JP2008138132A - Reinforced polyester resin composition and molded article composed of this reinforced resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a reinforced polyester resin composition which can obtain a molded article excellent in moldability, mechanical strength, external appearance, weatherability and the like and a molded article composed of this reinforced resin composition. <P>SOLUTION: The reinforced polyester resin composition comprises component (A) of 100 pts.wt. polyester resin, component (B) of 0-19 pts.wt. acrylic resin, component (C) of 1-20 pts.wt. graft copolymer composed of 5-99 wt.% copolymer segment formed of a nonpolar polar α-olefin monomer and 1-95 wt.% vinyl(co)polymer segment formed of at least one vinyl monomer, component (D) of 30-200 pts.wt. inorganic filler, and component (E) of 0.1-20 pts.wt. colorant. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

The present invention relates to a reinforced polyester resin composition and a molded article made of the reinforced resin composition. More specifically, a polyester resin composition reinforced with an inorganic filler, which is excellent in moldability and can provide a molded article excellent in mechanical strength, appearance, weather resistance, etc., and an automobile comprising this reinforced resin composition, The present invention relates to trains, interior / exterior parts for vehicles such as trains, interior / exterior parts for aircraft such as airplanes, and particularly wiper parts.

Thermoplastic polyester resins such as polyethylene terephthalate resin (hereinafter may be abbreviated as PET) and polybutylene terephthalate resin (hereinafter may be abbreviated as PBT) have their own mechanical and electrical properties. In addition to being excellent in chemical resistance and heat resistance, it is also excellent as an engineering plastic, as well as various electrical and electronic equipment parts, interior and exterior parts for vehicles such as automobiles, trains and trains, and other general industrial products. Widely used as a manufacturing material. Furthermore, so-called fiber reinforced polyester resins, in which a reinforcing material, especially a fibrous reinforcing agent, is blended with these thermoplastic polyester resins have greatly improved mechanical properties, so that their range of use is expanding.

Conventionally, light and high strength / rigidity and excellent appearance are required for interior and exterior parts for vehicles such as automobiles, trains and trains, and interior and exterior parts for aircraft such as airplanes. Specifically, for example, indoor inner mirror stays, door handles, hanging leather, handle parts, wiper parts such as outdoor wiper arms, door handles, door mirror stays, roof rails and the like can be mentioned. For example, a reinforced thermoplastic resin, particularly a fiber reinforced polyester resin is used as a material for manufacturing these parts.

In order to improve the strength and rigidity of the resin molded product obtained from the fiber reinforced thermoplastic resin, it is necessary to increase the amount of the fibrous filler (reinforcing agent or reinforcing agent) to be blended with the thermoplastic resin as the base. However, increasing the compounding amount of the reinforcing agent decreases the moldability (fluidity) of the fiber reinforced resin composition, and the blended fibrous reinforcing agent tends to be raised on the surface of the product (molded product), thereby reducing the appearance of the product. There was a drawback of doing.

In addition, the above-mentioned interior / exterior parts for vehicles, fuselage parts, and electrical / electronic equipment parts are being reduced in weight by making them thinner and smaller for the purpose of cost reduction, resource saving, energy saving, environmental conservation measures, etc. Furthermore, for the raw resin used for manufacturing these parts, mechanical strength is improved, many excellent performances {excellent weather resistance (light), parts are difficult to fade, The demand for long-lasting properties has become more stringent, however, such that the gloss does not easily deteriorate, the inorganic reinforcing agent does not float on the surface of the product, and the appearance of the product does not easily change. In particular, parts made of fiber reinforced polyester resin (PET, PBT, etc.) have many excellent properties over a long period of time even when used outdoors exposed to strong sunlight, intense temperature changes, intense wind and rain, etc. There is a strong demand to maintain the same performance.

Among vehicle interior / exterior parts manufactured from fiber-reinforced polyester resin compositions and interior / exterior parts for aircraft, parts that require mechanical properties and weather resistance are used for automobiles, trains, trains, airplanes, etc. There are wiper parts. The wiper component mainly includes a wiper blade and a wiper arm, and the wiper blade is a component in which a wiping portion that contacts and wipes a surface to be wiped such as a windshield surface is attached in the longitudinal direction, and is entirely What was shape | molded with the resin material is common.

The wiper blade is supported by a wiper arm, and a base (head) coupled to the wiper arm is connected to a wiper motor via a plurality of link members. The wiper arm reciprocates by the operation of the wiper motor, and accordingly, the wiping portion of the blade wipes the surface to be wiped such as the windshield surface. Because of this mechanism, it demonstrates high performance in various properties such as rigidity, mechanical strength, heat resistance, weather resistance, hydrolysis resistance, and appearance characteristics for wiper parts, especially wiper arm manufacturing materials. It is requested.

For the purpose of further improving the strength of the fiber reinforced polyester resin, not only is a fiber reinforcing agent typified by glass fiber added to the base resin PET, PBT, etc., but the base resin and the fibrous reinforcing agent In order to improve the adhesion (affinity) of the interface, the surface of the fibrous reinforcing agent is treated with a polyfunctional compound (for example, epoxy silane, isocyanate compound, polycarboxylic acid anhydride, etc.), or fibrous reinforcing. A resin composition blended with a base resin together with an agent has been proposed (see, for example, Patent Document 1).

In addition, as a fibrous reinforcing agent to be blended in a PBT composition or the like, by using a specific compound, for example, a fibrous reinforcing agent surface-treated with an epoxy resin and an aminosilane coupling agent, the electrical strength of the reinforced resin composition can be increased. Techniques for improving characteristics and mechanical properties have been proposed (see, for example, Patent Documents 2 to 5).

Furthermore, for the purpose of improving the mechanical strength, at least a part of (B) a sizing agent containing an amino-based silane coupling agent and a novolac-type epoxy resin is attached to at least part of (A) 100 parts by weight of the polyester resin. There has been proposed a glass fiber reinforced polyester resin composition containing 10 to 150 parts by weight of glass fiber and 0.1 to 3 parts by weight of (C) an epoxy compound (see, for example, Patent Document 6). This glass fiber reinforced polyester resin composition is described as having improved mechanical strength.

Furthermore, as a resin composition having excellent weather resistance (light) and little change in appearance, (A) 100 to 55% by weight of polybutylene terephthalate resin, (B) aromatic polycarbonate resin, or polyethylene terephthalate resin 0 to (C) 3 to 200 parts by weight of an inorganic filler treated mainly with an acrylic compound, and (D) 0.01 to 10 parts by weight of a coloring component with respect to 100 parts by weight of a resin component consisting of 45% by weight There has been proposed a reinforced polybutylene terephthalate resin composition obtained by blending (see, for example, Patent Document 7).

Furthermore, as a method for improving the mechanical strength and appearance characteristics of the wiper part, 20 to 150 parts by mass of a reinforcing material and 0.1 to 5 parts by mass of an epoxy group-containing substance are blended with respect to 100 parts by mass of the polyethylene terephthalate resin. A wiper part made of a reinforced polyethylene terephthalate resin composition has been proposed (see, for example, Patent Document 8).
Japanese Patent Publication No.51-7702 JP-A-9-301746 Japanese Patent Laid-Open No. 2001-172055 JP 2001-172056 A JP 2001-172057 A JP 2006-16557 A JP-A-9-104812 JP 2003-342454 A

However, recent requirements for interior / exterior parts for vehicles and airframes and raw material resins for producing these parts have become more severe, and the methods described in Patent Documents 1 to 8 have been difficult to cope with. In such a situation, the present invention is a polyester resin composition reinforced with an inorganic filler having high performance required (hereinafter sometimes referred to simply as a reinforced resin composition), and the reinforced resin. It aims at providing the molded article (product) manufactured from the composition. That is, the object of the present invention is as follows. 1. To provide a reinforced polyester resin composition having excellent fluidity and capable of producing a molded product having a reduced thickness and size. 2. To provide a reinforced polyester resin composition capable of obtaining a molded article excellent in mechanical strength, weather resistance, appearance and the like. 3. To provide a reinforced polyester resin composition capable of obtaining a molded product having many excellent characteristics such as mechanical strength, weather resistance, and appearance over a long period of time. 4). To provide a molded article made of a reinforced polyester resin composition having excellent properties such as mechanical strength, weather resistance, and appearance.

In order to achieve the above object, the first invention provides a reinforced polyester resin composition comprising the following components (A) to (E). (A) component: 100 parts by weight of a polyester resin, (B) component: 0 to 19 parts by weight of an acrylic resin, (C) component: formed from a nonpolar α-olefin monomer and a polar vinyl monomer. 1 to 20 parts by weight of a graft copolymer consisting of 5 to 99% by weight of a copolymer segment and 1 to 95% by weight of a vinyl (co) polymer segment formed from at least one vinyl monomer, (D) component: 30-200 weight part of inorganic fillers, and (E) component: 0.1-20 weight part of coloring agent.

Furthermore, in the second invention, there is provided a molded product characterized in that it is produced using a reinforced polyester resin composition containing the following components (A) to (E) as a raw material. (A) component: 100 parts by weight of a polyester resin, (B) component: 0 to 19 parts by weight of an acrylic resin, (C) component: formed from a nonpolar α-olefin monomer and a polar vinyl monomer. 1 to 20 parts by weight of a graft copolymer consisting of 5 to 99% by weight of a copolymer segment and 1 to 95% by weight of a vinyl (co) polymer segment formed from at least one vinyl monomer, (D) component: 30-200 weight part of inorganic fillers, and (E) component: 0.1-20 weight part of coloring agent.

The present invention is as described in detail below, has the following particularly advantageous effects, and its industrial utility value is extremely large. 1. The reinforced polyester resin composition according to the present invention is excellent in fluidity, and can produce a molded product that is thin and small. 2. The molded product obtained from the reinforced polyester resin composition according to the present invention is excellent in mechanical strength, weather resistance, appearance, and the like. 3. The molded product obtained from the reinforced polyester resin composition according to the present invention maintains many excellent properties such as mechanical strength, weather resistance, and appearance over a long period of time. 4). Since the molded product obtained from the reinforced polyester resin composition according to the present invention maintains many excellent characteristics over a long period of time, the reliability of the product is high and the commercial value is increased.

Hereinafter, the present invention will be described in detail. The base resin in the reinforced resin composition according to the present invention is a polyester resin as the component (A). {Hereinafter, it may be simply referred to as the component (A) or (A). }. This polyester resin is a conventionally known polyester resin, and may be described as a dicarboxylic acid or a derivative thereof (A1) {hereinafter referred to simply as component (A1) or (A1). } And the diol component (A2) {hereinafter, simply referred to as the component (A2) or (A2). } Is a polyester resin obtained by polycondensation.

Examples of the dicarboxylic acid or its derivative (A1) include aromatic dicarboxylic acids, alicyclic dicarboxylic acids, aliphatic dicarboxylic acids, and lower alkyl or glycol esters thereof. Of these, aromatic dicarboxylic acids or esters of these lower alkyls or glycols are preferred, and terephthalic acid or these lower alkyl esters are particularly preferred. The dicarboxylic acid or its derivative (A1) may be a single type or a mixture of two or more types.

Aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-diphenylether dicarboxylic acid, 4,4'-benzophenone dicarboxylic acid, 4,4'-diphenoxy Examples include ethanedicarboxylic acid, 4,4′-diphenylsulfonedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.

Examples of the alicyclic dicarboxylic acids include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Examples of the aliphatic dicarboxylic acids include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid.

Examples of the diol component (A2) include aliphatic diols, alicyclic diols, and aromatic diols. As the aliphatic diols, aliphatic diols having 2 to 20 carbon atoms are preferable. Specifically, ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5- Examples include pentanediol, neopentyl glycol, 1,6-hexanediol, and 1,8-octanediol. Among these, a diol having 2 to 4 carbon atoms is preferable. The diol component (A2) may be a single type or a mixture of two or more types.

As the alicyclic diols, those having 2 to 20 carbon atoms are preferable. Specific examples include 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, and the like. Aromatic diols include xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, bis (4-hydroxyphenyl) sulfone, and the like.

The polyester resin as the component (A) can include other copolymerization components by substituting a part of the above (A1) or (A2). Other copolymer components include hydroxycarboxylic acids such as lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, and p-β-hydroxyethoxybenzoic acid, Monofunctional components such as alkoxycarboxylic acids, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid, and benzoylbenzoic acid are included. Furthermore, trifunctional or more polyfunctional components such as tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol and pentaerythritol are also included.

As the component (A), polyalkylene terephthalate is preferable. Specifically, polybutylene terephthalate (PBT) resin or polyethylene terephthalate (PET) resin is preferable from the viewpoint of availability and price. The PBT resin is a resin having an ester-bonded structure having a terephthalic acid unit as a main component as the component (A1) and a 1,4-butanediol unit as the main component as the component (A2). When the proportion of the terephthalic acid unit in the component (A1) and the proportion of the 1,4-butanediol unit in the component (A2) are too low, the crystallization speed of the resulting PBT resin is lowered and the moldability is lowered. There is. Therefore, the proportion of terephthalic acid units in the component (A1) is usually preferably 70 mol% or more. Among these, 80 mol% or more is preferable, more preferably 95 mol% or more, and particularly preferably 98 mol% or more. The proportion of 1,4 butanediol units in the component (A2) is usually preferably 70 mol% or more. Among these, 80 mol% or more is preferable, more preferably 95 mol% or more, and particularly preferably 98 mol% or more.

When the polyester resin of component (A) is produced, the charge ratio of the component (A1) and the diol component (A2) of the dicarboxylic acid or derivative thereof, that is, the ratio of the component (A1) to the component (A2) is preferably 1. 0.0 moles to 1.0-5.0 moles, more preferably 1.0 moles to 1.5-4.5 moles, even more preferably 1.0 moles to 2.0-4.0 moles.

The component (A) can be produced by the following methods: (i) direct polymerization method and (ii) transesterification method. (I) In the direct polymerization method, a dicarboxylic acid is used as the component (A1), and (ii) in the transesterification method, an alkyl of dicarboxylic acid or an ester of glycol is used as the component (A1). Moreover, it is divided roughly into a batch method and a continuous method by the raw material supply or the extraction form of the produced polymer {method of extracting the produced (molten) polymer from a reaction tank or the like}, and any method may be used. From the viewpoints of raw material basic unit, ease of by-product processing, etc., (i) direct polymerization method is preferable, and from the viewpoint of quality stability of PBT resin and energy efficiency required for production, it is preferable to use a continuous method. preferable.

When the component (A) is produced by the direct polymerization method (i), for example, the following method can be used. (A1) component and (A2) component, if necessary, other copolymerization components, in the presence of a polycondensation catalyst and a cocatalyst, other additives are added as necessary, and the ester is continuously or batchwise. Perform oligomerization reaction to prepare oligomers. In this esterification reaction, the above raw material components are charged into a single esterification reaction tank or the first tank of an esterification reaction tank composed of a plurality of tanks, and a catalyst, a promoter, and other additives are added as necessary. The reaction is carried out while distilling off water produced by the reaction while stirring in an inert gas atmosphere. After completion of the esterification reaction, the reaction mixture is used in the same reaction vessel as the esterification reaction vessel, or the reaction mixture is removed from the esterification reaction vessel to a single polycondensation reaction vessel, or the first polycondensation reaction vessel comprising a plurality of vessels. Transfer to the tank and add polycondensation catalyst, co-catalyst and other additives to the reaction mixture after transfer, if necessary, and continuously while adjusting the temperature and pressure while stirring in an inert gas atmosphere The polycondensation reaction is carried out either batchwise or batchwise.

The form and structure of the esterification reaction tank and polycondensation reaction tank are not particularly limited, and are conventionally known as a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower type continuous reaction tank, and a combination thereof. Can be used as is. Among these, at least one polycondensation reaction tank is preferably equipped with a stirring device. The stirring device depends on the type, shape, size, etc. of the tank. In addition to the conventionally known stirring blades composed of a power unit, bearings, shafts, stirring blades, etc., a turbine stator type high-speed rotary stirring machine, disk Examples thereof include a stirrer capable of rotating at high speed such as a mill type stirrer and a rotor mill type stirrer.

When performing the esterification reaction or polycondensation reaction, it is preferable to use a catalyst. As a catalyst that can be used in carrying out these reactions, a catalyst that is conventionally used in producing a polyester resin can be used as it is. Examples of the catalyst that can be used for the esterification reaction and polycondensation reaction include (a) titanium compounds, (b) periodic table group 1 metal compounds and / or periodic table group 2 metal compounds, tin compounds, and the like. A cocatalyst can be used in combination. (A) Specific examples of titanium compounds include inorganic titanium compounds such as titanium oxide and titanium tetrachloride, titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate, and titanium phenolates such as tetraphenyl titanate. Etc. Of these, titanium alcoholates are preferable, tetraalkyl titanates are more preferable, and tetrabutyl titanate is particularly preferable.

(B) Examples of the metal of the periodic table Group 1 metal compound include lithium, sodium, potassium, rubidium, and cesium. Examples of the metal-containing compound include various organic acid salts such as acetate, phosphate and carbonate, hydroxides, oxides, alcoholates and the like. (B) Examples of the metal of the Group 2 metal compound of the periodic table include beryllium, magnesium, calcium, strontium, and barium. Examples of the metal-containing compound include various organic acid salts such as acetate, phosphate and carbonate, hydroxides, oxides, alcoholates and the like. From the viewpoints of handling, availability, and catalytic effect, compounds such as lithium, sodium, potassium, magnesium, and calcium are preferred. Considering the color tone of the polyester resin obtained, a lithium or magnesium compound is preferable, and a magnesium compound is particularly preferable. Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Magnesium acetate is particularly preferable. These (a) and (b) may be one kind or a mixture of two or more kinds.

Examples of tin compounds include dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, triphenyltin hydroxide, triisobutyltin Examples include acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid, and butylstannic acid.

Co-catalysts include antimony compounds such as antimony trioxide, germanium compounds such as germanium dioxide and germanium tetroxide, manganese compounds, zinc compounds, zirconium compounds, cobalt compounds, orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc. In addition, esters of these phosphorus compounds, metal salts of phosphorus compounds, and the like can be given.

The (a) titanium compound and (b) the periodic table group 1 metal catalyst and / or the periodic table group 2 metal catalyst may be added to the component (A1), the esterification reaction tank, or the transesterification. From the reaction liquid phase part such as a polycondensation reaction tank following the reaction tank, it may be added to the upper surface of the reaction liquid, or may be added directly to the reaction liquid phase part. It can also be added to the oligomer piping. In this case, the addition method is to stabilize the supply amount and reduce adverse effects such as heat denaturation, and the catalyst is water, copolymer component 1,4-butanediol, copolymer component polytetramethylene. It is preferable to dissolve in (A2) liquid such as ether glycol and add as a solution. In this case, the concentration of the catalyst component is usually in the range of 0.01 to 20% by weight, particularly in the range of 0.05 to 10% by weight, particularly in the range of 0.08 to 8% by weight. preferable.

In the case where the component (A) of the present invention contains a PBT resin, when (a) a titanium compound is used as a catalyst for producing a PBT resin, the theoretical yield of the obtained PBT resin is 10 to 10 in terms of titanium atoms. It can be used in the range of 80 ppm, preferably 15 to 70 ppm, more preferably 20 to 60 ppm, particularly preferably 30 to 50 ppm. (A) By using a titanium compound in such a range, the residual amount of the titanium compound in the obtained PBT resin is 10 to 80 ppm, preferably 15 to 70 ppm, more preferably 20 to 60 ppm in terms of titanium atoms. Especially preferably, it can be 30-50 ppm. If the amount of this (a) titanium compound used is too large, the amount of titanium compound remaining in the resulting PBT resin will increase, resulting in a decrease in the color tone of the PBT resin, a decrease in hydrolysis resistance, a solution haze due to the deactivation of the titanium catalyst, and foreign matter. In some cases, it may cause an increase. On the other hand, if the amount is too small, the polymerizability of the raw material mixture is lowered, which is not preferable.

The amount of the catalyst (b) Periodic Table Group 1 metal compound and / or Group 2 metal compound used in the catalyst is 1 to 50 ppm in terms of each metal atom, preferably 1 ppm to the theoretical yield of the PBT resin obtained, It can be used in the range of 3 to 40 ppm, more preferably 5 to 30 ppm, particularly preferably 10 to 20 ppm. By setting it as such usage-amount, the residual amount of (b) periodic table group 1 metal compound and / or periodic table group 2 metal compound in PBT resin obtained is 1-50 ppm in each atom conversion, Preferably it is 3-40 ppm, More preferably, it is 5-30 ppm, Most preferably, it can be 10-20 ppm. If the amount of the periodic table group 1 metal compound and / or the periodic table group 2 metal compound is too large, the moldability of the reinforced resin composition finally obtained or the molded product obtained from the reinforced resin composition On the other hand, if the amount is too small, the interfacial adhesion between the PBT resin and the inorganic filler and the heat shock resistance may be lowered, which is not preferable.

When a tin compound is used as a catalyst for producing a PBT resin, the amount used is 200 ppm or less, preferably 100 ppm or less, particularly preferably 10 ppm or less, in terms of tin atom, based on the theoretical yield of the obtained PBT resin. . If the amount of tin compound used is too large, the amount of tin compound remaining in the resulting PBT resin will increase and the color tone of the resulting PBT resin will deteriorate, so it is preferable to make it as small as possible.

The amount of metal remaining (contained) such as titanium atoms remaining (contained) in the polyester resin is determined by recovering the metal in the polymer by a method such as wet ashing, then atomic emission, atomic absorption, Inductively Coupled Plasma (ICP), etc. It is possible to measure by making full use of this method.

The reaction conditions in the esterification reaction step depend on the types of (A1) and (A2), the type / amount of catalyst, the presence / absence / type / amount of promoter, the type of other compounds, the amount of addition (use), etc. The temperature condition is usually selected in the range of 180 to 260 ° C. In this reaction temperature range, 200 to 245 ° C is preferable, and 210 to 235 ° C is particularly preferable. The pressure condition is usually selected in the range of 10 to 133 kPa. In this pressure range, 13 to 101 kPa is preferable, and 60 to 90 kPa is particularly preferable. The reaction time is usually selected in the range of 0.5 to 10 hours, with 1 to 6 hours being particularly preferred. The oligomer as the esterification reaction product (or transesterification product) is transferred to the polycondensation reaction step. Although the esterification rate of an oligomer is arbitrary, it is 90% or more normally, Preferably it is 95% or more, and the number average molecular weight of this oligomer is 300-3000 normally, Preferably it is 500-1500.

The reaction conditions in the polycondensation reaction step depend on the types of (A1) and (A2), the type / amount of the catalyst, the presence / absence / type / amount of the cocatalyst, the type of other compounds, the amount of addition (use), etc. The temperature condition is usually selected in the range of 210 to 280 ° C. In this reaction temperature range, 220 to 250 ° C is preferable, and 230 to 240 ° C is particularly preferable. In addition, when using several reaction tanks, it is preferable that the temperature of the at least 1 reaction tank is 230-240 degreeC. The pressure condition is usually 27 kPa or less, preferably 20 kPa or less, and particularly preferably 13 kPa or less. When the polycondensation reaction is performed in a plurality of polycondensation tanks, the pressure in at least one of the reaction tanks is preferably 1.3 kPa or less in order to suppress coloring and deterioration of the product. It is preferable to use a high vacuum of 0.5 kPa or less, particularly 0.3 kPa or less. The reaction time is usually selected in the range of 1 to 12 hours, and particularly preferably in the range of 3 to 10 hours.

The polyester resin obtained by the polycondensation reaction is usually extracted from the bottom of the polycondensation reaction tank through the extraction line equipped with a filter for removing foreign substances in the flow path, in the form of a melted strand from the head, water, etc. And is cut by a cutter to form pellets, chips, or other granular materials. Further, in the polycondensation reaction step of the polyester resin, once a polyester resin having a relatively small molecular weight, for example, an intrinsic viscosity of about 0.1 to 0.9 dL / g, is produced by melt polycondensation, The molecular weight can also be increased by solid phase polycondensation (solid phase polymerization) at a temperature below the melting point.

The polyester resin of the component (A) obtained by the above reaction is not limited in the terminal carboxyl group concentration, but is generally preferably lower. Specifically, 30 μeq / g or less is preferable. If the terminal carboxyl group concentration exceeds 30 μeq / g, the residence heat stability of the reinforced resin composition and the hydrolysis resistance of the molded product obtained from the reinforced resin composition may be lowered. Even if it is too low, the effect of improving the mechanical strength and the heat shock resistance may be lowered. Therefore, the range of 5 to 25 μeq / g, particularly 5 to 20 μeq / g is preferable.

(A) Although there is no restriction | limiting in the intrinsic viscosity of the polyester resin of a component, The value measured at the temperature of 30 degreeC using the mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio). However, the PBT resin is preferably in the range of 0.7 to 1.5 dL / g, and the PET resin is preferably in the range of 0.5 to 1.5 dL / g. Two or more kinds of polyester resins having different intrinsic viscosities can be mixed to adjust the intrinsic viscosity. In that case, the intrinsic viscosity of the mixture is preferably 0.5 to 1.5 dL / g. If the intrinsic viscosity of each polyester resin is too small, the mechanical properties are not exhibited. On the other hand, if it is too large, the moldability is lowered and the processing becomes difficult.

The polyester resin as component (A) is preferably a polyester resin mainly composed of PBT resin from the viewpoint of mechanical strength and moldability. However, since the PBT resin has an extremely high crystallization rate, the surface appearance of the obtained molded product may be impaired. In such a case, it is preferable to use a PET resin having a slightly lower crystallization rate than the PBT resin in order to suppress deterioration of the surface appearance of the molded product. The blending ratio when the PBT resin and the PET resin are used in combination is preferably in the range of PBT / PET = 95/5 to 50/50 (weight ratio), and more preferably in the range of 85/15 to 55/45.

The acrylic resin as the component (B) in the reinforced resin composition according to the present invention has an effect of further improving the mechanical strength of the reinforced resin composition and the appearance of a molded product obtained from the reinforced resin composition. The (B) component acrylic resin is preferably a (co) polymer containing a methyl methacrylate unit as a main component and containing 0 to 5% by weight of other acrylate units. The acrylic resin as the component (B) preferably has a weight average molecular weight in the range of 30,000 to 250,000.

The acrylic ester units that can be copolymerized with methyl methacrylate units are specifically methyl acrylate, ethyl acrylate, acrylic acid-n-butyl, acrylic acid-iso-butyl, acrylic acid-t-butyl. Acrylic acid alkyl esters such as 2-ethylhexyl acrylate, cyclohexyl acrylate, methyl cyclohexyl acrylate, bornyl acrylate, isobornyl acrylate, adamantyl acrylate, cycloalkyl acrylates, phenyl acrylate, acrylic Acrylic acid aromatic esters such as benzyl acid, acrylic acid-substituted aromatic esters such as fluorophenyl acrylate, chlorophenyl acrylate, fluorobenzyl acrylate, chlorobenzyl acrylate, and fluoromethacrylate Le, acrylic acid alkyl halide esters such as acrylic acid fluoroethyl, hydroxy alkyl acrylate, glycidyl acrylate, ethylene glycol ester and acrylic acid polyethylene glycol esters. One or two or more of these acrylate units can be used. Of these, methyl acrylate is preferred.

(B) The compounding quantity of the acrylic resin of a component is 0-19 weight part with respect to 100 weight part of polyester resins. When the blending amount of the component (B) exceeds 19 parts by weight, the dispersion tends to be poor, the mechanical strength of the finally obtained reinforced resin composition is lowered, and the molded product obtained from this reinforced resin composition Appearance tends to deteriorate, which is not preferable. (B) The especially preferable compounding quantity of a component is 3-15 weight part.

The component (C) in the reinforced resin composition according to the present invention functions to improve the adhesion between the polyester resin and the inorganic filler, weather resistance, mechanical strength, and the like. The component (C) includes a specific amount of a copolymer segment (hereinafter abbreviated as A segment) formed from a nonpolar α-olefin monomer and a polar vinyl monomer, and at least one vinyl type. Multi-phase structure type graft copolymer (hereinafter referred to as multi-phase structure type graft copolymer) comprising a specific amount of vinyl-based (co) polymer segment (hereinafter abbreviated as B segment) formed from monomers. .)

  Examples of the nonpolar α-olefin monomer constituting the A segment include ethylene, propylene, butene-1, hexene-1, octene-1, 4-methylpentene-1.

  The polar vinyl monomer constituting the A segment refers to a monomer having a vinyl group copolymerizable with a nonpolar α-olefin monomer. Specifically, α, β- such as acrylic acid, methacrylic acid, fumaric acid, maleic anhydride, itaconic acid, itaconic anhydride, bicyclo (2,2,1) -5-heptene-2,3-dicarboxylic acid, etc. Unsaturated carboxylic acids and their metal salts, methyl acrylate, ethyl acrylate, -n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, Α, β-unsaturated carboxylic acid esters such as n-butyl methacrylate and isobutyl methacrylate, vinyl acetate, vinyl propionate, vinyl caproate, vinyl caprylate, vinyl laurate, vinyl stearate, vinyl trialkyl acetate Vinyl esters such as glycidyl acrylate, glycidyl methacrylate, ita Unsaturated glycidyl group-containing monomers such as phosphate mono-glycidyl ester. From the viewpoint of reactivity with the polyester resin, preferred polar vinyl monomers are glycidyl acrylate, glycidyl methacrylate, acrylic acid, methacrylic acid, maleic anhydride, methyl acrylate, and ethyl acrylate. The ratio of the non-polar α-olefin monomer of the A segment and the polar vinyl monomer is not particularly limited, but the polar vinyl monomer is preferably in the range of 1 to 80% by weight.

  Specific examples of the A segment include ethylene-acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-isopropyl acrylate copolymer, ethylene-acrylic acid-n-butyl. Copolymer, ethylene-isobutyl acrylate copolymer, ethylene-acrylic acid-2-ethylhexyl copolymer, ethylene-methyl methacrylate copolymer, ethylene-ethyl methacrylate copolymer, ethylene-isopropyl methacrylate copolymer Polymer, ethylene-methacrylic acid-n-butyl copolymer, ethylene-isobutyl methacrylate copolymer, ethylene-methacrylic acid-2-ethylhexyl copolymer, ethylene-vinyl acetate copolymer, or saponified product thereof, ethylene- Vinyl propionate copolymer, ethylene-acrylic Ethyl - maleic anhydride copolymer, ethylene - ethyl acrylate - glycidyl methacrylate copolymer, ethylene - vinyl acetate - glycidyl methacrylate copolymer, ethylene - like glycidyl methacrylate copolymer. The copolymer formed from these nonpolar α-olefins and polar vinyl monomers may be one kind or a mixture of two or more kinds. Among these copolymers, ethylene-glycidyl methacrylate copolymer, ethylene-ethyl acrylate-glycidyl methacrylate copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate-maleic anhydride copolymer A coalescence or the like is preferable from the viewpoint of adhesiveness (affinity) with a polyester resin and an inorganic reinforcing agent.

  Specific examples of vinyl monomers constituting the B segment include aromatic vinyl compounds such as styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, α-methylstyrene, α-ethylstyrene, and the like. Monomers, (meth) acrylic acid monomers such as (meth) acrylic acid methyl (meth) acrylate and ethyl (meth) acrylate and alkyl esters having 1 to 20 carbon atoms, (meth) ) Vinyl cyanide monomer such as acrylonitrile and vinyl ester monomers such as vinyl acetate and vinyl propionate. Among these monomers, from the viewpoint of adhesion (affinity) with the acrylic resin of the component (B), (meth) acrylic acid ester monomers are preferable, and among them, (meth) methyl acrylate is preferable. preferable.

  The weight average molecular weight of the B segment is usually selected in the range of 1,000 to 1,000,000. When the weight average molecular weight is less than 1,000, the adhesiveness with the acrylic resin of the component (B) tends to be lowered, and when it exceeds 1,000,000, the finally obtained reinforced resin composition Since melt viscosity tends to be too high and moldability tends to decrease, neither is preferred. A more preferable range of the weight average molecular weight is a range of 5,000 to 500,000, and a range of 7,000 to 300,000 is particularly preferable.

  The form (morphology) of the multiphase structure type graft copolymer of component (C) is such that one of the two segments has a particle diameter of 0.001 to 10 μm, preferably 0.01. The form dispersed in ˜5 μm is preferable. When the particle size is less than 0.001 μm or exceeds 10 μm, the dispersibility when blended with the polyester resin is poor, for example, the appearance is deteriorated, the impact resistance is reduced, or the polyester resin and the inorganic filler are filled. Improvement effects such as adhesiveness with agents are insufficient. The compounding quantity of a multiphase structure type graft copolymer is the range of 1-20 weight part with respect to 100 weight part of polyester resins. If the blending amount is less than 1 part by weight, the weather resistance and mechanical strength of the finally obtained reinforced resin composition cannot be improved. If the blending amount is more than 20 parts by weight, the fluidity (moldability) is deteriorated, Mechanical strength and appearance may be reduced due to poor dispersion. Among these, a preferable blending amount is in the range of 3 to 15 parts by weight.

  The multiphase structure type graft copolymer of the component (C) in the present invention is a combination in which the A segment is 5 to 99% by weight and the B segment is 1 to 95% by weight. When the A segment is less than 5% by weight, the adhesiveness (affinity) between the polyester resin and the inorganic filler constituting the finally obtained reinforced resin composition becomes insufficient, and the mechanical strength is improved. The goal is not achieved. When the A segment exceeds 99% by weight, the compatibility with the acrylic resin of the component (B) becomes insufficient. A preferred ratio of the A segment in the multiphase structure type graft copolymer of the component (C) is in the range of 20 to 95% by weight.

  The multiphase structure type graft copolymer of the component (C) in the present invention can be produced by a conventionally known production method, that is, a chain transfer method, an ionizing radiation irradiation method or the like. An example of the manufacturing method is described in Japanese Patent Application Laid-Open No. 2000-344959, and can be easily manufactured.

  Specific examples of the multiphase structure type graft copolymer of component (C) in the present invention include ethylene-glycidyl methacrylate-g-polymethyl methacrylate copolymer, ethylene-methyl acrylate-g-polymethyl methacrylate copolymer. And an ethylene-ethyl acrylate-maleic anhydride copolymer. These are sold by Nippon Oil and Fats Co., Ltd. as Modiper (trade name) A4200 (brand name, the same applies hereinafter), A5200, and A8200.

  The inorganic filler of component (D) in the present invention functions to reinforce the reinforced resin composition according to the present invention. The inorganic filler of component (D) may be appropriately selected from those conventionally used for reinforcing thermoplastic resins according to the purpose. Inorganic fillers can be categorized as fibrous, plate-like, or granular, based on their appearance. Specific examples of the fibrous filler include glass fiber, carbon fiber, mineral fiber, metal fiber, ceramic whisker, and wollastonite. Examples of the plate-like filler include glass flakes, mica and talc, and examples of the granular filler include silica, alumina, glass beads, and calcium carbonate.

  The standard for selecting the inorganic filler of component (D) varies depending on the properties to be imparted to the finally obtained molded product (product). For example, in order to impart mechanical strength and rigidity to a molded product, a fibrous material, particularly glass fiber, is selected. In the case of forming a molded article with little anisotropy and warpage, a plate-like product, particularly mica, glass flakes, etc. are selected. In consideration of the fluidity at the time of manufacturing the molded product, the granular material is selected so as to balance the entire physical properties. The resin material for vehicle / airframe interior / exterior parts is preferably in the form of fibers, of which glass fibers, carbon fibers, and basalt fibers are preferred, with glass fibers being particularly preferred. The blending amount of the inorganic filler (D) is selected in the range of 30 to 200 parts by weight with respect to 100 parts by weight of the polyester resin. If the blending amount is less than 30 parts by weight, the mechanical strength as an interior / exterior part for a vehicle / airframe cannot be sufficiently exhibited. If the blending amount is more than 200 parts by weight, the mechanical strength of the part is lowered and the appearance is poor. It is not preferable. A preferable range of the blending amount of the inorganic filler is 35 to 150 parts by weight.

  The inorganic filler of component (D) is preferably treated with a surface treatment agent in advance for the purpose of improving the affinity and adhesiveness with the interface with the resin component contained in the reinforced resin composition. As the surface treatment agent, a surface treatment agent containing at least an aminosilane compound and an epoxy resin is suitable. Examples of the aminosilane compound include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane. The compounding quantity of the aminosilane compound as a surface treating agent can be selected in the range of 0.1-8 weight% with respect to an inorganic filler. Among these, a preferable amount is 0.5 to 5% by weight.

The epoxy resin in the surface treatment agent is roughly classified into a novolac type epoxy resin and a bisphenol type epoxy resin, and a novolac type epoxy resin is preferable. As this novolak type epoxy resin, a polyfunctional type epoxy resin such as a phenol novolak type epoxy resin or a cresol novolak type epoxy resin is preferable. The compounding quantity of the epoxy resin as a surface treating agent can be selected in the range of 1-20 weight% in a surface treating agent. Among these, the range of 2 to 10% by weight is preferable.

The surface treatment agent is preferably attached to the surface of the inorganic filler of component (D). This processing method can be performed by a conventionally known method. Specifically, (1) A method in which a predetermined amount of an inorganic filler and a surface treatment agent are weighed and charged in a mixing machine such as a Henschel mixer and mixed by stirring. (2) A polyester resin, an inorganic filler and a treatment agent are mixed. (3) When the inorganic filler is a fibrous filler such as glass fiber, carbon fiber, basalt fiber, etc., at the stage of the spinning process such as bundling these single fibers And a method of attaching a surface treatment agent to these surfaces. The method (1) is capable of uniform mixing, and the method (3) is suitable when the fibrous filler is roving (or chopped strand) and is suitable for interior / exterior parts for vehicles and aircraft. It is especially preferable when setting it as the resin composition used.

  When the surface treatment is performed by the above method, the surface treatment agent adheres to at least part of the surface of the inorganic filler, and the mechanical properties of the reinforced resin composition according to the present invention can be improved. Inorganic functional group of aminosilane, inorganic filler surface of component (D), organic functional group of aminosilane and glycidyl group of epoxy resin, glycidyl group of epoxy resin and polyester resin of component (A), acrylic resin of component (B) It is speculated that the functional group contained in the multilayer structure graft copolymer of component (C) reacts with each other to improve the interfacial adhesive force between each component of the reinforced resin composition and the surface of the inorganic filler. .

Other components such as a urethane resin, an acrylic resin, an antistatic agent, a lubricant, and a water repellent can be added to the surface treatment agent as long as the properties are not impaired. Furthermore, surface treatment agents other than those described above, such as epoxy resins other than the novolak type and bisphenol type, epoxy silane coupling agents, and / or titanate coupling agents can also be used. The adhesion amount of the surface treatment agent other than the above to the inorganic filler is preferably in the range of 0.05 to 2.0% by weight. If the adhesion amount is 0.05% by weight or more, the mechanical strength of the finally obtained reinforced resin composition is more effectively improved, and if it is 2.0% by weight or less, a necessary and sufficient effect is obtained. Economical.

Whether or not the surface treatment agent is attached to the surface of the inorganic filler of component (D) is confirmed, for example, by observing the fracture surface of the reinforced resin composition containing the inorganic filler with an electron microscope. it can. That is, in the vicinity of the fracture surface, the surface treatment agent is attached to the inorganic filler in the portion where the resin remains without peeling from the surface of the inorganic filler (that is, the smoothness of the surface of the inorganic filler is low). Recognize.

Examples of the glass fiber glass that is suitably blended into the reinforced resin composition for manufacturing interior and exterior parts for vehicles and aircrafts include E glass, C glass, A glass, S glass, and S-2 glass. E glass having few alkaline components and good electrical properties is particularly preferred. The average fiber length of the glass fibers is preferably selected in the range of 0.1 to 20.0 mm. By making the average fiber length 0.1 mm or more, the reinforcing effect by the glass fiber is more effectively exhibited, and by making the average fiber length 20 mm or less, a melt-kneading operation with a polyester resin or a reinforced polyester resin composition It becomes easier to manufacture a molded product from the product. A more preferable range of the average fiber length is 1 to 10 mm. The preferable compounding quantity of the glass fiber to a reinforced resin composition is 30-150 weight part with respect to 100 weight part of polyester resins, More preferably, it is 35-120 weight part.

The colorant of the component (E) in the present invention colors the reinforced resin composition and further improves the weather resistance of a molded product obtained from the reinforced resin composition. Examples of the colorant include inorganic pigments, organic pigments, and organic dyes. Examples of the inorganic pigment include carbon black, metal powder, metal oxide or hydroxide, sulfide, silicate, carbonate, chromate and the like. Carbon black may be produced by any method such as the furnace method, the channel method, and the acetylene method.

Examples of the metal powder include aluminum powder, bronze powder, and copper powder. Examples of the metal oxide include zinc white, titanium oxide, antimony white, iron black, red rose, red lead, chromium oxide, nickel titanium yellow, chromium titanium yellow, and spinel green. Examples of the metal hydroxide include alumina white, satin white, and yellow iron oxide. Examples of the metal sulfide include zinc sulfide, lithopone, male yellow, silver vermilion, cadmium red, cadmium orange, cadmium yellow, antimony vermilion, barium sulfate, gypsum, and lead sulfate. Ultramarine is mentioned as a metal silicate. Examples of the metal carbonate include barium carbonate, lime carbonate powder, lead white, and magnesium carbonate. Examples of the metal chromate include yellow lead, zinc yellow, and barium chromate.

Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green, azo dyes such as nickel azo yellow, thioindigo, perinone, perylene, quinacridone, dioxazine, isoindolinone, Examples thereof include condensed polycyclic dyes such as quinophthalone, anthraquinone, heterocyclic and methine dyes. Among these colorants, carbon black is preferable from the viewpoint of the weather resistance of the reinforced resin composition, and carbon black having a nitrogen adsorption specific surface area of 30 to 100 m ² / g is particularly preferable.

The component (E) is preferably composed of at least one inorganic pigment and / or at least one organic dye / pigment, but is preferably composed mainly of an inorganic pigment from the viewpoint of weather resistance. In addition to these dyes and pigments, a dispersant for assisting dispersion can be added to the component (E). (E) The compounding quantity of a component shall be chosen in the range of 0.1-20 weight part with respect to 100 weight part of polyester resins. When the blending amount is less than 0.1 parts by weight, the weather resistance of the finally obtained reinforced resin composition is lowered, and when it is more than 20 parts by weight, the mechanical strength of the reinforced resin composition is lowered, both of which are not preferable. . (E) The preferable compounding quantity of a component is 1-15 weight part, and 3-10 weight part is especially preferable.

In the reinforced resin composition according to the present invention, within the range not impairing the effects of the present invention, in addition to the above components, other thermoplastic resins other than the polyester resin, and various conventionally known resin additives, for example, , Impact resistance improvers, mold release agents, antioxidants, heat stabilizers, crystallization accelerators, impact resistance improvers, flame retardants, ultraviolet absorbers, foaming agents, and the like can be blended.

Examples of thermoplastic resins other than polyester resins include polyamide (PA) resins, polycarbonate (PC) resins, liquid crystal polymers, polystyrene (PS) resins, acrylonitrile-butadiene-styrene (ABS) copolymers, acrylonitrile-styrene ( AS) copolymer, methyl methacrylate-styrene (MS) resin, polyphenylene sulfide (PPS) resin, polyacetal, polyphenylene oxide (PPO) resin, polyethylene (PE) resin, polypropylene (PP) resin, ethylene-propylene copolymer, etc. Olefin resins, fluorine resins such as polytetrafluoroethylene, and thermoplastic resins such as ionomer resins. When blending the above other thermoplastic resins, the type of other thermoplastic resin may be selected depending on the purpose of use of the finally obtained reinforced resin composition, the properties to be imparted to the resin composition, etc. It can mix | blend at 50 weight part or less with respect to 100 weight part of resin.

Examples of the impact resistance improver include thermoplastic elastomers and synthetic rubbers. Examples of the thermoplastic elastomer include olefin-based, styrene-based, acrylic-based, polyester-based, silicon-based, polyamide-based, and urethane-based elastomers. These thermoplastic resin elastomers are preferably modified in advance with a functional group such as a carbonyl group, an alkoxyl group, an ester group, an amide group, an amino group, or an epoxy group in order to enhance compatibility with the polyester resin.

Synthetic rubbers include isobutylene-isoprene rubber (IR), styrene-butadiene rubber (SBR), styrene-butadiene-styrene (SBS), ethylene-propylene rubber (EPR), acrylic rubber, ethylene-propylene-diene monomer (EPDM). ) And the like. Among these impact resistance improvers, styrene-based, acrylic-based, polyester-based, and silicon-based elastomers are preferable, and those having a core-shell structure are more preferable. The blending amount of the impact resistance improver is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the polyester resin, and more preferably 1 to 20 parts by weight.

As a mold release agent, hydrocarbon compounds, such as fatty acid ester which consists of a C12-C36 fatty acid residue and a C1-C36 alcohol residue, paraffin wax, and polyethylene wax, are mentioned, for example. The compounding amount of the release agent is preferably in the range of 0.01 to 2 parts by weight with respect to 100 parts by weight of the polyester resin.

Examples of the antioxidant include hindered phenol compounds, amine compounds, phosphorus compounds, and thioether compounds. Examples of hindered phenol compounds include 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] and the like.

Examples of amine compounds include N-phenyl-N′-isopropyl-p-phenylenediamine, N, N′-diphenyl-p-phenylenediamine, and 4,4′-bis- (4-α, α-dimethylbenzyl). Examples thereof include diphenylamine, a condensation reaction product of diphenylamine and acetone, N-phenylnaphthylamine, N, N′-di-β-naphthylphenylenediamine, and the like.

The phosphorous compound is preferably a phosphite-based or phosphonite-based organic compound, specifically, triaryl phosphite such as triphenyl phosphite, tri (nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, Cyclic neopentanetetrayl-bis- (2,4-di-t-butylphenyl-phosphite), di- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, etc. Examples thereof include phosphinite compounds such as heat-resistant phosphites and tetrakis (2,4-di-t-butylphenyl) -4,4-biphenylene phosphonite.

Thioether compounds include dilauryl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, lauryl stearyl thiodipropionate, tetrakis [methylene-3- (dodecylthio) propionate] methane, dialkyl (carbon (Equation 12-18) -3,3-thiodipropionate etc. are mentioned. Among these antioxidants, hindered phenol compounds and phosphorus compounds are preferable.

Particularly preferred as antioxidants are pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], triethylene glycol bis [3- (3-tert-butyl-5). -Methyl-4-hydroxyphenyl) propionate, and di- (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, tetrakis (2,4-di-t-butylphenyl) -4 , 4-biphenylene phosphonite, or a combination of a hindered phenol compound and a phosphorus compound. In particular, when a polybutylene terephthalate resin and a polycarbonate resin or a polyethylene terephthalate resin are used in combination, transesterification between different resins can be further suppressed by adding a phosphorus-based stabilizer, The obtained reinforced resin composition can exhibit more excellent thermal stability. Antioxidants can be used alone or in combination of two or more. The blending amount of the antioxidant is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the polyester resin, and more preferably 0.05 to 3 parts by weight.

The reinforced resin composition according to the present invention may be prepared by a conventionally known method, and among them, a method of melting and kneading using an extrusion kneader or the like is preferable. Specifically, for example, a predetermined amount of each of the above-described components (A) to (E) is weighed and mixed with an additional component as necessary using a mixer such as a Henschel mixer, a ribbon blender, or a V-type blender. And a method of melting and kneading with a melting and kneading machine. The kneader may be a method of feeding each component at once,
A method of feeding sequentially may be used. A method may be used in which a plurality of components constituting the reinforced resin composition are mixed in advance, the remaining components are fed from the middle while melting and kneading, and the melting and kneading are continued to produce the reinforced resin composition. Examples of the component fed from the middle include those that are easily thermally decomposed during melting and kneading, and fibrous fillers that are easily damaged. By feeding these components from the middle of the melting and kneading machine, the thermal decomposition of the (A) component to the (C) component and the (E) component and the damage of the fibrous filler in the (D) component are prevented, The mechanical strength of the reinforced resin composition obtained can be made excellent. The temperature at the time of melting and kneading varies depending on the types of components constituting the reinforced resin composition, the ratio of each component, the types of other additives, and the blending amount, but is preferably in the range of 230 to 290 ° C. .

The reinforced resin composition according to the present invention can mold (manufacture) a target molded product (product) by a conventionally known thermoplastic resin molding method. Examples of the molding method applicable to the reinforced resin composition according to the present invention include an injection molding method, a hollow molding method, an extrusion molding method, a compression molding method, a calendar molding method, and a rotational molding method. Among these, from the viewpoint of productivity of a molded product, molding by an injection molding method is preferable. If the conditions at the time of manufacturing a molded article by the injection molding method are exemplified, the resin temperature is increased by 15 to 50 ° C. from the melting point of the raw material resin, specifically, the range is 240 to 290 ° C. It is preferable to adjust to ° C. In particular, when the polyester resin is a PET resin, the mold temperature is preferably set in the range of 90 to 120 ° C. in order to sufficiently crystallize and stabilize the dimensions.

Molded products obtained by the above molding method can exhibit excellent mechanical strength, excellent appearance, and excellent weather resistance, so that interior and exterior parts for vehicles such as automobiles, trains, and trains, and interior and exterior parts for aircraft such as aircraft It is suitable for parts such as indoor inner mirror stays, door handles, leather straps, handle parts, wiper parts such as outdoor wiper arms, door handles, door mirror stays, roof rails, and the like.

Hereinafter, the wiper part as a representative example of the molded product according to the second invention of the present invention refers to a structure whose usage state is described in FIG. 4 of JP-A-2005-324661. In the present invention, the reinforced resin composition according to the present invention was used as a raw material, and a molded product imitating a wiper part (see below, FIG. 1 and FIG. 2) was produced, and its strength was measured. FIG. 1 is a perspective view of an example of a molded product imitating a wiper part, and FIG. 2 is a top view of a part assembled for the purpose of measuring strength. In the figure, 1 is a molded product made of a reinforced resin composition according to the present invention, 2 is a recess, 3 is a pivot shaft provided in the recess, 4 is an aluminum part, 5 is a protrusion, 6 is a recess, 7 Is a fixed part. The convex part 5 of the aluminum part is fitted into the concave part 2 of the molded product, and the rotating shaft 3 is fitted into the concave part 6 at that time. In FIG. 2, an arrow means a direction in which a load is applied. A reinforced resin composition used for wiper parts is required to have a flexural modulus (measured in accordance with ISO 178) showing a rigidity of 6000 MPa or more.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to the example as described below. In the following, methods for analyzing polyester resins {terminal carboxyl groups, intrinsic viscosity, metal content (residual amount), etc.}, methods for preparing the inorganic filler used, and the like are described below.

<Analytical method of polyester resin> (1) Terminal carboxyl group concentration (μeq / g): 0.5 g of PBT resin or oligomer was dissolved in 25 ml of benzyl alcohol, and 0.01 mol / L benzyl alcohol solution of sodium hydroxide was dissolved. Used and measured by titration method. (2) Intrinsic viscosity (IV): The viscosity was calculated in the following manner using an Ubbelohde viscometer. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1) and measuring the number of seconds of dropping only a polymer solution having a concentration of 1.0 g / dL and a solvent at a temperature of 30 ° C., IV = {(1 + 4K _H η _sp ) ^0.5 −1} / (2K _H C). In this equation, η _sp = (η / η ₀ ) −1, η is the polymer solution falling seconds, η ₀ is the solvent dropping seconds, C is the polymer solution concentration (g / dL), and K _H is Huggins It was a constant of 0.33. (3) Titanium in the resin, and periodic table group 1 and group 2 metal concentration: The resin is wet-decomposed with high-purity sulfuric acid and nitric acid for electronic industry, and high resolution ICP-MS (Inductively Coupled Plasma-Mass Measurement was performed using Spectrometer (manufactured by ThermoQuest).

(A-1) PBT: a polybutylene terephthalate resin having an intrinsic viscosity of 0.85 dL / g, a terminal carboxyl group concentration of 14.2 μeq / g, a titanium atom content of 45 ppm, and a magnesium atom content of 25 ppm belongs to. (A-2) PET: Polyethylene terephthalate resin having an intrinsic viscosity of 0.65 dL / g (trade name: Novapex GS385, manufactured by Mitsubishi Chemical Corporation).
(B-1) PMMA: polymethyl methacrylate (Kuraray Co., Ltd., trade name: Parapet HR-F-1).

(C-1) E-GMA-g-PMMA: ethylene-glycidyl methacrylate-g-polymethyl methacrylate copolymer (manufactured by NOF Corporation, trade name: Modiper A4200).
(C-2) E-EA-MAH-g-PMMA: ethylene-ethyl acrylate-maleic anhydride-g-polymethyl methacrylate copolymer (Nippon Yushi Co., Ltd., trade name: Modiper A8200).
(C-3) E-GMA: ethylene-glycidyl methacrylate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Bond First 2C).

<Preparation of Glass Fiber Treated with Surface Treatment Agent (D-1) to (D-4)> (D-1) GF1: 4% by weight of phenol novolac type epoxy resin, 1% by weight of γ-aminopropyltriethoxysilane A surface treatment agent comprising 2% by weight of a urethane emulsion and 93% by weight of deionized water was prepared. This surface treatment agent was applied to the surface of a glass fiber strand (glass average single fiber diameter 13 μm), and this strand was cut into a length of 3 mm to obtain a glass fiber chopped strand. The adhesion amount of the surface treatment agent to the obtained chopped strand surface was 0.7% by weight. In addition, the detail of the processing method of the glass fiber by the said surface treating agent is described in Unexamined-Japanese-Patent No. 2001-172055. (D-2) GF2: In the preparation example of (D-1) GF1 described above, the surface treatment agent was bisphenol type epoxy resin 4% by weight, γ-aminopropyltriethoxysilane 1% by weight, urethane emulsion 2% by weight. (D-2) GF2 was prepared in the same procedure as (D-1) except that it was replaced with a solution consisting of 93% by weight of deionized water.

(D-3) GF3: In the preparation example of (D-1) GF1 described above, the glass fiber was roving with an irregular cross-section glass fiber {manufactured by Nittobo Co., Ltd., oval (FF), cut at right angles to the length direction. The procedure was the same as that of (D-1) except that the cross section was elliptical and the minor axis / major axis was 7 μm / 28 μm = 1/4. (D-4) GF4: In the preparation example of (D-1) GF1 described above, the surface treatment agent was an acrylic ester copolymer (copolymer containing 2-ethylhexyl acrylate and methyl acrylate as main components) 4 weights %, Γ-aminopropyltriethoxysilane 1% by weight, urethane emulsion 2% by weight and deionized water 93% by weight. Details of the method for preparing glass fibers by the surface treatment agent are described in Japanese Patent Publication No. 2005-299047.

(D-5) Mica: Mica manufactured by Yamaguchi Mica Industry Co., Ltd. (trade name: A-21B).
(E-1) CB: Carbon black having a nitrogen adsorption specific surface area of 140 m ² / g (trade name: MA600B, manufactured by Mitsubishi Chemical Corporation).

[Example 1 to Example 12, Comparative Example 1 to Comparative Example 9] <Production Method and Evaluation of Reinforced Resin Composition> The above polyester resin, acrylic resin, graft copolymer, inorganic filler, and carbon black A ratio (parts by weight) shown in Table-1 to Table-3 was weighed, mixed for 10 minutes with a Henschel mixer, and the resulting mixture was a twin-screw extruder (Nippon Steel) with a barrel (cylinder) temperature set at 260 ° C. Made by Tokosha Co., Ltd., model: TEX-30C, barrel is composed of 9 blocks), and kneaded and pelletized. At the time of melting and kneading, the glass fiber was supplied by a side feed system from the fifth block from the extruder hopper side. Using the pelletized reinforced resin composition as a raw material, mechanical strength was obtained under the conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. using an injection molding machine (model: SG-75MIII, manufactured by Sumitomo Heavy Industries). A test piece conforming to ISO for measurement was molded, and the mechanical strength was measured. Moreover, the evaluation test of the intensity | strength of a molded article, surface appearance, and a weather resistance was done in accordance with the method shown below, and the evaluation result was shown to Table-1-Table-3.

(A) Tensile strength (MPa), tensile elongation (%): Measured according to ISO 527. (B) Flexural strength (MPa), flexural modulus (MPa): Measured according to ISO178. (C) Impact strength (kJ / m ² ): Notched Charpy impact strength measured according to ISO179.

(D) Strength of molded product (N): Shown as a perspective view in FIG. 1 using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., model: SH100) under conditions of a cylinder temperature of 265 ° C. and a mold temperature of 130 ° C. A molded product (part) 1 was molded. The molded product 1 has a length (L) of 100 mm, a height (H) of 30 mm, a width (W) of 50 mm, and a recess 2 having a width of 30 mm and a depth of 40 mm is formed on one end side in the length direction. A rotating shaft 3 having a diameter of 10 mm is provided inside the recess 2 (see FIG. 1). The aluminum part 4 has a length (L) of 300 mm, a height (H) of 30 mm, a width (W) of 50 mm, and a convex portion 5 having a width of 30 mm and a length of 40 mm on one end side in the length direction. The convex portion 5 is fitted into the concave portion 2 of the molded product 1. A fitting portion 6 for fitting the rotating shaft 3 of the component 1 is provided at the end of the convex portion 5 (see FIG. 1). As shown in FIG. 2, the strength of the molded product was measured by forming the molded product 1 and the aluminum part 4, and forming the rotating shaft 3 of the concave part 2 of the molded product 1 on the convex part 5 of the part 4. The strength of the molded product 1 was measured by combining it so as to fit into the recess 6. After fixing the end portion of the molded product 1 to the fixing portion 7, the component 4 was fitted, a load was applied to the end portion of the component 4 from the direction of the arrow, and the breaking load of the fitting portion was measured. It means that the strength of a molded product is excellent, so that this value is large.

(E) Appearance of molded product: Using an injection molding machine (manufactured by Sumitomo Heavy Industries Co., Ltd., model: SH100) under conditions of a cylinder temperature of 265 ° C. and a mold temperature of 130 ° C., the film gate mold is 100 mm long, 100 mm wide, A square flat test piece having a thickness of 3 mm was formed. About the surface of the obtained flat plate-shaped test piece, the floating state of the glass fiber was visually observed and evaluated. Evaluation criteria were as follows. 3: The glass fiber is hardly lifted up. 2: The glass fiber is slightly lifted but is within the allowable appearance range of a general molded product. 1: The glass fiber is partially lifted. The evaluation judgment results of 3 and 2 are molded products that are within the allowable range and have a good appearance.

(F) Weather resistance (ΔE): Fixed to a test piece fixing surface of a xenon arc tester (model: ATLAS Ci4000, manufactured by Toyo Seiki Co., Ltd.) using the flat plate test piece for appearance evaluation of the molded product of (e) above. Then, the black panel temperature of the testing machine was 63 ° C., a light beam having a wavelength of 340 nm, a light source intensity of 0.55 W / m ² , 102 minutes after irradiation, irradiation + fountain 18 minutes as one cycle, irradiation for 1250 hours, The total irradiation dose was 2500 kJ / m ² . The hue after irradiation of the surface of the molded product irradiated with light was measured with a spectrocolorimeter (Konica Minolta Sensing Co., Ltd., model: CM-3600d), and compared with the hue of the test piece before irradiation. The measurement was performed by diffuse illumination at 8 ° C., and light reception was performed by the SCE method. From the L value, a value, and b value of the molded product after irradiation and the difference between the L value, a value, and b value of the molded product before irradiation, ΔL, Δa, and Δb, ΔE = [(ΔL ) ² + (Δa) ² + (Δb) ² ] ^1/2 , a color difference ΔE was calculated and used as a hue index. A smaller ΔE means less change in appearance.

From Table-1 to Table-3, the following can be understood. 1. The molded product obtained from the reinforced resin composition according to the present invention is excellent in mechanical strength, appearance, and weather resistance (see Examples 1 to 12). 2. On the other hand, when the (B) component and the (C) component are not included in the reinforced resin composition, the weather resistance is poor (see Comparative Example 1, Comparative Example 6, and Comparative Example 7). 3. Even if the reinforced resin composition contains the component (B) and the component (C), if the component (B) is more than the amount specified in claim 1, the tensile strength, tensile elongation, bending strength, Charpy The impact strength is low and the strength of the molded product is inferior (see Comparative Example 4). 4). When the reinforced resin composition does not contain the component (B) and the component (C) is more than the amount specified in claim 1, the tensile strength, tensile elongation, bending strength, and Charpy impact strength are low, The strength is also inferior (see Comparative Example 9). 5. When the reinforced resin composition contains the component (B) but does not contain the component (C) (Comparative Example 5), or contains a copolymer that is not a multilayer structure graft copolymer defined in the present invention (Comparison) Example 8) has low tensile strength, bending strength, and Charpy impact strength, and the molded product has poor strength. 6). (D) component is included in the reinforced resin composition, but when it is less than the amount specified in claim 1, the tensile strength, bending strength, bending elastic modulus, Charpy impact strength are low, and the strength of the molded product is also inferior ( Comparative Example 2). 7. (E) component is included in the reinforced resin composition, but when it is more than the amount specified in claim 1, the tensile strength, tensile elongation, bending strength, Charpy impact strength are low, and the strength of the molded product is also inferior ( See Comparative Example 3).

  The reinforced polyester resin composition according to the present invention is to produce interior and exterior parts for vehicles such as automobiles, trains and trains, and interior and exterior parts for aircraft such as airplanes by a conventionally known method for molding a thermoplastic resin. Can do. Specifically, it is particularly suitable for indoor inner mirror stays, door handles, hanging leather, handle parts, wiper parts such as outdoor wiper arms, door handles, door mirror stays, roof rails, and the like.

It is a perspective view of an example of a molded product imitating a wiper part. It is the figure which looked at the state which assembled and fixed the components for the purpose of intensity | strength measurement.

Explanation of symbols

1: Molded product made of reinforced resin composition 2: Concave part 3: Rotating shaft provided in the concave part 4: Aluminum part 5: Convex part 6: Concave part 7: Fixed part

Claims (11)

A reinforced polyester resin composition comprising the following components (A) to (E): (A) component: 100 parts by weight of a polyester resin, (B) component: 0 to 19 parts by weight of an acrylic resin, (C) component: formed from a nonpolar α-olefin monomer and a polar vinyl monomer. 1 to 20 parts by weight of a graft copolymer consisting of 5 to 99% by weight of a copolymer segment and 1 to 95% by weight of a vinyl (co) polymer segment formed from at least one vinyl monomer, (D) component: 30-200 weight part of inorganic fillers, and (E) component: 0.1-20 weight part of coloring agent. The (A) component polyester resin contains at least a polybutylene terephthalate resin, and the polybutylene terephthalate resin is composed of (a) a titanium compound and (b) a periodic table group 1 metal compound and / or a periodic table group 2 metal compound. And (a) the content of the titanium compound is in the range of 10 to 80 ppm in terms of titanium atom, and (b) the content of the periodic table group 1 metal compound and / or the periodic table group 2 metal compound. The reinforced polyester resin composition according to claim 1, wherein is in the range of 1 to 50 ppm in terms of metal atoms. The reinforced polyester resin according to claim 1 or 2, wherein the vinyl monomer in component (C) is at least one monomer selected from derivatives such as acrylic acid, methacrylic acid and esters thereof. Composition. The polar vinyl monomer in component (C) is an α, β-unsaturated acid, a carboxyl group-containing vinyl monomer such as an ester thereof, or an epoxy-containing vinyl monomer such as glycidyl (meth) acrylic acid. The reinforced polyester resin composition according to any one of claims 1 to 3, which is at least one monomer selected from the group consisting of: 5. The inorganic filler as component (D) is a fibrous inorganic filler treated with a surface treatment agent containing at least an aminosilane compound and a novolac-type epoxy resin. 6. Reinforced polyester resin composition. The reinforced polyester resin composition according to any one of claims 1 to 5, wherein the inorganic filler of component (D) is a glass fiber. The reinforced polyester resin composition according to any one of claims 1 to 6, wherein the colorant of component (E) is carbon black. The reinforced polyester resin composition according to any one of claims 1 to 7, wherein the reinforced polyester resin composition is a material for manufacturing interior and exterior parts for vehicles and aircraft. A molded product produced by using a reinforced polyester resin composition containing the following components (A) to (E) as a raw material. (A) component: 100 parts by weight of a polyester resin, (B) component: 0 to 19 parts by weight of an acrylic resin, (C) component: formed from a nonpolar α-olefin monomer and a polar vinyl monomer. 1 to 20 parts by weight of a graft copolymer consisting of 5 to 99% by weight of a copolymer segment and 1 to 95% by weight of a vinyl (co) polymer segment formed from at least one vinyl monomer, (D) component: 30-200 weight part of inorganic fillers, and (E) component: 0.1-20 weight part of coloring agent. The reinforced polyester resin composition molded product according to claim 9, wherein the molded product is an interior / exterior part for a vehicle / airframe. The molded article according to claim 10, wherein the interior / exterior part for vehicle / airframe is a wiper part.

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