WO2020179772A1

WO2020179772A1 - Polyalkylene terephthalate resin molded article having engagement part

Info

Publication number: WO2020179772A1
Application number: PCT/JP2020/008847
Authority: WO
Inventors: 耕一坂田; 一也五島
Original assignee: ポリプラスチックス株式会社
Priority date: 2019-03-05
Filing date: 2020-03-03
Publication date: 2020-09-10
Also published as: JP7193382B2; JP2020143193A

Abstract

[Problem] The present invention addresses the problem of providing a molded article which has an engagement part, and which has excellent heat shock resistance and assemblability (crack resistance of the engagement part), and does not generate a harmful gas such as an isocyanate gas during production. [Solution] The problem above is solved by a molded article having an engagement part, the molded article being characterized by comprising a polyalkylene terephthalate resin composition which includes: (A) a polyalkylene terephthalate resin; (B) an acrylic core/shell polymer having an average particle diameter of 0.3 μm or less, and containing an acrylic rubber as a rubber of a core layer and a reactive functional group as a component of a shell layer; and (C) a glass fiber, and which excludes a carbodiimide compound.

Description

Polyalkylene terephthalate resin molded product having engaging portion

The present invention relates to a polyalkylene terephthalate resin molded product having an engaging portion. More specifically, the present invention relates to a polyalkylene terephthalate resin molded article having an engaging portion that is excellent in balance in both heat shock resistance and assembling with other members.

Polyalkyleneene terephthalate resins such as polybutylene terephthalate resin (hereinafter, also referred to as "PBT resin") are excellent in mechanical properties, electrical properties, other physical and chemical properties, and have good workability. It is used as an engineering plastic in a wide range of applications such as automobile parts and electrical / electronic parts. In particular, for the purpose of protecting external moisture, dust, or damage due to impact, a case material for accommodating a board on which electronic components are mounted, an insert molded product including a sensor case, a connector terminal, etc., a gear, It is preferably used in applications such as actuator cases that protect motors and the like.

On the other hand, these molded products have further improved heat shock resistance and impact resistance required for use as a case in order to withstand use in environments with severe temperature changes such as in the engine room of automobiles and outdoors. Is also required. In response to these demands, for example, Patent Document 1 discloses a polybutylene terephthalate resin composition in which a predetermined amount of a thermoplastic elastomer or a core-shell polymer is blended as an impact resistance improving agent with respect to a polybutylene terephthalate resin. Documents 2 and 3 describe polybutylene terephthalate resin compositions in which a core-shell polymer having a specific particle size and a predetermined amount of glass fibers are blended with a polybutylene terephthalate resin in a core layer made of acrylic rubber. It is disclosed.

Further, Patent Document 4 discloses a polybutylene terephthalate resin composition having excellent heat shock resistance, which is obtained by blending a carbodiimide compound, a fibrous filler, and an elastomer with a polybutylene terephthalate resin.

On the other hand, conventionally, snap fittings for assembling and assembling two units, parts, etc. by a snap-fit structure (a structure in which a protrusion or a hook provided in the other is engaged with a hole provided in one) are often used. There is. Further, a structure in which an uneven shape portion such as a boss or a rib is engaged with a corresponding shape portion of a mating member is often used. If the engaged members that make up the snap fitting, or both the engaging members and the engaged members are made of resin, it is easy to engage and disengage using the elasticity of both, and to prevent vibration. It is used for in-vehicle connectors and quick hangers for spiral hangers because it is less prone to fatigue. Further, in the case of the sensor or the actuator case as well, the support for fixing the built-in parts, the engaging portion such as the boss and the bearing may be provided with resin. However, when assembling the parts in these, the engaging part may be broken depending on the resin used.

Japanese Unexamined Patent Publication No. 2007-169367 JP-A-2009-155448 International Publication 2008/032636 Pamphlet International Publication No. 2009/150831 Pamphlet

An object of the present invention is to provide a molded article having an engaging portion, which is excellent in heat shock resistance and assemblability (resistance to cracking of the engaging portion) and does not generate harmful gas such as isocyanate gas during manufacturing. ..

The present inventor has an acrylic core shell having an average particle size of 0.3 μm or less, in which (A) a polyalkylene terephthalate resin and (B) the core layer rubber is an acrylic rubber and the shell layer component has a reactive functional group. We have found that the above problems can be solved by a molded product having an engaging portion, which comprises a polyalkylene terephthalate resin composition containing a mold polymer and (C) glass fiber and not containing a carbodiimide compound. The present invention has been completed.

That is, the present invention relates to the following (1) to (4).
(1) (A) Polyalkylene terephthalate resin and (B) Acrylic core-shell polymer having an average particle size of 0.3 μm or less, in which the rubber of the core layer is an acrylic rubber and the components of the shell layer have reactive functional groups. A molded product having an engaging portion, which comprises (C) glass fiber and a polyalkylene terephthalate resin composition containing no carbodiimide compound.
(2) The molded product according to (1), wherein the acrylic rubber is a polymer containing acrylic acid C ₁ to C ₁₂ alkyl esters as main components.
(3) The molded product according to (1) or (2), wherein the component of the shell layer is a hard resin component having a glass transition temperature of 0 ° C. or higher.
(4) The reactive functional group is one or more reactive functional groups selected from the group consisting of an epoxy group, a hydroxy group, a carboxy group, an alkoxy group, an acid anhydride group and a acidified group (1). The molded article according to any one of (3) to (3).

According to the present invention, it is possible to provide a molded article having an engaging portion which is excellent in heat shock resistance and assembling property (cracking resistance of the engaging portion) and does not generate harmful gas such as isocyanate gas during manufacturing. ..

It is a figure which shows the molded piece for snap fit evaluation. It is a schematic diagram which shows the state of the snap fit insertion test. It is a figure which shows the test piece used for 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 along the line CC 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 carried out with appropriate modifications as long as the effects of the present invention are not impaired. In the present invention, “AB” means “A or more and B or less”.

<Polyalkylene terephthalate resin composition>
In the polyalkylene terephthalate resin composition of the embodiment of the present invention, (A) a polyalkylene terephthalate resin and (B) an average particle in which the rubber of the core layer is an acrylic rubber and the component of the shell layer has a reactive functional group. It contains an acrylic core-shell polymer having a diameter of 0.3 μm or less, and (C) glass fiber, and does not contain a carbodiimide compound. Hereinafter, each component contained in the polyalkylene terephthalate resin composition will be described.

[(A) Polyalkylene terephthalate resin]
The (A) polyalkylene terephthalate resin, which is the base resin of the polyalkylene terephthalate resin composition according to the embodiment of the present invention, is a dicarboxylic acid component containing a dicarboxylic acid compound and / or an ester-forming derivative thereof as a main component, and a diol compound. And / or among the thermoplastic polyester resins obtained by reaction with a diol component containing an ester-forming derivative as a main component, terephthalic acid and / or an ester-forming derivative thereof is a main component as a dicarboxylic acid component, and as a diol component. The main component is alkylene glycol and/or its ester-forming derivative.

The polyalkylene terephthalate resin is a combination of a dicarboxylic acid component and a diol component other than the main component, and an oxycarboxylic acid component, a lactone component and the like (hereinafter, may be referred to as a copolymerizable monomer) as other copolymerizable monomers. Copolyester can also be used.

Examples of the dicarboxylic acid component other than the main component include aliphatic dicarboxylic acids (for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dotecandicarboxylic acid, hexadecane). Dicarboxylic acid of about C _4-40 such as dicarboxylic acid and dimer acid, preferably dicarboxylic acid of about C _4-14 ), alicyclic dicarboxylic acid (for example, hexahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid) , C _4-40 dicarboxylic acid such as hymic acid, preferably C _8-12 dicarboxylic acid), aromatic dicarboxylic acid other than terephthalic acid (for example, phthalic acid, isophthalic acid, methylisophthalic acid, methylterephthalic acid) , Naphthalenedicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenoxyetherdicarboxylic acid, 4,4'-dioxybenzoic acid, 4,4'-diphenylmethanedicarboxylic acid Acids, dicarboxylic acids of about _C8-16 such as 4,4'-diphenylketone dicarboxylic acid), or derivatives thereof (for example, esters capable of forming esters such as lower alkyl esters, aryl esters, and acid anhydrides) and the like. Can be mentioned. Examples of the dicarboxylic acid component preferable to be used in combination with terephthalic acid include isophthalic acid and naphthalenedicarboxylic acid, and two or more of these can be used in combination. However, it is preferable that 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more of the entire dicarboxylic acid component as the copolymerizable monomer is an aromatic dicarboxylic acid compound. Furthermore, if necessary, a polyvalent carboxylic acid such as trimellitic acid or pyromellitic acid or an ester-forming derivative thereof (alcohol ester or the like) may be used in combination. When such a polyfunctional compound is used in combination, a branched polyalkylene terephthalate resin can also be obtained.

Examples of the diol component other than the main component include aliphatic alkanediols (for example, ethylene glycol, trimethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, neopentyl glycol, hexanediol, octanediol, etc. An aliphatic diol of about C _2-12 such as decanediol, preferably an aliphatic alkanediol other than the aliphatic diol of about C _2-10 used as a main component), polyoxyalkylene glycol (C _2- Glyls having a plurality of oxyalkylene units of about ₄ such as diethylene glycol, dipropylene glycol, ditetramethylene glycol, triethylene glycol, tripropylene glycol, polytetramethylene glycol, etc., alicyclic diols (for example, 1,4- Cyclohexanediol, 1,4-cyclohexanedimethanol, hydride bisphenol A, etc.) and 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. You may. However, alkylene glycol is preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more of the entire diol component as the copolymerizable monomer. Further, if necessary, polyols such as glycerin, trimethylolpropane, trimethylolethane, and pentaerythritol or ester-forming derivatives thereof may be used in combination. When such a polyfunctional compound is used in combination, a branched thermoplastic polyester resin can also be obtained.

Oxycarboxylic acids (or oxycarboxylic acid components or oxycarboxylic acids) include, for example, oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, hydroxyphenylacetic acid, glycolic acid, and oxycaproic acid, or 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 from the range of, for example, 0.01 mol% or more and 30 mol% or less, and is usually 1 mol% or more and 25 mol% or less, preferably 3 mol%. It is about 20 mol% or more, more preferably about 5 mol% or more and 15 mol% or less. When a homopolyester and a copolyester are used in combination, the proportion of the homopolyester and the copolyester is 0.01 mol% or more and 30 mol% or less based on the total amount of the monomers. (Preferably 1 mol% or more and 25 mol% or less, more preferably 3 mol% or more and 20 mol% or less, particularly preferably 5 mol% or more and 15 mol% or less), and usually the former / the latter. =99/1 to 1/99 (mass ratio), preferably 95/5 to 5/95 (mass ratio), and more preferably 90/10 to 10/90 (mass ratio).

Preferred polyalkylene terephthalate resins include homopolyesters or copolyesters containing an alkylene terephthalate unit as a main component (for example, about 50 to 100 mol%, preferably about 75 to 100 mol%) [for example, polyethylene terephthalate (PET), polytri. Homopolyester such as methylene terephthalate (PTT), poly C _2-4 alkylene terephthalate such as polybutylene terephthalate (PBT)), copolyester containing alkylene isophthalate unit as main component and alkylene isophthalate unit as main component, alkylene terephthalate A copolyester containing a unit as a main component and an alkylene naphthalate unit as a copolymerization component] is included, and these can be used alone or in combination of two or more.

Particularly preferred polyalkylene terephthalate resins are homopolyester resins or copolyester resins containing 80 mol% or more (particularly 90 mol% or more) of C _2-4 alkylene terephthalate units such as ethylene terephthalate, trimethylene terephthalate, and tetramethylene terephthalate. Polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, isophthalic acid modified polyethylene terephthalate resin, isophthalic acid modified polytrimethylene terephthalate resin, isophthalic acid modified polybutylene terephthalate resin, naphthalenedicarboxylic acid modified polyethylene terephthalate resin, naphthalenedicarboxylic acid Modified polytrimethylene terephthalate resin, naphthalene dicarboxylic acid modified polybutylene terephthalate 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 polyalkylene terephthalate resin is not particularly limited as long as it does not impair the effects of the present invention. The amount of terminal carboxyl groups of the polyalkylene terephthalate resin is preferably 30 meq/kg or less, more preferably 25 meq/kg or less. If the amount of terminal carboxyl groups of the polyalkylene terephthalate resin is too large, the hydrolysis resistance may be impaired.

The intrinsic viscosity of the polyalkylene terephthalate resin is not particularly limited as long as the effect of the present invention is not impaired. The intrinsic viscosity of the polyalkylene terephthalate resin is preferably 0.6 to 1.3 dL/g, more preferably 0.7 to 1.2 dL/g. When a polyalkylene terephthalate resin having an intrinsic viscosity within this range is used, the polyalkylene terephthalate resin composition obtained will be particularly excellent in moldability. Also, the intrinsic viscosity can be adjusted by blending polyalkylene terephthalate resins having different intrinsic viscosities. For example, a polyalkylene terephthalate resin having an intrinsic viscosity of 0.9 dL / g can be prepared by blending a polyalkylene terephthalate resin having an intrinsic viscosity of 1.0 dL / g and a polyalkylene terephthalate resin having an intrinsic viscosity of 0.8 dL / g. You can The intrinsic viscosity of the polyalkylene terephthalate resin can be measured, for example, in o-chlorophenol at a temperature of 35°C.

As the polyalkylene terephthalate resin, 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 copolymerizable therewith, if necessary, are used in a conventional method. For example, those produced by copolymerization (polycondensation) by transesterification, direct esterification, etc. may be used.

[(B) Acrylic core-shell polymer]
The core-shell type polymer is a polymer having a multi-layer structure including a core layer (core portion) and a shell layer covering a part or all of the core layer (surface of the core layer). In the core-shell type polymer, preferably, the core layer has a rubber component (soft component), and the shell layer is preferably composed of a hard component.

The core layer is usually made of a rubber component in many cases, and an acrylic rubber is used in the embodiment of the present invention. The glass transition temperature of the rubber component is, for example, preferably less than 0 ° C. (for example, −10 ° C. or lower), more preferably −20 ° C. or lower (for example, about −180 to −25 ° C.), and further preferably −30 ° C. or lower. (For example, about −150 to −40 ° C.).

Acrylic rubber that can be used as a rubber component is an acrylic monomer [particularly, an alkyl acrylate (acrylic acid C ₁ to C ₁₂ alkyl ester such as butyl acrylate, preferably acrylic acid C ₁ to C ₈ alkyl ester, more preferably acrylic). acid C _{2 ~} C ₆ alkyl esters) acrylic acid esters such as is a polymer composed mainly of. The acrylic rubber may be an acrylic monomer alone or a copolymer (a copolymer of acrylic monomers, a copolymer of an acrylic monomer and another unsaturated bond-containing monomer, etc.), and may be an acrylic monomer. It may be a copolymer of a monomer (and other unsaturated bond-containing monomer) and a crosslinkable monomer.

Examples of the crosslinkable monomer include (meth) acrylic acid-based monomer {polyfunctional (meth) acrylate [for example, alkylene (meth) acrylate such as butylene di (meth) acrylate; ethylene glycol di (meth) acrylate, butylene. Glycoldi (meth) acrylate, poly (or oligo) ethylene glycol di (meth) acrylate (diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, etc., glycerin tri (meth) acrylate, trimethylol ethanetri (meth) ) Acrylate, Trimethylol Propane Di (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Di (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol Hexa (Poly) hydroxyalkanepoly (meth) acrylate such as (meth) acrylate] vinyl-based monomer (for example, vinyl (meth) acrylate, divinylbenzene, etc.); glycidyl (meth) acrylate, etc.}, polymerizable unsaturated Hydrolyzable condensable compound having a bond [for example, a silane coupling agent having a (meth) acryloyl group (such as (meth) acryloyloxyalkyltrialkoxysilane such as 3-trimethoxypropyl (meth) acrylate)], allyl type Examples thereof include compounds (for example, allyl (meth) acrylate, diallyl malate, diallyl fumarate, diallyl itaconate, monoallyl malate, monoallyl fumarate, triallyl (iso) cyanurate, etc.), and these crosslinkable monomers. , Can be used alone or in combination of two or more.

In the acrylic rubber, the ratio of acrylic acid ester (particularly, alkyl acrylate) is, for example, preferably 50 to 100% by mass, more preferably 70 to 99% by mass, and further preferably 80 to 100% by mass based on the whole acrylic rubber. It is about 98% by mass. Further, in the acrylic rubber, the ratio of the crosslinkable monomer is, for example, more preferably 0.1 to 10 parts by mass, further preferably 0.2 to 5 parts by mass, and further preferably 100 parts by mass of the acrylic ester. Is about 0.3 to 5 parts by mass.

Note that the core layer may further contain a non-rubber component (for example, a hard resin component described later) even when the core layer mainly contains acrylic rubber.

The structure of the core layer may be a uniform structure or a non-uniform structure (salami structure, etc.).

In the core-shell type polymer, the shell layer is usually composed of a hard resin component (or glassy resin component) in many cases. The glass transition temperature of the hard resin component can be selected from the range of, for example, 0 ° C. or higher (for example, 20 ° C. or higher), for example, 30 ° C. or higher (for example, about 30 to 300 ° C.), preferably 50 ° C. or higher (for example, 20 ° C. or higher). 60 to 250° C.), and more preferably 70° C. or higher (eg, 80 to 200° C.).

Such a hard resin component is usually composed of a vinyl-based polymer (a polymer of a vinyl-based monomer). In the vinyl-based polymer (resin), the vinyl-based monomer (vinyl-based monomer) is not particularly limited as long as the vinyl-based polymer can be adjusted to the glass transition temperature as described above, and for example, a methacrylic monomer [for example, , Alkyl methacrylates (eg, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and the like, C ₁ to C ₂₀ alkyl methacrylates, preferably C ₁ to C ₁₀ alkyl methacrylates, more preferably C ₁ ~ C ₆ alkyl methacrylate), aryl methacrylate (phenyl methacrylate, etc.), methacrylic acid ester such as cycloalkyl methacrylate (cyclohexyl methacrylate, etc.)] and the like, as well as the above-exemplified monomers [for example, acrylic monomers, aromatic vinyl monomers, etc.] (For example, styrene and the like), olefin-based monomers, vinyl cyanide-based monomers (for example, (meth)acrylonitrile and the like)], and the like. These vinyl-based monomers may be used alone or in combination of two or more. The vinyl-based monomer contains at least one selected from a methacrylic monomer, an aromatic vinyl-based monomer, and a vinyl cyanide-based monomer [particularly, at least a methacrylic acid ester (alkyl methacrylate such as methyl methacrylate)] as a polymerization component. In many cases, it is a polymer.

The shell layer may be a single layer or may be formed of a plurality of layers as long as it covers a part or all of the core layer.

In the core-shell type polymer, the ratio of the components of the core layer to the total of the core layer and the shell layer is preferably more than 80% by mass and less than 100% by mass, more preferably 85% by mass or more and 95% by mass or less (for example, about 90% by mass). , And more preferably 90% by mass or more and 92% by mass or less. When the proportion of the core layer is more than 80% by mass, a sufficient effect of improving heat shock resistance can be easily obtained. When the ratio of the core layer is 95% by mass or less, it is advantageous in terms of difficulty in producing the core-shell type polymer, and is therefore preferable in terms of availability and quality stability. The ratio of each component of the core layer and the shell layer can be confirmed by the analysis of calculating from the integrated value of the peak part derived from each component in the ¹ H-NMR chart, but usually, the core-shell type polymer is used. Since the compounding ratio of each monomer in the production is almost the same, it is possible to calculate based on this.

In the embodiment of the present invention, the (B) core-shell type polymer has a reactive functional group as a component of the shell layer, and therefore the heat shock resistance of the resin composition is particularly excellent.

Examples of the reactive functional group include an epoxy group, a hydroxy group, a carboxy group, an alkoxy group, an acid anhydride group, and an acid chloride group, and an epoxy group is preferable. The amount of the reactive functional group is preferably 1 mmol or more and 40 mmol or less, more preferably 2 mmol or more and 20 mmol or less, and further preferably 3 mmol or more and 15 mmol or less with respect to 100 g of the core-shell type polymer. By having a functional group of 1 mmol or more, heat shock resistance tends to be further excellent. On the other hand, when it is 40 mmol or less, the fluidity of the resin composition tends not to be lowered, which is preferable.

In the embodiment of the present invention, the average particle diameter of the (B) core-shell type polymer is 0.3 μm or less. If the average particle diameter exceeds 0.3 μm, the assembling property (crack resistance of the engaging portion) may be poor. When the average particle size is 0.3 μm or less, it is relatively easy to produce such a core-shell type polymer, which is also preferable in terms of production cost. Further, when the average particle diameter is 0.3 μm or less, the resulting polyalkylene terephthalate resin composition has excellent assemblability (crack resistance of the engaging portion). (B) The lower limit of the average particle size of the core-shell type polymer is not particularly limited, but if it is less than 0.01 μm, it becomes difficult to control the particle size at the time of manufacturing, so that the average particle size is 0.01 μm in terms of manufacturing cost. The above is preferable. In the present invention, the "average particle size" refers to the volume average particle size (μm) of the core-shell polymer in the latex state measured using MICROTRAC UPA150 manufactured by Nikkiso Co., Ltd.

Such a core-shell type polymer is a polyalkylene terephthalate resin under melt-kneading conditions at the time of extrusion or molding because the particle size is stabilized by the shell which is a hard component, especially when the shell layer is composed of a hard component. This is advantageous over other elastomers in that dispersion of the dispersed state (average particle size) in the composition can be suppressed.

[(C) Glass fiber]
The glass fiber is a glass fiber that is made by melting and drawing glass. When used in the form of fibers, the strength of ordinary alkaline glass is significantly reduced due to surface deterioration. Therefore, it is preferable to use non-alkali glass such as quartz glass as the glass used as a raw material. Further, the glass fiber can be suitably used from the viewpoint of availability, strength and rigidity.

[Carbodiimide compound]
The carbodiimide compound is a general term for chemical substances containing a functional group represented by the chemical formula -N=C=N-. In synthetic organic chemistry, carbodiimide compounds are mainly used as dehydration condensing agents. A commonly used example is the promotion of amide bonds or ester bond formation to carboxylic acids. When the carbodiimide compound is added to the polyalkylene terephthalate resin composition, the effect of improving the hydrolysis resistance and the heat shock resistance can be obtained, but the toxic isocyanate derived from the carbodiimide compound is obtained at the time of molding the resin composition or the like. Inconvenience such as generation of gas occurs. In the present embodiment, by not using the carbodiimide compound, it is possible to obtain the effect of not generating harmful gas such as isocyanate gas at the time of manufacturing the molded product having the engaging portion.

[Other ingredients]
The polyalkylene terephthalate resin composition of the embodiment of the present invention is generally added to a thermoplastic resin and a thermosetting resin in order to impart desired properties according to the purpose thereof without impairing the effect of the present invention. Known substances such as stabilizers such as antioxidants and ultraviolet absorbers, hydrolysis resistance improvers (eg epoxy resins, etc.), antistatic agents, flame retardants, flame retardant aids, dripping inhibitors, etc. Colorants such as dyes and pigments, mold release agents, lubricants, crystallization accelerators, crystal nucleating agents and the like can be added.

[Preparation method]
The polyalkylene terephthalate resin composition of the embodiment of the present invention can be easily prepared by using the equipment and methods generally used for preparing the resin composition. For example, after mixing each component, kneading with a single-screw or twin-screw extruder and extruding to prepare pellets, then molding method, once preparing pellets with different compositions, and mixing the pellets in a predetermined amount. It is possible to use any of a method of obtaining a molded product having a target composition after molding and a method of directly charging one or more of each component into a molding machine.

<Molded product>
The molded article of the embodiment of the present invention is obtained by molding the polyalkylene terephthalate resin composition of the present invention. The molding method is not particularly limited, and a known molding method can be adopted. The molded product according to the embodiment of the present invention is preferably an insert molded product obtained by insert molding the polyalkylene terephthalate resin composition of the present invention and an insert member made of a metal or an inorganic solid. The metal and the inorganic solid are not particularly limited, and examples of the metal include aluminum, magnesium, stainless steel, copper, and the like, and a metal conductor portion such as an electronic circuit formed on a resin substrate is also included in this example. Examples of the inorganic solid include ceramics and the like. Insert molding can be performed by a conventionally known method.

[Snap fit part]
The object to which the snap fit portion of the present invention is attached is not particularly limited. The engaging portion and the engaged portion may be attached to a plate-shaped object, a tubular object, or a housing-shaped object, or a combination thereof may be used. The engaging portion and the engaged portion may be fitted and detached, or may not be detached. The number of snap-fit portions attached to these objects is not particularly limited, and is one or more. When a plurality of snap-fit portions are provided, they can be provided at symmetrical positions or 180-degree offset positions in the pipe in consideration of force balance and resistance to disengagement during use.

Specifically, the snap-fit portion of the present invention includes a vehicle harness (wiring) connector, a quick joint for a spiral hanger, a piping fitting, a housing cover for a flat portion, a wiring joint between a television or the like and an antenna, and the like. Used for extending the ground wire. The snap-fit portion is provided on a part of the molded product, but may be integrally provided at the time of molding, or may be provided later by a fixing means such as fusion bonding, adhesion, screwing, and screwing. Further, when the snap-fit portion is provided at the end of the pipe or the like, a part of the snap-fit portion can be made to protrude to the outside of the pipe so that the inner surface of the pipe does not become thin, or the protrusion is formed on the outer surface of the pipe. If you don't like it, you can make it stick out inside the tube.

[Example]
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.

<Material>
(A) Polyalkylene terephthalate resin PBT resin manufactured by Polyplastics Co., Ltd., intrinsic viscosity 0.69 dl / g, terminal carboxyl group amount 24 meq / kg
(B) Acrylic core-shell polymer B-1: A butyl acrylate polymer (acrylic rubber) is used for the core layer, and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 90. Acrylic core-shell type polymer with mass%, average particle diameter 3 μm
B-2: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 90% by mass. , Average particle size 20 μm
B-3: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 90% by mass. , Average particle diameter 30 μm
B-4: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 80% by mass. , Average particle diameter 0.1 μm
B-5: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 80% by mass. , Average particle size 0.2 μm
B-6: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 80% by mass. , Average particle size 0.5 μm
B-7: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 80% by mass. , Average particle size 1.4 μm
B-8: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 80% by mass. , Average particle diameter 3.3 μm
B-9: Acrylic core-shell type polymer in which a butyl acrylate polymer (acrylic rubber) is used for the core layer and a methyl methacrylate polymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 80% by mass. , Average particle diameter 10.5 μm
B-10: Butyl acrylate polymer (acrylic rubber) is used for the core layer, methyl methacrylate / glycidyl methacrylate copolymer (vinyl copolymer) is used for the shell layer, and the ratio of the core layer is 90% by mass. Acrylic core-shell polymer in which the ratio of methyl methacrylate to glycidyl methacrylate is 9% by mass: 1% by mass, average particle diameter 3 μm
・(C) Glass fiber manufactured by Nippon Electric Glass Co., Ltd., product name: ECS03T-187
-Antioxidant manufactured by BASF Japan Ltd., product name: Irganox1010
・Hydrolysis resistance improver Epoxy resin manufactured by Mitsubishi Chemical Corporation, product name: Epicoat JER1004K

<Example 1, Comparative Examples 1 to 9>
(A) Each component is mixed with 100 parts by mass of the polyalkylene terephthalate resin at the ratio shown in Table 1, and then a cylinder temperature of 260 ° C. is used using a 30 mmφ twin-screw extruder (TEX-30 manufactured by Japan Steel Works). It was melt-kneaded and extruded at a discharge rate of 15 kg / h and a screw rotation speed of 130 rpm to obtain pellets made of a polyalkylene terephthalate resin composition. Next, various test pieces were prepared from these pellets by injection molding, and the following physical properties were evaluated. The results are also shown in Table 1.

[Melt viscosity]
After drying the above pellets at 140° C. for 3 hours, according to ISO11443, using Capirograph 1B (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the furnace viscosity was 260° C., the capillary was φ1 mm×20 mmL, and the melt viscosity was 1000 sec ⁻¹ . It was measured.

[Tensile strength]
After drying the pellets at 140 ° C. for 3 hours, an ISO3167 tensile test piece was injection-molded at a resin temperature of 260 ° C., a mold temperature of 80 ° C., an injection time of 15 seconds, and a cooling time of 15 seconds, in accordance with ISO527-1 and ISO527-1. Then, the tensile strength was measured.

[Assembly (Resistance to cracking of engaging part)]
A snap-fit insertion test was performed using a molded product for snap-fit evaluation as shown in FIG. In the snap-fit insertion test, it was determined whether or not the snap-fit portion would break when the snap-fit was assembled by applying the insertion force Fa as shown in FIG. 2 using the molded piece of FIG. The test was carried out with n=5, and one in which no break was found was marked with ◯ and one in which even one was broken was marked with x.

[Impact resistance (Charpy impact strength)]
The pellets were injection molded at a molding temperature of 260 ° C. and a mold temperature of 80 ° C. to prepare a Charpy impact test piece, and the Charpy impact strength was measured at 23 ° C. in accordance with ISO179 / 1eA.

[Heat shock resistance]
Using the pellet and an L-shaped plate-shaped metal insert member, the test pieces shown in FIGS. 3 and 4 were insert-molded by injection molding, and the heat shock resistance was evaluated. 3A and 3B are views showing the insert-molded test piece 20, where FIG. 3A is a top view, FIG. 3B is a cross-sectional view taken along the line BB in FIG. 3, and FIG. FIG. 7 is a cross-sectional view taken along the line CC in FIG. FIG. 4 is a view showing the insert member 22. The resin member 21 is molded using the resin composition pellet obtained as described above. Using the above pellets, the resin temperature is 260 ° C., the mold temperature is 65 ° C., the injection time is 25 seconds, the cooling time is 10 seconds, and the test piece molding mold [width w1 25mm x L1 70mm x L2 70 mm, thickness t1 Inside the L-shaped plate-shaped resin portion of 3.6 mm, width w2 21mm x L3 90mm x L4 90 mm, thickness t2 A mold for inserting an L-shaped iron plate of 1.6 mm (cross-sectional width w2 / thickness t2 ratio 13.1)] so that the thickness T of a part of the resin part is 1 mm as the minimum wall thickness. A test piece 20 was manufactured by insert injection molding. The two holes h1 and h2 near both ends of the L-shaped plate-shaped insert member shown in FIG. 4 are for fitting into pins in the mold to fix the insert member 22. The hole h3 of the resin member 21 shown in FIG. 3 is fixed by pressing the L-shaped plate-shaped insert member 22 with a pin in the mold, and when the resin is filled in that state, the resin flows around the pin. It is formed by doing. Further, FIG. 3 (A) shows the position of the side gate S1 (width: 4 mm, thickness: 3 mm) filled with the resin by a alternate long and short dash line. The side gate S1 is located above where the distance d1 from the lower end of the right side surface of the resin portion 21 is 1 mm.
A process of heating the obtained test piece 20 at 140 ° C. for 1 hour and 30 minutes using a thermal shock tester, lowering the temperature to −40 ° C., cooling for 1 hour and 30 minutes, and further raising the temperature to 140 ° C. Perform a heat shock resistance test with 1 cycle, measure the number of cycles until the molded product cracks, and measure the average fracture life of 5 samples of 100 cycles or more, and those with less than 100 cycles. It was evaluated as ×.

[Isocyanate gas]
1 L of odor is collected using a GL Sciences TENAX-TA tube connected to a suction pump (0.25 L / min) during injection molding, and after heating and desorption with Gestel's TDS3 / CIS, Agilent Technologies GC -Isocyanate was identified by MS (HP7890/5975C). Those in which isocyanate was not detected were evaluated as ◯, and those in which isocyanate was detected were evaluated as ×.

Claims

(A) a polyalkylene terephthalate resin,
(B) An acrylic core-shell type polymer having an average particle diameter of 0.3 μm or less, in which the rubber of the core layer is an acrylic rubber and the components of the shell layer have a reactive functional group.
(C) including glass fiber,
It is characterized by comprising a polyalkylene terephthalate resin composition containing no carbodiimide compound.
A molded product having an engaging portion.
The molded article according to claim 1 , wherein the acrylic rubber is a polymer containing a C 1 -C 12 alkyl acrylate as a main component.
The molded product according to claim 1 or 2, wherein the shell layer component is a hard resin component having a glass transition temperature of 0°C or higher.
Claims 1 to 3, wherein the reactive functional group is one or more reactive functional groups selected from the group consisting of an epoxy group, a hydroxy group, a carboxy group, an alkoxy group, an acid anhydride group, and a acidified group. The molded article according to any one of items.