JP5332081B2 - Resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to a resin composition excellent in low warpage and pin press-fit strength and having high reflection characteristics in a visible light region (400 to 700 nm wavelength).

  There have been many attempts to develop applications in fields where resinization has been difficult so far, and the required performance for resins tends to become more diversified and stricter.

  In recent years, with the progress of lightweight and high performance for electrical and electronic applications, connectors for use in mobile personal computers, cellular phones, PDAs, etc. are required to be thinner and more dimensional accuracy for miniaturization and weight reduction. It has become. Also in lighting fixtures, low power consumption and long-life semiconductor elements are used for backlights for LCD screens of personal computers, televisions, etc., lighting or automotive lights, instrument panels, accessory lighting fixtures, etc. The use is increasing, and the reflector made from a thermoplastic resin is used for the reflector used for this semiconductor element package from a viewpoint of easy workability and weight reduction. However, since the reflecting plate is required to have a high reflectance, the surface of the reflecting plate is usually subjected to plating. However, the process is complicated, so that the plating step is not necessary and the reflecting plate is not reflective. Development of a resin reflector having a high rate is desired, and various improvement methods have been proposed so far.

  Examples of methods for improving the above-described problems include a method of adding acicular titanium oxide to thermoplastic polyester (see Patent Document 1), a specific acicular oxidation in which a composition of polyphenylene ether resin, polyamide resin and rubber-like substance is treated with siloxane. A method of adding titanium (see Patent Document 2) and a method of adding a potassium titanate-containing compound to a thermoplastic resin (see Patent Document 3) have been proposed.

However, the materials proposed in Patent Document 1, Patent Document 2 and Patent Document 3 cannot be said to have sufficient warpage of the molded product and sufficient pin press-in strength when assembling the molded product, and in the visible light region. When the filling amount of the filler used for improving the reflectance is increased, there is a problem that the warpage of the molded product increases and the reflectance is lowered, which is not satisfactory in practice.
Japanese Patent Laid-Open No. 1-103649 (first and second items, examples) Japanese Patent Laid-Open No. 5-179135 (first and second items, examples) Japanese Patent Laid-Open No. 2003-195020 (first and second items, examples)

  The present invention eliminates the above-described conventional problems, maintains the product design freedom and productivity that are the characteristics of thermoplastic resins, and is excellent in low warpage, pin press-fit strength, and in the visible light region (400 It is an object of the present invention to provide a resin composition having high reflection characteristics at a wavelength of ˜700 nm.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

That is, the present invention
(1) (A) Melting viscosity measured at a shear rate of 1,000 (1 / sec) under the condition of melting point (Tm) + 10 ° C. is 0.5 to 80 Pa · s, and produced from p-hydroxybenzoic acid. structural units, 4,4'-dihydroxybiphenyl a structural unit produced from liquid crystalline polyester and / or 300 consists Haidorokino down or we generated structural units, structural units and isophthalic acid produced from terephthalic acid or al a structural unit produced (B) average fiber length of 2 μm to 10 μm and average fiber length (l) averaged with respect to 100 parts by weight of polyarylene sulfide resin having a melt viscosity of 80 Pa · s or less measured at 1000 ° C. and a shear rate of 1000 / sec. A resin composition comprising 10 to 250 parts by weight of acicular titanium oxide having a value (l / d) divided by fiber diameter (d) of 12 or more and 50 or less ,
(2 ) Further, (C) the inorganic filler excluding acicular titanium oxide has a melt viscosity of 0.5 to 80 Pa measured at a shear rate of 1,000 (1 / second) under the conditions of (A) melting point (Tm) + 10 ° C. · a s, p-hydroxybenzoic acid structural unit produced from 4,4' a structural unit produced from dihydroxybiphenyl, Haidorokino down or we generated structural units, structural units and isophthalic acid or we generated from terephthalic acid 5 to 150 parts by weight is blended with 100 parts by weight of the liquid crystalline polyester composed of the generated structural unit and / or polyarylene sulfide resin having a melt viscosity of 80 Pa · s or less measured at 300 ° C. and a shear rate of 1000 / second. comprising (1) Symbol placement of the resin composition,
( 3 ) A molded product formed by molding the resin composition according to (1) or (2) above,
(4) molded article is an electrical and electronic components (3), wherein the molded article, and (5) electric and electronic parts housing, a reflector or connector (4), wherein the molded article,
It is.

  Since the present invention is excellent in low warpage and pin press-in strength and excellent in high reflection characteristics in the visible light region (4000 to 700 nm wavelength), it is particularly necessary for electric / electronic components that require this characteristic. It can be used particularly practically for applications such as housings, reflectors and connectors.

  Hereinafter, the present invention will be described in detail. In the present invention, “weight” means “mass”.

The thermoplastic resin in the present invention, under the condition of (A) a melting point (Tm) + 10 ° C., melt viscosity measured at a shear rate of 1,000 (1 / second) Ri 0.5~80Pa · s der, p- Liquid crystalline polyester of structural units generated from hydroxybenzoic acid, structural units generated from aromatic dihydroxy compounds such as 4,4′-dihydroxybiphenyl and hydroquinone, and structural units generated from aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid A polyarylene sulfide resin having a melt viscosity of 80 Pa · s or less measured at 300 ° C. and a shear rate of 1000 / sec can be used. Specific examples thereof include a liquid crystal polymer (liquid crystalline polyester resins, liquid crystal polyester amide resin), one or a mixture of two or more can be mentioned selected from Po Leary sulfide resin.

Specific examples of the polyamide resin include ring-opening polymers of cyclic lactams, polycondensates of aminocarboxylic acids, such as polycondensates of a dicarboxylic acid and a diamine, and the like, specifically or nylon 4.6, , Aliphatic polyamides such as polynonanemethylene terephthalamide, nylon 6 / poly (hexamethylene terephthalamide), nylon 6/6 / poly (hexamethylene terephthalamide), nylon 6 / nylon 6/6 / poly (hexamethylene isophthalamide) ), poly (hexamethylene isophthalamide) / poly (hexamethylene terephthalamide), nylon 6 / poly (hexamethylene isophthalamide) / poly (hexamethylene terephthalamide), nylon 12 / poly (hexamethylene terephthalamide), Po Li (Methyl pentamethylenete And semi-aromatic nylons such as (rephthalamide) / poly (hexamethylene terephthalamide) .

  In particular, among the polyamides described above, the melting point (Tm) is preferably 280 ° C. or higher, more preferably 290 ° C. or higher, and particularly preferably 300 ° C. or higher, in order to obtain heat resistance that can withstand treatment steps such as reflow and actual use environments. .

  Here, the melting point (Tm) is 5 at a temperature of Tm1 + 20 ° C. after observing an endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature from 20 ° C./min in differential calorimetry. After maintaining for 20 minutes, the sample was once cooled to room temperature under a temperature-decreasing condition of 20 ° C./min, and the endothermic peak temperature (Tm 2) observed when measured again under a temperature-raising condition of 20 ° C./min.

The polyamide resin used in the present invention having a melting point of 280 ° C. or higher has a sulfuric acid solution relative viscosity (concentration of 1%) at 25 ° C. of 1.5 to 3 in order to obtain a balance between the pin press-fitting property and fluidity of the present invention. 0.5, more preferably 1.8 to 3.0, and still more preferably 2.0 to 2.7.

  A typical example of the liquid crystalline polymer is a resin that can form an anisotropic molten phase, and preferably has an ester bond. For example, a liquid crystalline polyester resin comprising a structural unit selected from an aromatic oxycarbonyl unit, an aromatic dioxy unit, an aromatic and / or aliphatic dicarbonyl unit, an alkylenedioxy unit, etc., and forming an anisotropic melt phase Or a liquid crystalline polyester amide resin comprising a structural unit selected from the structural unit and an aromatic iminocarbonyl unit, an aromatic diimino unit, an aromatic iminooxy unit, etc., and forming an anisotropic melt phase. Specifically, a liquid crystalline polyester comprising a structural unit produced from p-hydroxybenzoic acid and 6-hydroxy-2-naphthoic acid, a structural unit produced from p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid Structural units, aromatic dihydroxy compounds and / or aromatic dicals generated from A liquid crystalline polyester comprising a structural unit produced from an acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from 4,4′-dihydroxybiphenyl, an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid, and / or Or a liquid crystalline polyester comprising a structural unit produced from an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, or a structural unit produced from terephthalic acid A liquid crystalline polyester, a structural unit produced from p-hydroxybenzoic acid, a structural unit produced from ethylene glycol, a structural unit produced from 4,4′-dihydroxybiphenyl, a liquid crystalline polyester comprising a structural unit produced from terephthalic acid, p-hydroxybenzo Structural units produced from acids, structural units produced from ethylene glycol, liquid crystalline polyesters comprising structural units produced from terephthalic acid and isophthalic acid, structural units produced from p-hydroxybenzoic acid, structural units produced from hydroquinone, 4 , 4′-dihydroxybiphenyl structural unit, liquid crystalline polyester composed of terephthalic acid and isophthalic acid structural unit, p-hydroxybenzoic acid structural unit, ethylene glycol structural unit, aromatic dihydroxy Structural units generated from compounds, liquid crystalline polyesters composed of structural units generated from aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, and 2,6-naphthalenedicarboxylic acid, and liquid crystalline polyester amide resins include aromatic In addition to a structural unit selected from oxycarbonyl units, aromatic dioxy units, aromatic and / or aliphatic dicarbonyl units, alkylenedioxy units, etc., a different type containing a p-iminophenoxy unit generated from p-aminophenol. Polyesteramide that forms an isotropic melt phase.

Among the liquid crystalline polymer described above is preferably a liquid crystalline polyester resin, the mechanical properties, the point or these moldability, a structural unit derived from p- hydroxybenzoic acid, 4,4'-dihydroxybiphenyl, fragrance hydroquinone A liquid crystalline polyester having a structural unit generated from an aromatic dicarboxylic acid such as terephthalic acid and isophthalic acid is particularly preferably used.

  The liquid crystalline polymer used in the present invention preferably has a melt viscosity of 0.5 to 80 Pa · s, more preferably 1 to 50 Pa · s in order to suppress a decrease in fluidity when the filler is highly filled. Moreover, when trying to obtain a composition with more excellent fluidity, the melt viscosity is preferably 40 Pa · s or less.

  The melt viscosity is a value measured by a Koka flow tester under the condition of melting point (Tm) + 10 ° C. and shear rate of 1,000 (1 / second).

  Here, the melting point (Tm) is the Tm1 +20 after the observation of the endothermic peak temperature (Tm1) observed when the polymer having been polymerized is measured from room temperature under the temperature rising condition at 20 ° C./min in the differential calorimetry. This is the endothermic peak temperature (Tm2) that is observed when the temperature is kept at a temperature of 5 ° C. for 5 minutes, cooled to room temperature under a temperature drop condition of 20 ° C./minute, and then measured again under a temperature rise condition of 20 ° C./minute. .

  Typical examples of the polyarylene sulfide resin include polyphenylene sulfide (hereinafter sometimes abbreviated as PPS), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. Of these, polyphenylene sulfide is particularly preferably used. Such polyphenylene sulfide is a polymer containing a repeating unit represented by the following structural formula, preferably 70 mol% or more, more preferably 90 mol% or more. When the repeating unit is 70 mol% or more, the heat resistance is high. It is preferable at an excellent point.

  In addition, the polyphenylene sulfide resin can be composed of 30 mol% or less of the repeating unit with a repeating unit having the following structural formula, and may be a random copolymer or a block copolymer. Or a mixture thereof.

  Such polyarylene sulfide resins are generally known in the art, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the publication.

  In the present invention, the polyarylene sulfide resin obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, an organic solvent, hot water, Of course, it is possible to use it after various treatments such as washing with an acid aqueous solution, activation with a functional group-containing compound such as an acid anhydride, amine, isocyanate, or a functional group-containing disulfide compound.

  Specific methods for crosslinking / high molecular weight polyarylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Below, a method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. In this case, the heat treatment temperature is preferably 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, a target viscosity level can be obtained. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

As a specific method for heat-treating the polyarylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm ^-2 or less), Examples of the heat treatment method include a heat treatment temperature of 150 to 280 ° C, preferably 200 to 270 ° C, and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

  When the polyarylene sulfide resin is washed with an organic solvent, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing the polyarylene sulfide resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfoxide sulfone solvents such as dimethyl sulfoxide, dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether , Ether solvents such as tetrahydrofuran, halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, Alcohol / phenolic solvents such as cresol and polyethylene glycol, benzene and toluene Ene, and aromatic hydrocarbon solvents such as xylene may be used. Of these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are particularly preferably used. These organic solvents are used alone or in combination of two or more.

  As a specific method of washing with such an organic solvent, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and it is 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 polyarylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyarylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  The following method can be illustrated as a specific method when the polyarylene sulfide resin is treated with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a preferable chemical modification effect of the polyarylene sulfide resin by hot water washing. The operation of the hot water treatment is usually performed by adding a predetermined amount of polyarylene sulfide resin to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyarylene sulfide resin and water is preferably as much as possible, and is preferably used at a bath ratio of 200 g or less of polyarylene sulfide resin with respect to 1 liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating a polyarylene sulfide resin. That is, there is a method of immersing a polyarylene sulfide resin in an acid or an aqueous solution of an acid, and stirring or heating can be appropriately performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing the polyarylene sulfide resin, such as aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, chloroacetic acid and dichloroacetic acid. Halo-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, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, etc. Dicarboxylic acid and inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid are used. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The polyarylene sulfide resin subjected to the acid treatment is preferably washed several times with water in order to remove the remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the polyarylene sulfide resin by acid treatment is not impaired.

  The polyarylene sulfide resin used in the present invention has a melt viscosity of 80 Pa · s or less under conditions of 300 ° C. and a shear rate of 1000 / sec in order to improve fluidity and eliminate compositional unevenness in the obtained resin composition. It is preferably 50 Pa · s or less, and more preferably 30 Pa · s or less. Although there is no restriction | limiting in particular about the minimum of melt viscosity, It is preferable that it is 5 Pa.s or more. Two or more polyarylene sulfide resins having different melt viscosities may be used in combination.

  The melt viscosity of the polyarylene sulfide resin can be measured using a capilograph (manufactured by Toyo Seiki Co., Ltd.) apparatus under conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

  The (B) acicular titanium oxide in the present invention is different from the granular titanium oxide frequently used for conventional pigments, and is acicular, and the rutile type crystal structure is more stable. To preferred.

  (B) About the average fiber length of acicular titanium oxide, it balances with the high reflectance which is the effect of this invention, and intensity | strength fall suppression represented by the pin press-fit strength by the breakage of acicular titanium oxide at the time of composition manufacture For expression, 2 μm or more is essential, preferably 2.5 μm or more, and more preferably 5 μm. About an upper limit, it is 10 micrometers or less from a viewpoint of productivity and a reinforcement effect.

  Further, the value (l / d) obtained by dividing the average fiber length (l) by the average fiber diameter (d) is preferably 12 or more in order to express characteristics such as pin press-in strength and low warpage with high efficiency. The range of 12-50 is more preferable, and the range of 13-40 is more preferable.

  The average fiber length (l) and the average fiber diameter (d) are measured by obtaining a molded product from the obtained composition, partially cutting the molded product, placing it in a crucible, and applying electricity at 550 ° C. for 8 hours. Bake in a furnace. Thereafter, 100 mg of the incinerated material was collected, observed with a scanning electron microscope (S2100A manufactured by Hitachi, Ltd.), photographed at a magnification of 10000 times, randomly sampled 500 pieces, and the length of the longest part of each fiber (particle). The weight average value was taken as the average fiber length. Moreover, the weight average value of the shortest part was calculated as an average fiber diameter. In addition, in the case of combined use with other fillers or in combination with particulate titanium oxide, the filler is identified by point analysis and surface analysis of the filler with XMA at an observation magnification of 30000 times, and only acicular titanium oxide is picked up. Average fiber length and average fiber diameter were calculated. In the case of using granular titanium oxide together, the difference can be determined to some extent depending on the shape and thickness, but particles that cannot be determined by crushing during processing are included in the particulate titanium oxide and calculated. In addition, said (B) acicular titanium oxide used for this invention has the surface of a well-known coupling agent (For example, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent etc.), others It can also be used after being treated with a surface treatment agent.

In the present invention, (A) a liquid crystalline polymer having a melt viscosity of 0.5 to 80 Pa · s measured at a shear rate of 1,000 (1 / second) under the condition of melting point (Tm) + 10 ° C. and / or 300 ° C., compounding ratio of the needle-like titanium oxide against the melt viscosity measured at a shear rate of 1000 / sec to polyarylene sulfide resins or less 80 Pa · s, the low warping property, improvement of the pins press-fitting strength, and the visible light region (400 (A) Melting viscosity measured at a shear rate of 1,000 (1 / sec) under conditions of (A) melting point (Tm) + 10 ° C. in order to obtain a high reflection characteristic at a wavelength of ˜700 nm is 0.5 to 80 Pa · s. there liquid crystalline polymer and / or 300 ° C., polyarylene sulfide resins 1 00 parts by weight with respect to the melt viscosity measured at a shear rate of 1000 / sec or less 80Pa · s, (B) an average fiber length of 2μm or less 10 to 250 parts by weight of needle-like titanium oxide, preferably 20 to 200 parts by weight, more preferably 25 to 150 parts by weight.

  Further, in the present invention, in order to further improve the pin press-fit strength and other mechanical properties, (C) an inorganic filler other than acicular titanium oxide can be added. For example, glass fiber can be used as a specific example of the fibrous filler. , PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, Examples include titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc. The type of glass fiber or carbon fiber is generally used for resin reinforcement If there is no particular limitation, for example, long fiber tape Flop and short fiber type, chopped strands, may be selected from such milled fiber. The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  Moreover, iron, copper, stainless steel, aluminum, brass, etc. can be illustrated as a specific example of the metal seed | species of the said metal fiber.

  Specific examples of non-fibrous fillers include mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes, Examples thereof include metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes and the like. Moreover, silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin etc. can be illustrated as a specific example of the metal seed | species of metal powder, metal flakes, and a metal ribbon.

Here, specific examples of metal species of the metal powder, metal flake and metal ribbon include specific examples of metal oxides such as silver, nickel, copper, zinc, aluminum, magnesium, stainless steel, iron, brass, chromium and tin. Specific examples of nitrides such as SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope) and ZnO (aluminum dope) include AlN (aluminum nitride), BN (boron nitride), Si ₃ N ₄ Examples thereof include (silicon nitride).

  In the present invention, when used as a reflector, glass fibers, glass flakes, glass beads, glass microballoons, metal oxides (alumina, zinc oxide, titanium oxide), and talc are preferred from the relationship between mechanical properties and reflectance. Used.

  The inorganic filler excluding the above-mentioned (C) acicular titanium oxide used in the present invention has a known coupling agent (for example, silane coupling agent, titanate coupling agent, aluminum coupling agent) on the surface. Etc.) and other surface treatment agents.

The addition amount of the component (C) in the present invention is preferably added within a range that does not impair the low warpage property, pin press-fitting strength and reflection property of the present invention. Specifically, (A) melting point (Tm) + 10 ° C. And a liquid crystalline polymer having a melt viscosity of 0.5 to 80 Pa · s measured at a shear rate of 1,000 (1 / sec) and / or a melt viscosity of 80 Pa · measured at 300 ° C. and a shear rate of 1000 / sec. 5-150 parts by weight is preferable with respect to the polyarylene sulfide resins 1 00 parts by weight is s or less, more preferably 10 to 100 parts by weight.

  In the present invention, when (B) acicular titanium oxide and (C) an inorganic filler other than acicular titanium oxide are used in combination, the ratio of the amount of (B) / (C) added to component (A) is (B) / (C) = 62.5 / 37.5 to 99/1 is preferable from the balance of the low warpage property, pin press-in strength, and high reflection characteristics in the visible light region (400 to 700 nm wavelength), (B) / (C) = 65/35 to 95/5 is more preferable.

  In the resin composition of the present invention, other components, for example, antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphites, and substituted products thereof) are within the range not impairing the effects of the present invention. , Weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants, pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (nigrosine, etc.), crystal nuclei Agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cations Antistatic agents such as polyoxyethylene sorbitan monostearate Emissions antistatic agents, betaine-based amphoteric antistatic agent, etc.), can be added a flame retardant, other polymers.

  The resin composition of the present invention is usually produced by a known method. For example, it is prepared by premixing other necessary additives such as component (A), component (B), and component (C), or without supplying them to an extruder or the like and sufficiently melt-kneading them. Is done. Moreover, when adding the inorganic filler except (C) acicular titanium oxide, in order to suppress the breakage of the fiber of the fibrous filler, it is preferable to add the component (A) and other necessary additives from the origin of the extruder. It is adjusted by charging and supplying the components (B) and (C) to the extruder using a side feeder.

  When producing a resin composition, for example, melt-kneading at 180 to 350 ° C. using a single-screw extruder, twin-screw, three-screw extruder and kneader-type kneader equipped with a “unimelt” (R) type screw. To obtain a composition.

  In addition, when adding a large amount of (B) acicular titanium oxide and (C) inorganic filler other than acicular titanium oxide, for example, the amount of addition exceeds 250 parts by weight with respect to 100 parts by weight of (A) component (B) And as a method of obtaining a highly filled resin composition with a filler added with component (C), for example, as disclosed in JP-A-8-1663, extruding the head portion of the extruder, roughly pulverizing, and uniformly blending, Or the method of compressing and molding a raw material into a tablet is mentioned. In particular, the method of tableting by compressing the raw material is preferable from the viewpoint of the quality stability of the obtained composition.

  The resin composition molding method of the present invention can be melt-molded by an ordinary molding method (injection molding, press molding, injection press molding, etc.), and in particular, from the point of mass production, injection molding and injection are possible. Press molding is preferred.

  The resin composition of the present invention is useful for metal substitute applications, ceramic substitute applications, lighting applications, and high-precision parts (low dimensional change). Specifically, various cases, gear cases, LED packages, and LED lamp-related parts. , Connectors, relay cases, switches, variable capacitor cases, optical pickup lens holders, optical pickup slide bases, lamp reflectors, various terminal boards, transformers, printed wiring boards, liquid crystal panel frames, power modules and their housings, plastic magnets, semiconductors, LCD parts, projector lamp covers, FDD carriages, FDD chassis, actuators, HDD parts such as chassis, electrical and electronic parts represented by computer-related parts, VTR parts, TV parts, irons, hair dryers, rice cookers vessel Products, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc (registered trademark) / compact disc / digital video disc, lighting parts, refrigerator parts, air conditioner parts, household electrical appliance parts, Optical equipment such as office computer-related parts, telephone-related parts, facsimile-related parts, printer head and copying machine parts such as print heads and transfer rolls, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches, etc. , Precision machinery related parts: alternator terminal, alternator connector, IC regulator, light dimmer potentiometer base, motor core sealant, insulator member, power seat gear housing, air conditioner thermostat base, air conditioner Panel switch board, horn terminal, electrical component insulation plate, lamp housing, ignition device case, air pressure sensor, fuse connector, vehicle speed sensor and other automotive / vehicle related parts, personal computer housing, mobile phone housing, mobile phone base station antenna case In other information and communication fields, it is useful for chip antennas, wireless LAN antennas, ETC (Electronic Toll Collection System), antennas for satellite communications, and other various applications. Suppression of warpage due to distortion of molded parts during molding, and high reflection characteristics due to excellent strength and surface smoothness such as pin press-fit strength, etc. There is a pickup lens for electrical and electronic parts. It is useful for a small housing represented by a holder, a reflector used in an LED package and a reflector for illumination, or a narrow pitch connector used for connecting a portable device, a recording medium, and the like.

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

Reference Example 1 Thermoplastic resin Polyamide resin: Hexamethylenediamine-adipic acid equimolar salt 12% by weight (360 g), Hexamethylenediamine-isophthalic acid 25% by weight (750 g), Hexamethylenediamine-terephthalic acid 62% by weight (1860 g) of a mixed aqueous solution (solid raw material concentration 60% by weight) was charged into a pressure polymerization can, heated with stirring, reacted at a water vapor pressure of 3.43 MPa for 3.5 hours, and then the reaction mixture was discharged from the bottom of the polymerization can It was discharged from the outlet and collected. The relative viscosity (1% concentration) of the sulfuric acid solution of the polyamide prepolymer obtained here was 1.45. This was subjected to solid state polymerization at 220 ° C. for 10 hours under vacuum to obtain a polyamide having a relative viscosity of 2.4 and 312 ° C.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after cooling to room temperature under a temperature drop condition of 20 ° C./minute, the endothermic peak temperature (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./minute was used.

LCP (liquid crystal polymer): p-hydroxybenzoic acid 870 g (6.300 mol), 4,4′-dihydroxybiphenyl 327 g (1.890 mol), hydroquinone 89 g in a 5 L reaction vessel equipped with a stirring blade and a distillation tube. (0.810 mol), 292 g (1.755 mol) of terephthalic acid, 157 g (0.945 mol) of isophthalic acid, and 1367 g of acetic anhydride (1.03 equivalent of the total phenolic hydroxyl groups) were stirred in a nitrogen gas atmosphere. The mixture was reacted at 145 ° C. for 2 hours and then heated to 320 ° C. in 4 hours. 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 for 90 minutes, and the polycondensation was completed when the torque reached 15 kgcm. Next, the inside of the reaction vessel was pressurized to 1.0 kg / cm ² (0.1 MPa), the polymer was discharged to a strand-like material via a die having one circular discharge port having a diameter of 10 mm, and pelletized by a cutter.

  In this liquid crystalline polyester, the p-oxybenzoate unit is 70 mol% with respect to the total of the p-oxybenzoate unit, the 4,4′-dioxybiphenyl unit and the 1,4-dioxybenzene unit, The oxybiphenyl unit is 70 mol% with respect to the total of 4,4'-dioxybiphenyl units and 1,4-dioxybenzene units, and the terephthalate unit is 65 mol% with respect to the total of terephthalate units and isophthalate units. , Tm (melting point of the liquid crystalline polyester) was 314 ° C., and the melt viscosity measured at a temperature of 324 ° C. and a shear rate of 1,000 / s using a Koka flow tester was 15 Pa · s.

  The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after cooling to room temperature under a temperature drop condition of 20 ° C./minute, the endothermic peak temperature (Tm 2) observed when measured again under a temperature rise condition of 20 ° C./minute was used.

  PPS (polyphenylene sulfide): A sodium sulfide nonahydrate 6.005 kg (25 mol), sodium acetate 0.11 kg (1.35 mol), and N-methyl-2-pyrrolidone (NMP) 5 kg were charged into an autoclave equipped with a regulated stirrer. Then, the temperature was gradually raised to 205 ° C. through nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated at 270 ° C. Reacted for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water, then heated to 100 ° C., poured into 10 kg of NMP, stirred for about 1 hour, filtered, and washed several times with hot water. This was put into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour, filtered, washed with ion-exchanged water of about 90 ° C. until the pH of the filtrate reached 7, Drying under reduced pressure at 80 ° C. for 24 hours yielded dry PPS. Using a capillograph (manufactured by Toyo Seiki Co., Ltd.) and an orifice with a hole diameter of 1.0 mm and a length of 10 mm and measuring at a resin temperature of 310 ° C. and a shear rate of 1000 / sec, the melt viscosity of PPS Was 30 Pa · s.

Reference Example 2 Acicular titanium oxide B-1: FTL-300 (average fiber length 5.15 μm, average fiber diameter 0.27 μm, l / d = 19.1, manufactured by Ishihara Sangyo Co., Ltd.)
B-2: FLT-100 (average fiber length 1.68 μm, average fiber diameter 0.13 μm, l / d = 12.9, manufactured by Ishihara Sangyo Co., Ltd.)

Reference Example 3 Other filler C-1: Tismo N (potassium titanate fiber, average fiber length 16 μm, average fiber length 0.45 μm, 1 / d = 35.5, manufactured by Otsuka Chemical Co., Ltd.)
C-2: “Taipeke” CR-50 (rutile titanium oxide, average particle size 0.25 μm, manufactured by Ishihara Sangyo Co., Ltd.)
C-3: LMS-400 (talc, average particle size 3.8, manufactured by Fuji Talc)

Examples 1-2 , Comparative Examples 1-4
A thermoplastic resin of Reference Example 1, acicular titanium oxide of Reference Example 2 and other fillers of Reference Example 3 were blended in a ribbon blender in the amounts shown in Table 1, and PCM30 with a three-hole strand die head (biaxial extruder; Ikekai Iron Works) The product was melt-kneaded at the resin temperature shown in Table 1 at a screw speed of 150 rpm to obtain pellets. Subsequently, after drying for 5 hours with a 130 degreeC hot-air dryer, evaluation mentioned later was performed.

Comparative Example 5
The thermoplastic resin of Reference Example 1 and the acicular titanium oxide of Reference Example 2 were blended in the amounts shown in Table 1 using a ribbon blender, and Table 1 was prepared using PCM30 with a three-hole strand die head (2-screw extruder; manufactured by Ikekai Tekko Co., Ltd.). Melt-kneading was performed at a resin temperature shown in FIG. Subsequently, after drying for 5 hours with a 130 degreeC hot-air dryer, evaluation mentioned later was performed.

Examples 3 and 4
The thermoplastic resin of Reference Example 1 and the acicular titanium oxide of Reference Example 2 were blended in a ribbon blender in the amounts shown in Table 1, and tableted at room temperature using a rotary tableting machine manufactured by Tsukishima Kikai Co., Ltd. equipped with an automatic raw material supply feeder. Thus, a 6 mm diameter × 3 mm long columnar tablet (tablet-type resin composition) (maximum value 6 mm, minimum value 3 mm) was obtained. Subsequently, after drying with a 130 degreeC hot-air dryer for 5 hours, the following evaluation was performed.

(1) Fiber length and fiber diameter Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), under the temperature conditions of the resin temperature and mold temperature shown in Table 1, 70 mm length x 70 mm width x 1 mm thickness (fin gate) ), The protruding pin side is the front side, the left corner on the side opposite to the gate is cut out at 1 cm × 1 cm, placed in a crucible, and baked in an electric furnace at 550 ° C. × 8 hours. Thereafter, 100 mg of the incinerated material was collected, observed with a scanning electron microscope (S2100A manufactured by Hitachi, Ltd.), photographed at a magnification of 10000 times, randomly sampled 500 pieces, and the length of the longest part of each fiber (particle). The weight average value was the average fiber length. Moreover, the weight average value of the shortest part was calculated as an average fiber diameter. In addition, when (B) acicular titanium oxide and other fillers other than (C) acicular titanium oxide are used in combination, the filler composition is identified by point analysis and surface analysis by XMA with magnification up to 30000 times. (B) The acicular titanium oxide and the others were separated, and the average fiber length and the average fiber diameter of only acicular titanium oxide were calculated.

(2) Warp characteristics Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), under the temperature conditions of the resin temperature and mold temperature shown in Table 1, 70 mm length x 70 mm width x 0.5 mm thickness (center 20 mm) Fingate) was created, and the maximum amount of warpage when one of the four corners was suppressed was measured.

  (3) Pin press fit characteristics Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.) A molded product with holes was obtained.

  Next, insert a steel pin with an outer diameter of 1.1 mm and a length of 8 mm into the cylindrical hole, using a small hammer to insert a length of 8 mm. No cracks and breaks were observed in the cylindrical hole portions of less than 4 molded products. The obtained molded product was evaluated as Δ, and a molded product in which no cracks or breakage was observed in the cylindrical hole portions of all 20 molded products was determined as ◯.

(4) Light reflection characteristics (light reflectivity)
Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), a corner forming product (film gate) of 50 mm length x 50 mm width x 2 mm thickness is molded under the resin temperature and mold temperature conditions shown in Table 1. The diffuse reflectance of wavelengths from 400 to 800 nm was measured for this molded product using an ultraviolet near infrared spectrophotometer (UV-3150: manufactured by Shimadzu Corporation), and the reflectance of three wavelengths of 450, 550 and 650 nm was measured. Evaluated. It can be said that the larger this value, the better the light reflection characteristics.

  As is apparent from the results in Table 1, the molded product obtained from the resin composition of the present invention has little warpage during molding, and is excellent in balance between pin press-in strength and light reflection characteristics required during assembly. I understand. For this reason, it is used for small housings typified by pickup lens holders for electrical and electronic parts that require these characteristics, reflectors and reflectors used in LED packages, or for connecting portable devices and recording media. Useful for narrow pitch connectors.

Claims (5)

(A) a structural unit produced from p-hydroxybenzoic acid having a melt viscosity of 0.5 to 80 Pa · s measured at a shear rate of 1,000 (1 / second) under the condition of melting point (Tm) + 10 ° C., 4,4'-dihydroxybiphenyl a structural unit produced from Haidorokino down or we generated structural units, the liquid crystalline polyester and / or 300 ° C. consisting generated structured units and isophthalic acid or al a structural unit produced from terephthalic acid, shear With respect to 100 parts by weight of the polyarylene sulfide resin having a melt viscosity of 80 Pa · s or less measured at a speed of 1000 / sec, (B) the average fiber length is 2 μm or more and 10 μm or less , and the average fiber length (l) is the average fiber diameter ( A resin composition comprising 10 to 250 parts by weight of acicular titanium oxide having a value (l / d) divided by d) of 12 or more and 50 or less . Further, (C) the inorganic filler excluding acicular titanium oxide was melt melt viscosity measured at a shear rate of 1,000 (1 / sec) under the condition of (A) melting point (Tm) + 10 ° C. at 0.5 to 80 Pa · s. Yes, consisting of a structural unit generated from p-hydroxybenzoic acid, a structural unit generated from 4,4′-dihydroxybiphenyl, a structural unit generated from hydroquinone, a structural unit generated from terephthalic acid, and a structural unit generated from isophthalic acid 2. The liquid crystalline polyester and / or blended in an amount of 5 to 150 parts by weight with respect to 100 parts by weight of a polyarylene sulfide resin having a melt viscosity of 80 Pa · s or less measured at 300 ° C. and a shear rate of 1000 / second. Resin composition. A molded product formed by molding the resin composition according to claim 1. 4. The molded article according to claim 3, wherein the molded article is an electric / electronic part. The molded article according to claim 4, wherein the electrical / electronic component is a casing, a reflector, or a connector.