WO2018038072A1

WO2018038072A1 - Method for producing thermoplastic aromatic polyester resin composition, method for producing insert-molded article, and method for inhibiting reduction in heat shock resistance

Info

Publication number: WO2018038072A1
Application number: PCT/JP2017/029855
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: JPWO2018038072A1; CN109642032A; JP6990184B2

Abstract

[Problem] The present invention addresses the problem of providing a method for producing a thermoplastic aromatic polyester resin composition containing a coloring agent and having superior heat shock resistance, and a method for producing an insert-molded article. The present invention addresses the problem of providing a method for inhibiting a reduction in the heat shock resistance of a thermoplastic aromatic polyester resin composition containing a coloring agent. [Solution] A method for producing a thermoplastic aromatic polyester resin composition having superior heat shock resistance, the method comprising a step for mixing thermoplastic aromatic polyester resin A with coloring agent composition B containing thermoplastic aromatic polyester resin a and coloring agent b. A method for inhibiting reduction in the heat shock resistance of a thermoplastic aromatic polyester resin composition containing a coloring agent, the method comprising mixing thermoplastic aromatic polyester resin A with coloring agent composition B containing thermoplastic aromatic polyester resin a and coloring agent b.

Description

Method for producing thermoplastic aromatic polyester resin composition, method for producing insert-molded product, and method for suppressing deterioration of heat shock resistance

The present invention relates to a method for producing a thermoplastic aromatic polyester resin composition excellent in heat shock resistance, a method for producing an insert-molded article, and a decrease 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 integrally molded with 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 an insert molded 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. In addition, when coloring the resin, a colorant such as carbon black is not directly blended into the thermoplastic aromatic polyester resin to be colored, but once in the same or different thermoplastic aromatic polyester resin. Later, by blending with a resin to be colored, it was found that even a colored thermoplastic aromatic polyester resin composition can suppress a decrease in heat shock resistance compared to a non-colored product, and the present invention has been completed.

An object of the present invention is to provide a method for producing a thermoplastic aromatic polyester resin composition containing a colorant and having excellent heat shock resistance. Moreover, it makes it a subject to provide the manufacturing method of the insert molded article using the resin composition obtained by this method. Furthermore, it is an object of the present invention to provide a method for suppressing the heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant.

The process for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to the present invention comprises a thermoplastic aromatic polyester resin A, a thermoplastic aromatic polyester resin a and a colorant b. And B is blended.

In the present invention, the content of the colorant 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 can comprise so that content of the coloring agent b in a coloring agent composition may be 5 to 50 mass%.

In the present invention, it is preferable that the thermoplastic aromatic polyester resins A and a include a polybutylene terephthalate resin.

In the present invention, the colorant b can be configured to include 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 can be 5 nm or more and 40 nm or less.

Further, in the present invention, a thermoplastic aromatic polyester resin composition for insert molded products can be obtained.

The method for producing an insert-molded product according to the present invention includes a step of injection-molding the thermoplastic aromatic polyester resin composition obtained by any one of the methods described above into a mold in which an insert member is disposed.

The method for suppressing deterioration in heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant according to the present invention comprises a thermoplastic aromatic polyester resin A, a thermoplastic aromatic polyester resin a, and a colorant b. Colorant composition B is blended.

According to the present invention, a method for producing a thermoplastic aromatic polyester resin composition containing a colorant and having excellent heat shock resistance can be provided. Moreover, the manufacturing method of the insert molded product using the resin composition obtained by this method can be provided. Furthermore, 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.

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.

[Method for Producing Resin Composition]
The method for producing the thermoplastic aromatic polyester resin composition (hereinafter also referred to as “resin composition”) of the present embodiment comprises the thermoplastic aromatic polyester resin A, the thermoplastic aromatic polyester resin a, and the colorant b. It has the process of mix | blending the coloring agent composition B to contain. The resin composition obtained by this production method is excellent in heat shock resistance despite being colored.

(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.

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 composition B)
The colorant composition B contains a thermoplastic aromatic polyester resin a and a colorant b. Since the kind of resin that can be used as the thermoplastic aromatic polyester resin a, the obtaining method, and the like are the same as those of the above-described thermoplastic aromatic polyester resin A, description thereof is omitted here. The thermoplastic aromatic polyester resin a may be the same type of resin as the thermoplastic aromatic polyester resin A among the above-described resins, or may be a different type of resin. The resin of the same type as A is preferably contained in an amount of 50% by mass to 100% by mass in all resin components. Especially, it is preferable that the thermoplastic aromatic polyester resin a is a polybutylene terephthalate resin, and it is more preferable that both of the thermoplastic aromatic polyester resins A and a are polybutylene terephthalate resins.

The content of the thermoplastic aromatic polyester resin a is preferably 50% by mass or more and 95% by mass or less in the total colorant composition B.

The intrinsic viscosity (IV) of the thermoplastic aromatic polyester resin a is not particularly limited as long as it does not impair the effects of the present invention. However, the colorant b is easily kneaded uniformly, and the colored resin composition is treated with the thermoplastic aroma. From the viewpoint of facilitating uniform blending with the group A polyester resin A, it is preferably 0.60 to 1.30 dL / g, and more preferably 0.70 to 1.20 dL / g. The intrinsic viscosity (IV) of the thermoplastic aromatic polyester resin a can be measured by the same method as described above.

The colorant b can be selected from known colorants according to the color required for the molded product. Examples of the colorant b include inorganic pigments, organic pigments, dyes, and the like. 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 diameter of the colorant b is not particularly limited, but is preferably 5 nm or more and 40 nm or less, or 10 nm or more and 30 nm or less, and more preferably 15 nm or more and 25 nm or less. The average primary particle diameter of the colorant b is an arithmetic average particle diameter obtained by observing 1000 particles with an electron microscope for the colorant b before being blended in the resin composition.

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 content of the colorant b in the colorant composition B is not particularly limited, but is 5% by mass or more and 50% by mass or less, 10% by mass or more and 30% by mass or less, or 15% by mass or more in the colorant composition B. It is preferable that it is 25 mass% or less. When the content of the colorant b in the colorant composition B is 5% by mass or more, it is not necessary to extremely increase the amount of the colorant composition B to be blended with the thermoplastic aromatic polyester A. Management of raw materials and processes is easy, and when the content of the colorant b in the colorant composition B is 50% by mass or less, the colorant b is easily dispersed uniformly in the thermoplastic aromatic polyester resin composition. .

The dispersion state of the colorant b in the colorant composition B is not particularly limited as long as the effects of the present invention are not impaired. For example, when the thermoplastic aromatic polyester resin a and the colorant b are melt-kneaded to produce the colorant composition B, a colorant composition having improved dispersibility by removing aggregates using a filter. B can be used. Further, if the aperture of the filter is made finer or the number of filters is increased, the productivity may be lowered. Therefore, the dispersion state can be appropriately adjusted while considering the productivity. The dispersion state of the colorant b in the colorant composition B is such that when the colorant composition B is a film having a thickness of 200 μm, there are 5 or more aggregates having a particle diameter of 100 μm or more per 10 m ² of the film. It is preferable that there are no more.

The colorant composition B can be blended with other resins such as thermoplastic resins such as styrene resins and acrylic resins, and thermosetting resins as necessary. In addition, the colorant composition B includes various additives such as stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), flame retardants, lubricants, mold release agents, antistatic agents, dispersants, plasticizers. You may mix | blend an agent, a nucleating agent, etc. 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 total colorant composition B.

The colorant composition B can be produced by kneading the thermoplastic aromatic polyester resin a and the colorant b by an ordinary method. For example, the thermoplastic aromatic polyester resin a, 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 colorant composition B can be in various forms such as powder, pellets and strips.

(Other ingredients)
In the method for producing a thermoplastic aromatic polyester resin composition of the present embodiment, various additives can be blended in the thermoplastic aromatic polyester resin composition. 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).

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

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.

The blending amount of the colorant composition B (thermoplastic aromatic polyester resin a and colorant b) is preferably selected so that the molded product is sufficiently colored. For example, when the content of the colorant b in the colorant composition B is 5% by mass or more and 50% by mass or less, the content of the colorant b in the total thermoplastic aromatic polyester resin composition is as described above. When the content is 0.05% by mass or more and 5.0% by mass or less, preferably 0.1% by mass or more and 3.0% by mass or less, the blending amount of the colorant composition B is 1 in the total resin composition. It is preferable to set it as mass% or more and 10 mass% or less, and it is more preferable to set it as 2 mass% or more and 6 mass% or less.

[Thermoplastic aromatic polyester resin composition]
By the above production method, it is possible to suppress a decrease in heat shock resistance of the colored thermoplastic aromatic polyester resin composition. As a result, a thermoplastic aromatic polyester resin composition containing a colorant and having excellent heat shock resistance can be obtained. The thermoplastic aromatic polyester resin composition may be a powder mixture or a molten mixture (pellets or the like).

This thermoplastic aromatic polyester resin composition can achieve both sufficient colorability and heat shock resistance. For example, in a molded product formed using a resin composition colored black using carbon black as the colorant b, L ^* a ^* b ^* L ^* in the color system measured according to JIS Z8729: 2004 ^. It has excellent jetness with a value (lightness) of 25 or less (preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less). At the same time, in the cycle test of repeating the cycle of cooling at −40 ° C. for 1.5 hours and then heating at 180 ° C. for 1.5 hours, the number of cycles until cracks occur in the molded product is 150 cycles or more. Or 180 cycles or more.

Therefore, this thermoplastic aromatic polyester resin composition can be suitably used as a resin composition for colored insert molded products. Colored insert molded products using this resin composition have sufficient colorability (lightness, saturation, or jetness), and even when used in an environment with a large temperature change, heat shock destruction Can be prevented.

“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 mechanical strength was not significantly different, but the heat shock resistance was significantly reduced in the colored molded product.

[Insert molded product]
The thermoplastic aromatic polyester resin composition obtained by the above production method is excellent in heat shock resistance and is particularly suitable for producing an insert-molded product. The insert-molded article has a resin member formed using a thermoplastic aromatic polyester resin composition and including the resin composition, and an insert member including a metal, an alloy, or an inorganic solid material.

The metal, alloy, or inorganic solid material constituting the insert member is not particularly limited, but is preferably one that does not deform or melt when it comes into contact with the resin during molding. Examples thereof include metals such as aluminum, magnesium, copper, and iron, alloys of the above metals such as brass, and inorganic solids such as glass and ceramics.

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.

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, so heat shock breakdown occurs even in colored molded products having thin portions and weld lines in the resin member. Can be prevented. The insert-molded product can be, for example, an insert-molded product in which the resin member has a thin portion with a thickness of 0.3 mm to 5 mm.

[Method of suppressing heat shock resistance reduction]
The method for suppressing deterioration in heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant is a colorant composition containing a thermoplastic aromatic polyester resin A, a thermoplastic aromatic polyester resin B, and a colorant C. Is a method of blending. The mechanism that can suppress the decrease in heat shock resistance of the colored product by this method is not clear at this stage, but as described above, the colorant is directly blended into the resin to be colored by the present inventors' research. Instead, it was found that the heat shock resistance was improved by blending with a colored resin once blended with the same or different kind of thermoplastic aromatic polyester resin as the colored resin. The thermoplastic aromatic polyester resin A, the colorant composition B and the blending method used in this method are as described above.

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, Examples 1 to 3, Comparative Examples 1 to 4]
Using the materials shown below, kneading was performed at 250 ° C. with a twin-screw extruder (manufactured by Nippon Steel Works, cylinder diameter 30 mmφ) at the contents shown in Tables 1 and 2, and Reference Example 1 and Examples 1 to 3 And the thermoplastic aromatic polyester resin composition pellets of Comparative Examples 1 to 4 were prepared. Reference Example 1 is an example of an uncolored resin composition. In Comparative Examples 1 to 4, the colorant was added directly to the thermoplastic aromatic polyester resin A, not as the colorant composition B. This is an example. Further, the dispersibility of the colorant compositions 1 to 3 used in Examples 1 to 3 is such that aggregates having a particle diameter of 100 μm or more are present in 10 m ^{2 of a} 200 μm-thick film formed using each colorant composition. A case where the number was 10 or less was judged as “excellent”, a case where the number was more than 10 and 50 or less was judged as “good”, and a case where the number was more than 50 and less than 300 was judged as “good”.

(Thermoplastic aromatic polyester resin)
Thermoplastic aromatic polyester resin: Polybutylene terephthalate resin (PBT) having an intrinsic viscosity of 0.68 dL / g, manufactured by Wintech Polymer Co., Ltd.
(Colorant composition / colorant)
Colorant composition 1: Polybutylene terephthalate resin (manufactured by Wintech Polymer Co., Ltd., polybutylene terephthalate resin having an intrinsic viscosity of 0.68 dL / g, 80% by mass) and carbon black 1 (manufactured by Mitsubishi Chemical Corporation, average primary particles) Carbon black having a diameter of 22 nm, 20% by mass) Dispersibility: Excellent Colorant composition 2: Polybutylene terephthalate resin (manufactured by Wintech Polymer Co., Ltd., polybutylene terephthalate resin having an intrinsic viscosity of 0.68 dL / g, 80% by mass ) And carbon black 1 (manufactured by Mitsubishi Chemical Corporation, carbon black with an average primary particle size of 22 nm, 20% by mass), dispersibility: good colorant composition 3: polybutylene terephthalate resin (manufactured by Wintech Polymer Co., Ltd., unique) A polybutylene terephthalate resin having a viscosity of 0.68 dL / g, 0 mass%) and carbon black 1 (Mitsubishi Chemical Corporation, carbon black with an average primary particle size of 22 nm, 20 mass%), dispersibility: yes Carbon black 2: Wilber Ellis Co., Ltd., with an average primary particle size of 30 nm Carbon black Carbon black 3: Carbon black with an average primary particle size of 13 nm manufactured by Wilber Ellis Co., Ltd. Carbon black 4: Carbon black with an average primary particle size of 13 nm, manufactured by Wilber Ellis Co., Ltd. (surface acid-treated product)
Carbon black 5: Carbon black with an average primary particle size of 22 nm manufactured by Mitsubishi Chemical Corporation

(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 test pieces shown in FIGS. 1 and 2 were insert molded by injection molding using the thermoplastic aromatic polyester resin composition pellets obtained in the reference examples, examples and comparative examples and metal insert members. 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 the minimum wall thickness in a mold that inserts an insert member having a square pillar part of 14 mm × 14 mm × height 24 mm in part inside the square columnar resin part. A test piece was manufactured by insert injection molding. About the obtained insert molded product, heat shock resistance was evaluated by the method mentioned later. 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 square columnar insert member 2 in a square columnar resin member 1 formed using a thermoplastic aromatic polyester resin composition. The resin member 1 is molded using the resin composition pellets obtained as described above. 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 corner | angular part of the resin member 1 and the corner | angular part of the insert member 2 are arrange | positioned so that it may be located in a mutually different direction. 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.) for the above test piece, the cycle of cooling at −40 ° C. for 1.5 hours and then heating at 180 ° C. for 1.5 hours is repeated every 20 cycles. The weld was observed. 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. The heat shock resistance is excellent when the number of cycles is 150 or more, and the heat shock resistance is particularly excellent when the number of cycles is 170 or more. The smaller the difference from the value of Reference Example 1, the more the heat shock resistance from uncolored products can be suppressed.

(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 can be seen from Table 1, the insert molded products formed using the resin compositions of Examples 1 to 3 were more resistant to non-colored products (Reference Example 1) than the molded products of Comparative Examples 1 to 4. A decrease in heat shock resistance is suppressed, and by using this production method, a decrease in heat shock resistance of a resin composition containing a colorant can be suppressed. In addition, the insert molded products formed using the resin compositions of Examples 1 to 3 can have 150 cycles or more in the evaluation of heat shock resistance, and are excellent in heat shock resistance. 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.

1 Resin member 2 Insert member 10 Test piece

Claims

Thermoplastic aromatic polyester resin composition excellent in heat shock resistance, comprising a step of blending thermoplastic aromatic polyester resin A and colorant composition B containing thermoplastic aromatic polyester resin a and colorant b Manufacturing method.
The thermoplastic aromatic polyester excellent in heat shock resistance 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. A method for producing a resin composition.
The production of the thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to claim 1 or 2, wherein the content of the colorant b in the colorant composition B is 5% by mass or more and 50% by mass or less. Method.
The method for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to any one of claims 1 to 3, wherein the thermoplastic aromatic polyester resins A and a include a polybutylene terephthalate resin.
The method for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to any one of claims 1 to 4, wherein the colorant b contains an inorganic pigment or an organic pigment.
The method for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to any one of claims 1 to 5, wherein the colorant b contains a black pigment, a red pigment, an orange pigment, or a white pigment.
The method for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to any one of claims 1 to 6, wherein the colorant b contains carbon black or carbon nanotubes.
The method for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to any one of claims 1 to 7, wherein the average primary particle diameter of the colorant b is 5 nm or more and 40 nm or less.
The method for producing a thermoplastic aromatic polyester resin composition having excellent heat shock resistance according to any one of claims 1 to 8, wherein a thermoplastic aromatic polyester resin composition for an insert molded article is obtained.
A method for producing an insert-molded article, comprising a step of injection-molding the thermoplastic aromatic polyester resin composition obtained by the method according to any one of claims 1 to 9 into a mold in which an insert member is disposed. .
Heat shock resistance of a thermoplastic aromatic polyester resin composition containing a colorant, which comprises a thermoplastic aromatic polyester resin A and a colorant composition B containing a thermoplastic aromatic polyester resin a and a colorant b The method of suppressing sex decline.