JP2007161747A - Interior or exterior vehicle or aircraft furnishings - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide interior or exterior vehicle or aircraft furnishings prepared by molding a fiber-reinforced polyester resin composition and simultaneously improved in mechanical properties, hydrolysis resistance, and appearance. <P>SOLUTION: Provided are interior or exterior vehicle or aircraft furnishings prepared by molding a fiber-reinforced polyester resin composition comprising (A) 100 pts.wt. polyester resin, (B) 30 to 150 pts.wt. fibrous filler treated with a surface treating agent essentially consisting of an aminosilane and a novolak epoxy resin, and (C) 0.1 to 3 pts.wt. epoxy compound. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to interior / exterior parts for vehicles / airframes such as automobiles, trains / trains, aircrafts, etc., especially wipers, formed by molding a fiber-reinforced polyester resin composition having excellent moldability, mechanical strength, and hydrolysis resistance. Regarding parts.

  Thermoplastic polyester resins such as polyethylene terephthalate (hereinafter sometimes abbreviated as PET) and polybutylene terephthalate (hereinafter sometimes abbreviated as PBT) have chemical and heat resistance as well as mechanical and electrical properties. Therefore, they are widely used as engineering plastics as general industrial materials such as electric machines, electronic parts, and automobile parts. Furthermore, a so-called fiber reinforced resin, in which a fibrous reinforcing material (filler) is blended with the thermoplastic resin, has improved the mechanical properties of the resin and has expanded its application range.

  Conventionally, light and high strength / rigidity and good appearance are demanded for interior / exterior parts for vehicles / airframes such as automobiles, trains / trains, and aircraft. 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, etc. Fiber reinforced polyester resin is used.

  In order to increase the strength and rigidity of a resin molded product formed by molding a fiber reinforced resin, it is necessary to increase the content of the fibrous filler. However, when the content of the fibrous filler is increased, there is a problem that the molding fluidity of the fiber reinforced resin composition is lowered or the fibrous filler is easily exposed on the surface of the resin molded product, and the appearance is lowered. It was.

  In addition, these vehicle / airframe parts and electrical / electronic parts mentioned above have been made thinner and lighter due to the miniaturization for environmental conservation measures by recent resource saving and energy saving. On the other hand, demands for improvement of mechanical strength and long-term maintenance have become more severe. In particular, polyester resins such as PBT and PET are easily hydrolyzed in a high-temperature and high-humidity atmosphere, and mechanical properties are liable to deteriorate. Therefore, long-term retention of the resin properties has been an issue. There was a request for improvement of degradability.

  Among the interior / exterior parts for vehicles / airframes formed by molding a polyester resin composition, there are wiper parts used for, for example, automobiles, trains and airplanes as molded articles particularly requiring mechanical characteristics. The wiper component mainly includes a wiper blade and a wiper arm. The blade is formed integrally with a wiping portion in the longitudinal direction in contact with a surface to be wiped such as a glass surface and wiped, and the whole is made of a resin material. An integrally molded one is common.

  The wiper blade is supported by a wiper arm, and a base (head) connected to the arm is connected to the wiper motor via a plurality of link members. When the motor operates, the wiper arm reciprocally rotates, and accordingly, the wiping portion of the blade wipes the surface to be wiped such as the glass surface. From such a mechanism, various properties such as rigidity, mechanical strength, heat resistance, hydrolysis resistance, and appearance characteristics are required at a high level for wiper parts, particularly wiper arms.

  On the other hand, for the purpose of further improving the strength of the polyester resin, a PBT composition containing glass fiber and a polyfunctional compound (epoxysilane, isocyanate compound, polycarboxylic acid anhydride, etc.) has been proposed (for example, Patent Document 1).

  Further, by using glass fibers whose surface is treated with a specific compound, for example, an epoxy resin and an aminosilane coupling agent, the glass fibers to be contained in the PBT composition etc., the electrical properties of the resulting resin composition, Methods for improving the mechanical properties have been proposed (see, for example, Patent Documents 2 to 5).

  Furthermore, as a method for improving the mechanical strength and appearance characteristics of wiper parts, reinforced PET resin molding containing 20 to 150 parts by mass of a reinforcing material and 0.1 to 5 parts by mass of an epoxy group-containing substance with respect to 100 parts by mass of polyethylene terephthalate resin. A body has been proposed (see, for example, Patent Document 6).

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 2003-342454 A

  However, recent requirements for interior / exterior parts for vehicles and aircraft have become more severe, and it has become difficult to cope with the methods described in Patent Documents 1 to 6 described above. In other words, in the prior art, with the rapid progress of weight reduction for each part, a material with low specific gravity, high mechanical strength, high hydrolysis resistance, and good appearance characteristics at the same time, and good productivity. It has become difficult to provide.

  In view of such circumstances, the present inventors have developed a resin composition for vehicle / airframe interior / exterior parts, in particular, a fiber-reinforced polyester resin composition that has simultaneously improved various properties such as mechanical properties and hydrolysis resistance. We conducted an intensive study. In particular, as a use for this, the inventors have intensively studied a fiber reinforced polyester resin composition that exhibits an excellent effect on wiper parts for vehicles and aircrafts.

  The present inventors have paid attention to the adhesion to the fibrous filler used in the polyester resin composition, particularly the resin on the surface thereof, and have eagerly investigated the relationship between the surface treatment and various properties such as mechanical strength of the fiber reinforced polyester resin. investigated. As a result, a polyester resin composition using an aminosilane coupling agent and a novolac type epoxy resin treated with a specific surface treatment agent as a fibrous filler, and an epoxy compound was blended with the fibrous filler and the polyester. It has been found that the adhesion to the resin is significantly improved.

Furthermore, the present inventors paid attention to the metal compound contained in the polyester resin to be used, especially the metal compound derived from the polymerization catalyst of the polyester resin, and intensively studied the relationship with various properties in the fiber reinforced polyester resin.
As a result, a resin molded product obtained by molding a polyester resin composition using a polyester resin, particularly PBT, containing a specific amount of a titanium compound and a metal compound of Group 1 or 2 of the Periodic Table has a mechanical strength. The inventors have found that the hydrolysis characteristics and appearance characteristics are remarkably improved, and the present invention has been completed.

  That is, the gist of the present invention is as follows: (A) 100 parts by weight of a polyester resin, (B) 30 to 150 parts by weight of a fibrous filler treated with a surface treatment agent containing at least aminosilane and a novolac type epoxy resin, and ( C) It exists in the interior and exterior parts for vehicles and airframes formed by molding a fiber reinforced polyester resin composition containing 0.1 to 3 parts by weight of an epoxy compound, particularly a wiper part.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a vehicle / airframe interior / exterior part made of a fiber-reinforced polyester resin composition having improved mechanical properties and hydrolysis resistance, in particular, a wiper part with high productivity and high reliability. Product value is increased by obtaining products. As a result, it is expected to be widely used in products and parts in many fields such as the electric / electronic equipment field and the machine field in addition to the vehicle / airframe field.

  Hereinafter, the contents of the present invention will be described in detail. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

(A) Polyester Resin As the (A) polyester resin used in the present invention, any conventionally known polyester resin can be used. Specifically, for example, a polyester resin composed of a dicarboxylic acid or a derivative thereof and a diol component can be given. As the dicarboxylic acid or derivative thereof, aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and aliphatic dicarboxylic acid, and lower alkyl or glycol esters thereof are preferable. 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. These may be used alone or in combination of two or more.

As aromatic dicarboxylic acids, terephthalic acid, phthalic acid, isophthalic acid, octophthalic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4′-benzophenone dicarboxylic acid, 4,4 ′ Preferred examples include -diphenoxyethanedicarboxylic acid, 4,4'-diphenylsulfone dicarboxylic acid, and 2,6-naphthalenedicarboxylic acid.
Preferred examples of the alicyclic dicarboxylic acid include 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, and the like. Preferred examples of the aliphatic dicarboxylic acid include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.

  As the diol component, aliphatic diols, alicyclic diols and aromatic diols are preferred. The aliphatic diol is preferably an aliphatic diol having 2 to 20 carbon atoms, such as ethylene glycol, 1,4-butanediol, diethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, Preferred examples include polypropylene glycol, polytetramethylene glycol, dibutylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,8-octanediol, and the like. Of these, those having 2 to 4 carbon atoms are preferred.

As the alicyclic diol, those having 2 to 20 carbon atoms are preferable. Specifically, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedi Methylol and the like are listed as preferred examples.
Preferred examples of the aromatic diol include xylylene glycol, 4,4′-dihydroxybiphenyl, 2,2-bis (4-hydroxyphenyl) propane, and bis (4-hydroxyphenyl) sulfone. These may be used alone or in combination of two or more.

  In the (A) polyester resin used in the present invention, lactic acid, glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid, etc. Monofunctional components such as hydroxycarboxylic acid, alkoxycarboxylic acid, stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t-butylbenzoic acid and benzoylbenzoic acid, and tricarballylic acid, trimellitic acid, trimesic acid, pyro Trifunctional or higher polyfunctional components such as merit acid, gallic acid, trimethylol ethane, trimethylol propane, glycerol and pentaerythritol may be used as the copolymer component.

  More preferable examples of the (A) polyester resin include polyalkylene terephthalate, and more preferable examples include polybutylene terephthalate resin (PBT) or polyethylene terephthalate resin (PET) from the viewpoint of price. Here, PET has a high specific gravity and a slight difficulty in crystallization speed. On the other hand, PBT alone has a very high solidification speed, so that the surface appearance of the molded product tends to be deteriorated. The polyester mainly composed of is more preferable, and specifically, for example, it is preferable to use a mixture of PBT and PET as the polyester resin. The blending ratio is preferably in the range of PBT / PET = 95/5 to 50/50 (weight ratio).

  Although there is no restriction | limiting in the intrinsic viscosity of (A) polyester resin used for this invention, The temperature is 30 degreeC using the mixed solvent of 1,1,2,2-tetrachloroethane / phenol = 1/1 (weight ratio). As the values measured in Step 1, the PBT is preferably 0.7 to 1.5, and the PET is preferably 0.5 to 1.5. Intrinsic viscosity may be adjusted by using two or more types of intrinsic viscosity polyester resins together. However, if the intrinsic viscosity is too small, the mechanical properties are not exhibited. become.

  In addition, you may use other resin together with (A) polyester resin within the range which does not inhibit the meaning of this invention. For example, in order to further improve the appearance and dimensional accuracy of the molded product, an amorphous resin such as a styrene polymer, an acrylonitrile-styrene copolymer, or a polycarbonate polymer is used in an amount of 80 wt. It is preferable to add less than or equal to parts. Among them, polycarbonate resin having high heat resistance is preferable. In order to improve toughness, impact modifiers such as thermoplastic elastomers or core-shell polymers may be added.

  Examples of the thermoplastic elastomer include olefins, styrenes, polyesters, polyamides and urethanes. Of these, polyester-based thermoplastic elastomers are preferred from the viewpoint of compatibility with polyester resins. As the core-shell polymer, for example, a silicon-based or diene-based elastomer alone or a copolymer obtained by copolymerizing / grafting two or more kinds of elastomer component systems selected from the above can be used. Other resins added to the polyester resin may be modified 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 the compatibility with the polyester resin.

  The PBT used in the present invention is a resin having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded. A polybutylene terephthalate homopolymer having terephthalic acid as the only dicarboxylic acid unit and tetramethylene glycol as the only diol unit may be used. Of course, as the dicarboxylic acid unit, one or more dicarboxylic acids other than the above-mentioned terephthalic acid and / or Or the polybutylene terephthalate copolymer containing 1 or more types of diols other than the said tetramethylene glycol as a diol unit may be sufficient.

  However, if the proportion of terephthalic acid units or 1,4-butanediol units is too low in all dicarboxylic acid units or in all diol units, the crystallization rate of PBT decreases and the moldability of the resulting PBT decreases. There is. Therefore, the proportion of terephthalic acid units in all dicarboxylic acid units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98% or more. The proportion of 1,4 butanediol units is usually 70 mol% or more, preferably 80 mol% or more, more preferably 95 mol% or more, and particularly preferably 98% or more.

  The PBT used in the present invention may be a resin having a structure in which a terephthalic acid unit and a 1,4-butanediol unit are ester-bonded as described above, and may have an appropriate crystallization rate. (A) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound, and (a) the content of the titanium compound is 10 ppm or more and 80 ppm or less in terms of titanium atom, It is desirable that the content of the Group 1 metal compound and / or the Group 2 metal compound is 1 ppm or more and 50 ppm or less in terms of metal atoms.

  The PBT preferably used in the present invention is a polycondensation of an oligomer obtained by an esterification reaction (or transesterification reaction) between 1,4-butanediol and terephthalic acid (or dialkyl terephthalate). By using (a) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound as a catalyst (polycondensation catalyst) used in this polycondensation, (a), ( Since the dispersion of the metal compound of b) can be made favorable, the effect of the present invention can be expected with a small amount of inclusion.

These polycondensation catalysts can be used at any time. Specifically, examples of the usage method include the following methods (1) to (4). Hereinafter, (a) a titanium compound may be referred to as a titanium catalyst, and (b) a group 1 metal compound and a group 2 metal compound may be referred to as a group 1 metal catalyst and a group 2 metal catalyst, respectively.
(1) A method of using both (a) and (b) in the esterification reaction (or transesterification reaction) and bringing them into the polycondensation reaction.
(2) A method in which (a) and (b) are partially used in the esterification reaction (or transesterification reaction) and added at the start of the polycondensation reaction or during the reaction.
(3) A method in which one of the catalysts (a) and (b) is used in the esterification reaction (or transesterification reaction), and the other is added at the start of the polycondensation reaction or during the reaction.
(4) A method in which neither (a) nor (b) is used in the esterification reaction (or transesterification reaction), and both are added at the start of the polycondensation reaction.

  The (a) titanium compound used in the present invention is not particularly limited. Specifically, for example, inorganic titanium compounds such as titanium oxide and titanium tetrachloride; titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate and tetrabutyl titanate And the like; and titanium phenolates such as tetraphenyl titanate; Of these, titanium alcoholates are preferable, tetraalkyl titanates are more preferable, and tetrabutyl titanate is particularly preferable.

  The (b) Group 1 metal compound and / or Group 2 metal compound used in the present invention is not particularly limited. Specifically, for example, the Group 1 metal compound may be hydroxylated with lithium, sodium, potassium, rubidium, or cesium. Compounds; oxides; alcoholates; various organic acid salts such as acetates, phosphates, carbonates, etc., and examples of group 2 metal compounds include beryllium, magnesium, calcium, strontium, Various compounds such as barium hydroxides; oxides; alcoholates; various organic acid salts such as acetates, phosphates and carbonates; These may be used alone or in combination.

  Among them, lithium, sodium, potassium, magnesium, calcium, and other compounds are preferable from the viewpoints of handling and availability, and catalytic effect, and lithium or magnesium compounds that are excellent in catalytic effect and color tone are preferable, especially magnesium compounds. Is preferred. Specific examples of the magnesium compound include magnesium acetate, magnesium hydroxide, magnesium carbonate, magnesium oxide, magnesium alkoxide, and magnesium hydrogen phosphate. Of these, organic acid salts are preferable, and magnesium acetate is particularly preferable.

  In the PBT used in the present invention, the content of the (a) titanium compound is preferably 10 ppm or more and 80 ppm or less in terms of titanium atoms. When there is too much content of this titanium compound, the color tone of PBT and hydrolysis resistance fall, and the solution haze and foreign material increase by deactivation of a titanium catalyst may arise. On the other hand, if the amount is too small, the polymerizability of PBT decreases. Therefore, the content of the (a) titanium compound is preferably 70 ppm or less, particularly 60 ppm or less, more preferably 50 ppm or less, and particularly preferably 40 ppm or less, and the lower limit thereof is 15 ppm or more, especially 20 ppm or more, and particularly preferably 30 ppm or more. .

  The content of the (b) Group 1 metal compound and / or Group 2 metal compound in the PBT used in the present invention is preferably 1 ppm or more and 50 ppm or less in terms of each metal atom. When there is too much content of this 1st group metal compound and / or 2nd group metal compound, the moldability of the resin composition of this invention and the hydrolysis resistance of the resin molded product obtained may fall. On the other hand, even if the amount is too small, the adhesion between PBT and glass fiber and heat shock resistance may decrease. Therefore, the content of (b) Group 1 metal compound and / or Group 2 metal compound is 40 ppm or less, preferably 30 ppm or less, more preferably 20 ppm or less, particularly preferably 15 ppm or less, and the lower limit thereof is 3 ppm or more, especially 5 ppm or more. In particular, it is preferably 10 ppm or more. The metal content such as titanium atom can be measured using a method such as atomic emission, atomic absorption, Inductively Coupled Plasma (ICP) after recovering the metal in the polymer by a method such as wet ashing.

  Examples of the PBT polycondensation catalyst used in the present invention include the titanium compounds and (b) Group 1 metal compounds and / or Group 2 metal compounds described above, but other polycondensation catalysts include, for example, tin and its Compounds. Tin is usually used as a tin compound, specifically, for example, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Triphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, tributyltin chloride, dibutyltin sulfide, butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannic acid, etc. Can be mentioned.

  However, in general, tin and tin compounds deteriorate the color tone of PBT. Therefore, the content of tin compounds in the PBT used in the present invention is preferably low, and is preferably not contained. Specifically, it is preferable that the content of the tin compound is usually 200 ppm or less, particularly 100 ppm or less, more preferably 10 ppm or less in terms of tin atoms.

  In the production of PBT used in the present invention, in addition to the titanium catalyst, group 1 metal catalyst and group 2 metal catalyst, antimony compounds such as antimony trioxide; germanium compounds such as germanium dioxide and germanium tetroxide; manganese Reaction assistants such as compounds; zinc compounds; zirconium compounds; cobalt compounds; phosphorous compounds such as orthophosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, and their esters and metal salts;

  Although the terminal carboxyl group concentration of PBT used for this invention is arbitrary, generally the lower one is preferable. Specifically, it is preferably 30 μeq / g or less, more preferably 5 to 25 μeq / g, and particularly preferably 5 to 20 μeq / g. If it exceeds 30 μeq / g, the hydrolysis resistance and residence heat stability may be lowered, and if it is too low, the effect of improving the mechanical strength and the heat shock resistance may be lowered.

  Next, the manufacturing method of PBT used for this invention is demonstrated. The production method of PBT used in the present invention is arbitrary. Generally, depending on the raw materials used, a method using a dicarboxylic acid as a main raw material (direct polymerization method) and a method using a dicarboxylic acid dialkyl ester as a main raw material (transesterification) Law). The former has a difference in that water is mainly produced in the initial esterification reaction, and the latter mainly produces alcohol in the initial transesterification reaction.

  In addition, the PBT production method used in the present invention is generally continuous with the batch method, depending on the raw material supply or the extraction form of the polybutylene terephthalate resin that is the generated polymer (the method in which the generated (molten) polymer is extracted from the reaction tank or the like). Broadly divided into laws. The initial esterification reaction or transesterification reaction is performed in a continuous operation, followed by polycondensation in a batch operation, or the initial esterification reaction or transesterification reaction is performed in a batch operation, followed by polycondensation in a continuous operation. The method of performing is known.

  As the method for producing PBT used in the present invention, it is preferable to use a direct polymerization method from the viewpoint of the superiority of the raw material basic unit, the ease of processing of by-products, etc., and for the quality stability and production of the obtained PBT. From the viewpoint of energy efficiency, it is preferable to use a so-called continuous method in which an esterification reaction and a polycondensation reaction are continuously performed.

  The aforementioned Group 1 metal catalyst and / or Group 2 metal catalyst used in the production of the PBT used in the present invention can be supplied to the esterification reaction tank or transesterification reaction tank, but the supply position is not particularly limited. The reaction solution may be supplied from the reaction solution gas phase portion to the upper surface of the reaction solution or directly to the reaction solution liquid phase portion. Moreover, in this case, it may be supplied together with the raw material terephthalic acid or the titanium catalyst, or may be supplied independently. Among these, from the viewpoint of the stability of the catalyst, it is preferable to supply the terephthalic acid and the titanium catalyst independently from the terephthalic acid and the titanium catalyst and to the upper surface of the reaction liquid from the reaction gas phase.

  As a method for supplying the group 2 metal catalyst, for example, when the group 2 catalyst is solid at room temperature, it can be supplied to the reaction solution as a solid, but the supply amount is stabilized, and adverse effects such as heat denaturation are caused. In order to reduce, it is preferable to dissolve in a solvent such as water or 1,4-butanediol and supply as a solution. The concentration of the Group 2 metal catalyst in this solution is usually 0.01% by weight or more, preferably 0.05% by weight or more, and particularly preferably 0.08% by weight or more, and the upper limit is 20% by weight or less. It is preferably 10% by weight or less, particularly preferably 8% by weight or less.

  Moreover, you may add a group 1 metal catalyst and / or a group 2 metal catalyst to the polycondensation reaction tank following an esterification reaction tank or a transesterification reaction tank, and the oligomer piping attached to it. In this case, the addition method also stabilizes the supply amount and reduces adverse effects such as heat denaturation, such as water, a solvent such as 1,4-butanediol, and a copolymer component such as polytetramethylene ether glycol. It is preferable to melt | dissolve and supply as a solution, and the density | concentration in this case is the same as the above-mentioned solution density | concentration.

  As a specific example of the method for producing PBT used in the present invention, for example, in the case of a continuous esterification method using a direct polymerization method, the following method may be used. A dicarboxylic acid component mainly composed of terephthalic acid, which is a raw material, and a diol component mainly composed of 1,4-butanediol are mixed in a raw material mixing tank to form a slurry, and in one or a plurality of esterification reaction tanks In the presence of a titanium catalyst and a Group 1 metal catalyst and / or a Group 2 metal catalyst, the temperature condition is usually 180 to 260 ° C, preferably 200 to 245 ° C, more preferably 210 to 235 ° C. The pressure (indicating absolute pressure; hereinafter the same) conditions are usually 10 to 133 kPa, preferably 13 to 101 kPa, more preferably 60 to 90 kPa, and usually 0.5 to 10 hours. Preferably, the esterification reaction is continuously performed for 1 to 6 hours.

  Any conventionally known esterification reaction tank or transesterification reaction tank can be used. Specifically, for example, a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower-type continuous reaction tank, and the like can be mentioned. These may be used as a single tank or as a plurality of reaction tanks in which the same or different reaction tanks are connected in series or in parallel. Among them, it is preferable to use a reaction tank having a stirring device. As the stirring device, in addition to a normal stirring device including a power unit, a bearing, a shaft, a stirring blade, etc., a turbine stator type high-speed rotary stirrer, a disc mill type stirrer Alternatively, a rotor mill type stirrer or the like capable of high speed rotation may be used.

  Next, the obtained oligomer as the esterification reaction product (or transesterification reaction product) is transferred to a polycondensation reaction tank. Although the esterification rate of this oligomer is arbitrary, it is usually 90% or more, preferably 95% or more, and the number average molecular weight is usually 300 to 3000, preferably 500 to 1500.

  The form of the polycondensation reaction tank is arbitrary, and examples thereof include a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a tower-type continuous reaction tank, and the like, and these may be used in combination. Among these, at least one polycondensation reaction tank preferably has a stirrer, and the stirrer is the same as the esterification reaction layer described above.

  The form of stirring is not particularly limited, and in addition to the usual stirring method in which the reaction solution in the reaction tank is directly stirred from the top, bottom, side, etc. of the reaction tank, a part of the reaction solution is connected to the reactor by piping or the like. A method of circulating the reaction liquid by taking it outside and stirring it with a line mixer or the like may be used. Further, a horizontal reactor having a rotating shaft in the horizontal direction and excellent in self-cleaning may be used. .

  The polycondensation reaction is performed in the presence of a titanium catalyst and a group 1 metal catalyst and / or a group 2 metal catalyst. The reaction temperature is usually 210 to 280 ° C, preferably 220 to 250 ° C, particularly preferably 230 to 245 ° C. For example, when using several reaction tanks, it is preferable that the temperature of the at least 1 reaction tank is 230-240 degreeC. The reaction is preferably performed under stirring conditions. The polycondensation reaction time is usually 1 to 12 hours, preferably 3 to 10 hours. The pressure condition of the reaction atmosphere is usually 27 kPa or less, preferably 20 kPa or less, particularly preferably 13 kPa or less. For example, when a plurality of reaction vessels are used, the pressure in at least one of the reaction vessels is usually 1.3 kPa or less, particularly 0.5 kPa or less, particularly 0.3 kPa or less in order to suppress coloring and deterioration of the product. It is preferable to be under a high vacuum.

  The polymer obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted in the form of a strand, and while being cooled with water or after being cooled with water, it is cut with a cutter to form pellets and chips. And so on. Furthermore, the PBT polycondensation reaction step is to once produce a PBT having a relatively small molecular weight by melt polycondensation, for example, an intrinsic viscosity of about 0.1 to 0.9, and then at a temperature below the melting point of the PBT. Solid phase polycondensation (solid phase polymerization) may be performed.

(B) Fibrous filler treated with a surface treatment agent containing at least aminosilane and a novolak type epoxy resin (B) Fibrous filler used in the present invention (hereinafter sometimes simply referred to as “fiber”). , Treated with a surface treatment agent containing aminosilane (hereinafter sometimes referred to as “amino-based silane coupling agent”) and novolac type epoxy resin (hereinafter sometimes simply referred to as “epoxy resin”). And the treatment agent (hereinafter sometimes referred to as “bundling agent”) is attached to the surface.

  As a method of attaching, for example, as described in JP-A Nos. 2001-172055 and 53-106749, it may be processed before kneading with (A) polyester resin or the like, or at the time of kneading You may surface-treat by kneading | mixing with another component. By performing the surface treatment in this way, the sizing agent adheres to at least a part of the fiber surface, and the mechanical properties and hydrolysis resistance of the polyester resin composition of the present invention can be improved. Polyester resin composition by combining aminosilane inorganic functional group and glass fiber surface, aminosilane organic functional group and epoxy resin glycidyl group, and epoxy resin glycidyl group and polyester resin, which are highly reactive, respectively. It is considered that the interfacial adhesive force between the fibers and the epoxy resin can be improved among the constituent elements in the object.

  In the present invention, whether or not the sizing agent is attached to the surface of the fibrous filler can be determined by, for example, TEM observation of the fracture surface of the fiber-reinforced flame retardant polyester resin composition of the present invention. That is, in the vicinity of the fracture surface, the sizing agent is attached to the fibrous filler in a portion where the resin remains without peeling from the fiber surface such as glass fiber (that is, the fiber surface has low smoothness). Recognize.

  The epoxy resin in the sizing agent used in the present invention includes a novolac type epoxy resin. 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 content of the novolak type epoxy resin in the sizing agent used in the present invention is preferably 1 to 20% by weight, and more preferably 2 to 10% by weight.

  Preferred examples of the amino silane coupling agent in the sizing agent used in the present invention include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyltrimethoxysilane. As mentioned. The content of the amino silane coupling agent in the sizing agent used in the present invention is preferably 0.1 to 8% by weight, and more preferably 0.5 to 5% by weight.

  The sizing agent used in the present invention can contain components such as urethane resin, acrylic resin, antistatic agent, lubricant and water repellent within the scope of the present invention. Furthermore, an epoxy resin other than the novolac type, an epoxy silane coupling agent, and / or a titanate coupling agent may be included. The amount of sizing agent attached to the fibers is preferably 0.05 to 2% by weight. By making it 0.05% by weight or more, the mechanical strength is more effectively improved, and by making it 2% by weight or less, a necessary and sufficient effect is obtained and it is economical.

  Moreover, conventionally well-known arbitrary things can be used for the fiber used for this invention. Examples of the fiber include glass fiber, carbon fiber, potassium titanate fiber, metal fiber, ceramic fiber, aramid fiber, and PPS fiber. Among them, glass fiber is preferable because it has a high resin reinforcing effect and is excellent in productivity. As the glass fiber, for example, a long fiber type (roving) or a short fiber type (chopped strand) can be selected and used. The fiber diameter is preferably 6 to 16 μm, more preferably 6 to 13 μm, and still more preferably 6 to 11 μm. By adopting such a fiber diameter, the mechanical properties can be improved more effectively.

  As the cross-sectional shape substantially perpendicular to the longitudinal direction of the fiber, a cross-sectional shape other than a substantially perfect circle can be used. The irregular cross section refers to a fiber cross section having a high flatness ratio that is not an elongated flat shape such as an oval, an ellipse, or an eyebrows, or a so-called substantially circular shape such as a triangle, a V shape, or a star shape. Show. Here, the flatness ratio indicates a value obtained by dividing the maximum length in the longitudinal direction in the fiber cross-sectional shape by the maximum length (width) in the direction perpendicular thereto. The maximum length in the longitudinal direction when the surface shape is curved indicates a length measured along the curve (that is, a length obtained by correcting the curve into a straight line). The aspect ratio is preferably 2.3 to 30, more preferably 2.4 to 20, and even more preferably 2.5 to 12. By adopting such a modified cross-section fiber, the mechanical properties can be improved more effectively.

  Moreover, 0.1-20 mm is preferable and, as for the average fiber length of glass fiber, 1-10 mm is more preferable. By making the average fiber length 0.1 mm or more, the reinforcing effect by the glass fiber is more effectively expressed, and by making the average fiber length 20 mm or less, melt kneading with polybutylene terephthalate resin or glass fiber reinforced poly Molding of the butylene terephthalate resin composition becomes easier. The compounding quantity of the glass fiber employ | adopted by this invention is 30-150 weight part with respect to 100 weight part of (A) polyester resin, and 35-120 weight part is more preferable.

  Examples of the glass fiber used in the present invention include various glass fibers such as E glass, C glass, A glass, S glass, and S-2 glass, which are preferable examples. E glass having a low alkali content and good electrical characteristics. The glass fiber is more preferable.

(C) Epoxy Compound As the (C) epoxy compound used in the present invention, any conventionally known one can be used, and any of monofunctional, bifunctional or polyfunctional can be used. In the present invention, two or more of these may be used in combination. Of these, bifunctional or higher epoxy compounds, that is, compounds having two or more epoxy groups in one molecule are preferable. (C) The epoxy compound preferably has a molecular weight of 100 to 10,000. The (C) epoxy compound is preferably a glycidyl compound or an alicyclic epoxy compound obtained from a reaction between an alcohol, a phenolic compound, or a carboxylic acid and epichlorohydrin.

Specific examples of the (C) epoxy compound include glycidyl ether, diglycidyl ether, fatty acid glycidyl ester, diglycidyl ester, alicyclic diepoxy compound, and glycidyl imide compound. The glycidyl ether is preferably methyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, decyl glycidyl ether, stearyl glycidyl ether, phenyl glycidyl ether, butylphenyl glycidyl ether or allyl glycidyl ether. The diglycidyl ether is preferably neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, glycerin diglycidyl ether, propylene glycol diglycidyl ether, bisphenol A diglycidyl ether, or the like.
The fatty acid glycidyl ester is preferably benzoic acid glycidyl ester or sorbic acid glycidyl ester. The diglycidyl ester is preferably adipic acid diglycidyl ester, terephthalic acid diglycidyl ester or orthophthalic acid diglycidyl ester. The alicyclic diepoxy compound is preferably 3,4-epoxycyclohexylmethyl-3 ′, 4′-epoxycyclohexylcarboxylate. The glycidyl imide compound is preferably N-glycidyl phthalimide or the like. Among these, glycidyl ether compounds obtained from the reaction of bisphenol A and epichlorohydrin, particularly bisphenol A diglycidyl ether, are preferred, and bisphenol A glycidyl ether having an epoxy equivalent of 100 to 200 g / eq is particularly preferred.

  (C) Content of an epoxy compound is 0.1-3 weight part with respect to 100 weight part of (A) polyester resin, Preferably it is 0.15-2 weight part. If the amount is less than 0.1 parts by weight, the effect of further improving the mechanical properties is not recognized. If the amount is more than 3 parts by weight, the fluidity during molding and the like tends to deteriorate, and hydrolysis is promoted at the time of melting. It is not preferable because the decrease starts.

  The vehicle / airframe interior / exterior parts of the present invention are parts attached to the interior or exterior of a vehicle or body, for example, a physical property value of 6000 MPa or more is required as a flexural modulus indicating rigidity, mechanical strength, and Examples include parts that are required to have appearance characteristics and hydrolysis resistance at the same time. Specifically, for example, outdoor parts include wiper arms, door handles, door mirror stays, roof rails, and the like, and indoor parts include inner mirror stays, door handles, and the like. Among them, the wiper arm requires particularly high mechanical strength, and the effect of the present invention becomes remarkable.

  A release agent may be blended in the fiber-reinforced polyester resin composition constituting the interior / exterior part for vehicle / airframe of the present invention without departing from the gist of the present invention. The release agent is preferably a fatty acid ester composed of a fatty acid residue having 12 to 36 carbon atoms and an alcohol residue having 1 to 36 carbon atoms, paraffin wax and polyethylene wax. The compounding amount of the release agent is preferably 0.01 to 2 parts by weight with respect to 100 parts by weight of (A) polybutylene terephthalate resin.

In addition to the above, the fiber reinforced polyester resin composition constituting the interior / exterior part for vehicle / airframe of the present invention is not limited to the gist of the present invention, and various known additives, heat stabilizers, and crystallization promotion. Contains agents, inorganic fillers (talc, wollastonite, etc.), impact modifiers, flame retardants, UV absorbers, weathering agents, dyes, colorants (such as lubricants and pigments), foaming agents, and various resins You may do it.
Examples of the resin include styrenes such as various nylons and various nylon elastomers, liquid crystal polymers, polycarbonate resins, polystyrene, acrylonitrile-butadiene-styrene resins (ABS), acrylonitrile-styrene copolymers (AS), and methacrylstyrene resins (MS). Thermoplastic resins such as resins, acrylic resins, polyamides, polyphenylene sulfide resins, polyacetals and polyphenylene oxides; Olefin resins such as polyethylene, polypropylene and ethylene-propylene copolymers; Fluorine resins such as polytetrafluoroethylene; Isobutylene-isoprene Elastomers such as rubber, styrene-butadiene rubber, styrene-butadiene rubber-styrene, ethylene-propylene rubber, acrylic elastomer; Nomar resins, phenoxy resins, phenol resins, melamine resins, silicone resins may contain a thermosetting resin such as epoxy resin.

  The production method of the polyester resin composition constituting the interior / exterior part for vehicle / airframe of the present invention can be produced by any conventionally known method. Specifically, the components (A) to (C) described above may be kneaded. As the kneading method, each component may be combined with an additional component as necessary, a Henschel mixer, a ribbon blender, a V-type. After uniformly mixing with a blender or the like, the mixture may be kneaded with a single-screw or multi-screw kneading extruder, roll, Banbury mixer, lab plast mill (Brabender) or the like.

  Among these, it is preferable to produce by melt kneading, and it is usually performed at 230 to 290 ° C. Furthermore, in order to suppress decomposition during kneading, it is preferable to use the above heat stabilizer. Each component, including additional components, may be fed all at once or sequentially to the kneader. Moreover, you may use what mixed beforehand 2 or more types of components chosen from each component including an additional component. By adding a fibrous reinforcing filler such as glass fiber after the resin is melted from the middle of the extruder, it can avoid crushing and exhibit high characteristics.

  The polyester resin composition used in the present invention can be produced by various known molding methods such as injection molding, hollow molding, extrusion molding, compression molding, calendar molding, rotational molding, etc. Can be molded as A particularly preferable molding method is injection molding because of its good fluidity. In the injection molding, it is preferable to control the resin temperature within the range of 15 to 50 ° C. higher than the melting point of the resin, specifically 240 to 290 ° C. and the mold temperature 60 to 120 ° C. In particular, when the polyester resin is PET, the mold temperature is preferably set in the range of 90 to 120 ° C. in order to sufficiently crystallize and stabilize the dimensions.

  The present invention will be described more specifically with reference to the following examples.Materials, amounts used, ratios, processing contents, processing procedures, and the like shown in the following examples are appropriately determined unless departing from the gist of the present invention. Can be changed. Therefore, the scope of the present invention is not limited to the specific examples shown below.

(A) PBT production method (A-1 to A-2)
(A-1) :
Using the esterification step shown in FIG. 1 and the polycondensation step shown in FIG. 2, PBT was produced by the following method. First, a 60 ° C. slurry mixed at a ratio of 1.80 mol of 1,4-butanediol with respect to 1.00 mol of terephthalic acid was passed through the raw material supply line 1 from the slurry preparation tank in advance with an esterification rate of 99%. Was continuously fed to the reaction tank A for esterification having a screw type stirrer filled with PBT oligomer of 41 kg / h. At the same time, the bottom component of the rectifying column C at 185 ° C. (98% by weight or more is 1,4-butanediol) is supplied at 20 kg / h from the recirculation line 2 and the catalyst at 65 ° C. A 6.0 wt% 1,4-butanediol solution of tetrabutyl titanate was fed at 149 g / h (45 ppm relative to the theoretical polymer yield). The water content in this catalyst solution was 0.2% by weight. A 6.0 wt% 1,4-butanediol solution of magnesium acetate tetrahydrate at 65 ° C. was fed as a catalyst at 103 g / h from the group 2 metal catalyst supply line 15 (25 ppm relative to the theoretical polymer yield). The water content in this catalyst solution was 10.0% by weight.

  The internal temperature of the reaction tank A is 230 ° C., the pressure is 78 kPa, and water to be generated, tetrahydrofuran and excess 1,4-butanediol are distilled from the distillation line 5. Separated into boiling components. The high-boiling component at the bottom of the column after the system is stabilized is 98% by weight or more of 1,4-butanediol, and a part of the high-boiling component through the extraction line 8 so that the liquid level of the rectifying column C is constant. Extracted outside. On the other hand, the low boiling component was extracted from the top of the column in the form of gas, condensed by the condenser G, and extracted from the extraction line 13 to the outside so that the liquid level of the tank F was constant.

  A certain amount of the oligomer generated in the reaction tank A was extracted from the extraction line 4 using the pump B, and the liquid level was controlled so that the average residence time of the liquid in the reaction tank A was 2.5 hr. The oligomer extracted from the extraction line 4 was continuously supplied to the first polycondensation reaction tank a shown in FIG. After the system was stabilized, the esterification rate of the oligomer collected at the outlet of the reaction tank A was 96.5%.

  The internal temperature of the first polycondensation reaction tank a was 240 ° C., the pressure was 2.1 kPa, and the liquid level was controlled so that the residence time was 120 minutes. An initial polycondensation reaction was performed while extracting water, tetrahydrofuran and 1,4-butanediol from a vent line L2 connected to a decompressor (not shown). The extracted reaction liquid was continuously supplied to the second polycondensation reaction tank d.

  The internal temperature of the second polycondensation reaction tank d is 240 ° C., the pressure is 130 Pa, the liquid level is controlled so that the residence time is 75 minutes, and water is supplied from a vent line L4 connected to a decompressor (not shown). Further, the polycondensation reaction was advanced while extracting tetrahydrofuran and 1,4-butanediol. The obtained polymer was continuously extracted in a strand form from the die head g via the extraction line L3 by the extraction gear pump e, and was cut by the rotary cutter h. The obtained PBT had an intrinsic viscosity of 0.85 dL / g and a terminal carboxyl group concentration of 14,2 μeq / g. The content of titanium atoms was 45 ppm, and the content of magnesium atoms was 25 ppm.

(A-2) :
(A-1) was carried out in the same manner as (A-1), except that magnesium acetate tetrahydrate was not used and the residence time of the second polycondensation reaction tank d was 105 minutes. The obtained PBT had an intrinsic viscosity of 0.85 dL / g and a terminal carboxyl group concentration of 20.4 μeq / g. The content of titanium atoms was 45 ppm, and the content of magnesium atoms was 0 ppm.
Evaluation method of PBT characteristics

(1) Esterification rate:
It calculated from the acid value and saponification value by the following formula. The acid value was obtained by dissolving the oligomer in dimethylformamide and titrating with a 0.1N KOH / methanol solution. The saponification value was determined by hydrolyzing the oligomer with a 0.5N KOH / ethanol solution and titrating with 0.5N hydrochloric acid.
Esterification rate = (saponification value−acid value) / saponification value) × 100

(2) Terminal carboxyl group concentration:
0.5 g of PBT resin or oligomer was dissolved in 25 ml of benzyl alcohol, and titrated using a 0.01 mol / L benzyl alcohol solution of sodium hydroxide.

(3) Intrinsic viscosity (IV):
It calculated | required in the following way using the Ubbelohde type viscometer. That is, using a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1), at 30 ° C., the polymer solution having a concentration of 1.0 g / dl and the number of falling seconds of the solvent alone were measured, and obtained from the following formula. .

IV = ((1 + 4K _H η _sp ) ^0.5 −1) / (2K _H C) (2)
(Where η _sp = η / η ₀ −1, η is the polymer solution dropping time, η ₀ is the solvent dropping time, C is the polymer solution concentration (g / dL), and K _H is the Huggins constant. Yes, 0.33)

(4) Titanium and group 1 and group 2 metal concentrations in PBT:
PBT was wet-decomposed with high-purity sulfuric acid and nitric acid for electronic industry and measured using a high resolution ICP-MS (Inductively Coupled Plasma-Mass Spectrometer) (manufactured by ThermoQuest).

(B) Manufacturing method (B-1 to B-2) of glass fiber treated with surface treatment agent formed by blending aminosilane and novolac type epoxy resin
A glass fiber to which a sizing agent containing an amino-based silane coupling agent and a novolac-type epoxy resin was attached was produced according to the method described in JP-A-2001-172055.
Specifically, a sizing agent comprising 4% by weight of phenol novolac type epoxy resin, 1% by weight of γ-aminopropyltriethoxysilane, 2% by weight of urethane emulsion and 93% by weight of deionized water was prepared, and then glass fiber It was applied to the strand. This strand was cut into 3 mm. The amount of sizing agent attached to the obtained glass fiber chopped strands was 0.7% by weight. The glass fiber thus obtained is (B-1) described later, and (B-2) uses a bisphenol A type epoxy resin instead of the phenol novolac type epoxy resin.

<Raw materials used in Examples and Comparative Examples>
(A) Polyester resin (A-1) Polybutylene terephthalate: Production example (A-1) Inherent viscosity 0.85, titanium content 45 ppm, magnesium content 25 ppm
(A-2) Polybutylene terephthalate: Production example (A-2) Inherent viscosity 0.85, titanium content 45 ppm, magnesium content 0 ppm
(A-3) Polyethylene terephthalate: Mitsubishi Chemical Corporation, GS385, intrinsic viscosity 0.65.

(B) Glass fiber (B-1) Glass fiber (fiber diameter 13 μm) treated with a surface treating agent obtained by blending aminosilane and novolac epoxy resin; Production Example (B-1) above
(B-2) Glass fiber (fiber diameter 13 μm) treated with a surface treatment agent comprising aminosilane and bisphenol type epoxy resin blended; production example (B-2) above

(C) Polyfunctional compound such as epoxy compound (C-1) Diglycidyl ether of bisphenol A, epoxy equivalent 185 g / eq (Asahi Denka Co., Adeka Sizer EP-17)
(C-2) Tolylene diisocyanate (Wako Pure Chemical Industries)
(C-3) Pyromellitic anhydride (manufactured by Wako Pure Chemical Industries)

<Production Method and Evaluation of Glass Fiber Reinforced Polyester Resin Composition>
Polyfunctional compounds such as the above polyester resin, glass fiber, and epoxy compound have a specific gravity of 1.54 in Example 6 and Comparative Example 5 and a specific gravity of 1.4 in other Examples and Comparative Examples. The mixture was blended at a ratio shown in Table 1 so as to be 73, kneaded according to a conventional method using a twin screw extruder, and pelletized. Using this resin composition, a test piece for measuring mechanical properties was molded using an injection molding machine (model SG-75MIII) manufactured by Sumitomo Heavy Industries, Ltd. under conditions of a cylinder temperature of 250 ° C. and a mold temperature of 80 ° C. The mechanical properties and hydrolysis resistance were evaluated. Further, the surface appearance characteristics and the shortest molding time were evaluated according to the following methods.

Performance Evaluation Method (1) Tensile strength and tensile elongation Measured according to ISO527. The units of strength and elongation were MPa and%, respectively.
(2) Flexural strength and flexural modulus Measured according to ISO178. The units of strength and elastic modulus were both set to MPa.
(3) Charpy impact strength It measured based on ISO179. The strength is notched and the unit is KJ / m ² .

(4) Hydrolysis resistance test An ISO tensile test piece was wet-heated at 121 ° C in saturated steam at 203 kPa for 100 hours, the tensile strength before and after the treatment was measured, and the strength retention was determined according to the following formula. A higher numerical value indicates better hydrolysis resistance.
Strength retention (%) = (Tensile strength after treatment / Tensile strength before treatment) × 100

(5) Strength of molded product Using an injection molding machine (manufactured by Sumitomo Heavy Industries, SH100), the part 1 shown in FIG. 3 is molded at a cylinder temperature of 265 ° C. and a mold temperature of 130 ° C. to form an aluminum part 2 The strength was measured by fitting. The part 1 has a length (L) of 100 to 500 mm, a height (H) of 20 to 50 mm, a width (W) of 20 to 50 mm, a wall thickness of 1.5 to 5 mm, and a diameter that fits with the part 2 It has a pivot axis (A) of 8-12 mm. As shown in FIG. 4, after measuring the end of the molded product 2, the strength is measured by fitting the molded product 1 and applying a load to the end of the molded product 1 in a direction perpendicular to the rotation shaft and the rotation surface. In addition, the breaking load at the fitting portion was measured.

(6) Appearance of molded product Using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., SH100), a rectangular flat plate with a cylinder temperature of 265 ° C., a mold temperature of 130 ° C., a length of 100 mm, a width of 100 mm, and a diameter of 3 mm is formed with a film gate mold. Then, the glass fiber floating state on the surface of the flat plate test piece was classified by visual observation as in the following 1 to 5.
5: The glass fiber is hardly lifted up.
4: Although there is a slight lift, it is within the allowable appearance range of general molded products.
3: The glass fiber is partially lifted.
2: A glass fiber float is observed over a fairly wide range.
1: It is recognized as a whole and completely outside the allowable range.
The above-mentioned 5 and 4 levels were within the allowable range, and the molded article had a good appearance.

(7) Minimum cooling time during molding The minimum cooling time during molding is the injection molding machine (model SG-75MIII) manufactured by Sumitomo Heavy Industries, Ltd. with a resin temperature of 265 ° C. In the case of molding at a mold temperature of 130 ° C., the shortest cooling time during which no ejector trace of the ejector pin remains is shown. This time is an index of high cycle formability, and the smaller the value, the better the productivity. The molded product 3 has a cylindrical protrusion with an outer diameter (D2) of 16 mm and a height (H2) of 15 mm at the center of a cylindrical cup shape with an outer diameter (D1) of 70 mm and a height (H1) of 30 mm. It is a molded product. The thickness of the molded product is 2 to 2.5 mm, and the ejector pin has a structure in which six cup-shaped inner bottom surfaces are projected symmetrically. In the evaluation after ejecting the ejector pin, it was visually determined whether or not the convex shape protruded on the cup-shaped outer bottom surface.

Table 1 shows the following. Examples 1 to 6 in which the glass fiber (B-1) containing the novolac epoxy resin and the epoxy compound (C-1) were blended with various polyester resins were blended with the glass fiber alone of B-1 or From Comparative Examples 1 to 10 in which glass fibers (B-2) other than the present invention and other polyfunctional compounds (C-2, C-3) are blended, mechanical strength and hydrolysis resistance are compared when compared with similar compositions. Excellent, appearance characteristics of molded products and high cycle formability are equivalent or improved.
In Examples 1-5, the system which mix | blended both PBT and PET is excellent in the balance of mechanical strength, hydrolysis resistance, an external appearance characteristic, and a molding cycle characteristic. Moreover, in Examples 1-4, in the magnesium compound content in PBT, the direction which uses a magnesium compound containing material (A-1) is excellent in mechanical strength, hydrolysis resistance, and an external appearance characteristic. I understand.
From the above, by molding the polyester resin composition shown in the present invention, it is possible to obtain a vehicle interior / exterior structural component having excellent mechanical strength, appearance characteristics, and hydrolysis resistance with high productivity. I understand.

(A) Explanatory drawing of an example of esterification (or transesterification) reaction process in PBT production (A) Explanatory drawing of an example of a polycondensation process in PBT production Explanatory drawing of a molded product for strength measurement that was produced assuming fitting in wiper parts Explanatory drawing of the strength measurement method using a molded product that was prepared assuming fitting in wiper parts Explanatory drawing of molded products produced to evaluate high cycle performance during molding

Explanation of symbols

1: Raw material supply line 2: Recirculation line 3: Titanium catalyst supply line 4: Extraction line 5: Distillation line 6: Extraction line 7: Circulation line 8: Extraction line 9: Gas extraction line 10: Condensate Line 11: Extraction line 12: Circulation line 13: Extraction line 14: Vent line 15: 2A group metal catalyst supply line A: Reaction tank B: Extraction pump C: Rectification tower D: Pump E: Pump F: Tank G: condenser L1: extraction line L2: vent line L3: extraction line L4: vent line a: first polycondensation reaction tank c: extraction gear pump d: second polycondensation reaction tank e: extraction gear pump g : Dice head h: Rotary cutter

Claims (10)

(B) 30-150 parts by weight of a fibrous filler treated with a surface treatment agent containing at least aminosilane and a novolac type epoxy resin, and (C) 0.1 epoxy compound relative to 100 parts by weight of the polyester resin (A). An interior / exterior part for a vehicle / airframe formed by molding a fiber-reinforced polyester resin composition containing ˜3 parts by weight.   The interior / exterior component for a vehicle / airframe according to claim 1, wherein the epoxy compound (C) is a polyfunctional epoxy compound.   The interior / exterior part for a vehicle / airframe according to claim 1 or 2, wherein the (C) epoxy compound is bisphenol A glycidyl ether having an epoxy equivalent of 100 to 200 g / eq.   The interior / exterior component for a vehicle / airframe according to any one of claims 1 to 3, wherein the (A) polyester resin is a polyalkylene terephthalate containing a diol component having 2 to 4 carbon atoms.   The interior / exterior component for a vehicle / airframe according to any one of claims 1 to 4, wherein (A) the polyester resin comprises 50 to 95 parts by weight of polybutylene terephthalate and 50 to 5 parts by weight of polyethylene terephthalate.   The vehicle / airframe interior / exterior component according to claim 1, wherein the (B) fibrous filler is a glass fiber.   The polybutylene terephthalate contains (a) a titanium compound and (b) a Group 1 metal compound and / or a Group 2 metal compound, and the content of the (a) titanium compound is 10 ppm or more and 80 ppm or less in terms of titanium atoms. The content of the (b) Group 1 metal compound and / or the Group 2 metal compound is 1 ppm or more and 50 ppm or less in terms of the metal atom, and is for a vehicle / airframe according to claim 5 or 6 Interior and exterior parts.   8. The vehicle according to claim 7, wherein (a) the titanium compound and (b) the Group 1 metal compound and / or the Group 2 metal compound are polycondensation catalysts for producing polybutylene terephthalate. Interior and exterior parts for aircraft.   The interior / exterior part for a vehicle / airframe according to claim 7 or 8, wherein the polybutylene terephthalate resin contains a magnesium compound as the (b) Group 2 metal compound. The interior / exterior part for a vehicle / airframe according to any one of claims 1 to 9, wherein the part is a wiper part.

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