably 100 Pa · s or less, and still more preferably 50 Pa · s or less.

  In addition, this melt viscosity is a value measured with a temperature-increase type flow tester under the conditions of a melting point (Tm) + 20 ° C of a liquid crystal polyester resin and a shear rate of 1000 / sec.

  The method for producing the liquid crystal polyester resin used in the present invention is not particularly limited, and can be produced according to a known polyester polycondensation method. Examples of known polycondensation methods for polyesters include structural units derived from p-hydroxybenzoic acid, structural units derived from 4,4'-dihydroxybiphenyl, structural units derived from hydroquinone, structural units derived from terephthalic acid, and Taking the liquid crystalline polyester resin comprising a structural unit derived from isophthalic acid as an example, the following may be mentioned.

  (1) A process for producing a liquid crystalline polyester resin from p-acetoxybenzoic acid and 4,4'-diacetoxybiphenyl, diacetoxybenzene and terephthalic acid and isophthalic acid by a deacetic acid polycondensation reaction.

  (2) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acetylate a phenolic hydroxyl group, and then deacetylated and polymerized to obtain a liquid crystal polyester How to make a resin.

  (3) A method for producing a liquid crystalline polyester resin by dephenolization polycondensation reaction from phenyl p-hydroxybenzoate and 4,4'-dihydroxybiphenyl, hydroquinone and diphenyl terephthalate and diphenyl isophthalate.

  (4) A predetermined amount of diphenyl carbonate is reacted with p-hydroxybenzoic acid and an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid to make each into a phenyl ester, and then an aroma such as 4,4'-dihydroxybiphenyl and hydroquinone Group dihydroxy compound is added and the liquid crystal polyester resin is manufactured by dephenolation polycondensation reaction.

  Among them, (2) p-hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, hydroquinone, terephthalic acid, and isophthalic acid are reacted with acetic anhydride to acetylate the phenolic hydroxyl group, and then deacetylated polycondensation reaction is performed. The method for producing a liquid crystalline polyester resin is preferably used in terms of industrially excellent control of the degree of polymerization of the liquid crystalline polyester resin.

  As a method for producing the liquid crystalline polyester resin used in the present invention, it is also possible to complete the polycondensation reaction by solid phase polymerization. Examples of the treatment by solid phase polymerization include the following methods. First, the polymer or oligomer of the liquid crystal polyester resin is ground by a grinder. The pulverized polymer or oligomer is heated under nitrogen flow or under reduced pressure to polycondensation to a desired degree of polymerization to complete the reaction. The heating can be performed in the range of melting point −50 ° C. to melting point −5 ° C. (for example, 200 to 300 ° C.) of the liquid crystal polyester for 1 to 50 hours.

  The polycondensation reaction of the liquid crystalline polyester resin proceeds without a catalyst, but stannous acetate, tetrabutyl titanate, potassium acetate and sodium acetate, antimony trioxide, metallic magnesium and the like can also be used as a catalyst.

<Polyphenylene sulfide resin (B)>
The polyphenylene sulfide resin (B) (hereinafter sometimes simply referred to as a polyphenylene sulfide resin) as an embodiment of the present invention is a polymer having a repeating unit represented by the following structural formula,

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, and further 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula is preferable. In addition, less than 30 mol% of the repeating units of the polyphenylene sulfide resin may be composed of one or more repeating units having the following structure.

  Such polyphenylene sulfide resin can be obtained by a generally known method, that is, a method of obtaining a polymer having a relatively small molecular weight as described in JP-B-45-3368, JP-B-52-12240 or JP-A-61-7332. It can be produced by the method of obtaining a relatively large molecular weight polymer described in 1.

  In the present invention, the polyphenylene sulfide resin obtained as described above is crosslinked / polymerized by heating in air, heat-treated under an inert gas atmosphere such as nitrogen or under reduced pressure, organic solvent, hot water, acid It is also possible to use after being subjected to various treatments such as washing with an aqueous solution or the like, activation with a functional group-containing compound such as an acid anhydride, an amine, an isocyanate, and a functional group-containing disulfide compound.

  Specific methods for crosslinking / polymerizing the polyphenylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air and oxygen, or an atmosphere of a mixed gas of the oxidizing gas and an inert gas such as nitrogen and argon. In the heating vessel, a method can be exemplified in which heating is performed until a desired melt viscosity is obtained at a predetermined temperature. The heat treatment temperature in this case is preferably selected from the range of 150 to 280 ° C., more preferably 200 to 270 ° C., and the treatment time is preferably 0.5 to 100 hours, more preferably 2 A range of 50 hours is selected, but by controlling both of them, it is possible to obtain a target viscosity level. The apparatus for such heat treatment may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade, but in the case of efficient and more uniform treatment, heating with a rotary or stirring blade It is more preferred to use an apparatus.

  As a specific method in the case of heat treating polyphenylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, heating is carried out under an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm -2 or less) The method of heat-processing on the conditions of processing temperature 150-280 degreeC, preferably 200-270 degreeC, and the heat time 0.5 to 100 hours, preferably 2 to 50 hours can be illustrated. The apparatus for such heat treatment may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade, but in the case of processing efficiently and more uniformly, a heating apparatus with a rotary or stirring blade It is more preferable to use

  When washing polyphenylene sulfide resin with an organic solvent, as an organic solvent used for washing, as long as it does not have the function of decomposing polyphenylene sulfide resin etc., it can be used without particular limitation. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfoxide-sulfone solvents such as dimethylsulfoxide or dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether Ether solvents such as tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, dichloroethane, tetrachloroethane, chlorobenzene, and other halogen solvents, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, Alcohol and phenol solvents such as cresol and polyethylene glycol, and benzene and toluene Ene, and aromatic hydrocarbon solvents such as xylene may be used. Among these organic solvents, in particular, N-methylpyrrolidone, acetone, dimethylformamide and chloroform are preferably used. Moreover, these organic solvents are used by 1 type or 2 or more types of mixtures.

  As a specific method of washing with such an organic solvent, there is a method of immersing a polyphenylene sulfide resin in an organic solvent, etc. It is also possible to appropriately stir or heat as necessary. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide resin with an organic solvent, Arbitrary temperature of normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to be higher as the cleaning temperature is higher, a sufficient effect can usually be obtained at a cleaning temperature of normal temperature to 150 ° C. The polyphenylene sulfide resin subjected to the organic solvent washing is preferably washed several times with water or hot water to remove the remaining organic solvent. The temperature of the water washing is preferably 50 to 90 ° C, and more preferably 60 to 80 ° C.

  As a specific method in the case of treating polyphenylene sulfide resin with hot water, the following method can be exemplified. That is, in order to express the effect of the preferable chemical modification of polyphenylene sulfide resin by hot water washing, it is preferable that the water used is distilled water or deionized water. The operation of the hot water treatment is usually carried out by charging a predetermined amount of polyphenylene sulfide resin into a predetermined amount of water and heating and stirring under normal pressure or in a pressure vessel. The proportion of the polyphenylene sulfide resin and water is preferably as large as water, and preferably used at a bath ratio of 200 g or less of the polyphenylene sulfide resin to 1 liter of water.

  As a specific method in the case of acid-treating polyphenylene sulfide resin, the following method can be illustrated. That is, there is a method of immersing the polyphenylene sulfide resin in an acid or an aqueous solution of an acid, and if necessary, it is also possible to appropriately stir or heat. The acid to be used is not particularly limited as long as it does not decompose polyphenylene sulfide resin, and aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo such as chloroacetic acid and dichloroacetic acid. Substituted aliphatic saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid Acids and inorganic acid compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid are used. Among these acids, in particular, acetic acid and hydrochloric acid are more preferably used. The acid-treated polyphenylene sulfide resin is preferably washed several times with water in order to remove the remaining acid or salt. The temperature of the water washing is preferably 50 to 90 ° C, and more preferably 60 to 80 ° C. Further, water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferable chemical modification of the polyphenylene sulfide resin by acid treatment is not impaired.

  The content of the polyphenylene sulfide resin (B) in the liquid crystal polyester resin composition of the present invention is 1 with respect to a total of 100% by weight of the liquid crystal polyester resin (A), the polyphenylene sulfide resin (B) and the olefin elastomer (C). 40% by weight. If the amount of the polyphenylene sulfide resin (B) is less than 1% by weight, it is difficult to obtain the desired morphology described later, and the epoxy adhesion and the particle releasability are significantly reduced. It is easy to control to a desired morphology described later, and from the viewpoint of being excellent in epoxy adhesiveness and particle releasability, it is preferably 2% by weight or more. In addition, if the polyphenylene sulfide resin (B) is more than 45% by weight, the excellent heat resistance, fluidity and dimensional stability of the liquid crystal polyester resin are impaired, and it is difficult to obtain the desired morphology described later. Epoxy adhesion and particle releasability are significantly reduced. It is easy to control to the desired morphology described later, and from the viewpoint of being excellent in epoxy adhesion and particle releasability, it is preferably 30% by weight or less, more preferably 20% by weight or less, particularly preferably 12% by weight or less It is.

  The melt viscosity of the polyphenylene sulfide resin of the embodiment of the present invention is easy to control the melt viscosity ratio with the liquid crystal polyester resin described later in a preferable range, and is easy to obtain a desired morphology described later, It is preferable that it is 200 Pa.s (310 degreeC, shear rate 1000 / s) or less, 100 Pa.s or less is more preferable, and 60 Pa.s from a viewpoint from which a molded article which is excellent in epoxy adhesiveness and particle detachment resistance is obtained. The following are more preferable. The lower limit is preferably 1 Pa · s or more from the viewpoint of improvement in melt processability and formation of a molded article excellent in epoxy adhesiveness and particle detachment resistance by suppressing the amount of gas generation. A plurality of polyphenylene sulfide resins having different melt viscosities may be mixed and used as long as the melt viscosity falls within the above range.

  In the liquid crystal polyester resin composition of the present invention, since it is easy to obtain the desired morphology described later, from the viewpoint of obtaining a molded article excellent in epoxy adhesiveness and particle releasability, the liquid crystal polyester resin (A) Melting viscosity η (A) at a melting point of + 20 ° C. at a shear rate of 1000 / sec, the ratio of melt viscosity η (B) at a shear rate of 1000 / sec of a polyphenylene sulfide resin (B) at 310 ° C. (η (A) / η (() B) is preferably 0.25 or more, more preferably 0.30 or more, and still more preferably 0.35 or more. On the other hand, since it is easy to suppress the amount of gas generation and to obtain the desired morphology described later, η (A) / η from the viewpoint of obtaining a molded article excellent in epoxy adhesiveness and particle detachment resistance. (B) is preferably 10 or less, more preferably 8.0 or less, and still more preferably 5.5 or less.

  The melt viscosity of the polyphenylene sulfide resin in the present invention is a value measured by a Koka flow tester under the conditions of 310 ° C. and a shear rate of 1000 / sec.

<Olefin-based elastomer (C)>
The olefin elastomer (C) used in the present invention may be either an olefin polymer or an olefin copolymer.

  Examples of the olefin polymer or copolymer include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 dimethyl-1-hexene, 4,4 dimethyl-1-pentene, 4-ethyl-1-hexene, Α-olefins such as 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene and 12-ethyl-1-tetradecene Polymers obtained by polymerizing one or more kinds alone, α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like Copolymers with α, β-unsaturated carboxylic acids and their alkyl esters, etc. may be mentioned.

  Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1 -Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene , 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 Hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and combinations thereof To be mentioned. Among these α-olefins, a copolymer using an α-olefin having 4 to 12 carbon atoms is even more preferable.

  Other examples include polymers or copolymers of olefins containing reactive functional groups.

  For example, as olefins containing an epoxy group, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconate, etc. may be mentioned as examples of carboxyl groups and their salts, and olefins containing an acid anhydride group. And maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride and the like.

  In the case of introducing a monomer component containing such an epoxy group, carboxyl group, acid anhydride group, etc., it is copolymerized at the time of polymerization, or a radical initiator is used for the olefin polymer or the olefin copolymer. A method such as grafting can be used.

  When a monomer component containing an epoxy group, a carboxyl group, and an acid anhydride group is introduced, the introduced amount is 0.001 to 40 mol%, preferably 0.01 to 35 mol, with respect to the entire olefin resin. It is preferably in the range of%.

  In the present invention, an olefin-based copolymer containing an epoxy group is preferable from the viewpoint of easy formation of a desired morphology to be described later and excellent in epoxy adhesion and particle detachment resistance. As an olefin-type copolymer containing an epoxy group, the olefin copolymer which makes a glycidyl ester of (alpha) -olefin and (alpha), (beta)-unsaturated carboxylic acid an essential copolymerization component is mentioned. Ethylene is preferably mentioned as the above-mentioned α-olefin. Further, these copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, and It is also possible to copolymerize the alkyl ester etc. It is easy to form the desired morphology described later, and from the viewpoint of being excellent in epoxy adhesion and particle detachment resistance, 1 to 30% by weight of glycidyl ester of α, β-unsaturated carboxylic acid is used as an essential copolymerization component An olefin copolymer is preferable, and an olefin copolymer containing 3 to 20% by weight of a glycidyl ester of an α, β-unsaturated carboxylic acid as an essential copolymerization component is more preferable.

  The glycidyl ester of the above α, β-unsaturated carboxylic acid is

(R represents a hydrogen atom or a lower alkyl group), and specific examples thereof include glycidyl acrylate, glycidyl methacrylate and glycidyl ethacrylate, and among them, glycidyl methacrylate is preferably used. As a specific example of the olefin copolymer which makes glycidyl ester of alpha-olefin and alpha, beta- unsaturated carboxylic acid an essential copolymerization component, ethylene / propylene g glycidyl methacrylate copolymer ("g" is a graft) Represents the same, hereinafter the same), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer Polymers and ethylene / methyl methacrylate / glycidyl methacrylate copolymers may be mentioned. Among them, a copolymer selected from ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer and ethylene / methyl methacrylate / glycidyl methacrylate copolymer is preferably used.

  More specifically, Sumitomo Chemical "bond first" E (ethylene: glycidyl methacrylate = 88% by weight: 12% by weight), "bond first" 2C (ethylene: glycidyl methacrylate = 94% by weight: 6% by weight), " BondFirst 7 L (ethylene: glycidyl methacrylate: methyl acrylate = 70% by weight: 3% by weight: 27% by weight), "bond first" 7M (ethylene: glycidyl methacrylate: methyl acrylate = 67% by weight: 6% by weight: 27% %), BondFirst “CG 5001 (ethylene: glycidyl methacrylate = 81% by weight: 19% by weight), ALKEMA“ LOTADER ”AX 8900 (ethylene: glycidyl methacrylate: methyl acrylate = 68% by weight: 8% by weight: 24% by weight) But It can be shown.

  The content of the olefin-based elastomer (C) in the liquid crystal polyester resin composition of the present invention is excellent in epoxy adhesiveness and particle detachment resistance, so the total of the liquid crystal polyester resin (A) and the polyphenylene sulfide resin (B) It is preferable that it is 0.5 weight part or more with respect to 100 weight part, 1.0 weight part or more is more preferable, and 1.5 weight part or more is more preferable. On the other hand, it is easy to suppress deterioration of the liquid crystal polyester resin composition, particularly the olefin elastomer (C) at the time of molding, to control to a desired morphology to be described later, and to be excellent in epoxy adhesion and particle detachment resistance. Therefore, it is preferably 30 parts by weight or less, more preferably 20 parts by weight or less, still more preferably 10 parts by weight or less, and particularly preferably 5 parts by weight or less.

  The liquid crystal polyester resin composition of the present invention is a polyphenylene sulfide resin (B) such that the weight ratio (B / C) of the polyphenylene sulfide resin (B) to the olefin elastomer (C) is 0.30 to 6.9. And an olefin elastomer (C). If the B / C is less than 0.30, it is difficult to obtain the desired morphology described later, and the epoxy adhesion and the particle releasability are significantly reduced. B / C is preferably 0.70 or more, more preferably 1.0 or more from the viewpoint of easy control to a desired morphology described later and excellent in epoxy adhesion and particle detachment resistance. . On the other hand, if B / C is greater than 6.9, it is difficult to obtain the desired morphology described later, and the epoxy adhesion and the particle releasability are significantly reduced. B / C is preferably 6.4 or less, more preferably 5.9 or less from the viewpoint of easy control to the desired morphology described later and excellent in epoxy adhesion and particle detachment resistance. .

  Here, in the liquid crystal polyester resin composition of the present invention, when the olefin elastomer (C) contains a functional group such as an epoxy group which reacts with the terminal groups of the liquid crystal polyester resin (A) and the polyphenylene sulfide resin (B) And the reaction product in which the functional group of the olefin elastomer (C) and the terminal group of the liquid crystal polyester resin (A) and the polyphenylene sulfide resin (B) have reacted, but the reaction product is formed by a complex reaction between polymers There are circumstances where it is not practical to specify the structure because it has been done. Therefore, the present invention specifies the invention by the components to be blended.

Morphology of Liquid Crystalline Polyester Resin Composition
The liquid crystal polyester resin composition of the present invention is one in which the epoxy adhesion and the particle releasability are greatly improved. In order to develop such characteristics, an olefin type in the morphology observed with an electron microscope of the central surface of a 12.7 mm wide × 127 mm long × 3.2 mm thick molded article comprising the liquid crystalline polyester resin composition of the present invention The ratio (C ₁ / C ₂ ) of the area ratio C ₁ of the elastomer (C) component to the area ratio C ₂ of the olefin elastomer (C) component at the center of the cross section of the molded article in the thickness direction is 0.07 or more It is necessary to be there.
(Here, C ₁ is {area of component (C) on molded article surface) / {liquid crystal polyester resin (A) component on molded article surface, polyphenylene sulfide resin (B) component and olefin elastomer (C) component Total area}, and C ₂ is {area of olefin-based elastomer (C) component at center of cross-section in thickness direction of molded article} / {liquid crystal polyester resin (A) component at center of cross-section in thickness direction of molded article And the total area of the polyphenylene sulfide resin (B) component and the olefin elastomer (C) component).

The larger the value of C ₁ / C _2, the larger the proportion of component (C) present on the surface of the molded article than in the center of the molded article. When C ₁ / C ₂ is less than 0.07, the proportion of the component (C) present on the surface of the molded article is small, and the epoxy adhesion and the particle releasability are significantly reduced. From the viewpoint of increasing the proportion of the component (C) present on the surface of the molded article and being excellent in epoxy adhesion and particle releasability, C ₁ / C ₂ is preferably 0.10 or more, more preferably 0.15 or more. . The upper limit of C ₁ / C ₂ is not particularly limited, and the value of C ₂ may be zero. When the value of C ₂ is zero, the component (C) is present on the surface of the molded product but is not present at the center of the molded product, and thus it is particularly excellent in epoxy adhesion and particle release resistance. Show.

Here, the area ratio C ₁ or C ₂ of the olefin elastomer (C) component can be estimated by the following method. First, with respect to a 12.7 mm wide × 127 mm long × 3.2 mm thick molded article made of the liquid crystal polyester resin composition of the present invention, the center of the cross section obtained by cutting the central part of the molded article and the surface of the center The phase structure is photographed with a magnification of about 2000 to 20000 times with a scanning electron microscope. It is preferable to image | photograph by 2000-10000 times from a viewpoint of the ease of discrimination | determination of phase structure. Let the total weight S of the arbitrary 30 sheets of the said photography photograph be the total area S of a liquid-crystal polyester resin (A) component, a polyphenylene sulfide resin (B) component, and an olefin-type elastomer (C) component. Then, from the 30 sheets of photographs taken, the weight weighed by cutting out the area parts of the olefinic elastomer of component (C), after the area S _C of the olefinic elastomer of component (C), to calculate the S C _/ S.

  The liquid crystal polyester resin (A), the polyphenylene sulfide resin (B), and the olefin elastomer (C) can be identified by, after imaging the phase structure, carbon atoms and oxygen by energy dispersive X-ray analysis (EDX). It can be judged by contrasting with atoms and sulfur atoms.

  Here, in the case of a molded article of 12.7 mm wide × 127 mm long × 3.2 mm thick, the central part of the cross section in the thickness direction of the molded article is near the center of 127 mm long, specifically from the flow end to the length 63. The cross-section obtained by cutting the range of 5 mm ± 5 mm at a right angle to the flow direction of the resin refers to a depth near 1.6 mm, and specifically, as shown in FIG. Point to. In the width direction, it is not necessary to be in the vicinity of the surface of the molded product, and specifically, as shown in FIG.

  In addition, the surface of the central part of the molded article refers to the vicinity of the center of 127 mm in length, and specifically, as shown in FIG. 1, a range of 63.5 mm ± 5 mm in length from the fluid end may be photographed.

  Examples of the method for setting the morphology to the above preferred state include the following methods.

  (1) The weight ratio (B / C) of the olefin-based elastomer (C) to the polyphenylene sulfide resin (B) is in the above-mentioned preferable range.

  (2) Melt viscosity η (A) at melting point + 20 ° C. of liquid crystalline polyester resin (A) at a shear rate of 1000 / sec, melt viscosity η (B) at 310 ° C. of the polyphenylene sulfide resin (B) at a shear rate of 1000 / sec The ratio (η (A) / η (B)) of the above is the above-mentioned preferred range.

  (3) By setting the melting point of the liquid crystal polyester resin to the above-mentioned preferable range, the temperature at the time of production of the liquid crystal polyester resin composition and at the time of melt processing is set as a preferable range described later.

<Filler>
The liquid crystal polyester resin composition of the present invention is a filler for a total of 100 parts by weight of the liquid crystal polyester resin (A), the polyphenylene sulfide resin (B) and the olefin elastomer (C) from the viewpoint of improving the epoxy adhesion. 10 parts by weight or more is preferable, 15 parts by weight or more is more preferable, and 20 parts by weight or more is more preferable. In addition, from the viewpoint of improving fluidity and flexibility, the content of the filler is preferably 200 parts by weight or less, more preferably 150 parts by weight or less, and still more preferably 100 parts by weight or less.

  Although the filler (C) used by this invention is not specifically limited, For example, fillers, such as fibrous form, whisker form, plate shape, powder form, a granular form, can be mentioned. Specifically, as a fibrous or whisker-like filler, glass fiber, PAN-based or pitch-based carbon fiber, stainless fiber, metal fiber such as aluminum fiber or brass fiber, aromatic polyamide fiber, liquid crystalline polyester fiber, etc. Organic fiber, gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride Examples thereof include whiskers and needle-like titanium oxide. Plate-like fillers include mica, talc, kaolin, glass flakes, clay, molybdenum disulfide, and warastenite. The powdery and granular fillers include silica, glass beads, titanium oxide, zinc oxide, calcium polyphosphate and graphite. The above-mentioned filler used in the present invention may have its surface treated with a known coupling agent (for example, a silane coupling agent, a titanate coupling agent, etc.) or other surface treatment agent. Moreover, the above-mentioned filler used for this invention may use 2 or more types together.

  Among these fillers, in particular, glass fibers are preferably used in view of mechanical strength such as tensile strength and bending strength, and heat resistance. The type of glass fiber is not particularly limited as long as it is generally used for resin reinforcement, and can be selected and used from, for example, chopped strands and milled fibers of long fiber type and short fiber type.

  The glass fiber used in the present invention is preferably weakly alkaline in view of mechanical strength. In particular, glass fibers having a silicon oxide content of 50 to 80% by weight are preferably used, and more preferably glass fibers having a silicon oxide content of 65 to 77% by weight. Glass fibers are epoxy, urethane, acrylic, etc. coatings or focusing agents; coupling agents such as silane, titanate etc .; other surface treatment agents; thermoplastic resins such as α-olefins polymers; epoxy resins Or the like may be coated or focused with a thermosetting resin.

  The liquid crystal polyester resin composition of the present invention further contains an antioxidant, a heat stabilizer (for example, hindered phenol, hydroquinone, phosphite, thioethers and substituted products thereof) as long as the effects of the present invention are not impaired. UV absorbers (eg resorcinol, salicylates), color inhibitors such as phosphites, hypophosphites, lubricants and mold release agents (Montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, Stearamide and polyethylene wax, etc.) Coloring agent containing dye or pigment, carbon black as a conductive agent or coloring agent, crystal nucleating agent, plasticizer, flame retardant (brominated flame retardant, phosphorus flame retardant, red phosphorus, silicone flame retardant Blending usual additives selected from flame retardants, etc.), flame retardant aids, and antistatic agents It can be. The deterioration of the olefin elastomer (C) during melt processing is suppressed, and it is easy to obtain the above-described desired morphology, and from the viewpoint of obtaining a molded article excellent in epoxy adhesion and particle detachment resistance, Stabilizers are preferably used, among which hindered phenols and thioethers are preferably used. Alternatively, a polymer other than the liquid crystal polyester resin can be blended to further impart predetermined properties.

<Production Method of Liquid Crystalline Polyester Resin Composition>
In the present invention, the method for blending the polyphenylene sulfide resin (B), the olefin elastomer (C), the filler, the other additives, etc. with the liquid crystal polyester resin (A) is not particularly limited. For example, a dry blend method in which a solid filler, polyphenylene sulfide resin (B), olefin elastomer (C), and other additives are blended with a liquid crystal polyester resin (A), a liquid crystal polyester resin (A), Solution blending method in which polyphenylene sulfide resin (B), olefin elastomer (C), other liquid additives etc. are blended in filler, filler, polyphenylene sulfide resin (B), olefin elastomer (C), and Method of adding other additive at the time of polymerization of liquid crystalline polyester resin (A), liquid crystalline polyester resin (A) and filler, polyphenylene sulfide resin (B), olefin elastomer (C), and other additives are melted The method of knead | mixing etc. can be used and melt-kneading is preferable especially. A well-known method can be used for melt-kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single screw or twin screw extruder, etc., it can be melt-kneaded at a melting point or more of the liquid crystal polyester resin (A) at a melting point + 50 ° C. or less to make a liquid crystal polyester resin composition. Among them, a twin-screw extruder is preferred. When melt-kneading, deterioration of the olefin-based elastomer (C) is suppressed, and it is easy to obtain the above-described desired morphology. From the viewpoint of obtaining a molded article excellent in epoxy adhesiveness and particle detachment resistance, Melt-kneading at 360 ° C. or less is preferred.

  With regard to the twin-screw extruder, the kneading portion is made from the viewpoint of making the dispersibility of the liquid crystal polyester resin (A) and the filler, the polyphenylene sulfide resin (B) and the olefin elastomer (C) into the desired morphology described above. It is preferable to provide one or more places, and it is more preferable to provide two or more places. For example, when the filler is added from the side feeder, the installation location of the kneading section promotes the plasticization of the liquid crystal polyester resin and enhances the reactivity with the copolymer, so the upstream side of the filler side feeder In order to improve the dispersibility of the liquid crystal polyester resin and the filler at one or more locations, it is preferable to install one or more locations in total at two or more locations downstream of the side feeder.

  1) A method in which liquid crystal polyester resin (A), polyphenylene sulfide resin (B), olefin-based elastomer (C), and fillers and other additives are collectively fed from a backfill feeder and kneaded ((1) 2) Liquid crystalline polyester resin (A), polyphenylene sulfide resin (B), olefinic elastomer (C), and other additives are added from a backfill feeder and kneaded, and then fillers and other additives are added. Method of adding an additive from a side feeder and kneading (side feed method), 3) A master containing a liquid crystal polyester resin (A), a polyphenylene sulfide resin (B), an olefin elastomer (C) and other additives at high concentration Make a pellet, and then make the liquid crystal gel of the master pellet to a specified concentration. An ester resin (A) and a filler and a method of kneading (master pellet method), may be used any method.

  The liquid crystal polyester resin composition of the present invention has excellent surface appearance (color tone) and machine by performing known melt molding such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning and the like. Into heat-resistant and flame-retardant molded articles. The molded articles referred to here include injection molded articles, extruded articles, press molded articles, sheets, pipes, unstretched films, uniaxially stretched films, various films such as biaxially stretched films, unstretched yarns, super-stretched yarns, etc. Various fibers can be mentioned. In particular, injection molding is preferable from the viewpoint of processability. In the case of melt molding, deterioration of the olefin elastomer (C) is suppressed, and it is easy to obtain the above-described desired morphology. From the viewpoint of obtaining a molded article excellent in epoxy adhesion and particle detachment resistance, It is preferable to melt-mold at 360 ° C. or less.

  Molded articles obtained by molding the liquid crystal polyester resin composition of the present invention are, for example, various gears, various cases, sensors, LED lamps, connectors, sockets, resistors, relays, switches, coil bobbins, camera modules, capacitors, varicons. Case, optical pickup, oscillator, various terminal boards, transformer, plug, printed wiring board, tuner, speaker, microphone, headphone, small motor, magnetic head base, power module, housing, semiconductor, liquid crystal display part, FDD carriage, Electrical and electronic parts represented by FDD chassis, HDD parts, motor brush holders, parabola antennas, computer parts etc .; VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, Sound components such as audio equipment parts such as audio / laser disc (registered trademark) / compact disc, lighting parts, refrigerator parts, air conditioner parts, etc. Home, office electronic parts, office computer related parts, telephone related parts, facsimile Representative parts such as related parts, copier related parts, cleaning jigs, oilless bearings, stern bearings, various bearings such as underwater bearings, motor parts, mechanical parts represented by lighters, microscopes, binoculars, cameras, watches etc. Optical equipment, precision machine related parts; Alternator terminal, Alternator connector, IC regulator, Potentiometer base for light dimmer, various valves such as exhaust gas valve, various pipes related to fuel, exhaust system, intake system, air intake nozzle snorkel, intake manifold Rold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat for air conditioner Bases, motor insulators for air conditioners, motor insulators for vehicles such as power windows, heating warm air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, duplexers, starter switches, transmissions Wire Harnesses, Window Osher Nozzles, Air Conditioner Panel Switch Substrates, Fuels Coils for engaging solenoid valves, connectors for fuses, horn terminals, insulators for electrical parts, step motor rotors, lamp bezels, lamp sockets, lamp reflectors, lamp housings, lamp housings, brake pistons, solenoid bobbins, engine oil filters, igniter cases, etc.・ Vehicle related parts; Bottles for various medicines such as shampoos, rinses, liquid soaps, detergents; tanks for chemical solution storage, tanks for gas storage, tanks for cooling fluid, tanks for oil transfer, tanks for disinfectant, tanks for transfusion pumps, Fuel and gas storage tanks such as fuel tanks, canisters, washer fluid tanks and oil reservoir tanks; medical device application parts; soy sauce, sauces, ketchup, mayonnaise, seasonings such as dressings, fermented foods such as miso and vinegar, salad oil etc Fat food, sake, sake Food storage containers such as soft drinks such as Le, Mirin, whiskey, shochu and wine, carbonated drinks, juices, sports drinks, milk, coffee drinks, oolong tea, tea, soft drinks such as mineral water; and general household appliances parts It can be used for a tank, a bottle-shaped molded article, or a hollow container such as those tanks. Since it is excellent in epoxy adhesiveness and particle detachment resistance, it is useful to the molded article which has a junction part. The method of joining the joint is insert molding in the case of joining with metal; semiconductor laser welding, ultrasonic welding, heat welding, vibration welding, high frequency welding, spin welding, induction in the case of joining with metal or resin composition Welding represented by welding and the like; hot jet welding in the case of bonding with a resin composition; adhesion with an epoxy resin or a silicone resin, and the like, and in particular, excellent adhesion with an epoxy resin; It is useful for electrical / electronic parts such as relays and switches, coil bobbins, camera modules, sensors, connectors and the like represented by relay cases and relay bases having junctions. The molded article which used 2 or more types of said joining methods together may be sufficient.

  Hereinafter, the present invention will be described in more detail by way of examples, but the gist of the present invention is not limited to the following examples.

  The liquid crystal polyester resin used for each Example and a comparative example is shown next.

  The compositional analysis and the characteristic evaluation of the liquid crystalline polyester resin were performed by the following method.

(1) Composition Analysis of composition analysis LCP liquid crystal polyester resin ^(A), the was performed by 1 H- nuclear magnetic resonance spectrum ⁽¹ H-NMR) measurement. 50 mg of liquid crystalline polyester resin is weighed into an NMR sample tube, and dissolved in 800 μL of a solvent (pentafluorophenol / 1,1,2,2-tetrachloroethane-d ₂ = 65/35 (weight ratio) mixed solvent) to obtain UNITY INOVA 500 ¹ H-NMR measurement is performed at an observation frequency of 500 MHz and a temperature of 80 ° C. using a scanning NMR apparatus (manufactured by Varian), and the composition is determined from the peak area ratio derived from each structural unit observed around 7 to 9.5 ppm analyzed.

(2) Measurement of Melting Point (Tm) of Liquid Crystalline Polyester Resin (A) Observation by Differential Scanning Calorimeter DSC-7 (manufactured by PerkinElmer) when the temperature of the liquid crystalline polyester resin is raised from room temperature under temperature rising conditions of 20 ° C./min. After observation of the endothermic peak temperature (Tm ₁ ), after holding for 5 minutes at a temperature of Tm ₁ + 20 ° C, the temperature is once cooled to room temperature under a temperature decrease condition of 20 ° C / minute, and again under a temperature increase condition of 20 ° C / minute The endothermic peak temperature (Tm ₂ ) observed when the temperature was raised was taken as the melting point. In the following production examples, the melting point (Tm ₂ ) is described as Tm.

(3) Melt Viscosity Measurement of Liquid Crystalline Polyester Resin (A) Using a heightening type flow tester CFT-500D (orifice 0.5φ × 10 mm) (manufactured by Shimadzu Corporation), increase the melting point of the liquid crystalline polyester resin to 20 ° C. The melt viscosity was measured at a shear rate of 1000 / sec after holding for 5 minutes after loading the liquid crystalline polyester resin to melt the liquid crystalline polyester resin in a flow tester furnace.

(4) Melt viscosity measurement of polyphenylene sulfide resin (B) Using a heightening type flow tester CFT-500D (orifice 0.5φ × 10 mm) (manufactured by Shimadzu Corporation), inside a heightening type flow tester furnace set at 310 ° C. The melt viscosity was measured at a shear rate of 1000 / sec after holding for 5 minutes after loading the polyphenylene sulfide resin to melt the polyphenylene sulfide resin.

Production Example 1 Liquid Crystalline Polyester Resin (A-1)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 932 parts by weight of p-hydroxybenzoic acid, 251 parts by weight of 4,4'-dihydroxybiphenyl, 99 parts by weight of hydroquinone, 284 parts by weight of terephthalic acid, 90 parts by weight of isophthalic acid And 1252 parts by weight of acetic anhydride (1.09 equivalent of the total of phenolic hydroxyl groups) and reacted for 1 hour at 145 ° C while stirring under nitrogen gas atmosphere, then jacket temperature is changed from 145 ° C to 350 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 350 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-1) was obtained.

  Compositional analysis of the liquid crystal polyester resin (A-1) revealed that the proportion of structural units derived from p-hydroxybenzoic acid is 60.0 mol%, and the proportion of structural units derived from 4,4'-dihydroxybiphenyl is 12 .0 mol%, the proportion of structural units derived from hydroquinone is 8.0 mol%, the proportion of structural units derived from terephthalic acid is 15.2 mol%, the proportion of structural units derived from isophthalic acid is 4.8 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 75.2 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 330 degreeC and melt viscosity was 28 Pa.s.

Production Example 2 Liquid Crystalline Polyester Resin (A-2)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 870 parts by weight of p-hydroxybenzoic acid, 302 parts by weight of 4,4'-dihydroxybiphenyl, 119 parts by weight of hydroquinone, 247 parts by weight of terephthalic acid, 202 parts by weight of isophthalic acid And 1302 parts by weight of acetic anhydride (1.09 equivalent of the total of phenolic hydroxyl groups) and reacted for 1 hour at 145 ° C with stirring under a nitrogen gas atmosphere, then the jacket temperature is changed from 145 ° C to 330 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 330 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was further continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-2) was obtained.

  Compositional analysis of the liquid crystal polyester resin (A-2) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 53.8 mol% and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 13 .8 mol%, the proportion of structural units derived from hydroquinone is 9.2 mol%, the proportion of structural units derived from terephthalic acid is 12.7 mol%, and the proportion of structural units derived from isophthalic acid is 10.4 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 66.5 mol% relative to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 310 degreeC and melt viscosity was 30 Pa.s.

Production Example 3 Liquid Crystalline Polyester Resin (A-3)
1057 parts by weight of p-hydroxybenzoic acid, 151 parts by weight of 4,4'-dihydroxybiphenyl, 59 parts by weight of hydroquinone, 202 parts by weight of terephthalic acid, 22 parts by weight of isophthalic acid in a 5 L reaction vessel equipped with a stirring blade and a distillation tube And 1152 parts by weight of acetic anhydride (1.09 equivalent of the total of phenolic hydroxyl groups) and reacted for 1 hour at 145 ° C with stirring under a nitrogen gas atmosphere, then the jacket temperature is changed from 145 ° C to 365 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 365 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-3) was obtained.

  Compositional analysis of this liquid crystal polyester resin (A-3) revealed that 73.9 mol% of the structural unit derived from p-hydroxybenzoic acid and 7 ratio of the structural unit derived from 4,4'-dihydroxybiphenyl were obtained. .8 mol%, the proportion of structural units derived from hydroquinone is 5.2 mol%, the proportion of structural units derived from terephthalic acid is 11.7 mol%, and the proportion of structural units derived from isophthalic acid is 1.3 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 85.7 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 351 degreeC and melt viscosity was 31 Pa.s.

Production Example 4 Liquid Crystalline Polyester Resin (A-4)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 994 parts by weight of p-hydroxybenzoic acid, 126 parts by weight of 4,4'-dihydroxybiphenyl, 112 parts by weight of terephthalic acid, and an intrinsic viscosity of about 0.6 dl / g 216 parts by weight of polyethylene terephthalate and 960 parts by weight of acetic anhydride (1.10 equivalents of the total of phenolic hydroxyl groups) are charged, reacted at 145 ° C. for 1 hour while stirring under a nitrogen gas atmosphere, and then 4 from 145 ° C. to 320 ° C. The temperature was raised over time. Thereafter, the polymerization temperature was maintained at 320 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 20 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-4) was obtained.

  Compositional analysis of this liquid crystal polyester resin (A-4) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 66.7 mol% and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 6 .3 mol%, the proportion of ethylenedioxy units derived from polyethylene terephthalate was 10.4 mol%, and the proportion of structural units derived from terephthalic acid was 16.7 mol%. The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 83.3 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 313 degreeC and melt viscosity was 13 Pa.s.

Production Example 5 Liquid Crystalline Polyester Resin (A-5)
In a 5 L reaction vessel equipped with a stirring blade and a distillation tube, 932 parts by weight of p-hydroxybenzoic acid, 283 parts by weight of 4,4'-dihydroxybiphenyl, 99 parts by weight of hydroquinone, 284 parts by weight of terephthalic acid, 90 parts by weight of isophthalic acid And 1242 parts by weight of acetic anhydride (1.05 equivalents of the total of phenolic hydroxyl groups) and reacted at 145 ° C for 1 hour while stirring under a nitrogen gas atmosphere, then the jacket temperature is changed from 145 ° C to 350 ° C for 4 hours The temperature was raised. Thereafter, the polymerization temperature was maintained at 350 ° C., the pressure was reduced to 1.0 mmHg (133 Pa) in 1.0 hour, the reaction was continued, and the polymerization was completed when the torque required for stirring reached 8 kg · cm. Next, the inside of the reaction vessel is pressurized to 1.0 kg / cm ² (0.1 MPa), and the polymer is discharged into strands by means of a nozzle having one circular discharge port with a diameter of 10 mm, and pelletized by a cutter. A liquid crystal polyester resin (A-5) was obtained.

  Compositional analysis of this liquid crystal polyester resin (A-5) revealed that the proportion of structural units derived from p-hydroxybenzoic acid was 59.1 mol%, and the proportion of structural units derived from 4,4'-dihydroxybiphenyl was 13 .3 mol%, the proportion of structural units derived from hydroquinone is 7.9 mol%, the proportion of structural units derived from terephthalic acid is 15.0 mol%, and the proportion of structural units derived from isophthalic acid is 4.7 mol% The The total of the structural unit derived from hydroxybenzoic acid and the structural unit derived from terephthalic acid was 74.1 mol% relative to 100 mol% of the total structural units of the liquid crystal polyester resin. Moreover, Tm was 328 degreeC and melt viscosity was 8.8 Pa.s.

Preparation Example 6 Polyphenylene Sulfide Resin (B-1)
In a 70-liter autoclave equipped with a stirrer, 8267. 37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2962.50 g (71.10 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP) ) Charge 11434.50 g (115.50 mol), 516.60 g (6.30 mol) of sodium acetate, and 10500 g of ion-exchanged water, and gradually heat to 230 ° C. through nitrogen at normal pressure for about 3 hours, After distilling 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of residual water in the system per mole of the alkali metal sulfide charged was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of scattered hydrogen sulfide was 0.017 mol per mol of the alkali metal sulfide charged.

  Next, 10363.50 g (70.50 mol) of p-dichlorobenzene and 9078.30 g (91.70 mol) of NMP are added, the reaction vessel is sealed under nitrogen gas, and stirred at 240 rpm, 0.6 ° C./min. The temperature was raised to 270.degree. C. at a rate of and maintained at 270.degree. C. for 140 minutes. Thereafter, 2520 g (140 mol) of ion exchanged water was injected into the autoclave while cooling to 250 ° C. at a rate of 1.3 ° C./min. Thereafter, it was cooled to 200 ° C. at a rate of 1.0 ° C./min and then rapidly cooled to around room temperature.

  The contents were removed and after dilution with 26300 g of NMP, the solvent and solids were filtered off through a sieve (80 mesh) and the particles obtained were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion exchanged water, filtered off, and then washed with 70,000 g of a 0.05 wt% aqueous acetic acid solution, and filtered off. After washing with 70,000 g of ion exchanged water and filtering off, the obtained water-containing PPS particles were dried at 80 ° C. with hot air and dried at 120 ° C. under reduced pressure. Melt viscosity of the obtained polyphenylene sulfide resin (B-1) was 50 Pa · s.

Preparation Example 7 Polyphenylene Sulfide Resin (B-2)
In a 70 liter autoclave with stirrer and bottom valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 11.45 kg (115.50 mol) of pyrrolidone (NMP) and 10.5 kg of ion-exchanged water are charged and gradually heated to 245 ° C. through nitrogen at normal pressure over about 3 hours, 14.78 kg of water and After distilling .28 kg, the reaction vessel was cooled to 200.degree. The amount of residual water in the system per mole of the alkali metal sulfide charged was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of scattered hydrogen sulfide was 0.02 mol per mol of alkali metal sulfide charged.

  After cooling to 200 ° C., 10.48 kg (71.27 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas, and 0.1. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After 100 minutes of reaction at 270 ° C, the bottom valve of the autoclave was opened and the contents were flushed in a container with a stirrer over 15 minutes while pressurizing with nitrogen, and stirred for a while at 250 ° C to remove most of the NMP .

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and suction-filtered with a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter and suction filtered to obtain a cake. The resulting cake and 90 liters of ion-exchanged water were charged into a stirrer-equipped autoclave, and acetic acid was added to a pH of 7. After purging the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. After that, the autoclave was cooled and the contents were taken out.

  The contents were suction filtered with a glass filter, 76 liters of ion-exchanged water at 70 ° C. was poured into this, and suction filtered to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS. Melt viscosity of the obtained polyphenylene sulfide resin (B-2) was 5 Pa · s.

The olefin-based elastomer (C) and the filler (D) used in each Example and Comparative Example are shown below.
(C-1): Sumitomo Chemical Co., Ltd. “bond first” 2C (ethylene-glycidyl methacrylate copolymer, ethylene content 94 wt%, glycidyl methacrylate content 6 wt%)
(D-1): Nippon Electric Glass Co., Ltd. product milled fiber "EPG40M-10A"

Examples 1 to 9 and Comparative Examples 1 to 5
Liquid Crystal Polyester Resins (A-1) to (A-5) and Polyphenylene Sulfide Resins (B-1) to (B-) 2) The olefin-based elastomer (C-1) is introduced from the backfill feeder in the amount shown in Table 1, the filler (D-1) is introduced from the side feeder in the amount shown in Table 1, and the cylinder temperature is It set to melting | fusing point +10 degreeC of liquid crystalline polyester resin (A-1)-(A-5), and it melt-kneaded and was set as the pellet. After drying the pellet of the obtained liquid-crystalline-polyester resin composition at 150 degreeC using the hot-air dryer for 3 hours, evaluation of the following (5)-(8) was performed. The results are shown in Table 1.

(5) Calculation of the area ratio C ₁ of the olefin-based elastomer (C) component on the surface of the molded product FANUC ROBOSHOT α-30C (manufactured by FANUC LTD.) Injection molding machine, resin temperature is melting point + 20 ° C. of liquid crystal polyester resin, Injection molding was carried out with a mold temperature of 90 ° C., an injection speed of 120 mm / sec, and an injection pressure of 80 MPa, and test pieces of 12.7 mm width × 127 mm length × 3.2 mm thickness were produced. About the surface in the central part of the prepared test piece, after depositing with Pt / Pd, it is photographed at 5000 magnification using Hitachi scanning electron microscope H-3000, and any 30 pieces of the above-mentioned photograph are taken The total weight of the liquid crystal polyester resin (A) component, the polyphenylene sulfide resin (B) component and the olefin elastomer (C) component was defined as the total area S of Then, from the 30 sheets of photographs taken, the weight weighed by cutting the olefinic elastomer of component (C) surface areas, and the area S _C of the olefinic elastomer component (C), a material obtained by calculating the S C _{/ S} C _{It is one} .

  The liquid crystal polyester resin (A), the polyphenylene sulfide resin (B), and the olefin elastomer (C) can be identified by, after photographing the phase structure, carbon atoms, oxygen atoms, and energy dispersive X-ray analysis (EDX). It was judged by contrasting with sulfur atoms.

(6) Calculation of the area ratio C ₂ of the olefin elastomer (C) component at the center of the cross section in the thickness direction of the molded article and calculation of the ratio of C ₁ to C ₂ (C ₁ / C ₂ ) (5) The central part of the test specimen is cut at right angles to the flow direction of the resin, and S _C / S is calculated in the same manner as (5) for the range of depth 1.6 mm ± 100 μm from the outer surface of the molded article It was those as _{C 2,} a a _{C 1} calculated by dividing the _{C 2} value was defined as _C 1 / _{C 2} in (5).

(7) Epoxy adhesion (epoxy adhesion strength)
The resin temperature is set as the melting point of liquid crystal polyester resin + 20 ° C, mold temperature: 90 ° C, injection speed: 120 mm / sec, injection pressure: 80MPa with FANUC ROBOSHOT α-30C (FANUC Co., Ltd.) injection molding machine The resultant was injection molded to obtain a 3.2 mm thick ASTM No. 1 dumbbell test piece. The prepared test piece is cut into two equal parts, and an epoxy resin ("ECR-9250K" manufactured by Sumitomo Bakelite) is applied to a bonding area of 0.5 cm ² and a thickness of ² mm as shown in FIG. It was cured by curing at 120 ° C. for 30 minutes. Then, using a tensile tester (AG500C, manufactured by Shimadzu Corp.), the distance between spans was 100 mm, and the crosshead speed was 1 mm / min, and the load when the adhesive surface was peeled was measured in number n of tests 5. Moreover, about the thing which the adhesive surface did not peel and the base material destroyed, the value at that time was measured. The epoxy bond strength is shown as a value (MPa) obtained by dividing the load by the bond area. The higher the epoxy adhesion strength, the better the epoxy adhesion.

(8) Resistance to particle detachment Ten test pieces of 12.7 mm wide × 127 mm long × 3.2 mm thick prepared by the same method as (5) are housed in a SUS container and closed, and the container is It was opened after dropping 50 times from a height of 1.5 m. Next, the test piece and the particles dropped from the test piece were separated, and the number of particles was measured using "FPIA-3000" manufactured by Sysmex. The smaller the number of particles, the more excellent the particle releasability.

  From the results in Table 1, it can be seen that the liquid crystal polyester resin composition of the present invention is excellent in epoxy adhesion and particle detachment resistance. Therefore, it can be said that it is suitable for use in electrical and electronic component applications such as relays, switches, coil bobbins, camera modules, sensors, and connectors.

  The liquid crystal polyester resin composition of the present invention is particularly suitable for electrical / electronic parts and mechanical parts such as relays, switches, coil bobbins, camera modules, sensors, connectors and the like because it is excellent in epoxy adhesion and particle releasability. is there.

H Tensile test piece E cut into two equal parts Epoxy resin

Claims (8)

50% to 98% by weight of liquid crystal polyester resin (A), 1 to 45% by weight of polyphenylene sulfide resin (B) and olefin based elastomer (C), assuming that the total of (A), (B) and (C) is 100% by weight A liquid crystal polyester resin composition comprising 0.5 to 30% by weight and having a weight ratio (B / C) of polyphenylene sulfide resin (B) to olefin elastomer (C) of 0.30 to 6.9. The area ratio C _{1 of the} component (C) in the morphology observed by the electron microscope on the surface of the central part of the 12.7 mm wide × 127 mm long × 3.2 mm thick molded article, and the center of the cross section in the thickness direction of the molded article component (C) the ratio of the area ratio _{C 2} of the part _(C 1 / _{C 2)} is 0.07 or more, the liquid crystal polyester resin composition.
(Here, C ₁ is {area of component (C) on the surface of the molded article) / {total area of components (A), (B) and (C) on the surface of the molded article}, and C ₂ is , {Area of component (C) at center of molded product thickness direction cross section / {total area of components (A), (B) component and (C) component at center of molded product thickness direction cross section} is there.) Melting viscosity η (A) at a melting point of + 20 ° C. of the liquid crystalline polyester resin (A) and a shear rate of 1000 / sec,
The polyphenylene sulfide resin (B) according to claim 1, wherein a ratio (η (A) / η (B)) of melt viscosity η (B) at a shear rate of 1000 / sec at 310 ° C is 0.25-10. Liquid crystal polyester resin composition. The total of structural units derived from p-hydroxybenzoic acid and structural units derived from terephthalic acid is 60 to 77 mol% with respect to 100 mol% of the total structural units of the liquid crystal polyester resin (A). The liquid-crystal polyester resin composition as described. The liquid crystal polyester resin composition in any one of Claims 1-3 whose structural unit derived from a hydroquinone is 2-20 mol% with respect to 100 mol% of all the structural units of the said liquid-crystal polyester resin (A). The filler (D) is contained in an amount of 10 to 200 parts by weight with respect to a total of 100 parts by weight of the liquid crystal polyester resin (A), the polyphenylene sulfide resin (B) and the olefin elastomer (C). The liquid-crystal polyester resin composition in any one. A molded article comprising the liquid crystal polyester resin composition according to any one of claims 1 to 5. The molded article according to claim 6, which is a molded article having a joint. The molded article according to claim 6 or 7, wherein the molded article is any one selected from the group consisting of a relay, a switch, a coil bobbin, a camera module, a sensor, and a connector.