JP2014031523A - Thermoplastic polyester resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic polyester resin composition excellent in flame resistance, mechanical strength and laser printing property.SOLUTION: A thermoplastic polyester resin composition is produced by compounding (A) 100 pts.wt. of a thermoplastic polyester resin, (B) 5 to 60 pts.wt. of phosphinate represented by the general formula (1) or (2), (C) 0.1 to 20 pts.wt. of organosiloxane and (D) 0.01 to 30 pts.wt. of colemanite, and (C) the organosiloxane is (C-b) an organosiloxane polymer and is a solid state at 25°C, excluding an organosiloxane compound of which 40 mol% or more of an organic group bound to a silicon atom directly or through an oxygen atom is an aryl group.

Description

  The present invention relates to a thermoplastic polyester resin composition having excellent flame retardancy without containing a halogen-based flame retardant, and having excellent molding processability and mechanical properties, and a molded article using the same. . Furthermore, it is related with the thermoplastic polyester resin composition excellent in laser printability.

  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 have become more and more sophisticated, and it has become difficult to cope with conventional prescriptions. For example, recently, electronic parts such as connectors have been reduced in weight and size, and the thickness of molded products has been reduced. Accordingly, the resin composition used for molding may be required to have better mechanical properties and flame retardancy than before in order to cope with this.

  Conventionally, halogen-based flame retardants have been mainly used to improve the flame retardancy of thermoplastic polyester resins. However, a resin composition containing a halogen-based flame retardant may generate dioxins when incineration of used molded products, and it is required to use a non-halogen-based flame retardant. As one of methods for meeting this demand, it has been studied to use a phosphorus compound, in particular, a calcium salt or 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 and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.)

  Patent Document 1 describes the use of this calcium or aluminum salt of phosphinic acid as a flame retardant. However, in this method, it is necessary to add a large amount of a flame retardant in order to obtain good flame retardancy. As a result, there is a problem that moldability and mechanical properties of the resulting resin composition are deteriorated. It was.

  Patent Document 2 describes that an organic nitrogen compound such as melamine cyanurate is used in combination with a calcium or aluminum salt of phosphinic acid as a flame retardant. According to this method, the flame retardancy is considerably improved, but there is a problem that the mold contamination is severe due to remarkably much gas generation during molding.

  Here, as a method for imparting toughness to the resin composition, for example, a low elastic modulus polymer such as an elastomer is blended as described in Patent Document 3, for example. However, since the blending of the elastomer reduces the flame retardancy of the resin composition, it is difficult to achieve both toughness and flame retardancy with this method.

  Patent Document 4 describes that a special organic phosphorus compound is used as a flame retardant, and a flame retardant aid is added thereto. There are many types of flame retardant aids, including those known per se as flame retardants. The flame retardant aid described in this document covers a wide range from organic matter to inorganic matter, but in fact, in the resin composition, the balance of each component is important, and only the flame retardant aid is simply replaced. In this case, it is completely unknown whether or not the same effect and performance are achieved.

  Patent Document 5 describes that when melamine cyanurate and metal borate are mixed in a specific ratio with calcium or aluminum salt of phosphinic acid as a flame retardant, gas generation during molding is improved. There has been a problem that the mold contamination is severe without being remarkably improved by blending a nitrogen-based flame retardant such as melamine cyanurate having a low starting temperature.

  Patent Documents 6 and 7 describe blending a halogen-based flame retardant and a colemanite mineral (calcium borate pentahydrate) into a thermoplastic polyester resin composition.

  As described above, when an additive is added to the thermoplastic polyester resin composition to improve some performance, problems often arise in other performance. On the other hand, there is a demand for a resin composition that is well-balanced in various performances depending on the use of the molded product. For example, a thermoplastic polyester resin composition having high flame retardancy, high mechanical strength, excellent electrical characteristics, reduced mold deposits, and excellent laser printability It has been demanded.

JP-A-8-73720 Japanese Patent Laid-Open No. 11-60924 Japanese Patent Laid-Open No. 7-150022 WO2004 / 061008 JP 2006-117722 A JP 59-202253 A Japanese Patent No. 3456104

As described above, conventionally, various thermoplastic resin compositions have been disclosed, but it has been difficult to form a composition having flame retardancy and excellent balance in various performances.
The object of the present invention is a thermoplastic polyester resin composition under such circumstances, having high flame retardancy, high mechanical strength, excellent electrical characteristics, low mold deposit, laser It aims at providing the composition excellent in printability.

（式中、Ｒ¹及びＲ²は、それぞれ独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ¹同士は同一でも異なっていてもよく、Ｒ³は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの２つ以上の組み合わせからなる基を表し、Ｒ³同士は同一でも異なっていてもよい。ｎは０〜４の整数を表す。）
（２）（Ｃ）オルガノシロキサンが、（Ｃ−ａ）珪素原子に直接又は酸素原子を介して結合している有機基の４０モル％以上がアリール基であるオルガノシロキサン化合物であることを特徴とする（１）に記載の熱可塑性ポリエステル樹脂組成物。
（３）（Ａ）熱可塑性ポリエステル樹脂１００重量部に対する（Ｃ）オルガノシロキサンの配合量が、０．１〜１７重量部であることを特徴とする、（１）または（２）に記載の熱可塑性ポリエステル樹脂組成物。
（４）（Ａ）熱可塑性ポリエステル樹脂１００重量部に対する（Ｄ）コレマナイトの配合量が０．１〜１５重量部であることを特徴とする（１）〜（３）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（５）（Ａ）熱可塑性ポリエステル樹脂１００重量部に対する（Ｄ）コレマナイトの配合量が１．５〜１５重量部であることを特徴とする（１）〜（３）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（６）さらに、（Ｅ）強化充填材を、前記（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、１５０重量部以下の割合で含むことを特徴とする、（１）〜（５）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（７）（Ｃ−ａ）オルガノシロキサンの重量平均分子量が２００〜１００００であることを特徴とする（２）〜（６）いずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（８）（Ｃ−ａ）オルガノシロキサンが、ＲＳｉＯ_1.5（Ｒは有機基を示す。）で表される構造単位を含んでおり、かつ水酸基の含有量が１〜１０重量％のものであることを特徴とする、（２）〜（７）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（９）熱可塑性ポリエステル樹脂がポリエチレンテレフタレート又はポリブチレンテレフタレートであることを特徴とする、（１）〜（８）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（１０）（Ａ）熱可塑性ポリエステル樹脂がポリブチレンテレフタレート樹脂であることを特徴とする、（１）〜（８）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物。
（１１）（１）〜（１０）のいずれか１項に記載の熱可塑性ポリエステル樹脂組成物を射出成形して成る成形品。
（１２）（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、（Ｃ）オルガノシロキサン０．１〜２０重量部および（Ｄ）コレマナイト０．０１〜３０重量部を配合してなるレーザー印字性の改良された樹脂組成物。

（式中、Ｒ¹及びＲ²は、それぞれ独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ¹同士は同一でも異なっていてもよく、Ｒ³は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの２つ以上の組み合わせからなる基を表し、Ｒ³同士は同一でも異なっていてもよい。ｎは０〜４の整数を表す。）
（１３）（Ａ）熱可塑性ポリエステル樹脂１００重量部に対し、（Ｄ）コレマナイト０．０１〜３０重量部を配合してなるレーザー印字性の改良された樹脂組成物。 Under such circumstances, the inventor of the present application has made extensive investigations, and as a result, a flame retardant property is obtained by adding a phosphorus-based flame retardant to the thermoplastic polyester resin and adding a specific organosiloxane and colemanite. The inventors have found that a resin composition excellent in balance as a resin composition can be obtained, and has completed the present invention. In particular, the present invention is technically significant in that it has been found that a composition excellent in laser printability can be obtained without destroying the balance of physical properties of the resin composition by adding colemanite.
Specifically, the above problem has been solved by the following means.
(1) (A) 5 to 60 parts by weight of a phosphinic acid salt represented by the following general formula (1) or (2), and (C) an organosiloxane 0.1 to 100 parts by weight of a thermoplastic polyester resin. ~ 20 parts by weight and
(D) 0.01 to 30 parts by weight of colemanite is blended, and the (C) organosiloxane is (Ca) 40 mol% of the organic group bonded to the silicon atom directly or via an oxygen atom. A thermoplastic polyester resin composition as described above, which is an organosiloxane compound which is an aryl group and / or (Cb) an organosiloxane polymer, which is in a solid state at 25 ° C.

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.)
(2) The (C) organosiloxane is 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. The thermoplastic polyester resin composition according to (1).
(3) The heat described in (1) or (2), wherein the blending amount of (C) organosiloxane with respect to 100 parts by weight of (A) thermoplastic polyester resin is 0.1 to 17 parts by weight. A plastic polyester resin composition.
(4) (A) The blending amount of (D) colemanite with respect to 100 parts by weight of the thermoplastic polyester resin is 0.1 to 15 parts by weight, according to any one of (1) to (3) A thermoplastic polyester resin composition.
(5) (A) The blending amount of (D) colemanite with respect to 100 parts by weight of the thermoplastic polyester resin is 1.5 to 15 parts by weight, described in any one of (1) to (3) A thermoplastic polyester resin composition.
(6) Furthermore, (E) the reinforcing filler is included in a proportion of 150 parts by weight or less with respect to 100 parts by weight of the (A) thermoplastic polyester resin, any of (1) to (5) The thermoplastic polyester resin composition according to item 1.
(7) The thermoplastic polyester resin composition according to any one of (2) to (6), wherein the weight average molecular weight of (Ca) organosiloxane is 200 to 10,000.
(8) (C-a) The organosiloxane contains a structural unit represented by RSiO _1.5 (R represents an organic group) and has a hydroxyl group content of 1 to 10% by weight. The thermoplastic polyester resin composition according to any one of (2) to (7), wherein:
(9) The thermoplastic polyester resin composition according to any one of (1) to (8), wherein the thermoplastic polyester resin is polyethylene terephthalate or polybutylene terephthalate.
(10) The thermoplastic polyester resin composition according to any one of (1) to (8), wherein the (A) thermoplastic polyester resin is a polybutylene terephthalate resin.
(11) A molded article formed by injection molding the thermoplastic polyester resin composition according to any one of (1) to (10).
(12) Improvement of laser printability obtained by blending (C) 0.1-20 parts by weight of organosiloxane and (D) 0.01-30 parts by weight of colemanite with respect to 100 parts by weight of (A) thermoplastic polyester resin. Resin composition.

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.)
(13) A resin composition with improved laser printability, comprising 0.01 to 30 parts by weight of (D) colemanite to 100 parts by weight of (A) thermoplastic polyester resin.

  According to the present invention, a thermoplastic polyester resin composition having high flame retardancy, high mechanical strength, excellent electrical characteristics, low mold deposit, and excellent laser printability is obtained. It became possible to get. In particular, the present invention is extremely significant in that these characteristics are excellent in balance.

FIG. 1 is a schematic view showing a spiral long resin molded product prepared in the present embodiment.

  Hereinafter, the contents of the present invention will be described in detail. 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.

（式中、Ｒ¹及びＲ²は、それぞれ独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ¹同士は同一でも異なっていてもよく、Ｒ³は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの２つ以上の組み合わせからなる基を表し、Ｒ³同士は同一でも異なっていてもよい。ｎは０〜４の整数を表す。） The resin composition of the present invention comprises (A) 5 to 60 parts by weight of a phosphinic acid salt represented by the following general formula (1) or (2) with respect to 100 parts by weight of the thermoplastic polyester resin, (C) It is characterized by blending 0.1-20 parts by weight of organosiloxane and 0.01-30 parts by weight of (D) colemanite.

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.)

By adopting such a composition, a resin molded product having excellent mechanical strength can be obtained while ensuring flame retardancy without substantially using a halogen-based flame retardant.
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 (A) of the present invention is a polycondensation of a dicarboxylic acid compound and a dihydroxy compound, a polycondensation of an oxycarboxylic acid compound, or a polycondensation of a mixture of these compounds. The resulting polyester may be either a homopolyester or a copolyester. Dicarboxylic acid compounds constituting the thermoplastic polyester resin include terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid, diphenyl dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid and other aromatic dicarboxylic acids, 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.

  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.

  In the present invention, the thermoplastic polyester resin is usually a polycondensate composed mainly 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, Those which occupy 70% by weight or more, more preferably 90% by weight or more are used. The dicarboxylic acid compound is preferably an aromatic dicarboxylic acid, and the dihydroxy compound is preferably an aliphatic diol.

Of these, 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 thereof are polybutylene terephthalate and polyethylene terephthalate. In the present invention, polybutylene terephthalate is preferable. 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.
Moreover, in the composition of this invention, a glow wire characteristic can be improved, without reducing an electrical insulation characteristic, by adding a polyethylene terephthalate to a polybutylene terephthalate.

  The intrinsic viscosity of the thermoplastic polyester resin may be appropriately selected and determined. However, it is usually preferably 0.5 to 2 dl / g, and in particular, from the viewpoint of moldability and mechanical properties of the resin composition, 0.6 to It is preferably 1.5 dl / g. If a material having an intrinsic viscosity of less than 0.5 dl / g is used, the mechanical strength of the molded product obtained from the resin composition tends to be low, and conversely if it is greater than 2 dl / g, the fluidity of the resin composition decreases. However, moldability may be reduced.

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

(B) Phosphinate:
The phosphinic acid salt used in the present invention is a salt in which the anion moiety is represented by the following formula (1) or (2), and the cation moiety is preferably calcium or aluminum.

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.)

Examples of the alkyl group represented by R ¹ and R ² include a methyl group, an ethyl group, a propyl group, an isobutyl group, and a pentyl group, and 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 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 arylene group include a phenylene group and a naphthylene group, and examples of the substituent bonded thereto include the same groups 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.

  Especially in this invention, it is preferable to use the calcium or aluminum salt of the phosphinic acid whose anion part is represented by the following formula | equation (1 ') or (2') as a phosphinic acid salt mentioned above.

（式中、Ｒ¹及びＲ²は、それぞれ独立して、炭素数１〜６のアルキル基又は置換されていてもよいアリール基を表し、Ｒ¹同士は同一でも異なっていてもよく、Ｒ³は炭素数１〜１０のアルキレン基、置換されていてもよいアリーレン基、又はこれらの２つ以上の組み合わせからなる基を表し、Ｒ³同士は同一でも異なっていてもよい。ｎは０〜４の整数を表す。）

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.)

  The phosphinic acid salt is blended in an amount of 5 to 60 parts by weight per 100 parts by weight of the (A) thermoplastic polyester resin. If the blending amount is less than 5 parts by weight, it is difficult to sufficiently increase the flame retardancy of the resin composition. Conversely, if the blending amount exceeds 60 parts by weight, the mechanical properties of the resin composition are deteriorated or the mold deposit is large. Become. From the viewpoint of achieving both flame retardancy and mechanical properties, the blending amount is preferably 10 to 50 parts by weight, more preferably 15 to 45 parts by weight, and particularly preferably 20 to 45 parts by weight.

  Preferred phosphinates for use in the present invention include those having an anion moiety represented by the formula (1 ′): calcium dimethylphosphinate, aluminum dimethylphosphinate, calcium ethylmethylphosphinate, aluminum ethylmethylphosphinate, Examples thereof include calcium diethylphosphinate, aluminum diethylphosphinate, calcium methyl-n-propylphosphinate, aluminum methylmethyl-n-propylphosphinate, calcium methylphenylphosphinate, aluminum methylphenylphosphinate, aluminum diisobutylphosphinate and the like.

  As the anion moiety represented by the formula (2 ′), methylene bis (methylphosphinic acid) calcium, methylenebis (methylphosphinic acid) aluminum, phenylene-1,4-bis (methylphosphinic acid) calcium, phenylene-1 In the formula (2 ′), n = 0 is preferable, such as, 4-bis (methylphosphinic acid) aluminum.

  The phosphinic acid salts used in the present invention may be used alone or in combination of two or more in any ratio. Specifically, for example, from the viewpoints of flame retardancy and electrical characteristics, 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 from the resin composition of the present invention, the phosphinic acid salt used in the present invention uses a powder whose 90% by weight or more has a particle size of 100 μm or less, particularly 50 μm or less. Is preferred. 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 product. Here, the particle size is a value obtained by a laser diffraction method.

(C) Organosiloxane In the present invention, the following organosiloxane (Ca) and / or (Cb) is included at a ratio of 0.1 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin.
(Ca) an organosiloxane compound (Cb) organosiloxane polymer in which 40 mol% or more of organic groups bonded to silicon atoms directly or through oxygen atoms are aryl groups, and at 25 ° C. What is in a solid state The organosiloxane used in the present invention may satisfy both of the conditions (Ca) and (Cb), and preferably satisfies at least (Ca) It is.

  These organosiloxanes are preferably 0.1 to 17 parts by weight, more preferably 1.5 to 10 parts by weight, still more preferably 2 to 7 parts by weight, based on 100 parts by weight of the thermoplastic polyester resin. Blend. When the blending amount is small, the desired flame retardancy is not exhibited. Conversely, if the amount is too large, the flame retardancy is reduced. This is presumably because when the amount of the organosiloxane compound in the resin composition increases, the organosiloxane compound itself that is vaporized during the combustion of the resin composition burns, thereby reducing the flame retardancy.

(Ca) Organosiloxane compound:
The thermoplastic polyester resin composition of the present invention needs to contain an organosiloxane compound having an aryl group. 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.

  The organosiloxane compound used in the present invention is an organic silanol or a polymer thereof, and forms an organic group bonded to a silicon atom directly or through an oxygen atom, that is, a Si—C or Si—O—C bond. 40 mol% or more, preferably 50 mol% or more of the organic group is an aryl group. 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. Also good. Among these aryl groups, a phenyl group is preferable.

  A 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 burns. 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.

  Furthermore, as the phenyl group, a part thereof may be substituted with a hydroxyl group, but if the content of the hydroxyl group in the organosiloxane compound is too much, it is easily hydrolyzed under high temperature and high humidity. It is preferably 10% by weight.

  As described above, monomers and oligomers can be used as the organosiloxane compound, but those having a low molecular weight are liable to cause mold deposits, so the weight average molecular weight is preferably 200 or more, more preferably 800 or more, and particularly preferably 1000 or more. It is more preferable to use the following polymer. On the other hand, even if the molecular weight is too large, compatibility with the polyester resin is lowered, so that it may be difficult to prepare a uniform resin composition. Therefore, the weight average molecular weight of the organsiloxane compound is 10,000 or less, preferably 5000 or less. Here, the weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography (GPC).

  Of the organosiloxane compounds, a so-called silicone resin is particularly preferable. The silicone resin is usually a polymer composed of the following D units, T units, Q units, and the like, and the ends may be sealed with M units.

Among the silicone resins used in the present invention, those containing T units represented by RSiO _1.5 are preferred, especially those containing a large amount of T units, specifically those containing 50 mol% or more, especially those containing 80 mol% or more. In particular, those consisting of all T units except for the end-capping group 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 formulas (3) to (6), R represents 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 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, and among them, a methyl group is preferable. Examples of the alkenyl group include a vinyl group, a butenyl group, and an aryl group. Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, and a tolyl group, and among them, a phenyl group is preferable. In addition, 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 above formula, the 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—Ov are bonded to form Si—O—. Si bonds are formed. Examples of the hydrocarbon group bonded to the oxygen atom are the same as those shown as R in the above formula.

  In the present invention, among the above-described silicone resins, 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. As described above, those in which 50 mol% or more is an optionally substituted aryl group, preferably a phenyl group, are used.

Silicone resins having an aryl group content of less than 40 mol% have low compatibility with thermoplastic polyester resins, and the resulting resin composition may not exhibit 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.

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

(Cb) Organosiloxane polymer which is in a solid state at 25 ° C. An organosiloxane polymer is a polymer of an organosiloxane compound or an organosiloxane compound and a compound reactive with this (vinyl compound, Means a copolymer with a carbonate compound or the like). Moreover, being in a solid state at 25 ° C. means being in a state where it does not flow as a liquid at 25 ° C. and can be handled as a solid. Specific examples thereof include the following (Cb-1) to (Cb-4).

(Cb-1) An organosiloxane polymer supported on inorganic fine particles.
(Cb-2) A chain polymer of organosiloxane having a softening point higher than 25 ° C.
(Cb-3) An organosiloxane polymer that is crosslinked.
(Cb-4) Polyorganosiloxane core graft copolymer

(Cb-1) Organosiloxane polymer supported on inorganic fine particles (hereinafter sometimes referred to as supported polymer)
Examples of the inorganic fine particles include silica powder, titanium oxide powder, mica powder, clay powder, kaolin powder, magnesium hydroxide powder, and aluminum hydroxide powder, and silica powder is preferably used. Silica powders include dry process silica obtained by a gas phase process and wet process silica obtained by a wet process, both of which can be used.

As for the particle size of the inorganic fine particles, 90% by weight or more is preferably in the range of 0.01 to 100 μm, particularly 0.1 to 30 μm, as measured by a laser diffraction method. Among these, a powder having a specific surface area of 50 m ² / g or more is preferable, and a powder having a specific surface area of 100 m ² / g or more is more preferable. The inorganic fine particles may be treated with a surface treatment agent such as a silane coupling agent, whereby the bond with the organosiloxane polymer can be further strengthened. When the polymer has a functional group such as an epoxy group or a methacryl group, the bond is further strengthened.

  The organosiloxane polymer may be a polymer of an organosiloxane compound or a copolymer having a carbon chain as a copolymerization component in the molecular chain. Examples of the copolymer component include a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The organosiloxane polymer may have a functional group.

  As the functional group, a methacryl group or an epoxy group is preferable, and the polymer having these functional groups has good dispersibility because of good compatibility with the thermoplastic polyester resin, and has a high effect of improving toughness. Furthermore, since a crosslinking reaction with the polyester resin can be caused at the time of combustion, a reduction in flame retardancy is suppressed. The organosiloxane polymer may be linear or branched, but is preferably linear.

  The amount of the functional group in the organosiloxane polymer is usually about 0.01 to 1 mol%. It is more preferable that it is 0.03-0.5 mol%, especially 0.05-0.3 mol%. The method for supporting the organosiloxane polymer on the inorganic fine particles is arbitrary. For example, the polymer may be dissolved in a solvent and impregnated with inorganic fine particles, and then dried. The supported amount is usually 0.1 to 10 g per 1 g of inorganic fine particles, but 0.4 to 4 g is preferable.

  When an alkoxysilane having a functional group such as an epoxy group or the like is used as an adhesion promoter during loading, the bond between the inorganic fine particles and the polymer can be further strengthened. The bond between the inorganic fine particles and the polymer may be a simple physical bond such as adsorption or absorption, or may be caused by a chemical reaction. It is considered that the polymer supported on the inorganic fine particles forms a mild cross-linked structure with the thermoplastic polyester resin by synergistic action with the inorganic fine particles, thereby contributing to the improvement of flame retardancy as well as toughness.

  As the supported polymer, it is preferable to use a polymer in which an organosiloxane polymer is supported on silica. Commercially available products include “Si powder” and “Trefill F” from Toray Dow Corning.

(Cb-2) Organosiloxane polymer having a softening point of 25 ° C. or higher A typical organosiloxane polymer having a softening point of more than 25 ° C. is a so-called silicone resin, and the composition thereof is represented by the following formula (3). Indicated by
(R ¹ SiO _3/2 ) _a (R ² ₂ SiO _2/2 ) _b (R ³ ₃ SiO _1/2 ) _c (SiO _4/2 ) _d (XO _1/2 ) _e (3)

In Formula (3), X is a hydrogen atom or an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, or a heptyl group. R ¹ , R ² , and R ³ may be different from each other and are a hydrocarbon group or an epoxy group-containing organic group.

  Examples of the hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group; an alkenyl group such as a vinyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group; Aryl groups such as phenyl group, tolyl group, xylyl group, naphthyl group; aralkyl groups such as benzyl group, phenethyl group; chloromethyl group, 3-chloropropyl group, 3,3,3-trifluoropropyl group, nonafluorobutyl Examples include halogenated alkyl groups such as an ethyl group.

Examples of the epoxy-containing organic group include 2,3-epoxypropyl group, 3,4-epoxybutyl group, 4,5-epoxypentyl group and the like; 2-glycidoxyethyl group, 3-glycid Glycidoxyalkyl groups such as xylpropyl group and 4-glycidoxybutyl group; Epoxycyclohexylalkyl groups such as 2- (3,4-epoxycyclohexyl) ethyl group and 3- (3,4-epoxycyclohexyl) propyl group Is mentioned. The epoxy group-containing organic group is not essential, but the proportion of the epoxy group-containing organic group in the total of R ^{1 to} R ³ in formula (3) is preferably 0.1 to 40 mol%.

  If the content is less than 0.1 mol%, bleeding tends to occur during molding of a resin composition obtained by blending the content. Moreover, when it exceeds 40 mol%, there exists a tendency for the mechanical characteristics of a molding to fall.

Also, since when there is a phenyl group excellent in affinity for the thermoplastic polyester resin is preferably the formula (3) 10 mol% or more of total R ¹ to R ³ in the phenyl group, among others of R ¹ 10 It is preferable that at least 30 mol%, particularly at least 30 mol% is a phenyl group.

Furthermore, in order to reduce the steric hindrance of the organopolysiloxane molecule containing a bulky phenyl group and improve the spatial freedom, to facilitate the overlapping of the phenyl groups and enhance the flame retardancy, the formula (3) as R ¹ is in, so preferably it has a methyl group or a vinyl group, the proportion of the phenyl groups occupied in R ¹ is preferably 10 to 95 mol%, more preferably from 30 to 90 mol%.

  In Expression (3), a is a positive number, and b, c, d, and e are each 0 or a positive number. b / a is a number from 0 to 10, c / a is a number from 0 to 0.5, d / (a + b + c + d) is a number from 0 to 0.3, and e / (a + b + c + d) is from 0 to 0. It is a number of 0.4. A silicone resin having a b / a exceeding 10 has a softening point of 25 ° C. or lower and a low affinity with a resin. Moreover, the silicone resin in which d / (a + b + c + d) exceeds 0.3 tends to reduce the dispersibility of the resin.

  The weight average molecular weight of the organosiloxane polymer is preferably 500 to 50,000, particularly 500 to 10,000. Although the softening point should just be 25 degreeC or more, it is preferable that it is 40-250 degreeC, especially 40-150 degreeC. Silicone resins having a softening point of less than 25 ° C. may cause bleed when molding a resin composition obtained by blending this resin, contaminate the mold, reduce the mechanical properties of the molded product, There is a tendency that the silicone resin oozes out on the surface of the molded article during long-term use.

  In addition, a silicone resin having a too high softening point tends to be difficult to uniformly disperse during the preparation of the resin composition. The softening point is the temperature at which the silicone resin melts and turns into droplets when heated at a heating rate of 1 ° C./min using a melting point measuring machine (micro melting point apparatus manufactured by Yanagimoto Seisakusho Co., Ltd.). Is the softening point.

The silicone resin represented by the above formula (1) is, for example, a unit represented by (i) formula: R ⁴ SiO _3/2 (wherein R ⁴ is a monovalent hydrocarbon group), (ii) A unit represented by the formula: R ⁵ ₂ SiO _2/2 (wherein R ⁵ are the same or different monovalent hydrocarbon groups), (iii) Formula: R ⁶ ₃ SiO _1/2 (formula In which R ⁶ are the same or different monovalent hydrocarbon groups), and (iv) at least one selected from the group consisting of units represented by the formula: SiO _4/2 One or a mixture of silane or siloxane having a unit and a general formula: R ⁷ R ⁸ _f Si (OR ⁹ ) _(3-f) (wherein R ⁷ is an epoxy group-containing organic group, R ⁸ is a monovalent hydrocarbon group, R ⁹ is an alkyl group, f is an epoxy group-containing Al represented by 0, 1 or 2.) The Kishishiran or partial hydrolyzate thereof can be prepared by reacting with a basic catalyst.

  In the above production method, the main component is one or a mixture of two or more silanes or siloxanes having at least one unit selected from the group consisting of units represented by the above (i) to (iv). These silanes or siloxanes include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, vinyltrimethoxysilane, phenyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane. Dimethyldimethoxysilane, methylphenyldimethoxysilane, methylvinyldimethoxysilane, diphenyldimethoxysilane, dimethyldiethoxysilane, methylphenyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, dimethoxydiethoxysilane, Examples include decomposition condensates.

In addition, an epoxy group-containing alkoxysilane represented by the general formula: R ⁷ R ⁸ _f Si (OR ⁹ ) _(3-f) to be copolymerized with these silanes and siloxanes or a partially hydrolyzed product thereof is added to the silicone resin with an epoxy group. It is a component to introduce. R ⁷ in the formula is an epoxy group-containing organic group, and examples thereof include the same epoxy group-containing organic group as R ¹ , R ² , or R ³ .

Moreover, R < ⁸ > in a formula is a monovalent hydrocarbon group, and the monovalent hydrocarbon group similar to said R < ¹ >, R < ² > or R < ³ > is illustrated. R ⁹ in the formula is an alkyl group, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. F in the formula is 0, 1, or 2, preferably 0.

  As such an epoxy group-containing alkoxysilane, 3-glycidoxypropyl (methyl) dimethoxysilane, 3-glycidoxypropyl (methyl) diethoxysilane, 3-glycidoxypropyl (methyl) dibutoxysilane, 2 -(3,4-epoxycyclohexyl) ethyl (methyl) dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl (phenyl) diethoxysilane, 2,3-epoxypropyl (methyl) dimethoxysilane, 2,3- Epoxypropyl (phenyl) dimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropyltributoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 2- (3,4 Epoxycyclohexyl) ethyl triethoxysilane, 2,3-epoxypropyl trimethoxysilane, and 2,3-epoxypropyl triethoxysilane.

  Examples of the basic catalyst include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and cesium hydroxide; alkali metal alkoxides such as sodium-tert-butoxide, potassium-tert-butoxide, and cesium-tert-butoxide. An alkali metal silanol compound such as a sodium silanolate compound, a potassium silanolate compound, or a cesium silanolate compound; Preferably, a potassium-based or cesium-based basic catalyst is used. In the reaction, water may be added as necessary.

  During the reaction, cleavage and recombination of siloxane bonds occur randomly by the equilibration reaction, and as a result, the resulting epoxy group-containing silicone resin is in an equilibrium state. The reaction temperature is preferably 80 ° C. to 200 ° C. because the equilibration reaction does not proceed sufficiently when the reaction temperature is low, and the silicon atom-bonded organic group is thermally decomposed when the reaction temperature is too high, In particular, the temperature is preferably 100 ° C to 150 ° C.

  Further, by selecting an organic solvent having a boiling point of 80 to 200 ° C., the equilibration reaction can be easily performed at the reflux temperature. The equilibration reaction can be stopped by neutralizing the basic catalyst. For this neutralization, it is preferable to add a weak acid such as carbon dioxide or carboxylic acid. The salt produced by neutralization can be easily removed by filtration or washing with water.

(Cb-3) Crosslinked organosiloxane polymer This is a so-called silicone elastomer, which is synthesized by addition reaction curing, condensation reaction curing, radical reaction curing with an organic peroxide, and ultraviolet irradiation curing. Among these, those obtained by addition reaction curing or condensation reaction curing are preferable. Most preferred is an addition reaction curable silicone elastomer composition.

  The addition reaction curable silicone elastomer composition refers to a composition in which functional groups in two types of organopolysiloxane are bonded and crosslinked by an addition reaction to form an elastomer. Typical examples include silicone elastomer compositions comprising an organopolysiloxane containing an aliphatic unsaturated group such as a vinyl group or a hexenyl group, an organohydrogenpolysiloxane, and a platinum group compound catalyst.

  Aliphatic unsaturated group-containing organopolysiloxanes include vinyl dimethylsiloxy group-blocked dimethylpolysiloxane at both ends, vinyldimethylsiloxy group-blocked dimethylsiloxane / methylvinylsiloxane copolymer at both ends, and vinylmethylphenylsiloxy group-blocked dimethylsiloxane at both ends. -A methylphenylsiloxane copolymer is mentioned.

  Examples of the organohydrogenpolysiloxane include trimethylsiloxy group-capped methylhydrogen polysiloxane at both ends, trimethylsiloxy group-capped dimethylsiloxane / methylhydrogensiloxane copolymer, dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydro at both ends. Examples include a disiloxane copolymer and methylhydrogencyclopolysiloxane.

  Examples of the platinum group compound catalyst include fine-particle platinum, chloroplatinic acid, a platinum-olefin complex, a platinum-vinylsiloxane complex, a platinum-diketone complex, a palladium compound catalyst, and a rhodium compound catalyst. Among these, a platinum compound catalyst is preferable from the viewpoint of catalytic activity. This addition reaction curable silicone elastomer composition is usually cured by heating from the viewpoint of curability and productivity. In addition, the addition reaction curable silicone elastomer composition comprises an organopolysiloxane containing an aliphatic unsaturated group such as a vinyl group and an organopolysiloxane containing a mercaptoalkyl group. The composition which hardens | cures is mentioned.

  Condensation reaction curable type silicone elastomer composition is an elastomer by functional groups in two types of organopolysiloxanes, or functional groups in organopolysiloxanes and silicon compounds such as silica and silane, which are linked by a condensation reaction and crosslinked. Refers to the composition. Examples of the condensation reaction curable silicone elastomer composition include a dehydrogenation condensation type, a dehydration condensation type, a deacetic acid condensation type, a deoxime condensation type, a dealcohol condensation type, a deamidation condensation type, a dehydroxylamine condensation type, a dehydroxylation type, and a dehydration condensation type. An acetone condensation type composition is mentioned.

  Representative examples of the dehydrogenative condensation reaction curable silicone elastomer composition include a composition comprising a condensation reaction catalyst such as a silanol group-blocked diorganopolysiloxane, an organohydrogenpolysiloxane, and a heavy metal salt of an organic acid. As both-end silanol-blocked diorganopolysiloxane, both-end silanol-blocked dimethylpolysiloxane, both-end silanol-blocked dimethylsiloxane / methylphenylsiloxane copolymer, both-end silanol-blocked methyl (3,3,3-trimethyl) Fluoropropyl) polysiloxane. Since this diorganopolysiloxane has an action of suppressing the condensation reaction, a part of the terminal silanol group may be alkoxylated.

  Examples of the organohydrogenpolysiloxane that is a crosslinking agent include dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, trimethylsiloxy group-blocked methylhydrogenpolysiloxane, and methylhydrogencyclopolysiloxane. Illustrated. Examples of the condensation reaction catalyst include dibutyltin dilaurate, dibutyltin diacetate, tin octenoate, dibutyltin dioctate, tin laurate, ferric stanooctenoate, lead octenoate, lead laurate, and zinc octenoate.

  The dehydrogenative condensation curable silicone elastomer composition needs to be cured by heating from the viewpoints of curability and productivity. However, the dehydration condensation type, the deacetic acid condensation type, the deoxime condensation type, the dealcohol condensation type, The deamidation-condensation type, dehydroxylamine condensation-type, and deacetone-condensation type silicone elastomer compositions can be cured at room temperature into an elastomer in the presence of moisture. Among moisture-curable silicone elastomer compositions, silicone water-based elastomers that can form elastomers by removing water are particularly useful.

  This silicone water-based elastomer usually has (a) a substantially linear organopolysiloxane having at least two silanol groups in one molecule, (b) colloidal silica, alkali metal silicate, hydrolysis An aqueous organopolysiloxane emulsion composition comprising a cross-linking agent selected from the group consisting of possible silanes and partial hydrolysis condensates thereof, (c) a curing catalyst, (d) an emulsifier and (e) water is used.

  Here, the organopolysiloxane of component (a) is crosslinked by the action of component (b) to form a rubbery elastic body, and is a polymer having at least two silanol groups in one molecule. The position of the silanol group is not particularly limited, but it is preferably present at both ends. The organic group bonded to the silicon atom other than the silanol group is preferably an unsubstituted or substituted monovalent hydrocarbon group, such as an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; a vinyl group, an allyl group, or the like. Examples include alkenyl groups; aryl groups such as phenyl groups; aralkyl groups such as benzyl groups; alkaryl groups such as styryl groups and tolyl groups; and cycloalkyl groups such as cyclohexyl groups and cyclopentyl groups.

  Further, groups in which some or all of hydrogen atoms of these groups are substituted with halogen atoms such as fluorine, chlorine and bromine, such as 3-chloropropyl group, 3,3,3-trifluoropropyl group and the like can also be mentioned. . Among these, a methyl group, a vinyl group, and a phenyl group are preferable, and a methyl group is more preferable. However, all of them are not necessarily the same and may be a combination of different monovalent hydrocarbon groups. Moreover, substantially linear means that it may be a straight chain partially having a branched chain.

  The molecular weight of the organopolysiloxane is not particularly limited, but is preferably 5000 or more. This is because a reasonable tensile strength and elongation can be obtained when the molecular weight is 3000 or more, but the most preferable tensile strength and elongation can be obtained only when the molecular weight is 5000 or more. However, from the viewpoint of the possibility of emulsification into an emulsion, it is preferably 1000000 or less.

  Specific examples of such organopolysiloxanes include dimethylpolysiloxane, methylphenylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, methylvinylpolysiloxane, dimethylsiloxane / methyl, with both ends of the molecular chain blocked with silanol. A vinyl siloxane copolymer is mentioned. Such an organopolysiloxane can be synthesized, for example, by a method of hydrolytic condensation of a cyclic or branched organopolysiloxane or a method of hydrolyzing one or more of diorganodihalogenosilanes.

  The crosslinking agent of component (b) acts as a crosslinking component of component (a), and includes colloidal silica, alkali metal silicate, hydrolyzable silane, or a partial hydrolysis condensate thereof. Examples of the colloidal silica include fumed colloidal silica, precipitated colloidal silica, or colloidal silica having a particle diameter of 0.0001 to 0.1 μm stabilized with sodium, ammonia or aluminum ions. The blending amount of the colloidal silica is preferably 1 to 150 parts by weight, more preferably 1 to 70 parts by weight with respect to 100 parts by weight of the organopolysiloxane as the component (a).

  Examples of the alkali metal silicate include lithium silicate, sodium silicate, potassium silicate, and rubidium silicate. The blending amount of the alkali metal silicate is preferably 0.3 to 30 parts by weight, and more preferably 0.3 to 20 parts by weight with respect to 100 parts by weight of the organopolysiloxane of the component (a). As the hydrolyzable silane, a silane having at least three hydrolyzable groups bonded to a silicon atom in one molecule is used. This is because an elastomer cannot be obtained when the number is less than three.

  Examples of the hydrolyzable group include alkoxy groups such as methoxy group, ethoxy group and butoxy group; acyloxy groups such as acetoxy group; substituted or unsubstituted acetamide groups such as acetamide group and N-methylacetamide group; propenoxy An alkenyloxy group such as a group; a substituted amino group such as an N, N-diethylamino group; and a ketoxime group such as a methylethylketoxime group.

  Specific examples include methyltrimethoxysilane, vinyltrimethoxysilane, normal propyl orthosilicate, ethylpolysilicate, propylpolysilicate, methyltri (propanoxy) silane, and methyltri (methylethylketoxime) silane. Two or more kinds of such silanes can be mixed and used. The amount of the hydrolyzable silane or its partially hydrolyzed condensate is preferably 1 to 150 parts by weight with respect to 100 parts by weight of the component (a) organopolysiloxane.

  The component (c) curing catalyst is a component that accelerates the condensation reaction between the component (a) organopolysiloxane and the component (b) crosslinking agent, such as dibutyltin dilaurate, dibutyltin diacetate, and tin octenoate. Organic acid metal salts such as dibutyltin dioctate, tin laurate, ferric stanooctenoate, lead octenoate, lead laurate, zinc octenoate; tetrabutyl titanate, tetrapropyl titanate, dibutoxy titanium bis (ethyl acetoacetate), etc. And titanic acid esters; amine compounds such as n-hexylamine and guanidine or hydrochloric acids thereof.

  These curing catalysts are preferably preliminarily made into an emulsion form by using an emulsifier and water by an ordinary method. The addition amount of the curing catalyst is preferably 0.01 to 1.5 parts by weight, and more preferably 0.05 to 1 part by weight with respect to 100 parts by weight of the organopolysiloxane of component (a).

  The emulsifier of component (d) is a component that mainly emulsifies the organopolysiloxane of component (a), and examples include an anionic emulsifier, a nonionic emulsifier, and a cationic emulsifier. Examples of the anionic emulsifier include higher fatty acid salts, higher alcohol sulfates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl phosphinates, and polyethylene glycol sulfates.

  Examples of the nonionic emulsifier include polyoxyethylene alkylphenyl ethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyalkylene fatty acid esters, polyoxyethylene polyoxypropylenes, and fatty acid monoglycerides. It is done.

Examples of the cationic emulsifier include aliphatic amine salts, quaternary ammonium salts, and alkylpyridinium salts. These emulsifiers may be used alone or in a mixture of two or more. The amount of the emulsifier is preferably 2 to 30 parts by weight with respect to 100 parts by weight of the organopolysiloxane of component (a).

  The amount of water in component (e) is determined by emulsifying the organopolysiloxane in component (a), the crosslinking agent in component (b), and the curing catalyst in component (c) by the action of the emulsifier in component (d). The amount is not particularly limited as long as it is sufficient to prepare an aqueous emulsion.

  This silicone water-based elastomer emulsion can be prepared by uniformly mixing the components (a) to (e). For example, dimethylpolysiloxane having silanol groups at both ends is emulsified in water using an emulsifier such as a homomixer, homogenizer, or colloid mill in the presence of an emulsifier, and then a crosslinking agent such as colloidal silica or a curing catalyst is added. Both ends are mixed with each other by emulsifying in water using a cyclic diorganopolysiloxane such as octamethylcyclotetrasiloxane as an emulsifier, and then polymerizing under heating by adding a ring-opening polymerization catalyst. There is a method in which an emulsion of dimethylpolysiloxane blocked with is prepared, and a cross-linking agent such as colloidal silica or a curing catalyst is added thereto and mixed.

  Moreover, after preparing the base emulsion which consists of (a)-(e) component, the emulsion which was extremely excellent in storage stability can be obtained by adjusting the pH to 9-12. Examples of the pH adjuster include amines such as dimethylamine and ethylenediamine; and alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. Among these, organic amines are preferable, and examples of organic amines other than the above include monoethanolamine, triethanolamine, morpholine, and 2-amino-2-methyl-1-propanol. After adjusting the pH in this way, it is preferable to age at a constant temperature for a fixed period.

  The aging temperature is preferably a temperature at which the emulsion is not broken, that is, a range of 10 to 60 ° C, and more preferably a range of 15 to 50 ° C. The aging period is set according to the aging temperature, and for example, it is preferably 1 week or more under the temperature condition of 25 ° C. and 4 days or more under the temperature condition of 40 ° C.

  The organopolysiloxane emulsion thus obtained is excellent in storage stability at room temperature, and can be easily cured at room temperature to form an elastomer by removing water. On the other hand, when storage stability at room temperature is not required, the pH of the base emulsion may be less than 9. In addition, components other than those described above, for example, fillers, thickeners, pigments, dyes, heat-resistant agents, preservatives, penetrating aids such as aqueous ammonia, and the like can be appropriately added to the organopolysiloxane emulsion.

  In particular, when colloidal silica is not used as the crosslinking agent for the component (b), the viscosity of the organopolysiloxane emulsion is poor and it is difficult to obtain a thick elastomer. , Calcium carbonate, magnesium oxide, zinc dioxide, titanium dioxide powder, carbon black and the like are preferably added.

  Furthermore, these fillers are preferably colloidal because when they are colloidal, the tensile strength and elongation of the elastomer produced by the removal of moisture increase. Moreover, as a thickener, carboxymethylcellulose, methylcellulose, hydroxyethylcellulose, polyvinyl alcohol, polyacrylic acid, etc. can be used.

  In addition to this, the moisture-curable silicone elastomer composition is mainly composed of the above-mentioned both-end silanol-blocked diorganopolysiloxane (preferably having a viscosity at 25 ° C. of 1000 to 60000 centistokes), and is crosslinked. Deacetic acid condensation type silicone elastomer composition obtained by blending, for example, vinyl triacetoxysilane as an agent, dibutyltin diacetate or dibutyltin dilaurate as a catalyst, and further adding reinforcing fillers such as aerosil and kneading uniformly. In this deacetic acid condensation type composition, a deoxime condensation type silicone elastomer composition in which vinyltriacetoxysilane is replaced with vinyltrioximesilane, and similarly, vinyltriacetoxysilane is replaced with tetraethoxysilane or the like. Alcohol condensation type silicone elastomer composition. The cross-linking agent used is not limited to the cross-linking system as described above as long as it can elastomerize the silanol-blocked diorganopolysiloxane.

  Examples of the radical reaction curable silicone elastomer composition include a composition comprising an organopolysiloxane, a reinforcing filler and an organic peroxide, and additional fillers, heat resistance agents, flame retardants, pigments, organic solvents as additional components. Etc. can be contained. As the organopolysiloxane, both ends are blocked with trimethylsiloxy group, dimethylvinylsiloxy group, methylphenylvinylsiloxy group or silanol group, and the main chain is dimethylpolysiloxane, dimethylsiloxane / methylphenylsiloxane copolymer, dimethylsiloxane / Examples include raw rubber-like polymers such as methylvinylsiloxane copolymer, dimethylsiloxane / methylphenylsiloxane / methylvinylsiloxane copolymer, and methyl (3,3,3-trifluoropropyl) / methylvinylsiloxane copolymer. .

  An example of the reinforcing filler is fumed silica. Examples of organic peroxides include benzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl- Examples include 2,5-di (t-butylperoxy) hexene. This radical reaction curable silicone elastomer composition is usually cured by heating from the viewpoint of curability and productivity.

  In addition to this, the radical reaction curable silicone elastomer composition mainly comprises an organopolysiloxane raw rubber and a reinforcing filler, and contains additional fillers, heat-resistant agents, flame retardants, pigments, organic solvents and the like as additional components. And a composition that is cured by irradiation with β rays or γ rays, or a composition that is cured by irradiation with ultraviolet rays, which is composed of a silicon-bonded alkenyl group-containing organopolysiloxane, a sensitizer, and a reinforcing filler.

  The average primary particle size of the silicone elastomer is preferably 0.1 to 100 μm, more preferably 2 to 15 μm. Commercially available products include the Trefill E series manufactured by Toray Dow Corning Co., Ltd., specifically, Trefill E-500, E-505C, Trefill E-506S, Trefill E-507, Trefill E-508, E-600. , E-601, E-606 and the like.

(Cb-4) Polyorganosiloxane core graft copolymer Polyorganosiloxane core graft copolymer is a polyfunctional monomer and other copolymerizable monomers in the presence of polyorganosiloxane particles. A vinyl monomer composed of a polymer is polymerized to form a cross-linked structure in which the polyorganosiloxane component and the vinyl polymer component are intertwined with each other, and the vinyl monomer is further polymerized to form a shell. This is a composite rubber-based multilayer structure polymer in which (shell) is formed.

  The polyorganosiloxane particles may be modified polyorganosiloxanes containing other (co) polymers as well as particles composed only of polyorganosiloxanes. That is, the polyorganosiloxane particle may contain, for example, 5% by weight or less of polybutyl acrylate, butyl acrylate-styrene copolymer, etc. It is preferable from the viewpoint of flame retardancy.

  The polyorganosiloxane particles preferably have a number average particle diameter of 0.008 to 0.6 μm determined from observation with an electron microscope. The number average particle diameter is more preferably 0.01 to 0.2 μm, particularly preferably 0.01 to 0.15 μm. Those having an average particle diameter of less than 0.008 μm are difficult to obtain, and those having an average particle diameter exceeding 0.6 μm tend to deteriorate the flame retardancy of a resin composition using the same.

  The polyorganosiloxane particles have a toluene insoluble content (the amount of toluene insoluble when 0.5 g of the particles are immersed in 80 ml of toluene at room temperature for 24 hours) of 95% or less, more preferably 50% or less, especially 20% or less. Is preferable from the viewpoint of flame retardancy and impact resistance.

  Specific examples of the polyorganosiloxane particles include siloxanes selected from dimethylsiloxane, methylphenylsiloxane, diphenylsiloxane, etc., alone or in combination of two or more, bifunctional silane compounds, and vinyl polymerizable group-containing silane compounds. Can be obtained by copolymerization with a silane compound having three or more functional groups.

  A polyfunctional monomer which is one of vinyl monomers is a compound containing two or more polymerizable unsaturated bonds in the molecule. Specific examples thereof include allyl methacrylate, triallyl cyanurate, isocyanuric acid. Examples include triallyl, diallyl phthalate, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and divinylbenzene. These may be used alone or in combination of two or more. Among these, use of allyl methacrylate is particularly preferable from the viewpoints of economy and effects.

  Examples of other copolymerizable monomers that are vinyl monomers include aromatic vinyl monomers such as styrene, α-methyl styrene, paramethyl styrene, parabutyl styrene, acrylonitrile, methacrylo Vinyl cyanide monomers such as nitrile, methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, glycidyl acrylate, hydroxyethyl acrylate, hydroxybutyl acrylate, methacrylic acid (Meth) acrylic acid ester monomers such as methyl, ethyl methacrylate, butyl methacrylate, lauryl methacrylate, glycidyl methacrylate, hydroxyethyl methacrylate, itaconic acid, (meth) acrylic acid, fumaric acid, maleic acid, etc. Carboxyl group-containing vinyl Monomers, and the like. These may be used alone or in combination of two or more. From the viewpoint of reactivity and stability, it is preferable to use a (meth) acrylic acid ester monomer.

  The vinyl monomer forming the shell layer ensures compatibility between the graft copolymer and the resin when the graft copolymer is blended with the thermoplastic polyester resin, so that the graft copolymer is evenly mixed with the resin. It is also a component having an effect of dispersing. For this reason, it is preferable to mainly use the above (meth) acrylic acid ester monomer for the vinyl monomer forming the shell layer.

  As the polyorganosiloxane core graft copolymer, a polymer produced by continuous multi-stage seed polymerization in which the polymer in the previous stage is sequentially coated with the polymer in the subsequent stage is preferable. The basic polymer structure includes an inner core layer having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, which are crosslinking components having a low glass transition temperature, are intertwined with each other, and a matrix component of the resin composition It is a multilayer structure polymer which has an outermost shell layer which consists of an alkyl (meth) acrylate type polymer substance which improves adhesiveness. Furthermore, the innermost core layer is formed of a polymer composed of an aromatic vinyl monomer, and the intermediate layer is formed of a polymer having a structure in which a polyorganosiloxane component and a polyalkyl (meth) acrylate component are intertwined with each other. A polymer having a three-layer structure in which the outermost shell layer is formed of an alkyl (meth) acrylate polymer can also be used.

  The alkyl group of the alkyl (meth) acrylate has about 1 to 8 carbon atoms. Examples of such an alkyl group include an ethyl group, a butyl group, and a 2-ethylhexyl group. The alkyl (meth) acrylate polymer may be crosslinked with a crosslinking agent such as an ethylenically unsaturated monomer. Examples of the crosslinking agent include alkylene diol di (meth) acrylate and polyester di (meth) acrylate. , Divinylbenzene, trivinylbenzene, triallyl cyanurate, allyl (meth) acrylate, and the like.

  The polyorganosiloxane core graft copolymer is used in the presence of 40 to 90 parts by weight of polyorganosiloxane particles, preferably 60 to 80 parts by weight, more preferably 60 to 75 parts by weight. 5 to 10 parts by weight, preferably 1 to 5 parts by weight, more preferably 2 to 4 parts by weight, and 5 to 50 parts by weight of vinyl monomer for shell layer, preferably 10 to 39 parts by weight, More preferably, it is obtained by polymerizing 15 to 38 parts by weight so that the total amount becomes 100 parts by weight.

  Whether the amount of polyorganosiloxane particles is too small or too large, the flame retarding effect of the resin composition obtained using these particles tends to be low. Moreover, when there are too few vinylic monomers for cores, there exists a tendency for a flame-retarding effect and a toughness improvement effect to become low, and when too large, there exists a tendency for the toughness improvement effect to become low. Further, if the vinyl monomer for the shell layer is too little or too much, the flame retarding effect tends to be low. As such a polyorganosiloxane core graft copolymer, commercially available products such as METABRENE S-2001, S-2200 or SRK-200 manufactured by Mitsubishi Rayon Co., Ltd. may be used.

(D) Colemanite:
In the thermoplastic polyester resin composition of this invention, a colemanite is included in the ratio of 0.01-30 weight part with respect to 100 weight part of thermoplastic resins. Surprisingly, the laser printability is significantly improved by including colemanite. Heretofore, it has been known to add colemanite to a resin composition, but it has not been predicted that laser printability will be improved by adding colemanite. In particular, in the resin composition, it is known that the balance of physical properties such as fluidity is easily lost by adding an additive. However, even if colemanite is added to the composition of the present invention, such a balance of physical properties is obtained. Is extremely significant in that it is maintained. Furthermore, the inventors of the present application have found a tendency to suppress a decrease in fluidity by adding colemanite. In addition, according to the study of the present inventor, it was confirmed that the laser printability was improved in the composition of the present invention even when (B) phosphinic acid salt was not added. Therefore, when using for the use which does not require a flame retardance, it can also be set as the composition which does not add (B) phosphinic acid salt in the composition of this invention.

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

  The colemanite used in the present invention is a hydrous calcium borate mineral as a mineral, for example, which forms in evaporite deposits to form short columnar crystals and pseudorhombic crystals belonging to the monoclinic system. Either a dense lump or a round aggregate 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 a colemanite used for this invention, 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 the colemanite used in the present invention, for example, those sold under a trade name such as Koleman Material Colemanite, Kinsei Matec UBP or the like can be used. 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 amount of colemanite added is preferably 0.1 to 25 parts by weight, more preferably 1 to 20 parts by weight, and still more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin. By setting it as such a range, the flame retardance, fluidity | liquidity, mechanical strength, and laser printability of the thermoplastic polyester resin composition of this invention improve.
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.

  The average particle size of the above-described colemanite indicates a particle size at which the cumulative weight distribution is 50% in the particle size distribution obtained by measurement with a cedy graph (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.

  For example, if the colemanite used in the present invention is a naturally occurring ore, it can be pulverized using any conventionally known method such as a dry pulverization method or a wet pulverization method, and adjusted to a predetermined particle size. Good. 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.

  Moreover, the colemanite used for this invention may use what was surface-treated with surface treatment agents, 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 colemanite, as long as the effects of the present invention are not impaired, the surface treatment agent such as the silane coupling agent may include other components, specifically, for example, epoxy resin, urethane resin, acrylic resin. It may contain a resin, an antistatic agent, a lubricant, a water repellent and the like.

  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. Alternatively, the polyester resin composition of the present invention may be treated, or separately from untreated colemanite, a surface treatment agent may be added and surface treated.

(E) Reinforcing filler:
In order to increase the rigidity of the molded product, the thermoplastic resin composition is blended with a reinforcing filler such as glass fiber, but the product molded with the resin composition blended with the reinforcing filler, Since the reinforcing filler acts like a candle core at the time of combustion, there is a problem that it is easy to burn.
Therefore, in order to make a resin composition containing a reinforcing filler flame-retardant with a calcium or aluminum salt of phosphinic acid, special measures are required. However, as a result of investigation by the present inventor, in the composition of the present invention, by adding it at a ratio of 150 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyester resin, the mechanical properties can be reduced without reducing the combustibility. It was found that the strength can be increased.
The reinforcing filler that can be used in the present invention has an effect of improving the mechanical properties of a composition obtained by blending with a resin, and a conventional inorganic filler for plastics can be used. Preferably, a fibrous filler such as glass fiber, carbon fiber, basalt fiber, wollastonite, potassium titanate fiber is used. Of these, glass fibers are preferably used in view of mechanical strength, rigidity and heat resistance. Also, granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organic clays, carbon black, glass beads; plate-like fillers such as talc; scales such as glass flakes, mica and graphite A shaped filler can also be used.

(E) The compounding quantity of a reinforcement filler becomes like this. Preferably it is 150 weight part or less with respect to 100 weight part of (A) thermoplastic polyester resins, More preferably, it is 5-120 weight part. By setting the amount to 5 parts by weight or more, the reinforcing effect is sufficiently exerted, and by setting the amount to 150 parts by weight or less, it is possible to increase mechanical properties (particularly toughness) while maintaining good fluidity.
Conventionally, it has been known that when a reinforcing filler is added, the fluidity is lowered. However, in the present invention, the fluidity is not lowered even if the reinforcing filler is added.

  In the present invention, a metal borate may be further used in addition to the components described above. Examples of boric acid forming 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.

  Examples of the boric acid metal salt include 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.

  Condensed borates include alkaline earth metal borates such as trimagnesium tetraborate and calcium pyroborate; transition metal borates such as manganese tetraborate and nickel diborate; zinc tetraborate and tetraborate Examples thereof include borate salts of group 2B metals of the periodic table such as cadmium acid. 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 boric acid metal salt used in the present invention, it is preferable to use an alkaline earth metal or a Group 2B metal salt of the periodic table such as 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.

  By adding the boric acid metal salt, the combustion inhibiting action of the resin composition is improved. 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.

  Furthermore, various additives commonly used in thermoplastic resin compositions can be added to the resin composition of the present invention within a range that does not impair the object 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. The addition amount of these additives is usually 10 parts by weight or less, preferably 5 parts by weight or less with respect to 100 parts by weight of the thermoplastic polyester resin.

  In addition, polytetrafluoroethylene or fumed colloidal silica obtained by the suspension polymerization method can be added to further prevent dripping during combustion.

  The flame retardant polyester resin composition of the present invention may be supplemented with other thermoplastic resins, and can be used as long as the resin is stable at high temperatures. Specifically, for example, polycarbonate, polyamide, polyphenylene Examples thereof include oxides, polystyrene resins, polyphenylene sulfide ethylene, polysulfone, polyether sulfone, polyether imide, polyether ketone, and fluororesin.

  Preparation of the resin composition of this invention can be performed in accordance with the conventional method of resin composition preparation. Usually, the components 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.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The resin composition was evaluated by the following method.

Bending strength:
A combustion test piece of Subject 94 (hereinafter referred to as UL94) of Underwriters Laboratories with a thickness of 1.6 mm is injection-molded, and a bending test is performed using this with a span of 40 mm and a test speed of 2 mm / min. Carried out.

Flame retardant test:
According to the method of UL94, a flame retardancy test is performed using five test pieces (thickness 0.4 mm or 0.8 mm), and according to the evaluation method described in UL94, V-0, V-1, and V-2. And HB (V-0 indicates the highest flame retardancy). The total combustion time (total combustion time) is five total combustion times (including the combustion time at the time of the first flame contact and the second flame contact).

Glow-wire ignition temperature test (abbreviation: GWIT test):
A flat test piece having a thickness of 0.75 mm was subjected to a test method defined in IEC60695-2-13. Specifically, it is defined as a temperature 25 ° C higher than the maximum temperature of the tip that does not ignite by contacting a red hot rod of a predetermined shape (a nickel / chromium (80/20) wire with an outer diameter of 4 mm in a loop shape) for 30 seconds. The

  This test has the following background: In recent years, demands for electrical safety in electrical and electronic parts are becoming stricter than ever before. For example, according to the recently revised IEC 60335-1 standard of the International Electrotechnical Commission (abbreviated as IEC), in household electrical products such as refrigerators and fully automatic washing machines, equipment that operates without an operator attached. Among the components, electrical insulation components that support connections where a rated current exceeding 0.2 A flows during normal operation, and electrical insulation components (printed circuit boards, terminals) within a distance of 3 mm from these connections The material of the base, the plug, etc. is required to satisfy that the glowing rod ignition temperature (Glow-wire Ignition Temperature, abbreviated as GWIT) is 775 mm or more at a thickness of 0.75 mm.

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. A CTI of 500 V or higher is preferable as an electrical insulating property.

As gas evaluation, the following two tests were performed and evaluated.
1) 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 270 ° 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: Almost no mold deposit is recognized.
○: The mold deposit is slightly recognized.
Δ: Mold deposit is clearly recognized.
X: The mold deposit is thickly attached to the entire mold surface.

2) Total amount of generated gas (GC-MS) (unit: μg / g resin = ppm):
About 0.02 g of sample resin is weighed, put into a sample tube, and heat-treated at 270 ° C. for 10 minutes under a helium flow of 30 ml / min using TD-20 and column UA1701 manufactured by Shimadzu Corporation. The total amount of generated gas was collected by a cooled cryotrap.

  As conditions, column UA1701 (after holding at 50 ° C. for 2 minutes, after raising the temperature by 260 ° C. (10 ° C./10 min), and further by 300 ° C. (5 ° C./10 min)) was collected at an inlet temperature of 270 ° C. Was introduced into the GC, the total ion chromatogram of the generated gas was measured, and the detected amount was prepared and quantified using n-decane as an internal standard (unit: μg / g resin = ppm).

Liquidity:
The spiral flow length of the resin composition was evaluated using SE50 manufactured by Sumitomo Heavy Industries, Ltd. as an injection molding machine. The injection pressure was 170 MPa, the injection speed was 100 mm / sec, the cylinder temperature was 270 ° C., the injection time was 2 sec, the cooling was 7 sec, the mold temperature was 80 ° C., and the suck back was 1 mm. Moreover, the shape of the evaluated resin molded product is a long resin molded product having a cross section of 1 mm in thickness and a width of 1.5 mm, and has a spiral shape. The size of the spiral long resin molded product is 90 mm × 105 mm as the distance between the centers of the long resin molded products. This spiral long resin molded product is shown in FIG.

Release properties:
Molding in shallow cup shape (wall thickness 3mm, outer diameter 100mm, depth 20mm) using FANUC injection molding machine (α-100iA) under conditions of resin temperature 270 ° C, mold temperature 80 ° C, cycle 25 seconds The product was continuously injection-molded, and the releasability was measured by visually observing the presence or absence of protrusion pins. The pin mark was clearly recognized as x, the faintly recognized mark as ◯, and the pin mark as unacceptable as ◎.

Laser printability:
(1) Laser marking property evaluation method:
The test piece was subjected to laser marking with an Nd-YAG laser under the following conditions and evaluated.
The apparatus uses a marker engine SL475H / HF manufactured by NEC Corporation, high output: 50 W or more, output current value of laser marking: 10 A or 15 A, oscillation wavelength: 1060 nm, ultrasonic Q switch: 2 kHz, scanning speed: 200 mm / sec It was. For the marking design, different markings were applied to the two plates. One plate was marked so as to fill a square of 20 × 20 mm, and another one was marked with 10 letters of alphabet (ABCDEFGHIJ) with a font of 5 mm.

The laser marking property was determined by visually observing the two plates subjected to the laser marking process, making a comprehensive judgment, and dividing them into ranks of ◎, ○, Δ, and × based on the following criteria.
A: Very clear markings are made and good.
○: Clear marking is made and can be easily recognized.
Δ: Marking symbol can be recognized.
X: Marking is not made at all, or the recognition of the pattern is difficult.

    In addition, the laser marking property evaluation (recognition degree of the laser-marking portion) was determined by quantifying how much the color was changed from the original material by the laser marking process. Specifically, a laser marking process is performed so as to fill a square of 20 × 20 mm, and a rising foam height before and after the laser marking is observed using a 3D laser microscope (manufactured by Keyence Corporation: VK-8700), and a printed part The raised foam height was evaluated. It becomes clear that the larger the numerical value of the rising foam height, the more easily the visibility of the laser printing portion tends to be excellent due to irregular reflection of light.

  The raw materials used in the examples are as follows.

(A) Thermoplastic polyester resin:
(A-1) PBT: NOVADURAN (registered trademark) 5020 manufactured by Mitsubishi Engineering Plastics, polybutylene terephthalate resin having an intrinsic viscosity of 1.20 dl / g (A-2) PBT: NOVADURAN (registered trademark) manufactured by Mitsubishi Engineering Plastics 5008, polybutylene terephthalate resin (A-3) PBT having an intrinsic viscosity of 0.85 dl / g: manufactured by Mitsubishi Chemical Corporation, Novapet (registered trademark) PBK1, intrinsic viscosity 0.64 dl / g (phenol and 1,1,2 , Measured in a mixed solvent of 1: 1 (weight ratio) of 2-tetrachloroethane at 30 ° C.)
(A-4) PTMG copolymer PBT (polyester ether copolymer): NOVADURAN (registered trademark) 5510 manufactured by Mitsubishi Engineering Plastics Co., Ltd., polytetramethylene ether glycol unit (number average molecular weight = about 1016) content of 20% by weight Copolymerized polybutylene terephthalate resin. Tg = 22 ° C. Intrinsic viscosity = 1.3 dl / g (measured at 30 ° C. in a 1: 1 (weight ratio) solvent mixture of phenol and 1,1,2,2-tetrachloroethane)

(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, directly or through an oxygen atom in a silicon atom Content of phenyl groups bonded to each other: 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% by weight, phenyl group content: 100 mol%, Silicone resin end-capped with trimethylsilyl groups

(C-3) Silicone compound-3: SR-21 (trade name) manufactured by Konishi Chemical Industry, Mw: 3800, hydroxyl group content: 6% by weight, 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%, phenyl group content: 100 mol%, average molecular formula: (PhSiO3 _{/ 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, phenyl group content: 70 mol%, propyl group 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: 50 mol%

(C-7) Silicone compound-7: Z6800 (trade name), triphenylsilanol, phenyl group content: 100 mol%, average molecular formula: Ph ₃ SiOH, manufactured by Toray Dow Corning Silicone

(C-8) Silicone compound-8: manufactured by Shin-Etsu Chemical Co., Ltd., octaphenyltetracyclosiloxane, Mw: 793, hydroxyl group content: 0 wt%, phenyl group content 100 mol%, average molecular formula: 7)
In addition, all of C-1 to C-8 show a solid state at 25 ° C.

(C-9) Silicone compound-9: KR-511 (trade name) manufactured by Shin-Etsu Chemical Co., Ltd., methylphenyl silicone oligomer, phenyl group content: 50 mol%, not in a solid state at 25 ° C.

(C-10) Silicone compound-10: manufactured by Momentive Performance Materials Japan TSR165 (trade name), polymethylphenylmethoxysiloxane, phenyl group content: 50 mol%, not in a solid state at 25 ° C.

(C-11) Silicone compound-11: DC4 7081 manufactured by Toray Dow Corning Silicone Co., Ltd. Silica-supported silicon powder-polydimethylsiloxane having 60% by weight of methacrylic group supported on 40% by weight of silica, and powdered. Hydroxyl content: 0 wt%, phenyl group content 0 mol%, solid state at 25 ° C.
(C-12) Silicone compound-12: SH200 (trade name) manufactured by Toray Dow Corning Silicone Co., polydimethylsiloxane, Mw: 4 × 10 ⁴ , hydroxyl group content 0 wt%, phenyl group content weight 0 mol% , Viscosity 60000 centistokes, not in solid state at 25 ° C.

(D-1) Zinc borate: manufactured by BORX, 2ZnO.3B ₂ O ₃ .3.5H ₂ O, average particle diameter: 9 μm
(D-2) Colemanite-1: manufactured by Kinsei Matech Co., Ltd., calcium borate ore (mainly 2CaO.3B ₂ O ₃ .5H ₂ O), average particle size: 15 μm
(D-3) Colemanite-2: manufactured by Kinsei Matech Corporation, calcium borate ore (mainly 2CaO · 3B ₂ O ₃ · 5H ₂ O), average particle size: 5 μm

(E-1) Glass fiber: 03JA-FT592 (trade name) manufactured by Owens Corning, diameter 10.5 μm

(F-1) Melamine cyanurate: Sun Chemical Co., MCA (trade name), average particle size: 5 μm
(F-2) Melamine polyphosphate: Ciba Special, melapur200 / 70 (trade name), average particle size: 8 μm

(G) Fluororesin: Sumitomo 3M TF1750 (trade name)

(H-1) Antioxidant: Phenol-based antioxidant Irganox 1010 (trade name) manufactured by Ciba Specialty Chemicals
(H-2) Phosphorous stabilizer: ADK STAB PEP36 (trade name) manufactured by Asahi Denka Co., Ltd.
(H-3) Phosphorous stabilizer: Almost equimolar mixture of mono- and di-stearyl acid phosphate (“ADEKA STAB AX-71” manufactured by ADEKA)
(H-4) Mold release agent: Paraffin wax FT100 (trade name) manufactured by Nippon Seiki Co., Ltd.
(H-5) Lubricant: calcium stearate, manufactured by NOF Corporation (H-6) Pigment: carbon black, manufactured by Mitsubishi Chemical Corporation, MCF # 960, particle size: 16 nm

  In the weight ratio shown in the table below, components other than glass fiber are mixed together with a super mixer (SK-350 type manufactured by Shinei Machinery Co., Ltd.), and the mixture is L / D = 42 twin screw extruder (Nippon Steel Works, Ltd.). Made of TEX30HSST), side feed the glass fiber, and extrude under the conditions of discharge rate 20kg / h, screw rotation speed 250rpm, barrel temperature 260 ° C to obtain pellets of polybutylene terephthalate resin composition It was. The obtained pellet was formed into a test piece according to the evaluation method.

As apparent from the above table, when an organosiloxane polymer (C-12) outside the scope of the present invention is used, the flame retardancy is insufficient. Further, from the comparison of Examples 4, 5, 7 and the like and Comparative Example 13, even when the same amount of colemanite is added, it is more preferable to employ the organosiloxane polymer within the scope of the present invention. It can be seen that the printability tends to be more excellent.
In addition, it is generally known that in a composition containing a relatively large amount of filler, the filler becomes a crystal nucleus of PBT, which is a crystalline resin, and promotes crystallization, resulting in a decrease in fluidity. Even if it contains a kind of colemanite, it was recognized that the composition of the present invention tends to suppress a decrease in fluidity.
Moreover, it is recognized that GWIT is improved by employing a resin having a high aromatic ring concentration as in Examples 23 and 24. Furthermore, it is well known that the use of such a resin reduces the CTI, but surprisingly no decrease was observed in the present invention.
Furthermore, as is clear from Comparative Examples 10 and 11, it was found that when a nitrogen-containing compound such as melamine cyanurate or melamine polyphosphate was used, mold deposits were generated.

The thermoplastic polyester resin composition of the present invention can have the following characteristics.
(1) Even when it is a molded product having a thickness of 1 mm or less, it has excellent flame retardancy and mechanical properties.
(2) Even if the content of the halogen-based flame retardant is 1% by weight or less or not included at all, the flame retardancy can be sufficiently ensured, so that dioxins are not generated during incineration and environmental pollution is small.
(3) Since it can be excellent in releasability, the risk of deformation and the like can be reduced during molding.
(4) Since it can be made excellent in fluidity, it can be thin-walled and processed in large numbers, and can be excellent in productivity.
(5) Since there is very little mold deposit, productivity at the time of shaping | molding can be improved.
(6) Laser printing on injection-molded products is possible, brands and the like can be written, and the utility value is high.
(7) It has excellent tracking resistance and can be used for a wide range of applications in the electrical and electronic fields.
(8) Excellent glow wire characteristics, and according to the recently revised International Electrotechnical Commission (IEC) IEC 60335-1 standard, operators are attached to household electrical appliances such as refrigerators and fully automatic washing machines. Insulating material parts that support connection parts through which current exceeding 0.2 A flows during normal operation, and electrical insulation materials that are within a distance of 3 mm from these connection parts It can be used for parts.
(9) Even if the content of organic nitrogen compounds such as melamine cyanurate and melamine polyphosphate is reduced (for example, 2% by weight or less of the composition), sufficient flame retardancy can be ensured.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. The resin composition was evaluated by the following method. Examples 2 to 24 are reference examples.

Claims (8)

(A) For 100 parts by weight of the thermoplastic polyester resin,
(B) 5-60 parts by weight of a phosphinate represented by the following general formula (1) or (2),
(C) 0.1-20 parts by weight of organosiloxane and
(D) Combining 0.01 to 30 parts by weight of colemanite,
The (C) organosiloxane is a (Cb) organosiloxane polymer which is in a solid state at 25 ° C. (provided that the organic group 40 bonded to a silicon atom directly or through an oxygen atom is used. A thermoplastic polyester resin composition, which is an organosiloxane compound in which mol% or more is an aryl group.

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 6 carbon atoms or an optionally substituted aryl group, and R ¹ may be the same or different, and R ³ Represents an alkylene group having 1 to 10 carbon atoms, an arylene group which may be substituted, or a group comprising a combination of two or more thereof, and R ³ may be the same or different, and n is 0 to 4. Represents an integer.) 2. The thermoplastic polyester resin composition according to claim 1, wherein the blending amount of (C) organosiloxane with respect to 100 parts by weight of (A) thermoplastic polyester resin is 0.1 to 17 parts by weight. The thermoplastic polyester resin composition according to claim 1 or 2, wherein the blending amount of (D) colemanite with respect to 100 parts by weight of (A) thermoplastic polyester resin is 0.1 to 15 parts by weight. The thermoplastic polyester resin composition according to claim 1 or 2, wherein the blending amount of (D) colemanite with respect to 100 parts by weight of (A) thermoplastic polyester resin is 1.5 to 15 parts by weight. Furthermore, (E) reinforcement filler is included in the ratio of 150 weight part or less with respect to 100 weight part of said (A) thermoplastic polyester resins, The any one of Claims 1-4 characterized by the above-mentioned. A thermoplastic polyester resin composition. The thermoplastic polyester resin composition according to any one of claims 1 to 5, wherein the thermoplastic polyester resin is polyethylene terephthalate or polybutylene terephthalate. (A) The thermoplastic polyester resin composition according to any one of claims 1 to 5, wherein the thermoplastic polyester resin is a polybutylene terephthalate resin. The molded article formed by injection-molding the thermoplastic polyester resin composition of any one of Claims 1-7.

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