JP2005015792A - Polyphenylene sulfide resin composition for laser welding, and composite molded product using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a PPS resin composition for a laser welding excellent in the balance between laser weldability and heat resistance, and a composite molded product using it. <P>SOLUTION: The polyphenylene sulfide resin composition for a laser welding is obtained by mixing (A) 100 wt.pts. of a polyphenylene sulfide resin with (B) 1-600 wt.pts. of a filler, wherein the composition has 205°C or lower crystallization temperature on cooling. The composite molded product is obtained by laser welding a molded product that is produced from the composition. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a laser-welded polyphenylsulfide resin composition having extremely excellent laser weldability and heat resistance, and a composite molded body using the same, and further to a composite molded body obtained by laser welding to another article. Is.

  Polyphenylene sulfide resins are widely used in electrical / electronic parts and automobile parts because they have a good balance of mechanical properties, heat resistance, chemical resistance and thin-wall fluidity.

  Conventionally, in joining parts due to the complexity of product shape, joining with an adhesive, mechanical joining with a bolt or the like has been performed. However, adhesives have problems of adhesive strength, and mechanical joining with bolts and the like has problems of cost, labor for fastening, and weight increase. On the other hand, external heat welding such as laser welding and hot plate welding, friction heat welding such as vibration welding and ultrasonic welding can be performed in a short time, and no adhesive or metal parts are used. Since problems such as cost, weight increase and environmental pollution do not occur, assembly by these methods is increasing.

  Laser welding, which is one of the external heating weldings, is, for example, irradiating a laser beam onto a superimposed resin molded body as disclosed in Patent Document 1, transmitting one irradiated and absorbing the other to melt, It is a method of fusion, and is a method that is spreading in a wide range of fields by taking advantage of three-dimensional joining, non-contact processing, and the absence of burrs.

  In this construction method, in the resin material applied to the laser beam transmission side molded body, the characteristic of transmitting the laser beam is essential, and when a molded body having a low laser beam transmittance is used for the laser beam transmission side molded body, The possibility of causing problems such as smoking is suspected.

  Crystalline thermoplastic resins such as polyphenylene sulfide, which are widely used to replace metals for various applications, have very low laser beam transmittance, and the thermoplastic resin is used as a molded product on the laser beam transmission side. When applying the welding method, the thickness limit is very strict due to its low laser beam transmittance, and it is necessary to deal with the thinning to improve the laser beam transmittance, and the degree of freedom in product design is small.

  Patent Document 2 describes that the welding condition width is widened by controlling the melting point by using a polybutylene terephthalate-based copolymer in the laser welding method. A great improvement cannot be expected. Therefore, an improvement in the degree of freedom in the thickness design of the molded article cannot be expected, and the moldability of the polybutylene terephthalate resin is impaired.

In Patent Document 3, an attempt is made to balance with other properties such as heat resistance while maintaining laser beam transmittance by reinforcing the filler with respect to polyamide, and although laser weldability is certainly satisfied, When considering compounding, it cannot be said that the dimensional stability is sufficient, and problems such as deformation and cracking of the molded product may occur.
JP-A-60-214931 (pages 2 and 3) JP 2001-26656 A (paragraphs [0008] to [0024]) JP 2002-348371 A (2nd page, Example)

  The present invention eliminates the above-mentioned conventional problems, does not lower the product design freedom by injection molding, which is a characteristic of polyphenylene sulfide, and is excellent in balance between laser weldability and heat resistance. It is an object to provide a resin composition for laser welding that is extremely practical as a molded body.

  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 polyphenylene sulfide resin composition comprising 1 to 600 parts by weight of (B) filler with respect to 100 parts by weight of (A) polyphenylene sulfide resin, and the temperature-falling crystallization temperature of the composition is 205 ° C. or lower. A laser-welded polyphenylene sulfide resin composition,
(2) The above (1) wherein (B) filler is at least one selected from (B1) glass fiber having a single fiber diameter of 12 μm or more, and (B2) non-fibrous filler having an average particle diameter of 30 μm or more. The polyphenylene sulfide resin composition for laser welding as described,
(3) The polyphenylene sulfide resin composition for laser welding according to the above (1) or (2), wherein the refractive index of the (B) filler is 1.6 to 1.8,
(4) The above (1) to (3), further comprising (C) 1 to 200 parts by weight of an amorphous resin having a glass transition temperature of 130 ° C. or higher with respect to 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition for laser welding according to any one of
(5) (C) Amorphous resin having a glass transition temperature of 130 ° C. or higher is (C1) polyamideimide resin, (C2) polyarylate resin, (C3) polyethersulfone resin, (C4) polyetherimide resin, (C5) The polyphenylene sulfide resin composition for laser welding according to the above (4), which is at least one selected from polysulfone resins,
(6) Laser welding as described in any one of (1) to (5) above, further comprising (D) an antioxidant in an amount of 0.01 to 5 parts by weight per 100 parts by weight of (A) polyphenylene sulfide resin. Polyphenylene sulfide resin composition,
(7) The laser welding polyphenylene according to any one of (1) to (7), further comprising (E) an elastomer in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the (A) polyphenylene sulfide resin. A sulfide resin composition,
(8) Laser welding according to any one of (1) to (7) above, further comprising (F) 0.01 to 5 parts by weight of (F) silane compound with respect to 100 parts by weight of (A) polyphenylene sulfide resin Polyphenylene sulfide resin composition,
(9) 0.01-5 parts by weight of (G) crystal nucleating agent with respect to 100 parts by weight of (A) polyphenylene sulfide resin with respect to the polyphenylene sulfide resin composition according to any one of (1) to (8) A polyphenylene sulfide resin composition obtained by blending, wherein the composition has a temperature-falling crystallization temperature of 225 ° C. or lower.
(10) A molded article on the laser beam transmission side comprising the laser welding resin composition according to any one of (1) to (9) above, wherein the thickness of the transmission part of the welded part is 5 mm or less. Laser welded compact,
(11) A method for producing a laser-welded molded article, wherein the laser-welded resin composition according to any one of (1) to (9) is injection-molded at a mold temperature of 100 ° C. or lower,
(12) A composite molded article obtained by laser welding a molded article comprising the resin composition for laser welding according to any one of (1) to (9) above,
(13) A composite molded article obtained by laser welding a molded article made of the laser welding resin composition according to any one of (1) to (9) as a laser beam transmission side molded article, wherein the molded article on the laser beam absorption side is , The composite molded article according to (12) above, comprising a polyphenylene sulfide resin,
(14) A method for producing a composite molded article, comprising heat-treating a molded article comprising the laser-welded resin composition according to any one of (1) to (9) above, after laser welding.

  The laser-welded polyphenylene sulfide resin composition of the present invention is excellent in balance between laser weldability and heat resistance. Therefore, it is useful for laser welding of resin moldings for various uses such as electrical / electronic related equipment, precision machinery related equipment, office equipment, automobile / vehicle related parts, building materials, packaging materials, furniture, daily necessities.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The laser-welded polyphenylene sulfide (hereinafter referred to as PPS) resin composition of the present invention is a PPS resin composition obtained by blending 1 to 600 parts by weight of (B) filler with respect to 100 parts by weight of (A) PPS resin. And the temperature-falling crystallization temperature of the composition needs to be 205 ° C. or lower. By setting the temperature-falling crystallization temperature of the laser welding PPS resin composition within the above range, it is possible to obtain a composition extremely excellent in laser weldability for the first time. The PPS resin composition having a temperature-falling crystallization temperature of 205 ° C. or lower is prepared by using a PPS resin having a low temperature-falling crystallization temperature and appropriately selecting the blending amount of the filler.

(1) PPS resin The PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula,

  A polymer containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is preferable from the viewpoint of heat resistance. Moreover, PPS resin can be comprised with the repeating unit etc. which have the following structure in less than 30 mol% of the repeating unit.

  In order to set the temperature-falling crystallization temperature of the PPS resin composition of the present invention within the range specified in the present invention, a PPS resin used for blending has a low temperature-falling crystallization temperature, but the temperature-falling crystallization temperature is 200 ° C. It is preferable that the temperature be 195 ° C. or lower. The lower limit is preferably 170 ° C. or higher in terms of heat resistance. In order to obtain a PPS resin having a low temperature-falling crystallization temperature, a PPS resin having a high molecular weight (low melt flow rate (MFR)) is preferable. The MFR of the PPS resin is preferably 500 g / 10 min or less, particularly preferably 350 g / 10 min or less, and further preferably 200 g / 10 min or less. The lower limit of MFR is preferably 30 g / 10 min or more in terms of fluidity loss. The MFR is a value obtained by drying 5 g of PPS resin powder at 130 ° C. for 3 hours and retaining the powder at 315.5 ° C. for 5 minutes, applying a 5 kg load (based on JIS-K7210).

  Further, copolymerization of a metaphenylene sulfide unit and a paraphenylene sulfide unit is preferable because the temperature-lowering crystallization temperature can be lowered as the melting point is lowered. Furthermore, it is preferable to use a trihalo or higher polyhaloaromatic compound together at the start of polymerization because a branched or crosslinked polymer is formed and the temperature-falling crystallization temperature can be lowered.

(Polymerization of PPS resin)
Generally, the PPS resin is a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368 or a method for obtaining a polymer having a relatively large molecular weight described in JP-B-52-12240. Can be manufactured by. The difference between the former and the latter is the presence or absence of an alkali metal carboxylate as a polymerization aid in the polymerization system.

  In the former, since no alkali metal carboxylate is added to the polymerization system, the degree of polymerization does not increase, the molecular weight is relatively small, and the temperature-falling crystallization temperature is high. Moreover, since it is a polymer that also contains a large amount of impurities, it is colored by heating at the time of producing a composition or a molded article, and the laser weldability is lowered.

  In the latter case, an alkali metal carboxylate is added to the polymerization system, so that the degree of polymerization is increased, the molecular weight is relatively large, the temperature-falling crystallization temperature is lowered, and it is relatively easy to be within the scope of the present invention. In addition, the content of impurities is small, coloring due to heating can be suppressed, and laser weldability is excellent.

  The latter can satisfy the conditions specified in the present invention relatively easily, but it is necessary to adjust the reaction conditions so that the PPS resin provides a PPS resin composition satisfying the range specified in the present invention. is there. However, it is possible to adjust the fluidity of the PPS resin by using the former PPS resin together.

  Further, as described above, the polyphenylene sulfide copolymer in which a metaphenylene sulfide unit is introduced into a PPS resin having a paraphenylene sulfide unit has a lower temperature-lowering crystallization temperature than a polymer having only a paraphenylene sulfide unit. It is. The copolymerization ratio (molar fraction) of these units is preferably 1 mol% or more, preferably 3 mol% or more of the metaphenylene sulfide unit based on the total amount of the metaphenylene sulfide unit and the paraphenylene sulfide unit. Is more preferable. The upper limit is preferably less than 15 mol% from the viewpoint of heat resistance. As the copolymerization mode, either random copolymerization or block copolymerization may be used, but random copolymerization is preferred from the viewpoint of a balance between laser weldability and heat resistance.

  Furthermore, as described above, the combined use of a trihalo or higher polyhaloaromatic compound at the start of polymerization can lower the temperature-falling crystallinity. In this case, the copolymerization amount of the polyhaloaromatic compound is preferably 0.01 mol% or more, and 0.04 mol% or more of the polyhaloaromatic compound with respect to the total amount of the polyhaloaromatic compound and the dihaloaromatic compound. It is particularly preferable that it is 0.06 mol% or more. The upper limit is preferably 0.1 mol% or less from the viewpoint of fluidity loss. Specific examples of the polyhaloaromatic compound include 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,3,5-tribromobenzene, 1,2,4-tribromobenzene and the like. It is done. In addition, active hydrogen-containing halogen aromatic compounds and halogen aromatic nitro compounds can be used in combination with dihaloaromatic compounds.

(Post-processing)
In the present invention, as means for obtaining improved laser weldability and improved mechanical properties by lowering the crystallization temperature of the PPS resin, the heat treatment, organic solvent washing, acid treatment or carboxylic acid metal salt aqueous solution treatment, etc. It is effective to apply the processing.

  Among the post-treatment methods of PPS described above, the heat treatment can be performed for the purpose of removing impurities that cause coloring. However, excessive heat treatment causes oxidation coloring and is not preferable because laser weldability is lowered. Specific heat treatment conditions are as follows. That is, the heat treatment of the PPS resin is usually performed in a temperature range of 200 to 260 ° C., but heating at a high temperature causes oxidation coloring. Therefore, in this invention, it is preferable to carry out in the temperature range of 120-220 degreeC, More preferably, it is good to carry out in the temperature range of 150-200 degreeC. The heating time is preferably 5 to 20 hours, more preferably 10 to 15 hours. The atmosphere of the heat treatment is preferably performed in an inert atmosphere such as a nitrogen atmosphere since the laser weldability is significantly lowered due to oxidation coloring when the atmosphere is an oxygen atmosphere.

  Next, organic solvent cleaning of the PPS resin will be described. Organic solvent cleaning is preferable because impurities that cause coloring can be removed. The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin. For example, N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloro Halogen solvents such as tan, tetrachloroethane, perchlorethane, chlorobenzene, alcohols and phenols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol Examples of the solvent include aromatic hydrocarbon solvents such as benzene, toluene, and xylene. Among these organic solvents, use of NMP, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and it is preferable to stir or heat for the purpose of making the effect of the present invention more remarkable. Although there is no restriction | limiting in particular in the usage-amount of the organic solvent with respect to PPS resin, it is preferable that it is 1-100 kg with respect to 1 kg of dried PPS resin, It is more preferable that it is 2-50 kg, It is further 3-15 kg preferable.

  There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. However, since cleaning efficiency tends to increase as the cleaning temperature increases, it is preferable to perform cleaning at a high temperature of 100 to 300 ° C.

  It is also possible to wash in a pressure vessel under pressure (preferably 250 to 300 ° C.) at a temperature equal to or higher than the boiling point of the organic solvent. Further, the cleaning time is not particularly limited, but in the case of batch cleaning, it is preferable to perform cleaning for 30 to 60 minutes or more for the purpose of making the effect of the present invention more remarkable. It is also possible to wash in a continuous manner.

  When the PPS resin produced by polymerization is washed with an organic solvent, it is preferably combined with water washing in order to further exhibit the effects of the present invention. Further, when a high-boiling water-soluble organic solvent such as N-methylpyrrolidone is used, it is preferable that the remaining organic solvent can be removed relatively easily by washing with water after washing with the organic solvent. The water used for these washings is preferably distilled water or deionized water. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  Next, the acid treatment will be described. It can be carried out for the purpose of removing impurities that cause oxidative coloring or improving the mechanical properties. However, excessive acid treatment is not preferable because the terminal substitution reaction of the PPS resin proceeds to raise the temperature-falling crystallization temperature and lower the laser weldability. Specific acid treatment conditions will be described. The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have an action of decomposing the PPS resin, but acetic acid, silicic acid, carbonic acid, and propyl acid are preferable, and acetic acid is more preferable. For example, acid treatment with a strong acid such as hydrochloric acid, sulfuric acid, phosphoric acid or the like having a pH of 2 or less causes excessive acid treatment, and the temperature-falling crystallization temperature rises, which tends to be undesirable in terms of laser weldability. is there. In addition, it is not preferable to decompose or deteriorate the PPS resin such as nitric acid.

  The acid treatment method includes a method of immersing the PPS resin in an acid or an aqueous solution of the acid, and is preferably stirred or heated for the purpose of making the effect of the present invention more remarkable, and the treatment time is 30 to 30 minutes. It is preferable that it is 60 minutes or more. Moreover, about the acid used for the acid treatment of PPS resin, it is preferable that pH is 3.5-5.5, and it is preferable that the usage-amount is 2-100 kg with respect to 1 kg of dried PPS resins, and 4-50 kg. It is more preferable that it is 5 to 15 kg. There is no restriction | limiting in particular in process temperature, Usually, it can carry out at room temperature, and when heating, it can carry out at 50-90 degreeC. For example, when acetic acid is used, it is preferable to immerse the PPS resin powder in an aqueous solution of PH4 kept at room temperature and stir for 30 to 60 minutes or more. The acid-treated PPS resin is washed several times with water in order to physically remove the remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  As the water used for washing, distilled water and deionized water are used in the sense that the effects of the present invention and preferred chemical modification of the PPS resin by acid treatment are not impaired. In the present invention, the above post-processing can be combined and can be repeated a plurality of times.

  Further, the carboxylic acid metal salt aqueous solution treatment is effective in balancing the effects of the present invention and the mechanical strength. Specific examples of the carboxylic acid metal salt used in the aqueous solution of the carboxylic acid metal salt of the PPS resin include lithium acetate, sodium acetate, potassium acetate, calcium acetate, magnesium acetate, lithium propionate, sodium propionate, potassium propionate, propionic acid. Calcium, magnesium propionate, lithium 2-methylpropionate, rubidium butyrate, lithium valerate, sodium valerate, potassium valerate, calcium valerate, magnesium valerate, cesium hexanoate, lithium heptanoate, lithium 2-methyloctanoate , Potassium dodecanoate, rubidium 4-ethyletradecanoate, sodium octadecanoate, sodium heneicosanoate, lithium cyclohexanecarboxylate, calcium cyclohexanecarboxylate, Magnesium hexanecarboxylate, cesium cyclododecanecarboxylate, cesium 3-methylcyclopentanecarboxylate, potassium cyclohexylacetate, calcium cyclohexylacetate, magnesium cyclohexylacetate, potassium benzoate, calcium benzoate, magnesium benzoate, potassium m-toluate, Lithium phenylacetate, calcium phenylacetate, magnesium phenylacetate, sodium 4-phenylcyclohexanecarboxylate, calcium 4-phenylcyclohexanecarboxylate, magnesium 4-phenylcyclohexanecarboxylate, potassium p-tolylacetate, calcium p-tolylacetate P-tolyl magnesium acetate, lithium 4-ethylcyclohexyl acetate, calcium 4-ethylcyclohexyl acetate, 4- Magnesium Le cyclohexyl acetate, other similar types of salts, and include such mixtures thereof, sodium acetate, calcium acetate, magnesium acetate is preferred. For the purpose of making the treatment effect more prominent, it is preferable to stir or heat, and the treatment time is preferably 30 to 60 minutes or more. The concentration of the aqueous solution of the carboxylic acid metal salt is preferably adjusted so that the amount of the carboxylic acid metal salt is 0.1 to 100 g per 1 kg of the PPS resin. The treatment temperature can usually be room temperature to 300 ° C. The PPS resin subjected to the carboxylic acid metal salt aqueous solution treatment is washed several times with water in order to physically remove salts and the like. The water washing temperature is preferably 50 to 95 ° C.

  Distilled water and deionized water are used as the water used for washing in the sense that the effects of the present invention and the preferred chemical modification of the PPS resin with an aqueous carboxylic acid metal salt solution are not impaired. In the present invention, the above post-processing can be combined and can be repeated a plurality of times.

(2) Filler In the present invention, it is necessary to add a filler (B) in order to further improve characteristics such as heat resistance and mechanical strength. Specific examples of the filler (B) to be added include non-fibrous fillers (which may be inorganic fillers or organic fillers) such as fibrous or plate-like, scale-like, granular, indeterminate shapes, and crushed products. Specifically, for example, organic fibers such as aromatic polyamide fibers, glass fibers, stainless fibers, metal fibers such as aluminum fibers and brass fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, Titanium oxide fiber, silicon carbide fiber, rock wool, alumina hydrate (whisker / plate), potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, talc, kaolin, silica (crushed / spherical) ), Quartz, calcium carbonate, glass beads, glass flakes, crushed and irregular shapes Glass, glass microballoon, clay, molybdenum disulfide, wollastonite, aluminum oxide (crushed), titanium oxide (crushed), metal oxides such as zinc oxide, metal hydroxides such as aluminum hydroxide, aluminum nitride, Examples thereof include calcium polyphosphate, graphite, metal powder, metal flake, metal ribbon, and metal oxide. Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. In addition, fillers such as carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes, PAN-based and pitch-based carbon fibers, and mica reduce laser weldability, but mainly color the PPS resin composition of the present invention. For this purpose, it is possible to add a small amount that does not impair the practical laser welding performance. The type of glass fiber or carbon fiber is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from long fiber type, short fiber type chopped strand, milled fiber, and the like.

  In the present invention, among the above fillers, glass fibers having a single fiber diameter of 12 μm or more, and non-fibrous fillers having an average particle diameter of 30 μm or more, from the infrared light transmittance essential for laser weldability. Is preferred. Among these, glass fibers having a single fiber diameter of 15 μm or more and non-fibrous fillers having an average particle diameter of 50 μm or more are preferable. Further, the upper limit of the single fiber diameter of such a glass fiber is preferably 35 μm or less from the viewpoint of a reinforcing material, and the upper limit of the average particle diameter of the non-fibrous filler is to avoid trouble of gate clogging during molding. From the viewpoint of the above, the upper limit is preferably 1000 μm or less. Moreover, it is preferable that it is a translucent filler, and specifically, as a material, E glass, C glass, H glass, alumina hydrate, translucent alumina, zinc oxide, translucent aluminum nitride, silica, Examples include natural quartz glass, synthetic quartz glass, metal hydroxides such as aluminum hydroxide, etc. The shape is fibrous or non-fibrous such as plate, scale, granular, indefinite shape, crushed product, etc. Is mentioned. The single fiber diameter is a value measured by a test method based on JIS-R3420 5,6. The average particle diameter is a number average obtained by a microtrack method in which ethanol is added to 0.70 g of a sample and ultrasonically dispersed for 3 minutes and laser light is irradiated.

  Among the translucent fillers, those having a refractive index of 1.6 to 1.8, preferably 1.63 to 1.77 are particularly preferred from the viewpoint of laser transmittance, specifically H glass, alumina water. Japanese products are particularly preferred. The refractive index referred to here is measured on the basis of the critical angle of total reflection using a 10 mm-square cubic test piece having the same composition, using a pull refractometer.

  The filler can be used in combination of two or more in order to obtain a balance between mechanical strength and molded product warp. For example, glass fiber and mica or glass flake and alumina (aluminum oxide) (pulverized), Examples thereof include glass fibers and glass beads, silica and crushed glass, milled fibers and crushed glass.

  The surface of the filler used in the present invention can be used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. .

  The blending amount of the (B) filler used in the present invention is preferably 1 to 600 parts by weight with respect to 100 parts by weight of the (A) PPS resin, from the balance of laser weldability, heat resistance, mechanical strength, etc. Is from 5 to 150 parts by weight, more preferably from 5 to 100 parts by weight, still more preferably from 10 to 70 parts by weight. (B) When there are too few compounding quantities of a filler, heat resistance, mechanical strength, etc. will run short, and when too large, mechanical strength and fluidity will fall and it is not practical.

(3) Amorphous Resin In the present invention, (C) an amorphous resin having a glass transition temperature of 130 ° C. or higher can be added for the purpose of improving laser weldability and low warpage. (C) Specific examples of the amorphous resin having a glass transition temperature of 130 ° C. or higher include cycloolefin polymer, cycloolefin copolymer, polycarbonate, polyphenylene ether, polysulfone, polyethersulfone, polyarylate, polyetherimide, and polyamideimide. Among them, polyamideimide, polyarylate, polyethersulfone, polyetherimide, polysulfone, and polyphenylene ether are preferable from the viewpoint of heat resistance and compatibility, and polyamideimide, polyarylate, polyethersulfone, and polyetherimide are preferable. Polysulfone is particularly preferred. (C1) Polyamideimide, (C2) Polyarylate, (C3) Polyethersulfone, (C4) Polyetherimide, and (C5) Polysulfone have particularly excellent laser transmittance particularly when they are compatible with PPS resin. It is particularly preferable in that it is obtained.

  The blending amount of the amorphous resin (C) having a glass transition temperature of 130 ° C. or higher used in the present invention is determined from the balance of laser weldability, low warpage, heat resistance, mechanical strength, etc. (A) PPS resin 100 It is 1-200 weight part with respect to a weight part, Preferably it is 1-150 weight part, More preferably, it is 1-70 weight part. (C) If the amount of the amorphous resin having a glass transition temperature of 130 ° C. or higher is too small, an improvement effect such as laser weldability and low warpage cannot be obtained, and if too large, heat resistance, mechanical strength, and flow It is impractical because the properties are reduced. In addition, the above amorphous resins can be used in combination of two or more in order to obtain a balance between laser transmittance and warpage of a molded product.

(4) Antioxidant In the present invention, (D) an antioxidant can be added in order to suppress a decrease in laser transmittance due to oxidative coloring. (D) Specific examples of the antioxidant include calcium hypophosphite, 2,6-di-t-butyl-4-methylphenol, tetrakis (methylene-3- (3,5-di-t-butyl-4- Hydroxyphenyl) propionate) phenolic compounds such as methane, tris (3,5-di-t-butyl-4-hydroxybenzidine) isocyanurate, dilauryl-3,3′-thiodipropionate, dimyristyl-3,3 ′ -Sulfur compounds such as thiodipropionate, phosphorus compounds such as trisnonylphenyl phosphite, distearyl pentaerythritol diphosphite, and the like are mentioned, among which calcium hypophosphite is preferable. (D) The compounding quantity of antioxidant is 0.01-5 weight part normally with respect to 100 weight part of (A) component, Preferably it is 0.05-3 weight part, More preferably, it is 0.1-1 weight. Part.

  Moreover, in order to suppress the laser transmittance fall by oxidation coloring, the said antioxidant can also be used in combination of 2 or more types.

(5) Elastomer Furthermore, in order to improve the impact resistance and cold resistance of the resin composition for laser welding in the present invention, (E) an elastomer can be added. Examples of (E) elastomers include olefin elastomers, modified olefin elastomers, and styrene elastomers.

  Examples of olefin elastomers include (co) polymers obtained by polymerizing α-olefins alone or two or more of ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, isobutylene, and the like, α- Copolymers of olefins with α, β-unsaturated acids and alkyl esters thereof such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Etc. Specific examples of the olefin elastomer include polyethylene, polypropylene, ethylene / propylene copolymer (“/” represents copolymerization, hereinafter the same), ethylene / butene-1 copolymer, ethylene / methyl acrylate copolymer. Ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, and the like.

  A modified olefin-based elastomer can be added to further improve the impact resistance and cold resistance of the resin composition for laser welding. The modified olefin elastomer is obtained by introducing a monomer component (functional group-containing component) having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into the above-described olefin elastomer. Examples of ingredients include maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo [2.2.1] 5-heptene-2,3-dicarboxylic acid, endobicyclo- [2.2.1] 5- Monomers containing an acid anhydride group such as heptene-2,3-dicarboxylic acid anhydride, single monomers containing an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid And monomers containing ionomers such as a monomer and a carboxylic acid metal complex.

  The method for introducing these functional group-containing components is not particularly limited, and the same olefinic (co) polymer as that used as the olefinic elastomer may be copolymerized when (co) polymerizing or olefinic (co). A method such as graft introduction into the polymer using a radical initiator can be used. The amount of the functional group-containing component introduced is in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on all monomers constituting the modified olefinic (co) polymer. Is appropriate.

  Specific examples of the olefin (co) polymer obtained by introducing a monomer component having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into a particularly useful olefin polymer include ethylene / propylene-g- Glycidyl methacrylate copolymer (“g” represents graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer Polymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-anhydrous Maleic acid copolymer, ethylene / methyl acrylate-g-maleic anhydride copolymer, Lene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / methyl methacrylate-g-maleic anhydride copolymer, ethylene / ethyl methacrylate-g-maleic anhydride copolymer, ethylene / methacrylic acid copolymer Examples thereof include a zinc complex of a polymer, a magnesium complex of an ethylene / methacrylic acid copolymer, and a sodium complex of an ethylene / methacrylic acid copolymer.

  Preferred are ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / butene-1-g-maleic anhydride. Examples thereof include an acid copolymer and an ethylene / ethyl acrylate-g-maleic anhydride copolymer.

  Particularly preferred are ethylene / glycidyl methacrylate copolymers, ethylene / methyl acrylate / glycidyl methacrylate copolymers, ethylene / methyl methacrylate / glycidyl methacrylate copolymers, and the like.

  On the other hand, specific examples of the styrene elastomer include styrene / butadiene copolymer, styrene / ethylene / butadiene copolymer, styrene / ethylene / propylene copolymer, styrene / isoprene copolymer, and the like. However, styrene / butadiene copolymers are preferred. More preferably, an epoxidized product of a styrene / butadiene copolymer is used.

  (E) The compounding quantity of an elastomer is 0.5-20 weight part normally with respect to (A) component, Preferably it is 0.8-10 weight part, More preferably, it is 1-6 weight part.

  In addition, the above elastomers can be used in combination of two or more in order to obtain a balance between impact resistance, cold resistance, and laser transmittance.

(6) Silane Compound It is also possible to add (F) a silane compound for the purpose of improving the effects of the present invention and the mechanical strength. (F) As a silane compound, various things besides an epoxy silane compound, an aminosilane compound, a ureido silane compound, and an isocyanate silane compound can be used. Specific examples of (F) silane compounds include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. -Containing alkoxysilane compounds, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2 -Ureidoethyl) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane Isocyanato group-containing alkoxysilane compounds such as lan, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- ( Amino group-containing alkoxysilane compounds such as 2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-hydroxypropyltrimethoxysilane, Examples thereof include hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltriethoxysilane. (F) The compounding quantity of a silane compound is 0.01-5 weight part with respect to 100 weight part of (A) PPS resin from the balance of the effect of this invention and mechanical strength, Preferably it is 0.05-3 weight. Part, more preferably 0.1 to 1 part by weight. (F) If the amount of the silane compound is too small, the effect of improving the present invention and mechanical strength cannot be obtained, and if too large, the fluidity is lowered and the gas during molding is increased, which is not practical. The above silane compounds may be used in combination of two or more in order to obtain a balance between the effects of the present invention and mechanical strength.

(7) Other additives In the PPS resin composition for laser welding in the present invention, other components such as a heat stabilizer (hindered phenol, hydroquinone, phosphite and These substitutes, etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol) , Stearamide, various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (such as nigrosine), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide) Etc.), antistatic agents (alkyl monkeys) Fate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (for example, Red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or their brominated series A combination of a flame retardant and antimony trioxide, etc.) and other polymers can be added.

  In the present invention, (G) a crystal nucleating agent (talc, silica, kaolin, clay, hydrotalcite, polyetheretherketone, etc.) can be blended.

  In the present invention, the blending of the (G) crystal nucleating agent is effective in that it is possible to suppress the variation for each part of the laser weldable molded product. (G) The addition of the crystal nucleating agent increases the temperature-falling crystallization temperature of the PPS resin composition, but when the (G) crystal nucleating agent is not blended, the temperature-falling crystallization temperature becomes 205 ° C. or lower in the PPS resin composition. On the other hand, when the (G) crystal nucleating agent is blended, the PPS resin composition blended with the (G) crystal nucleating agent has a low temperature crystallization temperature of 225 ° C. or lower, preferably 220 ° C. or lower. A composition having laser weldability and suppressed variation is obtained. (G) Specific examples of the crystal nucleating agent include talc, silica, kaolin, clay, hydrotalcite, polyether ether ketone, etc. Among them, laser weldability, and variations in laser weldability for each part of the molded product. From the viewpoint of suppression, talc and polyether ether ketone are preferred. The blending amount of the (G) crystal nucleating agent used in the present invention is such that the temperature-falling crystallization temperature of the PPS resin composition obtained as described above is 225 ° C. or lower, preferably 220 ° C. or lower. Although it varies depending on the type of nucleating agent, it is generally 0.01 to 5 parts by weight, preferably 0 based on 100 parts by weight of (A) PPS resin, from the balance of laser weldability and laser weldability variation for each part of the molded product. 0.02 to 3 parts by weight, more preferably 0.03 to 1 part by weight. (G) If the blending amount of the crystal nucleating agent is too small, the effect of suppressing variation in each part of the laser weldable molded product cannot be obtained, and if too much, the temperature-falling crystallization temperature is outside the upper limit of the range of the present invention, and the laser weldability. Damage.

(8) Blending of each component The method for producing the laser welding PPS resin composition of the present invention is usually produced by a known method. For example, (A) PPS resin, (B) filler, other necessary additives, and (C) amorphous resin having a glass transition temperature of 130 ° C. or higher, (D) antioxidant, (E) elastomer, (F It is prepared by premixing or supplying the silane compound and (G) crystal nucleating agent to an extruder or the like and sufficiently melting and kneading them. In addition, when (B) the filler is added, in order to suppress breakage of the fiber of the fibrous filler, preferably (A) a PPS resin, an additive, and (C) an amorphous material having a glass transition temperature of 130 ° C. or higher. Resin, (D) Antioxidant, (E) Elastomer, (F) Silane compound, (G) Crystal nucleating agent are charged from the extruder, and (B) Filler is supplied to the extruder using the side feeder. To be prepared.

  When producing a resin composition for laser welding, for example, 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. Can be melt kneaded into a composition.

(9) PPS resin composition The PPS resin composition for laser welding of the present invention is a PPS resin composition in which the temperature-falling crystallization temperature is 205 ° C. or lower or a crystal nucleating agent is blended for the purpose of improving laser weldability. Is 225 ° C. or lower, but is preferably 200 ° C. or lower for enhancing the effects of the present invention, or 220 ° C. or lower in a PPS resin composition containing a crystal nucleating agent. Although there is no restriction | limiting in particular about the minimum of temperature-fall crystallization temperature, Since heat resistance will fall when too low, it is preferable that it is 170 degreeC or more.

  In addition, the PPS resin composition of the present invention preferably has a chloroform extraction amount of 0.5% by weight or less for the purpose of improving laser weldability, but is 0 for enhancing the effects of the present invention. More preferably, it should be 3% by weight or less. The lower limit of the chloroform extraction amount is not particularly limited as long as the effects of the present invention and the heat resistance, mechanical strength, and the like are not impaired. In order to reduce the chloroform extraction amount in the PPS resin composition, a PPS resin having a low chloroform extraction amount may be used. To reduce the chloroform extraction amount of the PPS resin, the PPS resin after polymerization is treated with an organic solvent, Post-treatment such as acid treatment or heat treatment (especially organic solvent treatment is preferred, and when heat treatment is carried out, the above-mentioned preferred method is preferred). ) Is usually used until the desired amount of chloroform extraction is achieved.

  Further, the thermal deformation temperature at a load of 0.46 MPa of the composition molded body comprising the PPS resin composition of the present invention is preferably 230 ° C. or higher, but 240 ° C. or higher is particularly preferable in order to enhance the effect of the present invention. 260 ° C. or higher is more preferable.

  The parameters of the temperature-falling crystallization temperature, the chloroform extraction amount, and the heat distortion temperature of the PPS resin composition are described below.

  The temperature-falling crystallization temperature was obtained by taking about 10 mg as a sample from a molded product, pellet, pulverized product, etc. of the PPS resin composition, and using a differential scanning calorimeter (DSC-7 manufactured by Perkin Elmer Co., Ltd.) The temperature is lowered at a temperature of 340 ° C., held at 340 ° C. for 5 minutes, and the temperature is lowered at a rate of 20 ° C./min. .

  The amount of chloroform extracted is obtained by classifying the crushed sample with 32 to 60 mesh, washing it with 30 ml of methanol 5 times to remove the deposits, and then vacuum drying to weigh 2 g of the sample. A 2 g sample is subjected to total reflux extraction (Soxhlet extraction) with 20 g of chloroform using a Soxhlet extractor at 85 ° C. for 5 hours. Chloroform is recovered and vacuum dried at 23 ° C. for 1 hour. It is measured by a method of calculating a value obtained by dividing the weight after drying by the weight before extraction.

  The heat distortion temperature was measured at a resin temperature of 310 ° C. and a mold temperature of 130 ° C. according to ASTM-D648 using a 12.7 mm (width) × 3.2 mm (thickness) × 127 mm (length) test piece injection molded. The heat deformation temperature (load deflection temperature) under a load of 0.46 MPa.

(10) Molding and use of PPS resin composition The laser welding PPS resin composition of the present invention is generally thermoplastic such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, transfer molding, vacuum molding, and the like. Although it shape | molds by the well-known molding method of resin, an injection molding is preferable especially.

  The molded body thus obtained retains laser weldability, and further utilizes heat resistance and low warpage, and is used for molded articles used by laser welding, preferably for molded articles on the laser beam transmission side. A practical composite molded body can be provided by laser welding with a member. For example, it is useful for electrical / electronic applications, automotive applications, general miscellaneous goods applications, building materials, etc. Specifically, electronic component cases such as personal computers, liquid crystal projectors, mobile devices, mobile phones, and switch modules, remote controllers Internal joint parts, electrical parts module parts, engine compartment module parts, throttle body parts, intake manifolds, underhood parts, radiator parts, cockpit module parts used in instrument panels, etc., hollow containers, housings, and other information communication fields Components such as installed antennas that require shielding properties such as electromagnetic waves, or applications that require high dimensional accuracy in construction materials, especially automotive parts applications that are eager to replace metals due to weight reduction, electrical / electronic component applications Useful for molded products used by laser welding, etc. Ri, particularly in view of the laser welding strength, is useful in the molding of the laser beam transmission side of the laser welding bonding resin molding for various applications. Since the laser welding resin composition of the present invention is excellent in laser beam transmission, a good adhesive force can be obtained even when the thickness of the laser beam transmission part of the welded portion by the laser beam is 5 mm or less. If it is 5 mm or less, further 2.5 mm or less, stronger adhesive force can be obtained. In order to obtain substantial strength and productivity of the molded body, the lower limit thickness is preferably 0.1 mm.

Reference Example 1 Production of PPS Production of PPS-1 An autoclave equipped with a stirrer was charged with sodium sulfide 9 hydrate 6.005 kg (25 mol), sodium acetate 0.787 kg (9.6 mol) and NMP 5 kg, and gradually added 205 while passing nitrogen. The temperature was raised to 0 ° C., and 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C, 3.712 kg (25.25 mol) of 1,4-dichlorobenzene and 2.4 kg of NMP were added, sealed under nitrogen, heated to 270 ° C, heated at 270 ° C. Reacted for 2.5 hours. Next, the mixture was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed with hot water at 80 ° C. for 30 minutes three times. This was filtered, poured into 25 liters of an aqueous solution containing 10.4 g of calcium acetate, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and the pH of the filtrate reached 7. After washing with ion-exchanged water at about 90 ° C., it was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-1 having a cooling crystallization temperature of 180 ° C. and MFR of 100 g / 10 min. The same operation was repeated and used for the following examples.

  The MFR was determined by drying 5 g of PPS resin powder at 130 ° C. for 3 hours and retaining the powder at 315.5 ° C. for 5 minutes, applying a 5 kg load (based on JIS-K7210).

Production of PPS-2 An autoclave equipped with a stirrer was charged with 6.005 kg (25 mol) of sodium sulfide 9 hydrate, 0.656 kg (8 mol) of sodium acetate and 5 kg of NMP. Distilled 6 liters. Next, after cooling the reaction vessel to 180 ° C, 3.712 kg (25.25 mol) of 1,4-dichlorobenzene and 2.4 kg of NMP were added, sealed under nitrogen, heated to 270 ° C, heated at 270 ° C. Reacted for 2.5 hours. Next, the mixture was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed with hot water at 80 ° C. for 30 minutes three times. This was filtered, poured into 25 liters of an aqueous solution containing 10.4 g of calcium acetate, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and the pH of the filtrate reached 7. After washing with ion-exchanged water at about 90 ° C., it was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-2 with a cooling crystallization temperature of 185 ° C. and MFR of 160 g / 10 min. The same operation was repeated and used for the following examples.

Production of PPS-3 An autoclave equipped with a stirrer was charged with sodium sulfide nonahydrate 6.005 kg (25 mol), sodium acetate 0.761 kg (9.28 mol) and NMP 5 kg, and gradually heated to 205 ° C. through nitrogen, Distilled 3.6 liters of water. Next, after cooling the reaction vessel to 180 ° C., 3.712 kg (25.25 mol) of 1,4-dichlorobenzene, 3.27 g (0.018 mol) of 1,3,5-trichlorobenzene and 2.4 kg of NMP were added. The mixture was sealed under nitrogen, heated to 270 ° C., and reacted at 270 ° C. for 2.5 hours. Next, the mixture was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed with hot water at 80 ° C. for 30 minutes three times. This was filtered, poured into 25 liters of an aqueous solution containing 10.4 g of calcium acetate, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and the pH of the filtrate reached 7. After washing with ion-exchanged water at about 90 ° C., it was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-3 with a cooling crystallization temperature of 180 ° C. and MFR of 70 g / 10 min. The same operation was repeated and used for the following examples.

Production of PPS-4 Into an autoclave equipped with a stirrer was charged 6.005 kg (25 mol) of sodium sulfide 9 hydrate, 0.69 kg (8.25 mol) of sodium acetate and 4.1 kg of NMP, and the temperature was gradually raised to 205 ° C. through nitrogen. Then, 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C., 3.582 kg (24.4 mol) of p-dichlorobenzene, 0.188 kg (1.28 mol) of m-dichlorobenzene and 3.2 kg of NMP were added and sealed under nitrogen. The mixture was heated to 270 ° C. and reacted at 270 ° C. for 2.5 hours. Next, the mixture was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed with hot water at 80 ° C. for 30 minutes three times. This was filtered and dried under reduced pressure at 80 ° C. for 24 hours. The total amount of m-phenylene sulfide units and p-phenylene sulfide units was 5 mol%, m-phenylene sulfide units were cooled at a crystallization temperature of 180 ° C., and MFR was 160 g / 10. Minute PPS-4 was obtained. The same operation was repeated and used for the following examples.

Production of PPS-5 An autoclave equipped with a stirrer was charged with 6.005 kg (25 mol) of sodium sulfide 9 hydrate, 0.656 kg (8 mol) of sodium acetate and 5 kg of NMP. Distilled 6 liters. Next, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and 2.4 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated at 270 ° C. Reacted for 2.5 hours. Next, the mixture was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed with hot water at 80 ° C. for 30 minutes three times. 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, It was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-5 with a cooling crystallization temperature of 215 ° C. and MFR of 300 g / 10 min. The same operation was repeated and used for the following examples.

Production of PPS-6 A sodium sulfide nonahydrate (6.005 kg, 25 mol) and NMP (5 kg) were charged into an autoclave equipped with a stirrer, and 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., 3.763 kg (25.6 mol) of 1,4-dichlorobenzene and 1.8 kg of NMP were added, sealed under nitrogen, heated to 274 ° C., heated at 274 ° C. It reacted for 0.8 hours. The extraction valve provided at the lower part of the autoclave was opened at room temperature and normal pressure, the contents were extracted, and washed with hot water at 80 ° C. This was filtered, poured into 25 liters of an aqueous solution containing 10.4 g of calcium acetate, stirred for about 1 hour at 192 ° C. in a sealed autoclave, filtered, and the pH of the filtrate reached 7. After washing with ion exchange water at about 90 ° C., the polymer was dried at 120 ° C. for 8 hours, and then heat-treated at 215 ° C. to obtain PPS-6 with a temperature-falling crystallization temperature of 215 ° C. and MFR of 300 g / 10 min. The same operation was repeated and used for the following examples.

  PPS-7: PPS resin M3910 manufactured by Toray Industries, Inc. (Cooling crystallization temperature 210 ° C., MFR 3000 g / 10 min)

Reference Example 2 Filler glass fiber (GF1): T-747H (manufactured by NEC Glass) E glass, single fiber diameter 10.5 μm, refractive index (n _D ) 1.55
Glass fiber (GF2): T-187N (fibrous filler, manufactured by Nippon Electric Glass Co., Ltd.) E glass, single fiber diameter 17 μm, refractive index (n _D ) 1.55
Glass fiber (GF3): T-747T (fibrous filler, manufactured by Nippon Electric Glass Co., Ltd.) E glass, single fiber diameter 23 μm, refractive index (n _D ) 1.55
Glass fiber (GF4): EPDM70M10A (fibrous filler, manufactured by NEC Glass) E glass, milled fiber, single fiber diameter 9 μm, refractive index (n _D ) 1.55, average fiber length 70 μm
Glass flake (GFL): REFG311 (plate filler, SNG Petrotex) E glass, the average particle diameter was determined to be 58 μm by the microtrack method. Refractive index (n _D ) 1.55
Glass beads (GB1): EGB731B2 (manufactured by Potters Barotini) E glass, average particle size: 20 μm (microtrack method), refractive index (n _D ) 1.55
Glass beads (GB2): J-54 (Potters Barotini) A glass, average particle size: 300 μm (microtrack method), refractive index (n _D ) 1.52
E glass pulverized product (EG): E glass (manufactured by Nippon Electric Glass Co., Ltd.) was pulverized with a Henschel mixer, sieved with a 63 μm pass and 9.5 μm undercut, and an EG having an average particle size of 20 μm (microtrack method) was obtained. Obtained. Refractive index (nD) 1.55
H glass pulverized product (HG1): H glass (manufactured by Nippon Electric Glass Co., Ltd.) was pulverized with a Henschel mixer, sieved with a 63 μm pass and 9.5 μm undercut, and HG1 having an average particle size of 20 μm (Microtrack method) was obtained. Obtained. Refractive index (nD) 1.74
H glass pulverized product (HG2): H glass (manufactured by Nippon Electric Glass Co., Ltd.) was pulverized with a Henschel mixer and sieved with a 355 μm pass and 45 μm undercut to obtain HG2 having an average particle size of 150 μm (microtrack method). . Refractive index (nD) 1.74
Alumina hydrate (BM1): “Terases” BMT33 (manufactured by Otsuka Chemical Co., Ltd.) plate shape, average particle diameter 5 μm (microtrack method), refractive index (n _D ) 1.66
Alumina hydrate calcined body (BM2): “Terraces” BMT33-B (manufactured by Otsuka Chemical Co., Ltd.) plate shape, average particle diameter 5 μm (microtrack method), refractive index (n _D ) 1.68

The single fiber diameter is a value measured by a test method based on JIS-R3420 5,6. The refractive index (n _D ) is measured based on a method using a critical angle of total reflection by preparing a 10 mm square cubic test piece and using a Purfrich refractometer. The average particle diameter is a number average obtained by a microtrack method in which ethanol is added to 0.70 g of a sample and ultrasonically dispersed for 3 minutes and laser light is irradiated. The 355 μm pass means passing through the corresponding sieve, and the 9.5 μm undercut means not passing through the corresponding sieve.

Reference Example 3 Amorphous resin polyarylate (PAR): “U polymer” U-100 (manufactured by Unitika) Glass transition temperature (Tg) = 195 ° C.
Polyetherimide (PEI): “Ultem” 1010 (manufactured by GE Plastics, Japan) Glass transition temperature (Tg) = 215 ° C.
Polyethersulfone (PES): “Sumika Excel” 3600P (manufactured by Sumitomo Chemical Co., Ltd.) Glass transition temperature (Tg) = 220 ° C.
Polyamideimide (PAI): synthesized by an acid chloride method low temperature solution polymerization method using N, N-dimethylacetamide as a polymerization solvent. Details are shown below. In 65 liters of N, N-dimethylacetamide (DMAC), 12 kg of diaminodiphenyl ether (DDE) and 2.0 kg of metaphenylenediamine (MPDA) are dissolved, and cooled in an ice bath, powdered trimellitic anhydride monochloride (TMAC) ) 15 kg was added at such a rate that the internal temperature did not exceed 30 ° C. After all the TMAC was added, 1.7 kg of trimellitic anhydride (TMA) was added, and the mixture was stirred and held at 30 ° C. for 2 hours. The polymer solution which became viscous was put into 100 liters of water stretched on a cutter mixer, and the polymer was precipitated in a slurry state by stirring at high speed. The resulting slurry was dehydrated with a centrifuge. The dehydrated cake was washed with 200 liters of water at 60 ° C. and dehydrated again with a centrifuge. The obtained cake was dried using a hot air dryer under the conditions of 220 ° C./5 hours to obtain a powdery polymer having a glass transition temperature (Tg) = 275 ° C. The same operation was repeated and used for the following examples.
Polysulfone (PSU): “Udel” P-1700 (Amoco Engineering Polymers) Glass transition temperature (Tg) = 190 ° C.
In addition, the glass transition temperature was calculated | required at the temperature increase rate of 20 degreeC using the differential scanning calorimeter (DSC-7: manufactured by Perkin Elmer).

Reference Example 4 Antioxidant Antioxidant: “Calcium hypophosphite” (manufactured by Taihei Chemical Industrial Co., Ltd.)
Reference Example 5 Elastomer elastomer-1 (ER-1): “BF-E” (manufactured by Sumitomo Chemical Co., Ltd.) ethylene / glycidyl methacrylate = 97.6 / 2.4 (mol%) copolymer.
Elastomer-2 (ER-2): “Toughmer A4085” (manufactured by Mitsui Chemicals), ethylene / butene-1 = 90.8 / 9.2 (mol%) copolymer.

Reference Example 6 Silane Compound Silane Compound: “KBM303” (manufactured by Shin-Etsu Chemical Co., Ltd.) β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Reference Example 7 Crystal nucleating agent talc (TLC): “Hytron” (Takehara Chemical Industries) (Made by company)
Polyetheretherketone (PEEK): “PEEK450-PF” (manufactured by Victrex MC)

Examples 1-44, Comparative Examples 1-5
The PPS resin of Reference Example 1, the filler shown in Reference Example 2, the amorphous resin shown in Reference Example 3, the antioxidant shown in Reference Example 4, the elastomer shown in Reference Example 5, and the reference example 6 The silane compound and the crystal nucleating agent shown in Reference Example 7 were blended in the amounts shown in Tables 1 to 4 using a ribbon blender, and Tables 1 to 4 were added using PCM30 with a three-hole strand die head (2-screw extruder; manufactured by Ikegai Steel Corporation). Melt-kneading was performed at the resin temperature shown in FIG. Next, after drying in a hot air oven at 130 ° C. for 4 hours, the following evaluation was performed. The results are shown in Table 1.

  Moreover, about Example 6, 7, 10, 13, 15-17, 19-24, 26-37, 39 and Comparative Examples 1-3, evaluation shown in (7) was further performed. The results are shown in Table 2. Furthermore, about Example 33-37 and Comparative Examples 1-3, evaluation shown to (8) was performed. The results are shown in Table 3. Furthermore, the evaluation shown in (9) was performed for Example 7, Examples 41 to 44, and Comparative Examples 4 and 5. The results are shown in Table 4.

(1) Temperature drop crystallization temperature About 10 mg was sampled from PPS resin powder and PPS resin composition pellets, and heated using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer Co., Ltd. at a temperature rising rate of 20 ° C./min. Then, after holding at 340 ° C. for 5 minutes, the temperature of the crystallization peak (exothermic peak) when the temperature was lowered at a rate of 20 ° C./minute was measured and taken as the lowered crystallization temperature.

(2) Chloroform extraction amount PPS resin powder and PPS resin composition pellets are frozen and pulverized, the pulverized sample is classified with 32 to 60 mesh, washed 5 times with 30 ml of methanol to remove deposits, and then vacuum-dried sample. Weigh 2 g. A 2 g sample is subjected to total reflux extraction (Soxhlet extraction) with 20 g of chloroform using a Soxhlet extractor at 85 ° C. for 5 hours. Chloroform is recovered and vacuum dried at 23 ° C. for 1 hour. It is measured by a method of calculating a value obtained by dividing the weight after drying by the weight before extraction.

(3) Thermal deformation temperature 12.7 mm at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C. using an injection molding machine UH1000 (manufactured by Nissei Plastic Industrial Co., Ltd.) using an injection molding machine UH1000 (manufactured by Nissei Plastic Industrial Co., Ltd.) A test piece of (width) × 3.2 mm (thickness) × 127 mm (length) was injection molded. The measurement method was in accordance with ASTM-D648, and the thermal deformation temperature (load deflection temperature) under a 0.46 MPa load was evaluated.

(4) Laser welding strength evaluation (2.0 mm thickness)
Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), a laser beam transmission evaluation test piece having a thickness of 80 mm × 80 mm × 2.0 mm at a resin temperature and a mold temperature shown in Table 1 is prepared, and the test piece is further 24 mm × Each sample was processed to a thickness of 70 mm × 2.0 mm, the transmission sample and the absorption side sample were overlapped, the length L was 30 mm, the laser welding distance Y was 20 mm, laser welding was performed, and the tensile strength at break was measured.

  The welding conditions and welding strength measurement conditions are as follows.

  Laser welding conditions were used under the conditions that the best welding strength was obtained in the range of 15 to 35 W output and 1 to 50 mm / sec laser scanning speed. The focal length was 38 mm and the focal diameter was fixed at 0.6 mm. In addition, a general tensile tester (AG-500B) was used to measure the welding strength, and both ends of the test piece were fixed, and a tensile test was performed so that a tensile shear stress was generated at the welded portion. The tensile speed during strength measurement is 1 mm / min, and the span is 40 mm. The welding strength was the stress when the welded site was broken. In addition, the thermoplastic resin composition of the present invention was used for the laser beam transmission sample, and a material obtained by further adding 0.4 part of carbon black to the transmission side sample was used for the laser beam absorption side sample.

(5) Laser welding strength evaluation (4.5mm thickness)
Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industrial Co., Ltd.), a laser beam transmission evaluation test piece having a thickness of 80 mm × 80 mm × 4.5 mm at a resin temperature and a mold temperature shown in Table 1 is prepared, and the test piece is further 24 mm × Each sample was processed to a thickness of 70 mm × 4.5 mm, the transmission sample and the absorption side sample were overlapped, the length L was 30 mm, the laser welding distance Y was 20 mm, laser welding was performed, and the tensile strength at break was measured.

  The welding conditions and welding strength measurement conditions are as follows.

  Laser welding conditions were used under the conditions that the best welding strength was obtained in the range of 15 to 35 W output and 1 to 50 mm / sec laser scanning speed. The focal length was 38 mm and the focal diameter was fixed at 0.6 mm. In addition, a general tensile tester (AG-500B) was used to measure the welding strength, and both ends of the test piece were fixed, and a tensile test was performed so that a tensile shear stress was generated at the welded portion. The tensile speed during strength measurement is 1 mm / min, and the span is 40 mm. The welding strength was the stress when the welded site was broken. In addition, the thermoplastic resin composition of the present invention was used for the laser beam transmission sample, and a material obtained by further adding 0.4 part of carbon black to the transmission side sample was used for the laser beam absorption side sample.

(6) Low warpage Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), a square plate of 70 mm x 70 mm x 1 mm thickness is molded at the resin temperature and mold temperature shown in Table 1, and heat treated at 130 ° C for 1 hour. The warpage was evaluated.

  Evaluation was made by suppressing any one of the four sides of the square plate, and warping amounts were A: less than 0.8 mm, B: less than 1 mm, and C: 1 mm or more.

(7) Laser welding strength evaluation (5.0mm thickness)
Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), a laser beam transmission evaluation test piece having a thickness of 80 mm × 80 mm × 5 mm at a resin temperature and a mold temperature shown in Table 2 was prepared, and the test piece was further 24 mm × 70 mm × Each sample was processed to a thickness of 5 mm, the transmission sample and the absorption side sample were overlapped, the length L was 30 mm, the laser welding distance Y was 20 mm, laser welding was performed, and the tensile strength at break was measured.

  The welding conditions and welding strength measurement conditions are as follows.

  Laser welding conditions were used under the conditions that the best welding strength was obtained in the range of 15 to 35 W output and 1 to 50 mm / sec laser scanning speed. The focal length was 38 mm and the focal diameter was fixed at 0.6 mm. In addition, a general tensile tester (AG-500B) was used to measure the welding strength, and both ends of the test piece were fixed, and a tensile test was performed so that a tensile shear stress was generated at the welded portion. The tensile speed during strength measurement is 1 mm / min, and the span is 40 mm. The welding strength was the stress when the welded site was broken. In addition, the thermoplastic resin composition of the present invention was used for the laser beam transmission sample, and a material obtained by further adding 0.4 part of carbon black to the transmission side sample was used for the laser beam absorption side sample.

(8) Resistance to cold and heat Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), a metal piece having a length of 47.0 mm, a width of 47.0 mm, and a height of 28.6 mm at a resin temperature and mold temperature shown in Table 3 is gold. It fixed in the type | mold, resin of thickness 1.5mm was overmolded on the outer periphery of the said metal piece, and the cold-heat resistance evaluation test piece was produced. Evaluation uses THERMAL SHOCK CHANBER TSA-100S-W (manufactured by Tabai Co., Ltd.), and exposes 130 ° C (high temperature side) and -40 ° C (low temperature side) every hour, making this one cycle, and cracks are generated The number of cycles until the determination was made visually, and the average number of cycles of n = 3 was set to A: 1000 cycles or more, B: 300 cycles or more, C: 30 cycles or more, and D: less than 30 cycles.

(9) Evaluation of variation in laser welding strength (2.0mm thickness)
Using an injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), a laser beam transmission evaluation test piece having a thickness of 80 mm × 80 mm × 2 mm at a resin temperature and a mold temperature shown in Table 4 was prepared. The gate shape is a film gate. The test piece is cut to a thickness of 24 mm × 70 mm × 2 mm, and the cutting portion is 2 to 26 mm (gate portion) and 28 to 52 mm (center portion) from the gate side, with the horizontal direction as the longitudinal direction with respect to the film gate. ), 54 to 78 mm (terminal portion). The transmission sample and the absorption side sample were overlapped, the length L was 30 mm, the laser welding distance Y was 20 mm, laser welding was performed, and the tensile strength at break was measured.

  The welding conditions and welding strength measurement conditions are as follows.

  Laser welding conditions were used under the conditions that the best welding strength was obtained in the range of 15 to 35 W output and 1 to 50 mm / sec laser scanning speed. The focal length was 38 mm and the focal diameter was fixed at 0.6 mm. In addition, a general tensile tester (AG-500B) was used to measure the welding strength, and both ends of the test piece were fixed, and a tensile test was performed so that a tensile shear stress was generated at the welded portion. The tensile speed during strength measurement is 1 mm / min, and the span is 40 mm. The welding strength was the stress when the welded site was broken. In addition, for the evaluation of variation in laser welding strength, the maximum value-minimum value among the welding strength values of the gate portion, the central portion, and the terminal portion were set to A: less than 5 MPa, B: 5 MPa to 10 MPa, and C10 MPa or more. In addition, the thermoplastic resin composition of the present invention was used for the laser beam transmission sample, and a material obtained by further adding 0.4 part of carbon black to the transmission side sample was used for the laser beam absorption side sample.

Claims (14)

(A) A polyphenylene sulfide resin composition obtained by blending 1 to 600 parts by weight of (B) filler with respect to 100 parts by weight of polyphenylene sulfide resin, and the temperature-falling crystallization temperature of the composition is 205 ° C. or lower. A polyphenylene sulfide resin composition for welding. The laser welding according to claim 1, wherein (B) the filler is at least one selected from (B1) glass fiber having a single fiber diameter of 12 μm or more, and (B2) a non-fibrous filler having an average particle diameter of 30 μm or more. Polyphenylene sulfide resin composition. (B) The polyphenylene sulfide resin composition for laser welding according to claim 1 or 2, wherein the filler has a refractive index of 1.6 to 1.8. The laser according to any one of claims 1 to 3, further comprising (C) 1 to 200 parts by weight of an amorphous resin having a glass transition temperature of 130 ° C or more per 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition for welding. (C) Amorphous resin having a glass transition temperature of 130 ° C. or higher is (C1) polyamideimide resin, (C2) polyarylate resin, (C3) polyethersulfone resin, (C4) polyetherimide resin, (C5) The polyphenylene sulfide resin composition for laser welding according to claim 4, wherein the composition is one or more selected from polysulfone resins. 6. The polyphenylene sulfide resin composition for laser welding according to any one of claims 1 to 5, further comprising (D) an antioxidant in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the (A) polyphenylene sulfide resin. . The laser-welded polyphenylene sulfide resin composition according to any one of claims 1 to 6, further comprising (E) an elastomer in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the (A) polyphenylene sulfide resin. The polyphenylene sulfide resin composition for laser welding according to any one of claims 1 to 7, further comprising 0.01 to 5 parts by weight of (F) silane compound based on 100 parts by weight of (A) polyphenylene sulfide resin. Polyphenylene sulfide resin composition according to any one of claims 1 to 8, wherein (G) crystal nucleating agent is blended in an amount of 0.01 to 5 parts by weight with respect to 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition for laser welding, which is a sulfide resin composition, and the temperature-falling crystallization temperature of the composition is 225 ° C. or lower. A laser welded molded body comprising the resin composition for laser welding according to any one of claims 1 to 9, wherein the thickness of the welded portion is 5 mm or less. . A method for producing a laser-welded molded article, wherein the laser-welded resin composition according to any one of claims 1 to 9 is injection-molded at a mold temperature of 100 ° C or lower. A composite molded article obtained by laser welding a molded article comprising the resin composition for laser welding according to claim 1. A composite molded product obtained by laser welding the molded product comprising the laser welding resin composition according to claim 1 as a laser beam transmission side molded product, wherein the molded product on the laser beam absorption side contains a polyphenylene sulfide resin. The composite molded body according to claim 12, which is a waste. A method for producing a composite molded article, comprising: heat-treating a molded article comprising the resin composition for laser welding according to any one of claims 1 to 9 after laser welding.