JP2011132424A - Thermoplastic polyester resin composition, molded article using the same and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic polyester resin composition which produces only a scarce amount of dioxin when incinerated, and which is excellent in flame retardancy and in low warping property. <P>SOLUTION: The thermoplastic resin composition includes a phosphinic acid salt which is a calcium salt or an aluminum salt of phosphinic acid of which the anionic portion is expressed by formula (1) or (2), wherein each of R<SP>1</SP>, R<SP>2</SP>and R<SP>5</SP>-R<SP>7</SP>represents a 1-6C alkyl group or an aryl group, each of R<SP>3</SP>and R<SP>4</SP>represents a 1-10C alkylene group, arylene group or a group comprising two or more thereof, and n represents an integer of 0-4. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a thermoplastic polyester resin composition having a small amount of dioxins generated during incineration and excellent in flame retardancy and low warpage, a molded article using the same, and a method for producing the same.

  Thermoplastic polyester resins are widely used in electrical and electronic equipment parts, automobile parts and the like because of their excellent characteristics. Conventionally, various formulations have been developed for this resin in order to satisfy the required characteristics, thereby realizing higher functionality and higher performance.

However, in recent years, the required physical properties of thermoplastic polyester resins have become increasingly sophisticated, and it has become difficult to cope with conventional formulations. For example, recently, electronic parts such as connectors have been reduced in weight and size, and the thickness of molded products has been reduced.
UL94 is widely used as a measure of the flame retardancy of materials, and its grade is called UL94 V-0, 94 V-0, or simply V-0. This determination of flame retardancy is performed by a combustion test in which a flame of a gas burner is applied to a test piece of a prescribed size to check the degree of combustion of the test piece.
As shown in Table 1 below, 5VA, 5VB, V-0, V-1, V-2, and HB (from those having high flame resistance) In order).
Therefore, the resin composition used for molding is also required to have a high level of flame retardancy under a thinner wall than ever before in order to cope with this.
In particular, 5VA, the highest rank in the class, is one of the criteria for not piercing the sample, so it suggests that "do not leak fire or flame to the outside". This means that a material satisfying the 5VA grade is excellent in fire safety.

  Conventionally, halogen-based flame retardants have been mainly used as resin flame retardants. However, a resin containing a halogen-based flame retardant may generate dioxins when used products are incinerated, and a non-halogen-based flame retardant is required to be used. As one of the methods to meet this requirement, it has been studied to use a phosphorus compound, particularly a calcium salt or an aluminum salt of phosphinic acid whose anion portion is represented by the following formula (1) or (2) as a flame retardant. Yes.

(Wherein R ¹ , R ² and R ^{5 to} R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ³ and R ⁴ are each independently Represents a group consisting of an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a combination of two or more thereof, and n represents an integer of 0 to 4.)

  Patent Document 1 discloses a flame-retardant thermoplastic using a halogen-based flame retardant as a flame retardant of a flame-retardant thermoplastic polyester resin and using a glass fiber having a flat cross-sectional shape with a specific ratio as a fibrous reinforcement. A polyester resin composition is described. Although it is difficult to compare the examples and comparative examples in this document because there is a typographical error, the effects of glass fibers having an unusual cross-sectional shape as glass fibers are only low warpage, improved mechanical properties, and flame retardancy Is not allowed to improve. Moreover, since the thermoplastic polyester resin composition described in this document contains a halogen-based flame retardant, dioxins are generated during combustion.

  Patent Document 2 uses, as a flame retardant, a calcium or aluminum salt of phosphinic acid combined with an organic nitrogen compound such as melamine cyanurate, and further has a specific flame retardant polymer compound and a specific cross-sectional area. A flame-retardant polybutylene terephthalate resin composition using glass fibers is disclosed, and examples using flat-shaped glass fibers having a specific ratio are also described. Although this document discloses that the above configuration can achieve low warpage and improved mechanical properties, the flame retardant grade does not change from the conventional materials using halogenated flame retardants. (Fire safety) is not improved.

  Patent Document 3 discloses a flame retardant resin composition using a phosphate ester as a flame retardant, using melamine cyanurate in combination, and further using glass fibers having a specific cross-sectional area and a flat cross-sectional shape having a specific ratio. Things are disclosed. In this document, it is disclosed that fluidity, low warpage, and improvement in mechanical properties can be achieved by the above configuration, but the material and flame retardant grade using conventional halogen flame retardants are not changed, Flame retardancy (fire safety) is not enhanced.

  As described above, a thermoplastic polyester resin composition having a small amount of dioxin generated at the time of incineration and imparting low warpage and high flame retardancy under a thin wall has not been obtained.

Japanese Patent Publication No. 7-21105 JP 2007-91865 A JP 2009-96969 A

  The present invention aims to solve the above problems. That is, an object of the present invention is to provide a thermoplastic polyester resin composition having a small amount of dioxins generated during incineration and excellent in flame retardancy and low warpage.

  This inventor mix | blends the thermoplastic polyester resin, the fibrous reinforcement which has atypical cross-sectional shape, the calcium or aluminum salt of specific phosphinic acid as a flame retardant, and the organosiloxane compound containing a specific aryl group. Thus, the present inventors have found that a resin composition with a small balance of physical properties and excellent flame retardancy and low warpage is obtained by producing a small amount of dioxin during incineration.

Specifically, the above problem has been solved by the following means.
[1] (A) A phosphinic acid salt in which (B) an anionic part is a calcium or aluminum salt of phosphinic acid represented by the following general formula (1) or general formula (2) with respect to 100 parts by weight of the thermoplastic polyester resin. 5 to 40 parts by weight, (C) 0.5 to 20 parts by weight of an organosiloxane compound in which 40 mol% or more of the organic group bonded to the silicon atom directly or through an oxygen atom is an aryl group, (D) A thermoplastic polyester resin composition comprising 5 to 80 parts by weight of a fibrous reinforcing material satisfying the condition (1) and having a halogen concentration derived from a halogen flame retardant of 2000 ppm or less.
(In the general formulas (1) and (2), R ¹ , R ² and R ^{5 to} R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, R ³ and R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group, or a group composed of a combination of two or more thereof, and n represents an integer of 0 to 4.)
(Condition 1): Weight of a fibrous reinforcing material (D flat) having a flatness of 1.5 or more in the cross section represented by the following formula (3) and a fibrous reinforcing material (D circular) having a circular cross section The ratio satisfies the following formula (4).
Flatness ratio = major axis of the cross section of the fibrous reinforcement (a) / minor axis of the cross section of the fibrous reinforcement (b) Equation (3)
(D flat): (D circle) = 3: 7 to 10: 0 (weight ratio) Formula (4)
[2] The thermoplastic polyester resin composition according to [1], wherein the blending amount of the (B) phosphinate is 20 to 40 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. object.
[3] The organosiloxane compound (C) is an organosiloxane compound in which 50 mol% or more of organic groups bonded to silicon atoms directly or through oxygen atoms are aryl groups [1] Or the thermoplastic polyester resin composition as described in [2].
[4] The thermoplastic polyester resin composition according to any one of [1] to [3], wherein the organosiloxane compound (C) has a weight average molecular weight of 200 to 10,000.
[5] The (C) organosiloxane compound contains a structural unit represented by RSiO _1.5 (R represents an organic group), and the hydroxyl content in the (C) organosiloxane polymer is 1 to It is 10 weight%, The thermoplastic polyester resin composition as described in any one of [1]-[4] characterized by the above-mentioned.
[6] Any one of [1] to [5], wherein a blending amount of the (C) organosiloxane compound is 2 to 6 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. The thermoplastic polyester resin composition according to Item.
[7] [1] to [1], wherein 0.5 to 20 parts by weight of (E) at least one of a metal borate or an antimony compound is further included with respect to 100 parts by weight of the thermoplastic polyester resin (A). [6] The thermoplastic polyester resin composition according to any one of [6].
[8] Any one of [1] to [7], wherein a blending amount of the (D) fibrous reinforcing material is 20 to 70 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. The thermoplastic polyester resin composition according to one item.
[9] The amount of the (E) metal borate or antimony compound is 1 to 4 parts by weight based on 100 parts by weight of the (A) thermoplastic polyester resin [1] to [8] The thermoplastic polyester resin composition according to any one of the above.
[10] Calcium or aluminum salt of phosphinic acid in which (B ′) anion moiety is represented by the following general formula (1 ′) or general formula (2 ′) with respect to 100 parts by weight of the (A) thermoplastic polyester resin 20 to 40 parts by weight of the phosphinic acid salt, (C ′) 2 to 7 parts by weight of an organosiloxane compound in which 50 mol% or more of the organic group bonded to the silicon atom directly or through an oxygen atom is a phenyl group, The thermoplastic polyester according to [1], comprising (D) 15 to 70 parts by weight of a fibrous reinforcing material and (E) 1 to 5 parts by weight of at least one of a metal borate or an antimony compound. Resin composition.
(In the formula, R ¹¹ , R ¹² and R ^{15 to} R ¹⁷ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are alkylene groups or phenylene groups having 1 to 4 carbon atoms. N2 represents an integer of 0 to 4.)
[11] The thermoplastic polyester resin composition according to any one of [1] to [10], wherein the (A) thermoplastic polyester resin is a polybutylene terephthalate resin.
[12] A method for producing a molded article, comprising injection-molding the thermoplastic polyester resin composition according to any one of [1] to [11].
[13] A molded article produced by the method for producing a molded article according to [12].

  The thermoplastic polyester resin composition of the present invention produces little dioxin during incineration and is excellent in flame retardancy and low warpage.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

[Thermoplastic polyester resin composition]
The thermoplastic polyester resin composition of the present invention (hereinafter also referred to as the resin composition of the present invention) has (B) an anionic moiety represented by the following general formula (1) or general formula with respect to 100 parts by weight of the thermoplastic polyester resin (A). 5 to 40 parts by weight of a phosphinic acid salt which is a calcium or aluminum salt of phosphinic acid represented by the formula (2), (C) 40 mol% or more of an organic group bonded directly or through an oxygen atom to a silicon atom 0.5 to 20 parts by weight of an organosiloxane compound in which the aryl group is an aryl group, (D) 5 to 80 parts by weight of a fibrous reinforcing material satisfying the following condition (1), and the halogen concentration derived from the halogen flame retardant is 2000 ppm or less is there. Hereinafter, the resin composition of the present invention will be described in detail.

(A) Thermoplastic polyester resin:
The thermoplastic polyester resin that is the main component of the resin composition of the present invention is a polyester obtained by polycondensation of a dicarboxylic acid compound and a dihydroxy compound, polycondensation of an oxycarboxylic acid compound, or polycondensation of a mixture of these compounds. It may be either a homopolyester or a copolyester. Examples of the dicarboxylic acid compound constituting the thermoplastic polyester resin include alicyclic acids such as terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, and cyclohexanedicarboxylic acid. Aliphatic dicarboxylic acids such as dicarboxylic acid, adipic acid and sebacic acid can be mentioned.

  As is well known, these can be used in polycondensation reactions as ester-forming derivatives such as dimethyl esters in addition to free acids. Examples of the oxycarboxylic acid include paraoxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid. These can be polycondensed alone, but are often used in a small amount together with a dicarboxylic acid compound.

As the dihydroxy compound, aliphatic diols such as ethylene glycol, propylene glycol, butanediol, neopentyl glycol, and polyoxyalkylene glycol are mainly used. Hydroquinone, resorcin, naphthalenediol, dihydroxydiphenyl ether, 2,2-bis (4 Aromatic diols such as -hydroxyphenyl) propane and cycloaliphatic diols such as cyclohexanediol can also be used.
is there.

  In addition to these bifunctional compounds, trifunctional or higher polyfunctional compounds such as trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, and trimethylolpropane are introduced to introduce a branched structure. A small amount of a monofunctional compound such as a fatty acid can also be used.

  The thermoplastic polyester resin used in the resin composition of the present invention is usually a polycondensate mainly composed of a dicarboxylic acid compound and a dihydroxy compound, that is, a structural unit which is an ester of a dicarboxylic acid compound and a dihydroxy compound in calculation. Preferably, the resin occupies 70% by weight or more, more preferably 90% by weight or more. The dicarboxylic acid compound is preferably an aromatic dicarboxylic acid, and the dihydroxy compound is preferably an aliphatic diol.

Among the thermoplastic polyester resins, polyalkylene terephthalate in which 95 mol% or more of the acidic component is terephthalic acid and 95 mol% or more of the alcohol component is an aliphatic diol is preferable. Typical examples are polybutylene terephthalate and polyethylene terephthalate. These are preferably close to homoesters, that is, 95% by weight or more of the total resin is composed of a terephthalic acid component and a 1,4-butanediol or ethylene glycol component.
In the resin composition of the present invention, it is preferable that the thermoplastic polyester resin is polybutylene terephthalate from the viewpoint of good moldability.

  The intrinsic viscosity of the thermoplastic polyester resin used in the resin composition of the present invention may be appropriately selected and determined. Usually, it is preferably 0.5 to 2 dl / g, and among them, the moldability of the resin composition and the machine From the viewpoint of physical characteristics, it is preferably 0.6 to 1.5 dl / g. If a material having an intrinsic viscosity of 0.5 dl / g or more is used, the mechanical strength of a molded product obtained from the resin composition tends to be sufficiently high, and if it is 2 dl / g or less, the fluidity of the resin composition is improved. However, the moldability tends to be improved.

  In the present specification, the intrinsic viscosity of the thermoplastic polyester resin is a value measured at 30 ° C. in a 1: 1 (weight ratio) mixed solvent of tetrachloroethane and phenol.

(B) Phosphinate:
The resin composition of the present invention comprises (B) calcium or aluminum of phosphinic acid in which the anion moiety is represented by the following general formula (1) or general formula (2) with respect to 100 parts by weight of the (A) thermoplastic polyester resin. 5 to 40 parts by weight of phosphinic acid salt which is a salt.

In the formula, R ¹ , R ² and R ^{5 to} R ⁷ each independently represent an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ³ and R ⁴ each independently A group consisting of an alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group, or a combination of two or more thereof is represented. n represents an integer of 0 to 4.

Examples of the alkyl group represented by R ¹ , R ² and R ^{5 to} R ⁷ include a methyl group, an ethyl group, a propyl group, an isobutyl group, a pentyl group, etc., but an alkyl group having 1 to 4 carbon atoms, particularly a methyl group. Or an ethyl group is preferable. Examples of the aryl group include a phenyl group and a naphthyl group, and examples of the substituent bonded thereto include an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group, and an alkoxy group.

  The number of bonds of the substituent is usually 1 to 2. The aryl group is preferably a phenyl group or a group in which 1 or 2 alkyl groups having 1 to 2 carbon atoms are bonded thereto.

Examples of the alkylene group represented by R ³ and R ⁴ include a linear group such as a methylene group, an ethylene group, a propylene group, and a butylene group, and a branched chain group such as a 2-ethylhexylene group.
Among these, an alkylene group having 1 to 4 carbon atoms, particularly a methylene group or an ethylene group is preferable.

Examples of the optionally substituted arylene group represented by R ³ and R ⁴ include a phenylene group and a naphthylene group, and examples of the substituent bonded thereto include the same as those described above. The number of bonds of the substituent is usually one. The arylene group is preferably a phenylene group or a group in which an alkyl group having 1 to 2 carbon atoms is bonded thereto. Examples of the group consisting of two or more of these include a group in which a methylene group and a phenylene group are bonded, a group in which two phenylene groups are bonded to a methylene group, and a group in which two methylene groups are bonded to a phenylene group. Can be mentioned.

  Said n represents the integer of 0-4, Preferably it is 0-1, More preferably, it is 0.

  Among them, in the present invention, as the above-described (B) phosphinic acid salt, a calcium or aluminum salt (B ′) of phosphinic acid whose anion portion is represented by the following formula (1 ′) or (2 ′) is used. preferable.

(In the formula, R ¹¹ , R ¹² and R ^{15 to} R ¹⁷ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are alkylene groups or phenylene groups having 1 to 4 carbon atoms. N2 represents an integer of 0 to 4.)

  The phosphinic acid salt is blended in an amount of 5 to 40 parts by weight per 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount is 5 parts by weight or more, the flame retardancy of the resin composition of the present invention can be made sufficiently high. Conversely, if it is 40 parts by weight or less, the mechanical properties of the resin composition can hardly be lowered. . From the viewpoint of achieving both flame retardancy and mechanical properties, the blending amount of the (B) phosphinate is preferably 20 to 40 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, More preferably, it is 20-35 weight part, Most preferably, it is 20-35 weight part, More preferably, it is 20-32 weight part.

  Examples of the phosphinic acid salt in which the anion moiety preferably used in the present invention is represented by the above formula (1) include calcium dimethylphosphinate, aluminum dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, calcium diethylphosphinate , Aluminum diethylphosphinate, calcium methyl-n-propylphosphinate, aluminum methylmethyl-n-propylphosphinate, calcium methylphenylphosphinate, aluminum methylphenylphosphinate, aluminum diisobutylphosphinate and the like.

  Examples of the phosphinic acid salt in which the anion moiety preferably used in the present invention is represented by the formula (2) include methylene bis (methylphosphinic acid) calcium, methylenebis (methylphosphinic acid) aluminum, phenylene-1,4-bis ( Methyl phosphinic acid) calcium, phenylene-1,4-bis (methylphosphinic acid) aluminum, and the like, and those where n = 0 in the formula (2) are preferred.

  The phosphinic acid salts used in the present invention may be used alone or in combination of two or more at any ratio. Specifically, for example, from the viewpoint of improving flame retardancy and electrical properties, among the above-mentioned, an aluminum salt of diethylphosphinic acid and a calcium salt are preferable. In addition, from the viewpoint of mechanical strength and appearance of a molded product obtained by molding the resin composition of the present invention, the phosphinic acid salt used in the present invention has a particle size of 100 μm or less, particularly 50 μm or less, with 90% by weight or more. It is preferable to use a powder. Among them, the use of a powder having a particle size of 0.5 to 20 μm of 90% by weight or more is particularly preferable because it exhibits high flame retardancy and remarkably increases the toughness of the molded body. Here, the particle size is a value obtained by a laser diffraction method.

(C) Organosiloxane compound:
In the thermoplastic polyester resin composition of the present invention, 40 mol% or more of the organic groups bonded to silicon atoms directly or through oxygen atoms are aryl groups based on 100 parts by weight of the thermoplastic polyester resin (A). The organosiloxane compound is 0.5 to 20 parts by weight. This organosiloxane compound acts as a flame retardant that imparts a high degree of flame retardancy to the thermoplastic polyester resin composition when used in combination with the phosphinic acid salt described above.

  One of the mechanism of action is that when the resin composition is burned, the organosiloxane compound is vaporized and a large number of fine bubbles are generated in the resin composition. Is presumed to be inhibited.

  Moreover, the mold deposit of a thermoplastic polyester resin composition can be improved by including an organosiloxane compound. Furthermore, by using an organosiloxane compound in which more than 40 mol% of organic groups bonded directly to silicon atoms or through oxygen atoms are aryl groups, the mold deposit is improved and the flame retardancy is further improved. can do.

The thermoplastic polyester resin composition of the present invention is an organosiloxane polymer in which 40 mol% or more of organic groups bonded to silicon atoms directly or through oxygen atoms are aryl groups.
Specifically, the organosiloxane compound used in the present invention is an organic silanol or a polymer thereof, and is an organic group bonded to a silicon atom directly or through an oxygen atom, that is, Si—C or Si—O—. More than 40 mol% of the organic groups forming the C bond are aryl groups. In the organosiloxane compound used in the present invention, it is preferable that 50 mol% or more of organic groups bonded to silicon atoms directly or through oxygen atoms are aryl groups. Examples of the aryl group include a phenyl group and a naphthyl group, and these groups are substituted with 1 to 2 alkyl groups or alkoxy groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group. May be. As the aryl group, a phenyl group is particularly preferable.

  A polyester resin composition containing an organosiloxane compound generally tends to drop during combustion, but a resin composition containing an organosiloxane compound in which 40 mol% or more of the organic groups are aryl groups is difficult to drop during combustion, and Combustion is greatly suppressed. These actions of the organosiloxane compound are generally greater as the proportion of the aryl group in the organic group is higher. Accordingly, it is particularly preferable to use an organosiloxane compound in which 80 mol% or more, and all (100%) of the organic group is an aryl group, particularly a phenyl group.

  As the organosiloxane compound, any of a monomer such as triphenylsilanol, an oligomer such as octaphenyltetracyclosiloxane which is a cyclic tetramer thereof, and a polymer such as polydiphenylsiloxane can be used. . Some of these phenyl groups may be substituted with a methyl group, other alkyl groups, a methoxy group, other alkoxy groups, a phenoxy group, other aryloxy groups, or the like.

  A part of the phenyl group may be substituted with a hydroxyl group. However, if the content of the hydroxyl group in the organosiloxane polymer is too large, it is easily hydrolyzed under high temperature and high humidity. Therefore, the content of hydroxyl group in the (C) organosiloxane polymer is preferably 1 to 10% by weight.

  As described above, monomers and oligomers may be used as the organosiloxane polymer, but it is preferable to use a polymer having a weight average molecular weight of 200 or more from the viewpoint of reducing mold deposit, and particularly a polymer having 1000 or more is used. Is more preferable. The weight average molecular weight of the organsiloxane compound is preferably 10,000 or less from the viewpoint of improving compatibility with the thermoplastic polyester resin and facilitating the adjustment of a uniform resin composition, and more preferably 5000 or less. . That is, the weight average molecular weight of the (C) organosiloxane compound is preferably 200 to 10,000. Here, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

  Among the organosiloxane polymers, a so-called silicone resin is particularly preferable. The silicone resin is usually a polymer composed of D units, T units, Q units and the like represented by the following general formulas (4) to (6), and the terminal is an M unit represented by the following general formula (3). It may be sealed with.

As the silicone resin used in the present invention, those containing T units represented by RSiO _1.5 (R represents an organic group) are preferable from the viewpoint of reducing the total burning time in the flame retardancy test of UL94, and particularly T units. In particular, those containing 50 mol% or more, particularly those containing 80 mol% or more are preferred, and those containing all of the T units except for the end-capping groups are preferred.

In general, a silicone resin having a low T unit content has low heat resistance and low dispersibility in the resin composition. Here, the content of the T unit is a value measured by ²⁹ Si-NMR, that is, a value obtained by calculating the content from the peak area ratio attributed to the T unit in this measurement.

  In the general formulas (3) to (6), R represents an organic group, preferably a monovalent hydrocarbon group having 1 to 12 carbon atoms. Each R may be the same or different, and is usually either an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms. is there.

Examples of the alkyl group having 1 to 12 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a butyl group, a hexyl group, an octyl group, and a dodecyl group. Among them, a methyl group is preferable.
Examples of the alkenyl group having 2 to 12 carbon atoms include a vinyl group and a butenyl group.
Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group, a naphthyl group, and a tolyl group, and among them, a phenyl group is preferable. Note that 1 to 2 alkyl groups or alkoxy groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a methoxy group, and an ethoxy group may be bonded to the aryl group.

  In the general formulas (3) to (6), an oxygen atom of Si—O— is bonded to a hydrogen atom or a hydrocarbon group to form a hydroxyl group or a hydrocarbon oxy group, or two Si—O— -Is bonded to form a Si-O-Si bond. As a hydrocarbon group couple | bonded with an oxygen atom, the same thing as the C1-C12 monovalent hydrocarbon group shown as the preferable range of R to the said General Formula (3)-(6) is mentioned.

  In the present invention, among the silicone resin, 40 mol% of organic groups bonded to silicon atoms directly or through oxygen atoms, that is, organic groups forming Si—C or Si—O—C bonds. A silicone resin which is an aryl group which may be substituted is used. Among the silicone resins, it is more preferable to use a silicone resin that is an aryl group in which 50 mol% or more of organic groups bonded directly to silicon atoms or via oxygen atoms may be substituted. The aryl group is preferably a phenyl group.

Silicone resin having an aryl group content of 40 mol% or more of organic groups bonded directly to silicon atoms or through oxygen atoms is highly compatible with thermoplastic polyester resins, and the resulting resin composition Shows the desired high flame retardancy. Therefore, the aryl group content is preferably 80 mol% or more, more preferably 100% of the organic group. The content of the aryl group can also be measured by ²⁹ Si-NMR, and the content can be calculated from the peak area ratio attributed to aryl-Si and Si—O-aryl.

  Moreover, the silicone resin may improve flame retardancy by containing a small amount of hydroxyl groups. The hydroxyl group content is preferably 1 to 10% by weight of the silicone resin, more preferably 2 to 8% by weight. In addition, you may use a silicone resin individually or in combination of 2 or more types in arbitrary ratios.

The organosiloxane compound contains 0.5 to 20 parts by weight, preferably 1.0 to 10 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin (A). From the viewpoint of improving the flame retardancy by preventing the organosiloxane compound itself vaporized during combustion of the resin composition from burning, the (C) organosiloxane is used with respect to 100 parts by weight of the (A) thermoplastic polyester resin. More preferably, 2 to 7 parts by weight of the compound is blended, and (C ′) an organosiloxane compound in which 40 mol% or more of the organic group bonded directly to the silicon atom or through the oxygen atom is an aryl group is 2 to 2 parts. It is particularly preferable to blend 7 parts by weight. If the amount is within the preferred range, the desired flame retardancy is exhibited.
On the other hand, from the viewpoint of reducing the total burning time in the flame retardancy test of UL94, the blending amount of the (C) organosiloxane compound is 2 to 6 parts by mass with respect to 100 parts by weight of the (A) thermoplastic polyester resin. More particularly preferred.

(D) Fibrous reinforcing material The resin composition of the present invention comprises (D) 5 to 80 parts by weight of a fibrous reinforcing material that satisfies the following condition (1) with respect to 100 parts by weight of the thermoplastic polyester resin (A). .
(Condition 1): Weight of a fibrous reinforcing material (D flat) having a flatness of 1.5 or more in the cross section represented by the following formula (3) and a fibrous reinforcing material (D circular) having a circular cross section The ratio satisfies the following formula (4).
Flatness ratio = major axis of the cross section of the fibrous reinforcement (a) / minor axis of the cross section of the fibrous reinforcement (b) Equation (3)
(D flat): (D circle) = 3: 7 to 10: 0 (weight ratio) Formula (4)

  The (D) fibrous reinforcing material in the present invention improves the mechanical properties (tensile strength, bending strength, impact strength, etc.) of the resin composition, and at the same time improves the heat shock resistance of the molded product.

  As the fibrous reinforcement, any conventionally known whisker such as glass fiber, carbon fiber, basalt fiber, potassium titanate fiber, etc., used for improving rigidity and other mechanical properties by blending with a thermoplastic resin. Can be used. Among them, glass fiber or carbon fiber is preferable, and glass fiber is more preferable because it is particularly easy to obtain one having a flat cross section as described above.

  If the diameter of the fibrous reinforcing material (the major axis of the flat cross section) is too large, the flexibility is reduced, and if it is too thin, such as less than 1 μm, it is difficult to obtain a large amount and it is difficult to use at the chemical industry level. Therefore, the major axis of the flat cross section is preferably 1 to 100 μm, more preferably 2 to 50 μm. An average diameter of 3 to 40 μm, particularly 5 to 30 μm is particularly preferable because it is easily available and has a great effect as a reinforcing material.

  The length of the fibrous reinforcing material is preferably 0.1 mm or more from the viewpoint of the reinforcing effect. In general, the longer one has a greater reinforcing effect, but a long fibrous reinforcing material breaks and becomes shorter when a resin composition is prepared by melt-kneading. Therefore, when the resin composition of the present invention is prepared, even if a material having a length of 20 mm or more is used as a raw material for the fibrous reinforcing material, the effect is generally low, so that the average length is usually 0.3 to 5 mm. What is necessary is just to prepare the resin composition of this invention using a thing. The fibrous reinforcing material is usually used to prepare a resin composition as a chopped strand obtained by cutting a number of these fibers into a predetermined length. In addition, since mixing | blending of carbon fiber provides electroconductivity to a resin composition, glass fiber is used when the resin composition of high electrical resistance is desired.

  The (D) fibrous reinforcing material is blended in an amount of 5 to 80 parts by weight per 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount is 5 parts by weight or more, the reinforcing effect is sufficiently large, and if it is 80 parts by weight or less, mechanical properties such as impact resistance of the resin composition tend to be improved. The blending amount of the (D) fibrous reinforcing material with respect to 100 parts by weight of the (A) thermoplastic polyester resin is preferably 15 to 70 parts by weight. Moreover, it is more preferable that it is 20-70 weight part from a viewpoint of improving bending strength and improving mechanical strength.

In addition, as long as the resin composition of the present invention satisfies the above condition 1, a fibrous reinforcing material (D circular, flatness 1) having a general cross section of a circle (or a round shape) is expressed by the formula (3). You may use together with the fibrous reinforcement (D flat) which has the irregular cross-sectional shape whose flatness of the cross section represented is 1.5 or more.
Flatness ratio = major axis of the cross section of the fibrous reinforcement (a) / minor axis of the cross section of the fibrous reinforcement (b) Equation (3)

  When the fibrous reinforcing material has an irregular cross-sectional shape, it may have an irregular cross-sectional shape such as an eyebrow shape or a flat shape as long as the condition 1 is satisfied.

The fibrous reinforcing material (D flat) having an irregular cross-sectional shape in the present invention is represented by the above formula (3), where a is the major axis of the cross section perpendicular to the longitudinal direction of the fiber and b is the minor axis. The / b ratio (flatness) is 1.5 or more, preferably 1.5 to 10, more preferably 2.5 to 10, and particularly preferably 2.5 to 8. By using a fibrous reinforcing material having a flatness ratio of 2.5 or more, there is an effect of improving the flame retardancy, particularly improving the total burning time in the UL94 flame retardancy test.
Furthermore, in the resin composition of this invention, when it is set as the average fiber length L of a fibrous reinforcement, it is preferable that (Lx2) / (a + b) ratio (aspect ratio) is 10 or more, and 50-10 It is more preferable that Usually, in preparing a resin composition, a fibrous reinforcing material having an aspect ratio that is about 2 to 20 times larger than these values is used as a raw material in consideration of damage or the like.

  The flatness ratio (ratio of major axis to minor axis) of the (D) fibrous reinforcing material can be easily calculated from the measured values of the major axis and the minor axis with a microscope of the cross section of the fibrous reinforcing material. Commercially available fibrous reinforcing materials can utilize this value if the flatness is described in the catalog. In order to measure the reinforcing fiber length, a sample of about 5 g was cut out from a reinforcing resin composition containing a fibrous reinforcing material, and left in an electric furnace at a temperature of 600 ° C. for 2 hours to be ashed, and then the remaining fibrous state Measure for reinforcement. The fibrous reinforcing material is dispersed in a neutral surfactant aqueous solution so as not to break, and the dispersed aqueous solution is transferred onto a slide glass by a pipette and photographed with a microscope. With respect to this photographic image, 1000 to 2000 reinforcing fibers are measured using image analysis software, and the average fiber length can be calculated.

The cross-sectional shape of the (D) fibrous reinforcing material is, for example, a rectangular shape, an oval shape, an elliptical shape, or a saddle shape with a narrowed central portion in the longitudinal direction when cut at right angles to the length direction of the fiber. Some are listed. Examples of the cross-sectional shape of these fibrous reinforcing materials are described in Japanese Patent Application Laid-Open No. 2000-265046. The fiber-shaped reinforcing material having a saddle-shaped cross-section has a constricted central part, the strength of the part is low, and the central part may crack, and the constricted part may have poor adhesion to the base resin. Therefore, in order to improve mechanical properties, it is preferable to use a cross-sectional shape that is rectangular, oval, or elliptical, and it is more preferable that the cross-sectional shape is rectangular or oval.
The term “oval” is intended to include a shape composed of a smooth curve having different lengths and widths and rounded as a whole, and a shape composed of two arcs and two straight lines connecting these arcs.

In the resin composition of the present invention, the weight ratio of the fibrous reinforcing material (D flat) having a cross-sectional flatness of 1.5 or more and the fibrous reinforcing material (D circular) having a circular cross-section is represented by the following formula (4 Is satisfied.
(D flat): (D circle) = 3: 7 to 10: 0 (weight ratio) Formula (4)
By satisfy | filling said Formula (4), a flame retardance and a curvature amount can be improved. (D flat): (D circular) = 5: 5 to 10: 0 is preferable, (D flat) :( D circular) = 7: 3 to 10: 0 is more preferable, and (D flat) ): (D circle) = 10: 0 is particularly preferable.

  When the (D) fibrous reinforcing material is a glass fiber, glass fibers having a modified cross section that can be suitably used as the glass fiber include, for example, Japanese Patent Publication No. 3-59019, Japanese Patent Publication No. 4-13300, It can manufacture using the method as described in 4-32775 gazette etc. In particular, in an orifice plate having a large number of orifices on the bottom surface, an outer periphery of an orifice plate surrounding a plurality of orifice outlets and having a convex edge extending downward from the bottom surface of the orifice plate, or a nozzle tip having one or more orifice holes A glass fiber having a flat cross section produced using a nozzle chip for deformed cross section glass fiber spinning provided with a plurality of convex edges extending downward from the tip of the section is preferred.

  The glass fiber is preferably surface-treated with a silane coupling agent such as γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, etc. The adhesion amount is preferably 0.01% by weight or more of the glass fiber weight. Furthermore, if necessary, a lubricant such as a fatty acid amide compound, silicone oil, an antistatic agent such as a quaternary ammonium salt, a resin having a film forming ability such as an epoxy resin or a urethane resin, a resin having a film forming ability and a heat. What was surface-treated with what used a stabilizer, a flame retardant, etc. together can also be used.

  In the present invention, the glass fiber is preferably composed of A glass, C glass, E glass or the like, and in particular, E glass (non-alkali glass) does not adversely affect the thermal stability of the thermoplastic polyester resin. Is preferable. In addition, when using glass fiber, it is generally preferable to use a short fiber type (chopped strand) from the viewpoint of ease of handling, etc., especially in the case of a molded product that requires impact resistance characteristics. It is more preferable to use a long fiber type in order to keep the fiber length of the glass fiber in the molded product longer.

(E) Metal borate or antimony compound:
The resin composition of the present invention preferably contains 0.5 to 20 parts by weight of at least one of (E) a metal borate or an antimony compound with respect to 100 parts by weight of the (A) thermoplastic polyester resin. It is more preferable to include -5 parts by weight from the viewpoint of improving flame retardancy, warpage, and electrical insulation properties (CTI). On the other hand, from the viewpoint of further improving warpage, an embodiment comprising 1 to 4 parts by mass of at least one of (E) a metal borate or an antimony compound with respect to 100 parts by weight of the (A) thermoplastic polyester resin is also preferable.

  The average particle size of the metal borate or antimony compound indicates a particle size at which the cumulative weight distribution is 50% in the particle size distribution obtained by measurement with a sedigraph (X-ray transmission type particle size distribution measuring device). The Cedygraph is an apparatus that irradiates a suspension during sedimentation with X-rays and measures the particle size distribution from the amount of X-ray transmission.

  If the metal borate or antimony compound is an ore produced in nature, for example, it is pulverized using any conventionally known method such as a dry pulverization method or a wet pulverization method to obtain a predetermined particle size. Adjust it. Examples of the pulverizing means include pulverizing means such as a ball mill, a roller mill, a jet mill, a vibration mill, a planetary mill, and a stirring frame mill.

  In addition, the boric acid metal salt or antimony compound may be surface-treated with a surface treatment agent such as a silane coupling agent. As the surface treatment agent, any conventionally known one can be used. Specifically, examples of the silane coupling agent include surface treatment agents such as aminosilane, epoxysilane, allylsilane, and vinylsilane.

  Of these, aminosilane-based surface treatment agents are preferred. Specific examples of the aminosilane coupling agent include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, and γ- (2-aminoethyl) aminopropyltrimethoxysilane. .

  As the surface treatment agent for the borate metal salt or antimony compound, the surface treatment agent such as the silane coupling agent may have other components, specifically, for example, as long as the effects of the present invention are not impaired. An epoxy resin, a urethane resin, an acrylic resin, an antistatic agent, a lubricant, a water repellent, and the like may be included.

  Specific examples of the surface treatment method using such a surface treatment agent include a surface treatment agent previously prepared by a surface treatment agent, such as the methods described in JP-A Nos. 2001-172555 and 53-106749. In addition to the untreated metal borate salt or antimony compound, a surface treating agent may be added to the surface treatment to prepare the polyester resin composition of the present invention.

<< E-1 >> Boric acid metal salt In the present invention, a boric acid metal salt may be used in addition to the above-described (A) to (D). Examples of boric acid that forms a boric acid metal salt include non-condensed boric acid such as orthoboric acid and metaboric acid; condensed boric acid such as pyroboric acid, tetraboric acid, pentaboric acid, and octaboric acid; and basic boric acid. Is preferred. The metal that forms a salt with these may be an alkali metal, but among them, polyvalent metals such as alkaline earth metals, transition metals, and Group 2B metals of the periodic table are preferred. The metal borate may be a hydrate.

  The boric acid metal salt includes a non-condensed boric acid metal salt and a condensed boric acid metal salt. Non-condensed borate metal salts include alkaline earth metal borates such as calcium orthoborate and calcium metaborate; transition metal borates such as manganese orthoborate and copper metaborate; zinc metaborate and cadmium metaborate Examples thereof include borate salts of Group 2B metals of the periodic table. Of these, metaborate is preferred.

  Examples of the condensed borate include alkaline earth metal borates such as trimagnesium tetraborate and calcium pyroborate; transition metal borates such as manganese tetraborate and nickel diborate; zinc tetraborate, four Examples thereof include borate salts of Group 2B metals of the periodic table such as cadmium borate. Examples of the basic borate include basic borates of Group 2B metals of the periodic table such as basic zinc borate and basic cadmium borate. In addition, hydrogen borates corresponding to these borates (such as manganese orthoborate) can also be used.

As the borate metal salt that can be used in the present invention, it is preferable to use an alkaline earth metal or a Group 2B metal salt of the periodic table, for example, zinc borate or calcium borate. Zinc borates include zinc borate (2ZnO.3B ₂ O ₃ ), zinc borate.3.5 hydrate (2ZnO.3B ₂ O ₃ .3.5H ₂ O), etc. Calcium borate includes calcium borate anhydride (2CaO · 3B ₂ O ₃ ) and fired products. Among these zinc borates and calcium borates, hydrates are particularly preferable.

  Combining the boric acid metal salt improves the combustion inhibiting action of the resin composition. Phenomenologically, it foams during combustion and blocks the unburned part from the flame. The compounding amount of the boric acid metal salt is 0 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin, but it is preferable to add 1 part by weight or more in order to express the compounding effect, but the compounding is excessive. However, since the improvement in the effect commensurate with the increase in the amount of addition becomes a peak, the compounding amount of the boric acid metal salt is 1 to 10 parts by weight, especially 1 to 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. Is preferred.

Further, as the calcium borates, colemanite (an inorganic compound mainly composed of calcium borate and usually a hydrate represented by the chemical formula 2CaO.3B ₂ O ₃ .5H ₂ O) may be used. . The colemanite is HYPERLINK "http://stonesagasi.seesaa.net/article/15439337.html" Colemanite, any of calcium-based borate or colemanite called colemanite or chalrite. However, in particular, colemanite produced as a mineral is preferable because it is excellent in thermal stability.

  The colemanite is a hydrous calcium borate mineral as a mineral, for example, which forms in evaporite deposits and forms short columnar crystals and pseudorhombic crystals belonging to the monoclinic system, and the crystal form is granular or dense lump Any of the round assemblies can be used. There are many colors such as colorless, white, milky white, yellowish white, and gray, but in the present invention, colors of other colors can also be used.

When using a mineral as said colemanite, you may contain the impurity in the state produced. Such a composition of colemanite as a mineral is generally B ₂ O ₃ (45.2 to 42.18%), Fe ₂ O ₃ (0.35 to 0.03) in terms of mass% including impurities. _{%), SiO 2 (3.50~4.08%} ), Al 2 O 3 (0.51~0.16%), CaO (26.01~27.06%), SrO (0.62~1 .19%), MgO (1.06 to 1.43%), Na ₂ O ₃ (0.03 to 0.10%), K ₂ O (0.16 to 0.03), but other than the above The chemical composition may be included.

As said colemanite, what is marketed by brand names, such as a co-manufactured material colemanite, Kinsei Matec Co., Ltd. UBP, can be used, for example. The colemanite used in the present invention may be a natural product as described above as it is or a partly treated product. Specifically, for example, when colemanite is fired at 400 ° C. or higher, a part thereof becomes CaO · 2B ₂ O ₃ . It has been reported that this fired product has an antibacterial effect, an antifungal effect, an algal control effect, and the like.

         The average particle size of the colemanite is preferably 1 to 50 μm, more preferably 3 to 20 μm, and particularly preferably 3 to 10 μm. By setting it as such a range, it exists in the tendency for various physical properties, such as a softness | flexibility, and a flame retardance of the thermoplastic polyester resin composition of this invention to improve.

<< E-2 >> Antimony compounds:
The thermoplastic polyester resin composition of the present invention preferably contains the antimony compound in a proportion of 0 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin. By including the antimony compound, surprisingly, an improvement in flame retardancy that was not manifested only by the phosphorus flame retardant and the organosiloxane polymer was recognized.

  In particular, in resin compositions, it is known that the balance of physical properties such as fluidity is easily lost by adding an additive. However, in an embodiment containing an antimony compound of the resin composition of the present invention, an antimony compound is added. However, it is extremely preferable in that such physical property balance is maintained.

The antimony compound uses antimony oxide or a double salt of antimony oxide and another metal. Specific examples include antimony trioxide (Sb ₂ O ₃ ), antimony tetraoxide (Sb ₂ O ₄ ), Examples thereof include oxides such as antimony oxide (Sb ₂ O ₅ ) and antimonates such as sodium antimonate. Preferably, antimony trioxide, antimony pentoxide, or a double salt of antimony pentoxide and another metal oxide is used. The aspect used as a double salt of antimony pentoxide and another metal oxide is represented by the following general formula (7) or (8).

n11 (X ₂ O) · Sb ₂ O ₅ · m1 (H ₂ O) (7)
_{n12 (YO) · Sb 2 O} 5 · m2 (H 2 O) ····· (8)
(However, X represents a monovalent alkali metal element, Y represents a divalent alkaline earth metal element, n11 and n12 represent a number of 0 to 1.5, and m1 and m2 represent a number of 0 to 4. M1, m2, n11 and n12 are independently determined in the general formula (7) and the general formula (8).

The antimony compound is more preferably represented by the following general formula (9).
n13 (Na ₂ O) · Sb ₂ O ₅ (9)
(However, n13 shows the number of 0.65-1.5.)
In the general formulas (7) to (9), X includes lithium, sodium, potassium, cesium, and the like, and Y includes calcium, magnesium, barium, and the like. N11 and n12 are 0 to 1.5, preferably greater than 0, more preferably 0.3 or more, and particularly preferably in the range of 0.65 to 1.5. It is preferable that n11 to n13 be 0.65 or more because the desorption rate of adsorbed water is sufficiently high, so that the melt viscosity hardly changes. When n11 to n13 are 1.5 or less, the amount of relative antimony becomes a sufficient amount, and the effect as a flame retardant aid is sufficiently exhibited. Said m1-m3 is the number of 0-4, Preferably it is 0-2. If m1 to m3 are 4 or less, PBT is hardly hydrolyzed, which is preferable. In particular, a one-to-one double salt of sodium oxide and antimony pentoxide represented by Na ₂ O.Sb ₂ O ₅ (that is, n13 = 1) is preferable from the viewpoint of hydrolysis resistance. What is marketed by brand names, such as 1070L, is mentioned as an example of a preferable antimony compound.

         The average particle size of antimony is preferably 0.3 to 50 μm, more preferably 0.4 to 20 μm, particularly preferably 0.4 to 10 μm, and more preferably 0.5 to 1.5 μm. preferable. By setting it as such a range, it exists in the tendency for various physical properties, such as a softness | flexibility, and a flame retardance of the thermoplastic polyester resin composition of this invention to improve.

(Additive)
Furthermore, various additives commonly used in thermoplastic resin compositions can be added to the resin composition of the present invention within a range not departing from the spirit of the present invention. Examples of such additives include stabilizers such as antioxidants, ultraviolet absorbers, light stabilizers, hydrolysis inhibitors (epoxy compounds, carbodiimide compounds, etc.), antistatic agents, lubricants, mold release agents, dyes, Colorants such as pigments, plasticizers and the like can be mentioned. In particular, the addition of an antioxidant and a release agent is effective.

  Moreover, polytetrafluoroethylene obtained by an emulsion polymerization method, fumed colloidal silica, or the like can be added to further prevent dripping during combustion.

(Other resins)
The thermoplastic polyester resin composition of the present invention may be supplemented with other thermoplastic resins other than the thermoplastic polyester resin, and is preferably a resin that is stable at high temperatures. Specific examples of the other thermoplastic resins include polycarbonate, polyamide, polyphenylene oxide, polystyrene resin, polyphenylene sulfide ethylene, polysulfone, polyethersulfone, polyetherimide, polyetherketone, and fluorine resin. It is done.
The ratio of the thermoplastic polyester resin in the thermoplastic polyester resin composition of the present invention is preferably 40% to 100% and more preferably 50% to 100% in all resin components.

(Halogen flame retardant)
The halogen concentration derived from the halogen flame retardant in the entire thermoplastic resin composition of the present invention is 2000 ppm or less. From the viewpoint of minimizing the generation of dioxins when the thermoplastic polyester resin composition of the present invention and a molded body using the same are burned, the halogen concentration derived from the halogen flame retardant is preferably 1000 ppm or less, and 500 ppm. Or less, more preferably 100 ppm or less, and most preferably not detected. The halogen-based flame retardant referred to in the present invention means a flame retardant that causes generation of dioxins when the thermoplastic resin composition of the present invention is burned and contains a halogen atom. Regardless of whether the thermoplastic resin composition of the present invention is derived from a flame retardant, the halogen concentration is preferably 2000 ppm or less, more preferably 1000 ppm or less, and even more preferably 500 ppm or less. More preferably, it is 100 ppm or less, and most preferably not detected.
The halogen concentration derived from the halogen flame retardant in the thermoplastic polyester resin composition can be measured by fluorescent X-ray analysis.

  In the present invention, the halogen concentration was determined by the fundamental parameter (FP) method for the elements detected by measurement using the following apparatus and conditions. That is, the base polymer was set as a balance component, and the content of bromine and chlorine was calculated theoretically from the FP method for the detection elements obtained under the following apparatus and conditions.

Equipment: Desktop X-ray fluorescence analyzer (ZSX miniII)
X-ray tube: 50 W (40 kV, 1.2 mA), target: Pd
Spectroscopic crystals: for heavy elements: LiF200, for light elements: PET, TAP
Detector: For light elements: F-PC, For heavy elements: SC
Measurement area: Measurement area Diameter: φ30mm
Sample chamber: 12 sample turret type Sample size: outer diameter φ44mm, height 33mm
Sample rotation: 30 rpm
Measurement atmosphere: Vacuum pump: Gas for rotary pump detector: PR gas for F-PC 25 ml / min

(Method for producing thermoplastic polyester resin composition)
Preparation of the resin composition of this invention can be performed in accordance with the conventional method of resin composition preparation. Usually, the components (A) to (E) and various additives added as desired are mixed together and then melt-kneaded in a single-screw or twin-screw extruder. Also, the resin composition of the present invention can be prepared by mixing each component in advance or by mixing only a part of the components in advance and supplying them to an extruder using a feeder and melt-kneading them. Further, a master batch is prepared by melting and kneading a part of a polyester resin and a part of other components, and then the remaining polyester resin and other ingredients are blended and melt kneaded. Good.

  Specifically, for example, a predetermined amount of each of the components (A) to (D) described above and, if necessary, the component (E) and other additive components are weighed, and a ribbon blender, a V-type blender, and a Hensell mixer. And a method of mixing with a mixer such as a drum blender and melting and kneading with a melting and kneading machine. When melting and kneading, a method of feeding each component to the melting and kneading machine at once or a method of feeding sequentially may be used. Examples of the melting / kneading machine include various extruders, Brabender plastographs, lab plast mills, kneaders, and Banbury mixers. When melting and kneading, it is preferable to feed those which are easily decomposed or easily broken. Various additive components can be mixed in advance with the base resin and other additive components. (D) Since the fibrous reinforcing material is easily damaged when the raw material is kneaded, it is preferable to feed the fibrous reinforcing material in the middle and prepare the fibrous reinforcing material raw material so as to satisfy the condition (1). The heating temperature at the time of melting and kneading varies depending on the type of components contained in the reinforced resin composition, the ratio of each component, the type of other additives, the blending amount, etc., and is preferably in the range of 230 to 290 ° C.

[Molded body]
The molded product of the present invention can be obtained by applying the above-described method for injection molding the thermoplastic polyester resin composition of the present invention to any conventionally known thermoplastic resin molding method.

  Hereinafter, the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the following examples unless it exceeds the gist.

(Measurement method, evaluation method)
The resin composition was evaluated by the following method.

Bending strength:
A UL94 (Subject 94 of Underwriters Laboratories) combustion test piece having a thickness of 1.6 mm was injection-molded, and a bending test was performed using this with a span interval of 40 mm and a test speed of 2 mm / min.
This bending test indicates that the larger the numerical value, the better the mechanical properties, and it is preferably 120 MPa or more, more preferably 140 MPa or more, and particularly preferably more than 170 MPa.

Flame retardancy test (i): UL94 5V test 5VA and 5VB are collectively referred to as 5V. The 5V combustion test applies to those that have passed UL94V-0, and the 5V test piece includes Bar (strip shape) and Plaque (plate shape), and the Plaque test applies to those that have passed the Bar test. This is the highest class flammability class. According to the method of UL94, a flammability test is performed using Bar (125 × 13 × n / unit mm) and Plaque (150 × 150 × n / unit mm) of a predetermined thickness, and according to the evaluation method described in UL94, The minimum wall thickness that passed 5VA was determined.
Flame Retardancy Test (ii): UL94 V-0 Test According to the method of UL94, a flame retardancy test was conducted using five test pieces (thickness 0.8 mm), and according to the evaluation method described in UL94, V- It was classified into 0, V-1, V-2, and HB (V-0 indicates the highest flame retardancy). The total (total) burning time is the total burning time of five tubes (including the burning time during the first flame contact and the second flame contact).
The total combustion time is 50 seconds or less, preferably 25 seconds or less, more preferably 20 seconds or less, particularly preferably 10 seconds or less, and particularly preferably 8 seconds or less. preferable.

Comparative tracking index test (abbreviation: CTI test):
For the test piece (a flat plate having a thickness of 3 mm), the CTI was determined by the test method defined in the international standard IEC60112. CTI shows the resistance to tracking at a voltage in increments of 25V between 100V and 600V when wet-contaminated with an electric field applied to the surface of a solid electrical insulating material. The higher the value, the better. Means.
The CTI is preferably 500 V or higher.

Mold deposit:
Using SE50 manufactured by Sumitomo Heavy Industries, Ltd. as an injection molding machine, injection pressure 50 MPa, injection speed 80 mm / sec, cylinder temperature 260 ° C., injection time 3 sec, cooling 8 sec, mold temperature 80 ° C., zack back 3 mm A resin molded product having a thickness of 35 mm, a width of 14 mm, and a thickness of 2 mm was produced using a pin gate mold.

Continuous injection molding was performed under these conditions, and after 1000 shots, the state of the mold deposit (mold contamination) adhered to the mold was observed with the naked eye and evaluated according to the following criteria.
A: Mold deposit is hardly recognized.
○: Mold deposit is slightly recognized.
Δ: Mold deposit is clearly recognized.
X: The mold deposit is thickly attached to the entire mold surface.

(3) Evaluation of warpage of molded product:
A flat plate shaped product with a thickness of 1 mm and a size of 100 mm × 100 mm is molded under the following molding conditions. After adjusting for 24 hours or more in a 23 ° C., 50% humidity environment, the maximum warpage of the flat plate using a height gauge Was measured.
(Molding condition)
Injection molding machine; SH100 manufactured by Sumitomo Heavy Industries, Ltd.
Cylinder temperature: 260 ° C
Injection speed: 70mm / sec
Mold temperature: 80 ℃

  The raw materials used in the examples are as follows.

(A) Thermoplastic polyester resin:
(A-1) PBT: 5020 Polybutylene terephthalate resin having a NOVADURAN (registered trademark) 5020 manufactured by Mitsubishi Engineering Plastics Co., Ltd. and an intrinsic viscosity of 1.20 dl / g.

(A-2) PBT: 5008 Novaduran (registered trademark) 5008 manufactured by Mitsubishi Engineering Plastics Co., Ltd. Polybutylene terephthalate resin having an intrinsic viscosity of 0.85 dl / g.

(B) Phosphinate:
Aluminum diethylphosphinate: OP1240 (trade name) manufactured by Clariant.

(C) Organosiloxane compound:
(C-1) Silicone compound-1: 217 Flake (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., weight average molecular weight (Mw): 2000, hydroxyl group content: 7% by weight (wt)%, phenyl group content: 100 Mol%, average molecular formula: (PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.57 .

(C-2) Silicone compound-2: TMS217 (trade name) manufactured by Toray Dow Corning Silicone Co., Mw: 2000, hydroxyl group content: 2 wt (wt)%, phenyl group content: 100 mol%, C- A silicone resin obtained by subjecting one silicone compound to end-capping treatment with a trimethylsilyl group.

(C-3) Silicone compound-3: SR-21 (trade name) manufactured by Konishi Chemical Industries, Mw: 3800, hydroxyl group content: 6 wt (wt)%, phenyl group content: 100 mol%, average molecular formula: ( PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.48 .

(C-4) Silicone compound-4: SR-20 (trade name) manufactured by Konishi Chemical Industry, Mw: 6700, hydroxyl group content: 3 wt (wt)%, phenyl group content: 100 mol%, average molecular formula: ( PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.24 .

(C-5) Silicone compound-5: SH6018 (trade name) manufactured by Toray Dow Corning Silicone Co., Mw: 2000, hydroxyl group content: 6% by weight (wt)%, phenyl group content: 70 mol%, propyl group Content: 30 mol%, average molecular formula: (PhSiO _3/2 ) _0.7 (ProSiO _3/2 ) _0.3 (HO _1/2 ) _0.48 .

(C-6) Silicone compound-6: X40-9805 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl organosiloxane (phenyl group content around 50 mol%).

(C-7) Silicone compound-7: Z6800 (trade name) manufactured by Toray Dow Corning Silicone Co., triphenylsilanol (phenyl group content: 100 mol%).

(C-8) Silicone compound-8: manufactured by Shin-Etsu Chemical Co., Ltd., octaphenyltetracyclosiloxane (phenyl group content: 100 mol%).

(C-9) Silicone compound-9: KR-511 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone oligomer (phenyl group content around 50 mol%).

(C-10) Silicone compound-10: TSR165 (trade name) manufactured by Momentive Performance Materials Japan, polymethylphenylmethoxysiloxane (phenyl group content around 50 mol%).

(C-11) Silicone compound-11: SH200 (trade name) manufactured by Toray Dow Corning Silicone Co., Ltd., polydimethylsiloxane (hydroxyl group content 0 weight (wt)%, phenyl group content 0 mol%, viscosity 60000 centistokes) ).

(D) Glass fiber:
(D-1) 03JA-FT592 (trade name) manufactured by Owens Corning Co., Ltd., circular cross section, glass fiber having a diameter of 10.5 μm.
(D-2) Atypical cross-section glass fiber: CSH3PA860 (trade name) manufactured by Nittobo Co., Ltd., flatness = 2, aspect ratio 200, major axis 20 μm, minor axis 10 μm, and fiber length 3 mm.
(D-3) Atypical cross-section glass fiber: CSG3PA830 (trade name) manufactured by Nittobo Co., Ltd., flatness = 4, aspect ratio 171, major axis = 28 μm, minor axis = 7 μm, and fiber length 3 mm.

(E) Metal borate / antimony compound (E-1) Zinc borate: Firebrake 500 (trade name), B ₂ O ₃ 56.2% by weight (wt)%, ZnO 43.8% by weight (wt)% , Particle size 10 μm.
(E-2) Colemanite (calcium borate ore): UBP5M (trade name) manufactured by Kinsei Matech Co., Ltd., particle size 5 μm.
(E-3) Antimony trioxide: AT-3CN (trade name) manufactured by Suzuyu Chemical Co., Ltd., Sb content 83.5%, structural formula = Sb ₂ O ₃ , average particle size: 0.9 μm.

(F) Other additives (F-1) Melamine cyanurate: MX44 (trade name) manufactured by Nippon Synthetic Chemical Co., Ltd.

(F-2) Fluororesin: Sumitomo 3M TF1750 (trade name).

(F-3) Antioxidant: Phenol type antioxidant Irganox 1010 (trade name) manufactured by Ciba Specialty Chemicals.

(F-4) Phosphorus stabilizer: ADK STAB PEP36 (trade name) manufactured by Asahi Denka Co., Ltd.

(F-5) Mold release agent: Paraffin wax FT100 (trade name) manufactured by Nippon Seiki Co., Ltd.

[Examples 1 to 16 and Comparative Examples 1 to 9]
Components other than glass fiber are mixed together at a weight ratio shown in Table 2 and Table 3 with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and the mixture is a twin screw extruder with L / D = 42 (Japan) The steel sheet company, TEX30HSST) hopper, glass fiber is side-feeded, extruded at a discharge rate of 20 kg / hour, screw rotation speed of 250 rpm, barrel temperature of 260 ° C., and polybutylene terephthalate resin composition Pellets were obtained.

  From this resin composition pellet, using an injection molding machine (Model SE50 manufactured by Sumitomo Heavy Industries, Ltd.), a UL94 standard combustion test piece (bending test) having a resin temperature of 260 ° C. and a mold temperature of 80 ° C. and a thickness of 1.6 mm. Used as a piece), a UL94 standard combustion test piece with a thickness of 0.8 mm, a test piece with a thickness for each 5 V test (Bar (125 × 13 × n / unit mm)), and a test piece for measuring the amount of warping In addition, a comparative tracking index specimen (a flat specimen having a length of 10 cm and a thickness of 3 mm) was manufactured, and at the same time, mold deposit evaluation was performed under the molding conditions. Each thickness test piece (Plaque (150 × 150 × n / unit mm)) for the 5V test is an injection molding machine (model J150ED manufactured by Nippon Steel Works), resin temperature 260 ° C., mold temperature 80 ° C. Was molded. The evaluation results are shown in Table 2 and Table 3.

From Tables 2 and 3, the resin compositions of Comparative Examples 1 to 5 in which the weight ratio of the flat and circular fibrous reinforcing materials is outside the scope of the present invention are inferior in flame retardancy, and further warped. It turned out that the property was remarkably inferior. Further, it was found that the resin composition of Comparative Example 6 using an organosiloxane polymer in which the organic group bonded directly to the silicon atom or through the oxygen atom is not an aryl group was remarkably inferior in flame retardancy. It was.
In contrast, the thermoplastic polyester resin composition of the present invention was found to have good physical properties.

[Examples 101 to 117]
Furthermore, when the bromine density | concentration of Examples 1-17 was measured by the fluorescent X ray measuring method, it confirmed that all were 500 ppm or less. That is, the thermoplastic polyester resin composition of the present invention generates a small amount of dioxins during incineration.
From the above, it has been found that the thermoplastic polyester resin composition of the present invention generates little dioxin during incineration and is excellent in flame retardancy and low warpage.

Furthermore, from Table 2 and Table 3, it turned out that it can have the following characteristics in the more preferable aspect of the thermoplastic polyester resin composition of this invention.
(1) Even when it is a thin product satisfying the 5VA grade and is a molded product having a thickness of 1 mm or less, it can have excellent flame retardancy, mechanical properties, and low warpage.
(2) Since it has excellent releasability, there is little risk of deformation during molding.
(3) Since the gas generation during molding is small and the mold deposit can be extremely small, the productivity during molding is good.
(4) The strength of the weld part of the injection molded product can be increased.
(5) It has excellent tracking resistance and can be used for a wide range of applications in the electrical and electronic fields.

  The resin molded product obtained by molding the thermoplastic polyester resin composition of the present invention has a small amount of dioxin generated during incineration and has excellent flame retardancy and low warpage. Therefore, the resin composition of the present invention can be particularly suitably applied to a wide range of parts such as electric and electronic parts such as connectors and terminals. It can also be suitably applied to automobile parts and building material parts.

Claims (13)

(A) For 100 parts by weight of the thermoplastic polyester resin,
(B) 5-40 parts by weight of a phosphinic acid salt, wherein the anion moiety is a calcium or aluminum salt of phosphinic acid represented by the following general formula (1) or general formula (2):
(C) 0.5 to 20 parts by weight of an organosiloxane compound in which 40 mol% or more of the organic group bonded to the silicon atom directly or through an oxygen atom is an aryl group,
(D) 5 to 80 parts by weight of a fibrous reinforcing material that satisfies the following condition (1):
A thermoplastic polyester resin composition having a halogen concentration derived from a halogen-based flame retardant of 2000 ppm or less.
(In the general formulas (1) and (2), R ¹ , R ² and R ^{5 to} R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, R ³ and R ⁴ represent an alkylene group having 1 to 10 carbon atoms, an optionally substituted arylene group, or a group composed of a combination of two or more thereof, and n represents an integer of 0 to 4.)
(Condition 1): Weight of a fibrous reinforcing material (D flat) having a flatness of 1.5 or more in the cross section represented by the following formula (3) and a fibrous reinforcing material (D circular) having a circular cross section The ratio satisfies the following formula (4).
Flatness ratio = major axis of the cross section of the fibrous reinforcement (a) / minor axis of the cross section of the fibrous reinforcement (b) Equation (3)
(D flat): (D circle) = 3: 7 to 10: 0 (weight ratio) Formula (4)   2. The thermoplastic polyester resin composition according to claim 1, wherein the blending amount of the (B) phosphinate is 20 to 40 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin.   3. The organosiloxane compound according to claim 1 or 2, wherein the organosiloxane compound (C) is an organosiloxane compound in which 50 mol% or more of the organic groups bonded to silicon atoms directly or through oxygen atoms are aryl groups. The thermoplastic polyester resin composition described.   The weight average molecular weight of said (C) organosiloxane compound is 200-10000, The thermoplastic polyester resin composition as described in any one of Claims 1-3 characterized by the above-mentioned. The (C) organosiloxane compound contains a structural unit represented by RSiO _1.5 (R represents an organic group), and the hydroxyl group content in the (C) organosiloxane polymer is 1 to 10% by weight. It is a thermoplastic polyester resin composition as described in any one of Claims 1-4 characterized by the above-mentioned.   The heat according to any one of claims 1 to 5, wherein the amount of the (C) organosiloxane compound is 2 to 6 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. A plastic polyester resin composition.   7. The composition according to claim 1, further comprising 0.5 to 20 parts by weight of at least one of (E) a metal borate or an antimony compound with respect to 100 parts by weight of the (A) thermoplastic polyester resin. The thermoplastic polyester resin composition according to one item.   8. The blending amount of the (D) fibrous reinforcing material with respect to 100 parts by weight of the (A) thermoplastic polyester resin is 20 to 70 parts by weight, according to claim 1. Thermoplastic polyester resin composition.   The blending amount of the (E) borate metal salt or antimony compound with respect to 100 parts by weight of the (A) thermoplastic polyester resin is 1 to 4 parts by weight. The thermoplastic polyester resin composition described in 1. With respect to 100 parts by weight of the (A) thermoplastic polyester resin,
(B ′) 20-40 parts by weight of a phosphinic acid salt in which the anion moiety is a calcium or aluminum salt of phosphinic acid represented by the following general formula (1 ′) or general formula (2 ′);
(C ′) 2 to 7 parts by weight of an organosiloxane compound in which 50 mol% or more of the organic group bonded to the silicon atom directly or through an oxygen atom is a phenyl group,
(D) 15 to 70 parts by weight of a fibrous reinforcing material, and
(E) The thermoplastic polyester resin composition according to claim 1, comprising 1 to 5 parts by weight of at least one of a metal borate or an antimony compound.
(In the formula, R ¹¹ , R ¹² and R ^{15 to} R ¹⁷ each independently represent an alkyl group having 1 to 4 carbon atoms, and R ¹³ and R ¹⁴ are alkylene groups or phenylene groups having 1 to 4 carbon atoms. N2 represents an integer of 0 to 4.)   The thermoplastic polyester resin composition according to any one of claims 1 to 10, wherein the (A) thermoplastic polyester resin is a polybutylene terephthalate resin.   The manufacturing method of the molded object characterized by injection-molding the thermoplastic polyester resin composition of any one of Claims 1-11.   A molded article produced by the method for producing a molded article according to claim 12.