WO2018038075A1

WO2018038075A1 - Insert-molded article and method for suppressing decreases in heat shock resistance of resin composition

Info

Publication number: WO2018038075A1
Application number: PCT/JP2017/029860
Authority: WO
Inventors: 山田　真也; 隆二牛島; 一也五島
Original assignee: ウィンテックポリマー株式会社
Priority date: 2016-08-23
Filing date: 2017-08-22
Publication date: 2018-03-01
Also published as: JP7215902B2; CN109641377A; CN109641377B; JPWO2018038075A1

Abstract

[Problem] To address the problem of providing an insert-molded article which has exceptional heat shock resistance and in which there is used a thermoplastic aromatic polyester resin composition containing a colorant. Also, to address the problem of providing a method for suppressing decreases in the heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant. [Solution] An insert molded article that has exceptional heat shock resistance and has a resin member and an insert member, the resin member including a thermoplastic aromatic polyester resin composition that contains a thermoplastic aromatic polyester resin A and a colorant B that has an average primary particle size of 25 nm or greater. Also, a method for suppressing decreases in the heat shock resistance of a resin composition containing a colorant, the method comprising combining a colorant B that has an average primary particle size of 25 nm or greater with a thermoplastic aromatic polyester resin A for an insert-molded article.

Description

Method for suppressing deterioration of heat shock resistance of insert molded article and resin composition

The present invention relates to an insert-molded article excellent in heat shock resistance using a thermoplastic aromatic polyester resin composition containing a colorant, and a reduction in heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant. It relates to a suppression method.

Thermoplastic aromatic polyester resins represented by polybutylene terephthalate resin and polyethylene terephthalate resin have various properties such as electrical properties such as heat resistance, chemical resistance and tracking resistance, mechanical properties, and moldability. Are better. Therefore, a thermoplastic aromatic polyester resin composition is widely used as an engineering plastic for electronic parts such as housings or connectors of electronic devices, automobile parts, and the like. These parts are insert molding that integrally molds a metal or the like and a thermoplastic resin by filling the mold with a thermoplastic resin composition with an insert member made of metal or the like installed in the mold. It is often a product.

However, because the thermal expansion coefficient and shrinkage ratio due to temperature change are greatly different between the metal etc. constituting the insert molded product and the thermoplastic resin composition, the insert changes with the temperature change during use in an environment where heating and cooling are repeated. There is a case where so-called heat shock destruction that causes the molded article to break occurs. Heat shock breakage occurs especially in corners (sharp corners) of insert members, locations where stress changes are large (especially thin portions), and in parts where stress is likely to concentrate, and in molds during insert molding. The resin is likely to occur at a place where the strength is lower than other parts, such as a weld line that is a joint when the resin is diverted from the insert member and then circulates around the insert member and merges again. Therefore, heat shock resistance is required for the thermoplastic aromatic polyester resin composition. As a technique for improving the heat shock resistance of the thermoplastic aromatic polyester resin composition, there is a technique for reducing distortion by adding an elastomer to the resin composition (Patent Documents 1 to 3).
JP-A-3-285945 JP 2001-234046 A International Publication No. 2009/150831 Pamphlet

By the way, insert molded products used as electronic parts and automobile parts are often colored black using a colorant such as carbon black. The present inventors have found that a black-colored insert molded product tends to have lower heat shock resistance than a non-colored insert molded product. Therefore, the present inventors have conducted research on a method for preventing a reduction in heat shock resistance of an insert molded product colored in black or the like. Then, as a colorant such as carbon black used for coloring the resin, a colorant having an average primary particle diameter of 25 nm or more is blended in the thermoplastic aromatic polyester resin to be colored, thereby coloring the colored thermoplastic aroma. In order to complete the present invention, it is possible to suppress degradation of heat shock resistance as compared with non-colored products even with a group polyester resin composition, in particular, that a high effect can be obtained in an insert molded product in which the insert member is flat. It came.

An object of the present invention is to provide an insert-molded article having excellent heat shock resistance using a thermoplastic aromatic polyester resin composition containing a colorant. Another object of the present invention is to provide a method for suppressing the heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant.

The insert-molded article according to the present invention has a resin member and an insert member, and the resin member contains a thermoplastic aromatic polyester resin A and a colorant B having an average primary particle diameter of 25 nm or more. It is an insert-molded product that includes a resin composition and has excellent heat shock resistance.

In the present invention, the content of the coloring agent B in the thermoplastic aromatic polyester resin composition is preferably 0.05% by mass or more and 5.0% by mass or less. Moreover, it is preferable that the thermoplastic aromatic polyester resin A contains a polybutylene terephthalate resin.

In the present invention, the colorant B can be configured to contain an inorganic pigment or an organic pigment. Further, the colorant B can be configured to include a black pigment, a red pigment, an orange pigment, or a white pigment. The colorant B preferably contains carbon black or carbon nanotubes. The average primary particle diameter of the colorant B is preferably 27 nm or more and 50 nm or less.

In the present invention, the insert member is preferably a plate-like member containing a metal, an alloy or an inorganic solid material. The insert member has a main surface having a longitudinal direction and a width direction, and the ratio of the maximum value of the width to the maximum value of the thickness is 2 or more in a cross section cut along a plane perpendicular to the longitudinal direction. can do. The thickness of the insert member can be 0.1 mm or more and 3 mm or less.

In the present invention, at least a part of the insert member is covered with a resin member, and the thickness of the resin member in the covering portion can be 0.3 mm or more and 5 mm or less.

The heat shock resistance reduction inhibiting method according to the present invention is a resin composition containing a colorant, in which a colorant B having an average primary particle size of 25 nm or more is blended with a thermoplastic aromatic polyester resin A for insert molded articles. This is a heat shock resistance lowering suppression method.

According to the present invention, it is possible to provide an insert molded article having excellent heat shock resistance using a thermoplastic aromatic polyester resin composition containing a colorant. In particular, in the case of using a plate-like insert member, it is possible to provide an insert-molded product in which a decrease in heat shock resistance of a resin portion containing a thermoplastic aromatic polyester resin composition is suppressed. Moreover, the heat shock-resistant fall suppression method of the thermoplastic aromatic polyester resin composition containing a coloring agent can be provided.

It is a figure which shows the test piece used by the heat shock resistance test, Comprising: (A) is a perspective view, (B) is a top view. It is a figure which shows the insert member of the test piece shown in FIG. 1, Comprising: (A) is a perspective view, (B) is a top view. It is a figure which shows the test piece used by the heat shock resistance test, (A) is a top view, (B) is sectional drawing cut | disconnected by the BB line in (A), (C) is It is sectional drawing cut | disconnected by CC line in (A). It is a top view which shows the insert member used with the test piece shown in FIG. It is a figure which shows the test piece used by the heat shock resistance test, (A) is a top view, (B) is sectional drawing cut | disconnected by the BB line in (A), (C) is It is sectional drawing cut | disconnected by CC line in (A). It is a top view which shows the insert member used with the test piece shown in FIG.

Hereinafter, an embodiment of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with appropriate modifications within a range that does not impair the effects of the present invention.

[Insert molded product]
The insert molded product of this embodiment has a resin member and an insert member. Hereinafter, the resin member and the insert member will be described in this order.

(Resin member)
The resin member is formed using a thermoplastic aromatic polyester resin composition (hereinafter also referred to as “resin composition”) containing a thermoplastic aromatic polyester resin A and a colorant B having an average primary particle diameter of 25 nm or more. And containing the resin composition. Although this resin member is colored, a decrease in heat shock resistance is suppressed. Therefore, the insert molded product having this resin member is excellent in heat shock resistance.

(Thermoplastic aromatic polyester resin A)
The thermoplastic aromatic polyester resin A is a resin colored with a colorant. The thermoplastic aromatic polyester resin A is a reaction between a dicarboxylic acid component mainly composed of a dicarboxylic acid compound and / or an ester-forming derivative thereof and a diol component mainly composed of a diol compound and / or an ester-forming derivative thereof. Is a thermoplastic polyester resin obtained by the above-mentioned method, and contains an aromatic compound in at least one of a dicarboxylic acid component or a diol component.

Examples of the dicarboxylic acid component include aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane dicarboxylic acid, dodecane dicarboxylic acid, hexadecanedicarboxylic acid, dimer, and the like. Dicarboxylic acids of about C _4-40 such as acids, preferably dicarboxylic acids of about C _4-14 ), alicyclic dicarboxylic acids (for example, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, highmic acid, etc.) Dicarboxylic acids of about C _4-40 , preferably dicarboxylic acids of about C _8-12 ), aromatic dicarboxylic acids (eg phthalic acid, isophthalic acid, terephthalic acid, methyl isophthalic acid, methyl terephthalic acid, 2,6- Naphthalene dicarboxylic acid such as naphthalene dicarboxylic acid, 4,4 C _8-16 such as' -biphenyl dicarboxylic acid, 4,4'-diphenoxy ether dicarboxylic acid, 4,4'-dioxybenzoic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, etc. Degree dicarboxylic acid), or derivatives thereof (for example, derivatives capable of forming an ester such as lower alkyl ester, aryl ester, and acid anhydride). These dicarboxylic acid components can be used alone or in combination of two or more. Preferred dicarboxylic acid components include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid (particularly terephthalic acid and 2,6-naphthalenedicarboxylic acid). The dicarboxylic acid component preferably contains, for example, 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of aromatic dicarboxylic acid. Furthermore, you may use together polyvalent carboxylic acids, such as trimellitic acid and a pyromellitic acid, or its ester formation derivative (alcohol ester etc.) etc. as needed. When such a polyfunctional compound is used in combination, a branched thermoplastic polyester resin can also be obtained.

Examples of the diol component include aliphatic alkanediols (for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, decanediol. An aliphatic diol of about C _2-12 , preferably an aliphatic diol of about C _2-10 , and the like, a polyoxyalkylene glycol (a glycol having an alkylene group of about C _2-4 and having a plurality of oxyalkylene units), For example, diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc.), alicyclic diol (for example, 1,4-cyclohexanediol, , 4-cyclohexanedimethanol, and hydrogenated bisphenol A, etc.) or the like. In addition, aromatic diols such as hydroquinone, resorcinol, bisphenol, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis- (4- (2-hydroxyethoxy) phenyl) propane, and xylylene glycol are used in combination. May be. These diol components can be used alone or in combination of two or more. Preferred diol components include C _2-10 alkylene glycol (linear alkylene glycol such as ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol) and the like. The diol component preferably contains, for example, 50 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more of C _2-10 alkylene glycol. Furthermore, if necessary, a polyol such as glycerin, trimethylolpropane, trimethylolethane, pentaerythritol, or an ester-forming derivative thereof may be used in combination. When such a polyfunctional compound is used in combination, a branched thermoplastic polyester resin can also be obtained.

As the thermoplastic aromatic polyester resin A, as a copolyester in which two or more of the above-mentioned dicarboxylic acid component and diol component are combined, and other copolymerizable monomers (hereinafter sometimes referred to as copolymerizable monomers), A copolyester in which an oxycarboxylic acid component, a lactone component and the like are combined can also be used.

Examples of the oxycarboxylic acid (or oxycarboxylic acid component or oxycarboxylic acid) include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, oxycaproic acid, and derivatives thereof. . Lactones include C _3-12 lactones such as propiolactone, butyrolactone, valerolactone, caprolactone (eg, ε-caprolactone, etc.), and the like.

In the copolyester, the proportion of the copolymerizable monomer can be selected, for example, from the range of about 0.01 mol% to about 30 mol%, and is usually about 1 mol% to about 30 mol%, preferably 3 mol%. It is about 25 mol% or less, more preferably about 5 mol% or more and 20 mol% or less. Further, when the homopolyester and the copolyester are used in combination, the proportion of the homopolyester and the copolyester is such that the proportion of the copolymerizable monomer is 0.1 mol% or more and 30 mol% or less with respect to the total monomers (Preferably about 1 mol% or more and 25 mol% or less, more preferably about 5 mol% or more and about 25 mol% or less). Usually, homopolyester / copolyester = 99/1 to 1/99 (mass ratio) ), Preferably 95/5 to 5/95 (mass ratio), more preferably about 90/10 to 10/90 (mass ratio).

The preferred thermoplastic aromatic polyester resin A is a homopolyester or copolyester having an alkylene arylate unit such as alkylene terephthalate or alkylene naphthalate as a main component (eg, about 50 to 100 mol%, preferably about 75 to 100 mol%). [For example, polyalkylene terephthalate (eg, poly C _2-4 alkylene terephthalate such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT)), 1,4-cyclohexanedimethylene terephthalate (PCT ), polyalkylene naphthalate (e.g., polyethylene naphthalate, polypropylene naphthalate, poly C _2-4 alkylene naphthalate and polybutylene naphthalate), such Homopo Ester; main component an alkylene terephthalate and / or alkylene naphthalate unit (e.g., more than 50 mol%) includes copolyesters] containing as may be used in combination thereof singly or two or more.

Particularly preferred thermoplastic aromatic polyester resin A is 80 mol% or more (particularly 90 mol% or more) of C _2-4 alkylene arylate units such as ethylene terephthalate, trimethylene terephthalate, tetramethylene terephthalate, and tetramethylene-2,6-naphthalate. ) -Containing homopolyester resin or copolyester resin (for example, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polytetramethylene-2,6-naphthalene dicarboxylate resin, etc.).

Of these, polyethylene terephthalate resin and polybutylene terephthalate resin are preferable, and polybutylene terephthalate resin is particularly preferable.

The amount of terminal carboxyl groups of the thermoplastic aromatic polyester resin A is not particularly limited as long as the effects of the present invention are not impaired. The amount of terminal carboxyl groups of the thermoplastic aromatic polyester resin A is preferably 30 meq / kg or less, and more preferably 25 meq / kg or less.

The intrinsic viscosity (IV) of the thermoplastic aromatic polyester resin A is not particularly limited as long as the effect of the present invention is not impaired. The intrinsic viscosity of the thermoplastic aromatic polyester resin A is preferably 0.60 to 1.30 dL / g. From the viewpoint of improving moldability and heating / cooling durability, it is more preferably 0.65 to 1.20 dL / g. When the thermoplastic aromatic polyester resin A having an intrinsic viscosity in such a range is used, the colorant composition B is easily blended more uniformly. Moreover, the intrinsic viscosity can be adjusted by blending thermoplastic aromatic polyester resins A having different intrinsic viscosities. For example, by blending thermoplastic aromatic polyester resin A having an intrinsic viscosity of 1.0 dL / g and thermoplastic aromatic polyester resin A having an intrinsic viscosity of 0.8 dL / g, thermoplasticity having an intrinsic viscosity of 0.9 dL / g is obtained. Aromatic polyester resin A can be prepared. The intrinsic viscosity (IV) of the thermoplastic aromatic polyester resin A can be measured, for example, in o-chlorophenol at a temperature of 35 ° C.

The blending amount of the thermoplastic aromatic polyester resin A can be, for example, 40% by mass to 99% by mass in the total resin composition, and preferably 50% by mass to 90% by mass. When the blending amount of the thermoplastic aromatic polyester resin A is within this range, the thermoplastic aromatic polyester resin A exhibits its characteristics sufficiently, such as electrical characteristics such as heat resistance, chemical resistance and tracking resistance, mechanical It can be set as the resin composition excellent in various characteristics, such as a characteristic and moldability.

As the thermoplastic aromatic polyester resin A, a commercially available product may be used, and a dicarboxylic acid component or a reactive derivative thereof, a diol component or a reactive derivative thereof, and a monomer that can be copolymerized as necessary are commonly used. Those prepared by copolymerization (polycondensation) by the above-mentioned methods such as transesterification and direct esterification may be used.

(Colorant B)
The colorant B can be selected from known colorants according to the color required for the molded product. Examples of the colorant B include powdery or particulate colorants, and examples thereof include inorganic pigments, organic pigments, and dyes. Examples of inorganic pigments include carbon black (eg, acetylene black, lamp black, thermal black, furnace black, channel black, ketjen black), black pigments such as carbon nanotubes, red pigments such as iron oxide red, and molybdate. Examples thereof include orange pigments such as orange and white pigments such as titanium oxide. Examples of the organic pigment include a yellow pigment, an orange pigment, a red pigment, a blue pigment, and a green pigment. These colorants B can be used alone or in combination of two or more. The colorant B may have a surface treated with an acid or the like. In addition, when using an organic pigment or dye as the colorant B, since there is a tendency for the heat shock resistance to decrease less than that of the inorganic pigment, the heat resistance according to the present embodiment is used when the inorganic pigment is used as the colorant B. The effect of suppressing shock reduction is more easily obtained.

The average primary particle size of the colorant B is 25 nm or more. By controlling the average primary particle diameter of the colorant B to 25 nm or more, it is possible to suppress a decrease in heat shock resistance compared to a non-colored product, regardless of whether the shape of the insert member is a square pillar shape or a plate shape. it can. In particular, even in an insert molded product using a plate-like insert member in which it is difficult to suppress a decrease in heat shock resistance compared to a non-colored product, a decrease in heat shock resistance can be suppressed. The average primary particle diameter of the colorant B is preferably 25 nm or more and 50 nm or less, more preferably 27 nm or more and 40 nm or less, and particularly preferably 28 nm or more and 35 nm or less. When the average primary particle diameter of the colorant B exceeds 50 nm, the mechanical properties of the thermoplastic aromatic polyester resin composition may be deteriorated. The average primary particle size of the colorant B is an arithmetic average particle size obtained by observing 1000 particles of the colorant B before being blended in the resin composition with an electron microscope.

The content of the colorant B in the total thermoplastic aromatic polyester resin composition is preferably 0.05% by mass or more and 5.0% by mass or less, and 0.1% by mass or more and 3.0% by mass or less. More preferably, it is more preferably 0.2% by mass or more and 1.0% by mass or less. By making content with respect to all the resin compositions of the coloring agent B into 0.1 mass% or more and 5.0 mass% or less, it can color with sufficient brightness and chromaticity to a molded article. When carbon black is used as the colorant B, a thermoplastic aromatic polyester resin composition capable of forming a molded product having excellent jetness can be obtained by adjusting the content to the above.

The colorant B is a master batch in which a polyester resin such as a thermoplastic aromatic polyester resin A, a thermoplastic resin such as a styrene resin or an acrylic resin, or other resin such as a thermosetting resin is blended as necessary. It can also be. In addition, the master batch includes various additives such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), flame retardants, lubricants, mold release agents, antistatic agents, dispersants, plasticizers, A nucleating agent or the like may be blended. The content of the additive in this case can be, for example, more than 0% by mass and 20% by mass or less in the master batch.

The manufacturing method of the masterbatch containing the coloring agent B can be manufactured by kneading the base resin and the coloring agent B by an ordinary method. For example, the base resin, the colorant B and other additives can be introduced into a stirrer and mixed uniformly, and then melted and kneaded with an extruder. The resulting master batch can be in various forms such as powder, pellets, strips and the like.

(Other ingredients)
Various additives can be blended in the thermoplastic aromatic polyester resin composition of the present embodiment. For example, an elastomer can be blended for the purpose of further improving heat shock resistance.

Examples of the elastomer include olefin elastomers, vinyl chloride elastomers, styrene elastomers, polyester elastomers, butadiene elastomers, urethane elastomers, polyamide elastomers, silicone elastomers, and core shell elastomers. Specifically, ethylene ethyl acrylate (EEA) copolymer, methacrylate-butylene-styrene (MBS) copolymer, ethylene glycidyl methacrylate (EGMA) copolymer, polytetramethylene glycol (PTMG) A polyester elastomer or the like can be used. Examples of the ethylene ethyl acrylate (EEA) copolymer include a graft copolymer of ethylene ethyl acrylate and butyl acrylate and / or methyl methacrylate.

The blending amount of the elastomer is preferably 1% by mass or more and 30% by mass or less, and more preferably 5% by mass or more and 20% by mass or less in the thermoplastic aromatic polyester resin composition. By blending an elastomer in the thermoplastic aromatic polyester resin composition in an amount of 1% by mass to 30% by mass, a resin having further excellent heat shock resistance without impairing the mechanical properties of the thermoplastic aromatic polyester resin composition It can be a composition.

Moreover, an inorganic filler can be blended for the purpose of improving the mechanical properties of the obtained molded product. As an inorganic filler, a fibrous filler, a plate-like filler, or a granular filler can be mentioned. Examples of the fibrous filler include glass fiber, asbestos fiber, carbon fiber, silica fiber, alumina fiber, silica-alumina fiber, aluminum silicate fiber, zirconia fiber, potassium titanate fiber, silicon carbide fiber, whisker (silicon carbide, Inorganic fibers such as whiskers such as alumina and silicon nitride); organic fibers such as aliphatic or aromatic polyamides, aromatic polyesters, acrylic resins such as fluororesin and polyacrylonitrile, fibers formed of rayon, etc. . Examples of the plate-like filler include talc, mica, glass flake, and graphite. Examples of the particulate filler include glass beads, glass powder, milled fiber (for example, milled glass fiber), wollastonite (wollastonite), and the like. The wollastonite may be in the form of a plate, column, fiber, or the like. Of these inorganic fillers, glass fiber is preferable because it is inexpensive and easily available.

The average diameter of the fibrous filler is, for example, about 1 μm to 30 μm (preferably 5 μm to 20 μm, more preferably 10 to 15 μm), and the average length is, for example, 100 μm to 5 mm (preferably 300 μm to 4 mm, more preferably 500 μm). About 3.5 mm). The average primary particle diameter of the plate-like or powdery filler can be, for example, about 0.1 μm to 500 μm, preferably about 1 μm to 100 μm. These inorganic fillers can be used alone or in combination of two or more. The average diameter and the average length of the fibrous filler and the average primary particle diameter of the plate-like or granular filler are the fibrous filler, the plate-like or granular filler before being mixed in the resin composition. Is a value calculated by analyzing an image photographed by a CCD camera and calculating a weighted average. These can be calculated using, for example, a dynamic image analysis method / particle (state) analyzer PITA-3 manufactured by Seishin Corporation. The aspect ratio of the plate or powder filler is not particularly limited, and can be, for example, 1 or more and 10 or less.

The content of the inorganic filler is preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 40% by mass or less, and still more preferably 20% by mass or more, in the total thermoplastic aromatic polyester resin composition. It can be 35 mass% or less.

In addition, thermoplastic aromatic polyester resin compositions include stabilizers (antioxidants, UV absorbers, thermal stabilizers, etc.), flame retardants, lubricants, mold release agents, antistatic agents, dispersants, plasticizers, cores. Agents, fluidity improvers, etc. may be added. In this case, the content of the additive can be, for example, more than 0% by mass and 20% by mass or less in the total thermoplastic aromatic polyester resin composition.

In addition, an epoxy compound such as a bisphenol A type epoxy compound or a novolac type epoxy compound may be added to the thermoplastic aromatic polyester resin composition in order to improve hydrolysis resistance, heat shock resistance and the like. Further, if necessary, it may be used in combination with another resin (a thermoplastic resin such as a styrene resin or an acrylic resin, a thermosetting resin, or the like).

The thermoplastic aromatic polyester resin composition can achieve both sufficient colorability and heat shock resistance. For example, in a molded product made of a resin composition black-colored using carbon black as the colorant B, L ^* value (lightness) in the L ^* a ^* b ^* color system measured according to JIS Z8729: 2004 Has an excellent jetness of 25 or less (preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less). In addition, in a cycle test in which a cycle of cooling at −40 ° C. for 1.5 hours and then heating at 180 ° C. for 1.5 hours is repeated, the number of cycles until cracking occurs in the molded product is uncolored. The decrease with respect to the molded product can be further reduced.

Therefore, this thermoplastic aromatic polyester resin composition can be suitably used as a resin composition for colored insert molded products. The colored insert-molded product made of this resin composition has sufficient colorability (lightness, saturation, or jetness), and even when used in an environment with a large temperature change, heat shock breakdown is possible. It can be prevented from occurring. In particular, in an insert-molded product using a plate-like insert member, an effect of preventing heat shock breakdown is more easily obtained.

“Heat shock resistance” is a performance that can prevent the insert molded product from being destroyed by temperature changes when the insert molded product is used in an environment with a large temperature change. The impact resistance to prevent the molded product from breaking due to physical impact, toughness expressed by tensile fracture strain (elongation), etc., and the molded product deforms or resin when used at high temperature The performance is different from the heat resistance which prevents the composition from deteriorating. Moreover, it is clear from the comparison with the reference example 1 mentioned later and a comparative example that there is no correlation between heat shock resistance and mechanical strength. That is, in comparison between the uncolored molded product and the colored molded product, the heat shock resistance was significantly reduced in the colored molded product compared to the difference in mechanical strength. Furthermore, the tendency of the mechanical strength in the resin compositions of Examples and Comparative Examples to be inconsistent with the tendency of heat shock resistance to decline, and the heat resistance of both the plate-like insert member and the square pillar-like insert member is not the same. It was confirmed that the shock tendency was different.

The method for obtaining the thermoplastic aromatic polyester resin composition is not particularly limited. For example, the thermoplastic aromatic polyester resin A, the colorant B, and other compounding agents as required, in various forms such as powders, pellets, strips, etc., are premixed as necessary and then put into a melt kneader. . Subsequently, the thermoplastic aromatic polyester resin A, the colorant B, and other compounding agents are blended by heating to the melting point of the thermoplastic aromatic polyester resin A or higher and melt-kneading.

(Insert material)
The insert member is preferably a plate-like member made of a metal, an alloy, or an inorganic solid material. Among them, those that do not deform or melt when they come into contact with the resin during molding are preferable. For example, metals such as aluminum, magnesium, copper, and iron, alloys of the above metals such as brass, and inorganic solids such as glass and ceramics And the like.

The shape of the insert member is not particularly limited, and various shapes such as a rectangular column shape and a plate shape can be used. In particular, in a cross section having a main surface having a longitudinal direction and a width direction and cut by a plane perpendicular to the longitudinal direction of the plate, the ratio of the maximum value of the width to the maximum value of the thickness is 2 or more (For example, a wiring material such as a bus bar) is preferable. The thickness of the plate-like insert member is preferably 0.1 mm or more and 3 mm or less (for example, 0.5 mm or more and 2 mm or less). In addition, the cross-sectional shape of a plate-shaped insert member is not specifically limited, It can be set as an ellipse, a rectangle, a polygon, etc.

(Insert molded product)
The shape and size of the insert molded product are not particularly limited, and can be a shape according to the application. In particular, the thermoplastic aromatic polyester resin composition described above is excellent in heat shock resistance while maintaining colorability. Therefore, even in a colored insert molded product having a thin portion or a weld line in a resin member, heat shock resistance Therefore, it is possible to prevent a heat shock breakdown from occurring. In the insert molded product, for example, when at least a part of the insert member is covered with a resin member, the thickness of the resin portion covering the insert member is 0.3 mm or more and 5 mm or less (for example, 0.5 mm or more and 3 mm or less). It can be set as the insert molded product which has the thin part which is.

Here, the thickness of the resin portion covering the insert member is the thickness of the resin member in the covering portion in the portion where the resin member of the insert molded product covers the insert member, and the surface of the resin member in the covering portion To the length in the direction perpendicular to the surface of the insert member immediately below. For example, FIG. 3 shows an example of an insert molded product used in the example. In the insert molded product (test piece 20) in FIG. 3, the length T in the direction perpendicular to the surface of the insert member 22 directly below the surface of the resin member 21 in the covering portion where the resin member 21 covers the insert member 22 is It is the thickness of the resin part which coat | covers the member 22 (FIG.3 (C)). Further, there may be a case where a plurality of insert members are inserted into one insert-molded product with a resin member layer interposed therebetween. In this case, the thickness of the resin portion includes the thickness from the surface of the resin member of the insert-molded product to the insert member immediately below (outermost layer), and the thickness of the resin member layer sandwiched between the insert members. However, if any one of the thicknesses of the resin parts is within the thickness range of the resin part, it is desirable to consider heat shock resistance in the resin part. . Moreover, when the ratio of the resin part is extremely high (the insert member is too thin), the insert member may be deformed due to shrinkage of the resin part, and when the ratio of the resin part is extremely low (the resin part is too thin), From the viewpoint that the resin fluidity may be insufficient and molding failure may occur, the ratio between the thickness of the resin portion and the thickness of the insert member is as follows: resin portion thickness: insert member thickness = 1: 8-8 Is preferably 1: 1, more preferably 1: 5 to 5: 1.

The method for producing the insert-molded product is not particularly limited. For example, the insert member is previously mounted on the mold using the above-described thermoplastic aromatic polyester resin composition and the insert member molded in a desired shape in advance. The resin composition can be filled and molded by injection molding or extrusion compression molding on the outside.

EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the interpretation of the present invention is not limited by these examples.

[Reference Example 1, Example 1, Comparative Examples 1 to 4]
Using the materials shown below, kneaded at 250 ° C. with a twin-screw extruder (manufactured by Nippon Steel Works, cylinder diameter 30 mmφ) at the content ratio shown in Tables 1 and 2, and Reference Example 1, Example 1 and comparison The thermoplastic aromatic polyester resin composition pellets of Examples 1 to 4 were prepared. Reference Example 1 is an example of an uncolored resin composition, and Example 1 and Comparative Examples 2 to 4 are examples in which the colorant B is added directly to the thermoplastic aromatic polyester resin A. . In Comparative Example 1, a master batch in which the colorant B was previously melt-kneaded so as to have a concentration of 20% by mass in the thermoplastic polyester resin A was prepared, and the master batch was added to 2.5% of the entire resin composition. It is an example in the case of adding mass% (so that the colorant B in the entire resin composition is 0.5 mass%).

(Thermoplastic aromatic polyester resin)
Thermoplastic aromatic polyester resin A: Polybutylene terephthalate resin (PBT) having an intrinsic viscosity of 0.68 dL / g, manufactured by Wintech Polymer Co., Ltd.
(Coloring agent)
Carbon black 1: Carbon black manufactured by Wilber Ellis Co., Ltd., average primary particle size 30 nm Carbon black 2: Carbon black manufactured by Mitsubishi Chemical Co., Ltd., average primary particle size 22 nm Carbon black 3: Product manufactured by Wilbur Ellis Co., Ltd., average primary Carbon black with a particle size of 13 nm Carbon black 4: Carbon black with an average primary particle size of 13 nm (surface acid-treated product) manufactured by Wilber Ellis Co., Ltd.

(Inorganic filler)
Glass fiber: manufactured by Nippon Electric Glass Co., Ltd., trade name “ECS03T-187”, average diameter 13 μm
(Elastomer)
Ethylene ethyl acrylate (EEA) -based elastomer: manufactured by NOF Corporation, trade name “MODIPA A5300”, 70% by mass of ethylene ethyl acrylate (EEA) as a copolymer component, random copolymer of butyl acrylate and methyl methacrylate (BA- stat-MMA) is contained at 30% by mass.

<Evaluation>
[Heat shock resistance]
The heat shock resistance was evaluated in the following manner for each case using a quadrangular columnar shape, an L-shaped plate shape, or an I-shaped plate shape insert member.

(Heat shock resistance when using square pillar inserts)
Test specimens shown in FIGS. 1 and 2 by injection molding using the thermoplastic aromatic polyester resin composition pellets obtained in Reference Example 1, Example 1 and Comparative Examples 1 to 4 and a square columnar metal insert member. Was subjected to insert molding, and the heat shock resistance was evaluated. FIG. 1 is a view showing a test piece 10 that has been insert-molded, and FIG. 2 is a view showing an insert member 2. As shown in FIG. 1, the test piece 10 is obtained by embedding a metal quadrangular columnar insert member 2 in a quadrangular columnar resin member 1 containing a thermoplastic aromatic polyester resin composition. The resin member 1 is molded using the resin composition pellets obtained as described above. Using the above pellets dried at 140 ° C. for 3 hours, a mold for test piece molding (22 mm × 22 mm × height 28 mm) with a resin temperature of 260 ° C., a mold temperature of 65 ° C., an injection time of 25 seconds, and a cooling time of 10 seconds. The resin part has a thickness of 1 mm as a minimum thickness in a mold that inserts an insert member having a square columnar part of at least 14 mm × 14 mm × height 24 mm inside the square columnar resin part. Thus, a test piece was manufactured by insert injection molding. As shown in FIG. 2, the insert member 2 includes a quadrangular columnar upper portion 2 a, a quadrangular columnar lower portion 2 b, and a columnar constricted portion 2 c that connects both of them. As for the insert member 2, the lower part 2b and the narrow part 2c are embed | buried in the resin member 1, and the upper part 2a is exposed from the upper surface of the resin member 1 (refer FIG. 1 (A)). Furthermore, as shown in FIG. 1 (B), the corners of the resin member 1 and the corners of the insert member 2 are arranged so as to be located in different directions. That is, the corner portion of the insert member 2 is disposed so as to face the side surface of the resin member 1. And the distance of the front-end | tip of the corner | angular part of the insert member 2 and the side surface of the resin member 1 is about 1 mm. In the resin member 1, the vicinity of the tip of the corner (sharp corner) of the insert member 2 is a thin portion. In addition, when the resin member 1 is injection-molded, a gate for filling the molten resin composition pellets into the mold is a 1 mmφ pin gate at the center of the bottom surface (22 mm × 22 mm surface) of the resin member 1. Is provided. For this reason, the molten resin composition injected from the gate flows along the bottom surface of the resin member 1 and then fills the space in the mold along the insert member 2. At this time, the thick portion where the melted resin composition is easy to flow is filled first, and the thin portion is delayed in filling, so the vicinity of the minimum thick portion on each side surface (each of the four surfaces of 22 mm × 28 mm) of the resin member 1 A weld portion is generated (near the tip of the corner portion of the insert member 2).
Using the thermal shock tester (manufactured by Espec Co., Ltd.), the test piece 10 was repeatedly cooled at −40 ° C. for 1.5 hours and then heated at 180 ° C. for 1.5 hours, and 20 cycles. The weld was observed every time. The number of cycles when a crack occurred in the weld was evaluated as an index of heat shock resistance. The results are shown in Tables 1 and 2.

(Heat shock resistance when using an L-shaped plate-like insert member)
3, 4 by injection molding using the thermoplastic aromatic polyester resin composition obtained in Reference Example 1, Example 1 and Comparative Examples 1, 2, 4 and an L-shaped plate-like metal insert member. The test piece shown in Fig. 5 was insert-molded to evaluate heat shock resistance. FIG. 3 is a view showing the insert-molded test piece 20, (A) is a top view, (B) is a cross-sectional view taken along line BB in (A), and (C) is ( It is sectional drawing cut | disconnected by CC line in A). FIG. 4 is a view showing the insert member 22. The resin member 21 is molded using the resin composition pellets obtained as described above. Using the above pellets dried at 140 ° C. for 3 hours, a mold for test piece [width w ₁ 25 mm × L ₁ with a resin temperature of 260 ° C., a mold temperature of 65 ° C., an injection time of 25 seconds, and a cooling time of 10 seconds. Inside the L-shaped plate-shaped resin portion of 70 mm × L ₂ 70 mm and thickness t ₁ 3.6 mm, width w ₂ 21 mm × L ₃ 90 mm × L ₄ 90 mm, thickness t ₂ 1.6 mm (cross-sectional width w ₂ / thickness t ₂ ratio of 13.1) to insert a L-shaped iron plate] and test by insert injection molding so that the thickness T of a part of the resin part is 1 mm as the minimum thickness Piece 20 was produced. In FIG. 3, L ₅ and L ₆ are 92 mm. The two holes h ₁ and h _{2 in the} vicinity of both ends of the L-shaped plate-like insert member shown in FIG. 4 are for fitting the pins in the mold to fix the insert member 22. Holes h ₃ of the resin member 21 shown in FIG. 3, a pin in the mold and fixed pressing the L-shaped plate-shaped insert member 22, when filled with resin in this state, the resin flows around the pin It was formed by flowing. In FIG. 3A, the position of the side gate S ₁ (width: 4 mm, thickness: 3 mm) filled with resin is indicated by a one-dot chain line. The side gate S _1, the distance d ₁ from the right side surface lower end portion of the resin portion 21 is positioned above to be 1 mm. That is, in the resin member 21 of the test piece 20, a weld portion is generated at the merged portion where the flowed resin wraps around the insert member 22 and the merged portion where the pin pressing the insert member 22 wraps around.
The obtained specimen 20 is heated at 140 ° C. for 1 hour 30 minutes using a thermal shock tester, then cooled to −40 ° C., cooled for 1 hour 30 minutes, and further heated to 140 ° C. Was subjected to a heat shock resistance test with one cycle, the number of cycles until cracks occurred in the molded product was measured, and the average fracture life of five samples was evaluated as heat shock resistance.

(Heat shock resistance when using an I-shaped plate-like insert member)
5 and 6 are shown by injection molding using the thermoplastic aromatic polyester resin composition obtained in Reference Example 1, Example 1 and Comparative Examples 1 to 4 and an I-shaped plate-like metal insert member. A test piece was insert-molded to evaluate heat shock resistance. 5A and 5B are diagrams showing the insert-molded test piece 30, where FIG. 5A is a top view, FIG. 5B is a cross-sectional view taken along line BB in FIG. It is sectional drawing cut | disconnected by CC line in A). FIG. 6 is a view showing the insert member 32. The resin member 31 is molded using the resin composition pellets obtained as described above. Using the above pellets dried at 140 ° C. for 3 hours, a resin temperature of 260 ° C., a mold temperature of 65 ° C., an injection time of 25 seconds, and a cooling time of 10 seconds, a test piece molding die [width w ₁₁ 25 mm × L ₁₁ 120 mm, the inside of the I-shaped plate-shaped resin portion of the thickness _t 11 4 mm, a width _w 12 20mm × _L 12 150mm, thickness _t 12 1.6 mm (width _{w 12} / thickness _{t 12} ratio of the section 12. The test piece 30 was manufactured by insert injection molding into a mold in which the I-shaped iron plate of 5) was inserted] so that the minimum thickness of a part of the resin portion was 1.2 mm. Two holes h ₁₁ and h _{12 in the} vicinity of both end portions of the I-shaped insert member 32 are for fitting into the pins in the mold to fix the insert member 32. Holes h ₁₃ of the resin member 31 shown in FIG. 5, a pin in the mold and fixed pressed the I-shaped plate-shaped insert member 32, when filled with resin in this state, the resin flows around the pin It was formed by flowing. The diameter _{d 12} of the hole _{h 13} is 4 mm. Around the hole _{h 13} _is, L 14 _{15 mm,} the thickness _{t 13} of the resin member 31 in a range where the L 15 10 mm is set to 3 mm. In FIG. 5A, the position of the side gate S ₁₁ (width: 4 mm, thickness: 3 mm) for filling the resin is indicated by a one-dot chain line, and the side gate is the left end of the lower surface of the resin member 31. distance _{d 11} is located to the right to be a 1mm from. That is, in the resin member 21 of the test piece 20, a weld portion is generated at the merged portion where the flowed resin wraps around the insert member 22 and the merged portion where the pin pressing the insert member 22 wraps around.
The obtained test piece 30 was heated at 140 ° C. for 1 hour 30 minutes using a cold shock tester, then cooled to −40 ° C., cooled for 1 hour 30 minutes, and further heated to 140 ° C. Was subjected to a heat shock resistance test with one cycle, the number of cycles until cracks occurred in the molded product was measured, and the average fracture life of five samples was evaluated as heat shock resistance.

[Tensile strength and tensile breaking strain]
The obtained pellets were dried at 140 ° C. for 3 hours, and then ISO 1A type tensile test pieces were produced by injection molding under conditions of a molding temperature of 260 ° C. and a mold temperature of 80 ° C. Each of the obtained test pieces was evaluated according to the evaluation criteria defined in ISO527-1,2. The evaluation results are shown in Tables 1 and 2.

[Bending strength and flexural modulus]
The obtained pellets were dried at 140 ° C. for 3 hours, then injection-molded at a molding temperature of 260 ° C. and a mold temperature of 80 ° C. to produce a 80 mm × 10 mm × 4 mm bending test piece according to ISO 3167, and defined in ISO 178 Evaluation was conducted according to the evaluation criteria. The evaluation results are shown in Tables 1 and 2.

[Charpy impact strength]
The obtained pellets were dried at 140 ° C. for 3 hours, then injection-molded at a molding temperature of 260 ° C. and a mold temperature of 80 ° C. to prepare a notched Charpy impact test piece of 80 mm × 10 mm × 4 mm in accordance with ISO 3167, Charpy impact strength (notched) (kJ / m ² ) was measured according to ISO 179 / 1eA.

As is clear from Tables 1 and 2, the insert molded product made of the resin composition of Example 1 is a reference example in any case where the shape of the insert member is a square columnar, L-shaped or I-shaped plate. The difference from the value of 1 is small, and the decrease in heat shock resistance from the uncolored product (Reference Example 1) is suppressed. Therefore, even if this insert molded product contains a colorant, it can suppress the occurrence of heat shock destruction even when used in an environment with a large temperature change. In the case of using an L-shaped or I-shaped plate-shaped insert member, the insert molded article made of the resin composition of Comparative Example 1 can suppress a decrease in heat shock resistance when a square columnar insert member is used. The heat shock resistance is further reduced. The insert-molded product made of the resin composition of Comparative Examples 2, 3, and 4 has lower heat shock resistance in both cases where the shape of the insert member is a quadrangular columnar shape, or an L-shaped or I-shaped plate shape. Resulting in.

1, 21, 31

Resin member

2, 22, 32

Insert member

10, 20, 30 Test piece

Claims

Having a resin member and an insert member,
An insert-molded article excellent in heat shock resistance, wherein the resin member includes a thermoplastic aromatic polyester resin composition containing a thermoplastic aromatic polyester resin A and a colorant B having an average primary particle diameter of 25 nm or more.
The insert molded article according to claim 1, wherein the content of the colorant B in the thermoplastic aromatic polyester resin composition is 0.05% by mass or more and 5.0% by mass or less.
The insert molded article according to claim 1 or 2, wherein the thermoplastic aromatic polyester resin A contains a polybutylene terephthalate resin.
The insert molded article according to any one of claims 1 to 3, wherein the colorant B contains an inorganic pigment or an organic pigment.
The insert molded product according to any one of claims 1 to 4, wherein the colorant B contains a black pigment, a red pigment, an orange pigment, or a white pigment.
The insert molded product according to any one of claims 1 to 5, wherein the colorant B contains carbon black or carbon nanotubes.
The insert molded article according to any one of claims 1 to 6, wherein the average primary particle diameter of the colorant B is 27 nm or more and 50 nm or less.
The insert molded product according to any one of claims 1 to 7, wherein the insert member is a plate-like member containing a metal, an alloy, or an inorganic solid material.
The insert member has a main surface having a longitudinal direction and a width direction, and in a cross section cut by a plane perpendicular to the longitudinal direction, the ratio of the maximum value of the width to the maximum value of the thickness is 2 or more. The insert molded product according to claim 8.
The insert molded product according to claim 8 or 9, wherein the thickness of the insert member is 0.1 mm or more and 3 mm or less.
The insert molded product according to any one of claims 1 to 10, wherein at least a part of the insert member is covered with a resin member, and the thickness of the resin member in the covering portion is 0.3 mm or more and 5 mm or less.
A method for suppressing heat shock resistance reduction of a resin composition containing a colorant, in which a colorant B having an average primary particle size of 25 nm or more is blended with the thermoplastic aromatic polyester resin A for insert molded articles.