JP2010248351A - Flame retardant thermoplastic polyester resin composition - Google Patents

Abstract

（式中、Ｒ^１およびＲ^２は、一方が水素原子であり、他方が炭素数６〜１２のアリール基を表し、ＭはＣａ、Ｍｇ、Ａｌおよび／またはＺｎであり、ｍはＭの価数を表わす。）
【選択図】 なしDisclosed is a non-halogen flame-retardant thermoplastic polyester resin composition that is flame-retardant at a high level even with a small amount of flame retardant, and at the same time has high tracking resistance, and a molded product thereof.
(A) 5-100 parts by weight of a phosphinic acid salt represented by formula (1) and / or a polymer thereof, and 100 parts by weight of a thermoplastic polyester resin. A flame retardant thermoplastic polyester resin composition comprising 0 to 35 parts by weight, (D) 0 to 150 parts by weight of reinforcing filler, and (E) 0 to 5 parts by weight of a phosphorus stabilizer.
[Chemical 1]

(In the formula, ^one of R ¹ and R ² represents a hydrogen atom, the other represents an aryl group having 6 to 12 carbon atoms, M represents Ca, Mg, Al and / or Zn, and m represents a valence of M. Represents a number.)
[Selection figure] None

Description

The present invention relates to a flame retardant thermoplastic polyester resin composition having excellent flame retardancy without using a halogen-based flame retardant, and a resin molded article using the flame retardant thermoplastic polyester resin composition. More specifically, a flame retardant thermoplastic polyester resin composition having excellent hydrolysis resistance and flame resistance, and at the same time excellent electrical characteristics such as mechanical characteristics and tracking resistance, and a resin molded product using the same About.

Thermoplastic polyester resins are widely used for electrical and electronic equipment parts, automobile parts and the like because of their excellent characteristics. In particular, in the field of electrical and electronic equipment, in order to ensure safety against fire, there are many examples in which flame retardancy is imparted. In general, halogen-based flame retardants such as halogen compounds and antimony compounds have been used to impart flame retardancy to thermoplastic polyesters. However, these halogen-based flame retardants may generate dioxin compounds during combustion decomposition, which is not preferable in terms of environmental problems.

As a method for solving this problem, a method using a specific calcium phosphinate or aluminum salt has been proposed (see, for example, Patent Document 1). However, when such a phosphinic acid metal salt compound is used, there is a problem that the hydrolysis resistance of the polyester resin composition is lowered, and the mechanical properties are lowered when used under high temperature and high humidity.

As another method, blending an aromatic phosphinic acid metal salt with polyester fiber has been proposed (see, for example, Patent Document 2). However, the resin molded product obtained by this method is also insufficiently effective, and its practicability is unknown. Furthermore, there has been no suggestion about the flame retardancy effect and hydrolysis resistance when an aromatic phosphinic acid metal salt and a flame retardant aid are used in combination.

JP-A-8-73720 US Pat. No. 3,594,347

As described above, in the conventional method, it has been difficult to impart all of high hydrolysis resistance, environmentally safe flame retardancy, and excellent electrical characteristics to the thermoplastic polyester resin. The present invention has been made in view of such problems, is excellent in hydrolysis resistance, has few environmental problems, has a high level of flame retardancy, and also has high tracking resistance, The object is to provide a flame retardant thermoplastic polyester resin composition and a molded article thereof.

As a result of intensive studies to achieve the above object, the present inventor has achieved these multiple effects simultaneously when a specific phosphinate and a specific flame retardant aid are used in a specific amount ratio in the thermoplastic polyester resin. The present invention has been completed by finding that the present invention provides an extremely excellent flame-retardant thermoplastic polyester resin composition.

That is, the first gist of the present invention is as follows: (A) 5 to 40 parts by weight of the phosphinic acid salt represented by the formula (1) and / or its polymer with respect to 100 parts by weight of the thermoplastic polyester resin; (C) Flame retardant thermoplastic polyester resin comprising 0 to 35 parts by weight of flame retardant aid, (D) 0 to 150 parts by weight of reinforcing filler, and (E) 0 to 5 parts by weight of phosphorus stabilizer. Relates to the composition.

（式中、Ｒ^１およびＲ^２は、一方が水素原子であり、他方が炭素数６〜１２のアリール基を表し、ＭはＣａ、Ｍｇ、Ａｌおよび／またはＺｎであり、ｍはＭの価数を表わす。）

(In the formula, ^one of R ¹ and R ² represents a hydrogen atom, the other represents an aryl group having 6 to 12 carbon atoms, M represents Ca, Mg, Al and / or Zn, and m represents a valence of M. Represents a number.)

The second gist is that the flame retardant aid (C) is at least one selected from (C-1) an amino group-containing compound, (C-2) a silicon-containing compound, and (C-3) a boron-containing compound. The present invention relates to a flame retardant thermoplastic polyester resin composition which is one or more compounds.

The third aspect is that the flame retardant aid (C) is at least one compound selected from the group consisting of melamine cyanurate, melamine polyphosphate, melamine phosphate, silicone resin, and zinc borate. Relates to a heat-resistant thermoplastic polyester resin composition.

The fourth gist relates to a flame retardant thermoplastic polyester resin composition in which the amount of the (E) phosphorus stabilizer is 0.01 to 5 parts by weight with respect to 100 parts by weight of (A) the thermoplastic polyester resin. .

The fifth gist relates to a flame retardant thermoplastic polyester resin composition in which the (E) phosphorus stabilizer is a phosphite ester stabilizer.

The flame-retardant thermoplastic polyester resin composition of the present invention has the following excellent effects.
1) Even without using a halogen-based flame retardant, it has high hydrolysis resistance and flame retardancy, suppresses the generation of harmful substances during incineration after use, and reduces environmental pollution.
2) Even if the resin molded product is used at a high temperature, since the bleed-out of the flame retardant and the like to the surface of the resin molded product is suppressed, deterioration of characteristics such as the resin molded product surface appearance and electric resistance is suppressed.
3) Since it has excellent tracking resistance and mechanical strength, it can be expected to be used widely as a resin molded product for a wide range of electric and electronic fields.

Hereinafter, the constituent components of the resin composition of the present invention will be described in detail.
(A) Thermoplastic polyester resin (A) The thermoplastic polyester resin used in the present invention is a polycondensation of a dicarboxylic acid compound and a dihydroxy compound, a polycondensate of an oxycarboxylic acid compound, or these three polycondensations. The polyester of the present invention has the effects of the present invention for both homopolyester and copolyester.

(A) As an example of the dicarboxylic acid compound constituting the thermoplastic polyester resin, specifically, for example, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylethanedicarboxylic acid, cyclohexanedicarboxylic acid, Examples include known dicarboxylic acid compounds such as adipic acid and sebacic acid, and alkyl, alkoxy or halogen substituted products thereof. In addition, these dicarboxylic acid compounds may be polymerized as derivatives capable of forming an ester, specifically, lower alcohol esters such as dimethyl ester.

Specific examples of the dihydroxy compound include, for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, hydroquinone, resorcin, dihydroxyphenyl, naphthalenediol, dihydroxydiphenyl ether, cyclohexanediol, 2,2-bis (4- Examples thereof include dihydroxy compounds such as hydroxyphenyl) propane and diethoxylated bisphenol A, polyoxyalkylene glycols, and alkyl, alkoxy or halogen substituted products thereof. And these may use together 1 type, or 2 or more types in a desired ratio.

Specific examples of the oxycarboxylic acid include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid, and alkyl, alkoxy, or halogen substituted products thereof, and these compounds. The ester-forming derivatives of can also be used. And these may use together 1 type, or 2 or more types in a desired ratio.

In the present invention, in addition to a dihydroxy compound and an oxycarboxylic acid compound as a compound that polycondenses with a dicarboxylic acid compound, a trifunctional monomer, that is, trimellitic acid, trimesic acid, pyromellitic acid, pentaerythritol, trimethylol, etc. A thermoplastic polyester resin having a branched or cross-linked structure using a small amount of propane or the like can also be used.

In the present invention, a thermoplastic polyester resin obtained from the above-described dicarboxylic acids and various monomers that are polycondensed with these can be used. Two or more species may be used in combination at any ratio, and a modified product modified by a known method such as crosslinking or graft polymerization can also be used.

As the (A) thermoplastic polyester resin used in the present invention, polyalkylene terephthalate is preferable as the (A) thermoplastic polyester resin used in the present invention, and in particular, polybutylene terephthalate and / or polyethylene terephthalate, or these as a main component. It is preferable to use a copolymer.

The intrinsic viscosity of the (A) thermoplastic polyester resin used in the present invention is usually 0.5 to 2 dl / g. Among them, the intrinsic viscosity is preferably 0.5 to 1.5 dl / g from the viewpoint of moldability and mechanical properties. If the intrinsic viscosity is lower than 0.5 dl / g, the mechanical strength is extremely lowered. Conversely, if it is higher than 2 dl / g, the fluidity is lowered and the moldability is lowered.

(B) Phosphinic acid salt In the present invention, the (B) phosphinic acid salt and / or polymer thereof is a phosphinic acid salt represented by the following formula (1) and / or a polymer thereof.

(In the formula, ^one of R ¹ and R ² represents a hydrogen atom, the other represents an aryl group having 6 to 12 carbon atoms, M represents Ca, Mg, Al and / or Zn, and m represents a valence of M. Represents a number.)

In the present invention, the (B) phosphinic acid salt represented by the general formula (1) and / or a polymer thereof (hereinafter sometimes simply referred to as “component (B)”) is used alone. Or two or more of them may be used in combination at any ratio. The (B) phosphinic acid salt and / or polymer thereof used in the present invention, one of R ¹ and R ² in the above formula (1) is a hydrogen atom and the other is an aryl group having 6 to 12 carbon atoms. It is characterized by that. Specific examples of the aryl group having 6 to 12 carbon atoms include phenyl group, tolyl group, xylyl group, naphthyl group, and derivatives thereof. Of these, a phenyl group is preferred.

(B) component used for this invention is mix | blended 5-40 weight part with respect to 100 weight part of (A) thermoplastic polyester. If the blending amount is less than 5 parts by weight with respect to 100 parts by weight of the thermoplastic polyester resin (A), the development of flame retardancy is insufficient. Conversely, if it exceeds 40 parts by weight, the mechanical properties are lowered and economical. Also disadvantageous. Therefore, the amount of the component (B) used in the present invention is preferably 7 to 35 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin from the viewpoint of both flame retardancy and mechanical properties. Among them, the amount is preferably 10 to 35 parts by weight, more preferably 20 to 35 parts by weight, and particularly preferably 25 to 35 parts by weight.

In the present invention, from the viewpoint of the mechanical strength and appearance of the molded product obtained, the average particle size of the (B) phosphinic acid salt and / or polymer thereof used is 100 μm or less, especially 50 μm or less. It is preferable. The (B) phosphinic acid salt and / or polymer thereof having such an average particle size can be obtained by pulverizing and pulverizing by a conventionally known pulverization technique or the like. Among these, it is preferable to set the average particle size to 0.5 to 40 μm, particularly 10 to 40 μm because not only high flame retardancy is exhibited but also the toughness of the molded product is remarkably increased.

(C) Flame retardant aid The (C) flame retardant aid used in the present invention includes (C-1) an amino group-containing compound, (C-2) a silicon-containing compound, and (C-3). Examples include boron-containing compounds.

The compounding quantity of a flame-retardant adjuvant is 0-35 weight part with respect to 100 weight part of component (A). If it exceeds 35 parts by weight, the mechanical strength is adversely affected. The blending amount of the flame retardant aid is preferably 0.25 to 30 parts by weight, and more preferably 0.5 to 20 parts by weight.
(C-1) Amino group-containing compound As the (C-1) amino group-containing compound used as a flame retardant aid (C) in the present invention, a salt of an amino group-containing triazine is particularly preferred. As amino group-containing triazines (triazines having an amino group), amino group-containing 1,3,5-triazines are usually used. Specifically, for example, melamine, substituted melamine (2-methylmelamine, guanylmelamine etc.), melamine condensate (melam, melem, melon etc.), melamine cocondensation resin (melamine-formaldehyde resin etc.), cyanuric amides (Ammeline, ammelide, etc.), guanamine or derivatives thereof (guanamine, methylguanamine, acetoguanamine, benzoguanamine, succinoguanamine, adipoguanamine, phthaloguanamine, CTU-guanamine, etc.).

Examples of the salts of these triazines include salts of the triazines with inorganic acids and organic acids. Specifically, for example, inorganic acids include nitric acid, chloric acid (chloric acid, hypochlorous acid, etc.), phosphoric acid (phosphoric acid, phosphorous acid, hypophosphorous acid, polyphosphoric acid, etc.), sulfuric acid (sulfuric acid and Non-condensed sulfuric acid such as sulfurous acid, condensed sulfuric acid such as peroxodisulfuric acid and pyrosulfuric acid), boric acid, chromic acid, antimonic acid, molybdic acid, tungstic acid and the like. Of these, phosphoric acid and sulfuric acid are preferred as the acid.

On the other hand, organic acids include organic sulfonic acids (aliphatic sulfonic acids such as methanesulfonic acid, aromatic sulfonic acids such as toluenesulfonic acid and benzenesulfonic acid), and cyclic ureas (uric acid, barbituric acid, cyanuric acid, acetylene). Urea, etc.). _{C 1-4} alkanesulfonic acids such as methanesulfonic acid Of these, _{C 1-3} alkyl _{C 6-12} arene sulfonic acids such as toluene sulfonic acid, cyanuric acid are preferred.

Examples of salts of amino group-containing triazines include, for example, melamine cyanurate, melam, melem double salt, melamine phosphate (melamine polyphosphate, melamine polyphosphate, melam, melem double salt, etc.), melamine sulfate (melamine sulfate, Dimelamine sulfate, dimram pyrosulfate), melamine sulfonates (melamine methanesulfonate, melam methanesulfonate, melem methanesulfonate, melamine methanesulfonate, melam, melem double salt, melamine toluene sulfonate, melam toluene sulfonate, And melamine toluenesulfonate, melam, melem double salt, etc.). These may be used alone or in combination of two or more at any ratio.

As the (C-1) amino group-containing compound used in the present invention, an adduct of cyanuric acid or isocyanuric acid and a triazine-based compound is preferable, and usually an acid part and a base part are 1: 1 (molar ratio). In some cases, an adduct having a composition of 1: 2 (molar ratio) is preferred. Specific examples include melamine cyanurate, benzoguanamine cyanurate, acetoguanamine cyanurate, and melamine cyanurate is particularly preferable.

The production method of these adducts of cyanuric acid or isocyanuric acid and triazine compounds (hereinafter sometimes simply referred to as adducts) is arbitrary, and any conventionally known one can be used. Specifically, for example, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into an aqueous slurry and mixed well to form both salts in the form of fine particles, and then the slurry is filtered and dried. can get. The adduct need not be completely pure, and some unreacted triazine-based compound, or cyanuric acid or isocyanuric acid may remain.

Further, the average particle size of the adduct is preferably 0.01 to 100 μm from the viewpoint of flame retardancy, mechanical strength, heat and humidity resistance, residence stability, and surface properties of the resin molded product, and more preferably 1 to 100 μm. It is preferable that it is 80 micrometers. In addition, when the dispersibility of the adduct is low, a dispersant such as tris (β-hydroxyethyl) isocyanurate or a known surface treatment agent may be used in combination.

The amount of the (C-1) amino group-containing compound used in the present invention is 0 to 35 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, among which 5 to 30 parts by weight, and more preferably 10 to 25 parts. Part by weight, particularly 15 to 25 parts by weight is preferred. If this amount exceeds 40 parts by weight, the mechanical properties are liable to be lowered. The blending ratio (weight ratio) of the component (B) and the (C) amino group-containing compound is preferably (C) / (B) = 0-3, more preferably 0.1-2, and even more preferably. Is preferably 0.3 to 1.5. If this ratio is greater than 3, flame retardancy may be reduced.

(C-2) Silicon-containing compound In the present invention, the (C) silicon-containing compound used as a flame retardant aid is preferably an organosiloxane polymer. Here, the organosiloxane polymer is in a solid state at 25 ° C., and is a copolymer of an organosiloxane compound or an organosiloxane compound and a compound having this reactivity, specifically, for example, a copolymer of a vinyl compound, a carbonate compound and the like. It is a coalescence. In addition, being in a solid state at 25 ° C. means that it does not flow at 25 ° C. and can be handled as a solid.

Specific examples of the organosiloxane polymer (C-2) used in the present invention include the following (C-2-1) to (C-2-4).

(C-2-1) Organosiloxane polymer supported on inorganic fine particles In the present invention, an organosiloxane polymer supported on inorganic fine particles (hereinafter sometimes simply referred to as a supported polymer). ), Any known inorganic fine particles can be appropriately selected, determined, and used. Specific examples include silica powder, titanium oxide powder, mica powder, clay powder, kaolin powder, magnesium hydroxide powder, and aluminum hydroxide powder. Of these, silica powder is preferred. Examples of the silica powder include a dry process silica obtained by a vapor phase method and a wet process silica obtained by a wet process, and any of them can be used.

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

The organosiloxane polymer used here may be a polymer of an organosiloxane compound or a polymer chain having a carbon chain as a copolymerization component. As a copolymerization component, a C1-C20 chain | strand-like saturated or unsaturated hydrocarbon group, a halogenated hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group etc. are mentioned, for example.

Furthermore, 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%, more preferably 0.03 to 0.5 mol%, especially 0.05 to 0.3 mol%. preferable.

The method for supporting the organosiloxane polymer on the inorganic fine particles is arbitrary, and any conventionally known method can be used. Specifically, for example, there is a method in which an organosiloxane polymer is dissolved in a solvent and impregnated with inorganic fine particles, and then dried. The supported amount is usually 0.1 to 10 g with respect to 1 g of inorganic fine particles, and preferably 0.4 to 4 g.

In carrying, it is preferable to use an alkoxysilane having a functional group such as an epoxy group as an adhesion promoter because 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.

The supported polymer used in the present invention is preferably one in which an organosiloxane polymer is supported on silica. Specifically, for example, commercially available products such as “Si powder” and “Trefill F” manufactured by Toray Dow Corning Co., Ltd. Can be mentioned.

(C-2-2) Organosiloxane polymer having a softening point exceeding 25C The organosiloxane polymer having a softening point exceeding 25C used in the present invention is generally referred to as a silicone resin. It is what is shown by following formula (2).
(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 (2)

In the formula (2), 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 ratio of the epoxy group-containing organic group in the total of R ^{1 ′ to} R ³ in Formula (2) 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.

Further, because of excellent affinity The presence of phenyl group to the thermoplastic polyester resin, R ¹ in the formula (2) ^'is preferably more than 10 mol% of the total to R ³ is a phenyl group, among others R ^1' Of these, those in which 10 mol% or more, particularly 30 mol% or more of the above are phenyl groups are preferred.

Furthermore, in order to reduce the steric hindrance of organopolysiloxane molecules containing bulky phenyl groups and improve the spatial freedom, to facilitate the overlapping of the phenyl groups and enhance the flame retardancy, the formula (2) Since R ^{1 ′} in preferably has a methyl group or a vinyl group, the proportion of the phenyl group in R ^{1 ′} is preferably 10 to 95 mol%, more preferably 30 to 90 mol%.

In Expression (2), 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 having a softening point exceeding 25 ° C. is usually 500 to 50,000, preferably 500 to 10,000. Although the softening point should just exceed 25 degreeC, it is preferable that it is 40-250 degreeC especially 40-150 degreeC. When the softening point is 25 ° C. or lower, bleeding occurs during molding of a resin composition obtained by blending the resin composition to contaminate the mold, lower the mechanical properties of the molded product, or lengthen the molded product. There is a tendency to ooze out on the surface of the molded product during the period of use.

If the softening point is too high, it tends to be difficult to uniformly disperse the resin composition. The softening point was determined when the organosiloxane polymer was melted and changed 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 (2) 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 Wherein 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 0, 1, also 2. The term. The epoxy-containing alkoxysilane or its partial hydrolyzate represented by), 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) or a partially hydrolyzed product thereof, which is copolymerized with these silanes and siloxanes, is an epoxy group on a silicone resin. 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 .

R ⁸ in the formula is a monovalent hydrocarbon group, and examples thereof include the same monovalent hydrocarbon groups as R ^{1 ′} , R ^{2 ′} , or R ³ . 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 formed by neutralization can be removed by filtration or washing with water.

(C-2-3) Crosslinked organosiloxane polymer The crosslinked organosiloxane polymer used in the present invention is a so-called silicone elastomer, which is addition reaction curing, condensation reaction curing, organic peroxidation. It is synthesized by radical reaction curing with an object and ultraviolet irradiation curing. Among these, as the silicone elastomer used in the present invention, 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, both ends dimethylhydrogensiloxy group-capped dimethylsiloxane / methylhydro Examples include a gen siloxane copolymer and methyl hydrogen cyclopolysiloxane.

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. Specific examples of the condensation reaction curable silicone elastomer composition include, for example, dehydrogenation condensation type, dehydration condensation type, acetic acid condensation type, deoxime condensation type, dealcohol condensation type, deamidation condensation type, dehydroxylamine condensation type. Examples of the composition include a mold and a deacetone condensation type.

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 and the like. 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 cross-linking agent include dimethylhydrogensiloxy group-blocked dimethylsiloxane / methylhydrogensiloxane copolymer, both ends trimethylsiloxy group-blocked methylhydrogenpolysiloxane, methylhydrogencyclopolysiloxane, etc. Is mentioned. 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. As the organic group bonded to the silicon atom other than the silanol group, an unsubstituted or substituted monovalent hydrocarbon group is preferable, an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group; a vinyl group, an aryl 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. Further, the term “substantially linear” means that a part of the main chain includes 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 colloidal silica include fumed colloidal silica, precipitated colloidal silica, or colloidal silica having a particle size 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 thereof include a raw rubber polymer which is a methyl vinyl siloxane copolymer, a dimethyl siloxane / methyl phenyl siloxane / methyl vinyl siloxane copolymer, and a methyl (3,3,3-trifluoropropyl) / methyl vinyl siloxane 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.

(C-2-4) Polyorganosiloxane core graft copolymer Polyorganosiloxane core graft copolymer is a polyfunctional monomer and other copolymer in the presence of polyorganosiloxane particles. A vinyl monomer composed of possible monomers is polymerized to form a cross-linked structure in which the polyorganosiloxane component and the vinyl polymer component are intertwined with each other as a core. It is a composite rubber-based multilayer structure polymer formed by polymerization to form a shell.

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 composed of a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component, which are crosslinking components having a low glass transition temperature, 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 vinyl 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.

The compounding amount of the (C-2) silicon-containing compound used in the present invention is 0 to 35 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin, and particularly 0.01 to 10 parts by weight. preferable. If the amount is less than 0.01 part by weight, the effect of improving the toughness corresponding to the added amount is not exhibited. Conversely, if it exceeds 10 parts by weight, the flame retardancy may be lowered. Therefore, it is preferably 0.1 to 8 parts by weight, particularly 0.5 to 6 parts by weight.

(C-3) Boron-containing compound The boron-containing compound used in the present invention is preferably a metal borate. 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. The zinc borate compounds, include such as zinc borate (2ZnO · _3B 2 _{O 3)} and zinc borate · 3.5 hydrate _{(2ZnO · 3B 2 O 3 ·} 3.5H 2 O) is boric acid The calcium includes calcium borate (2CaO · 3B ₂ O ₃ ), calcium borate · pentahydrate (2CaO · 3B ₂ O ₃ · 5H ₂ O) and the like. 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 35 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. However, even if it is excessively added, the improvement in the effect commensurate with the increase in the amount of mixture will reach its peak, so the amount of the metal borate salt is 1 to 20 parts by weight relative to 100 parts by weight of the (A) thermoplastic polyester resin. It is preferably 1 to 10 parts by weight, particularly 3 to 5 parts by weight.

In the present invention, a dispersant may be further used for improving the dispersibility of the above-described (B) phosphinate and / or polymer thereof and (C) the flame retardant aid. This dispersant can be blended with (A) a thermoplastic polyester resin at the same time, or (B) a phosphinic acid salt and / or a polymer thereof and (C) a flame retardant aid can be treated in advance using this dispersant. It may be left. Specific examples of the dispersant include liquid dispersants described in JP-A No. 2004-269885.

The flame retardant dispersion treated with the dispersant may have a low viscosity and a low solid content, but may have a high viscosity and a high solid content. It is preferable that the amount ratio bring about a viscosity of 2000 to 10000 mPa · s upon mixing. Moreover, the weight ratio of the dispersant to the flame retardant component in the flame retardant dispersion is 1: 9 to 9: 1. And (A) For the purpose of improving the workability at the time of blending with the thermoplastic polyester resin and improving the dispersibility of the flame retardant, it is preferably granulated, specifically, for example, JP-A-2004-99893. It is preferable to granulate with the binder described in 1.

  Preferred binders include alkyl alkoxylates, polyethylene ethylene glycol, waxes (such as carnauba wax, montan wax, polyethylene wax). The melting point of the binder is preferably 50 to 200 ° C. The amount of the binder is 0.5 to 10 parts by weight with respect to 100 parts by weight of the flame retardant.

(D) Reinforcing filler In the present invention, it is preferable to further add (D) a reinforcing filler. The reinforcing filler has an effect of improving the mechanical properties of the composition by blending with a resin, and examples thereof include known inorganic fillers for plastics such as glass fiber, carbon fiber, basalt. Fibrous fillers such as fibers, wollastonite, potassium titanate fibers; granular or amorphous fillers such as calcium carbonate, titanium oxide, feldspar minerals, clays, organoclays, carbon black, glass beads; talc Plate-like fillers such as: scale-like fillers such as glass flakes, mica, and graphite can be blended. In view of mechanical strength, rigidity and heat resistance, glass fiber is preferred. Two or more of these inorganic fillers may be used in combination.

(D) The compounding quantity of a reinforcement filler is 0-150 weight part with respect to 100 weight part of (A) thermoplastic polyester resin, Preferably it is 5-120 weight part. When the amount is less than 5 parts by weight, the reinforcing effect cannot be obtained. When the amount is more than 150 parts by weight, fluidity and mechanical properties (particularly toughness) are deteriorated, which is not preferable.

Furthermore, to the resin composition of the present invention, a known substance which is generally added to a thermoplastic resin or the like is added in combination so as to impart desired characteristics according to the purpose within a range not impairing the object of the present invention. Can do. For example, crystallization accelerators, antioxidants, UV absorbers, stabilizers such as light stabilizers, antistatic agents, lubricants, mold release agents, colorants such as dyes and pigments, plasticizers, hydrolysis resistance improvers (Epoxy compounds, carbodiimide compounds, etc.) can be blended. In particular, the addition of an antioxidant and a release agent for improving the heat resistance is effective.

And it is preferable to mix | blend (E) phosphorus stabilizer for the mold deposit suppression of a flame retardant. As the phosphorus stabilizer, for example, organic phosphite compounds and metal phosphates are suitable. Specific examples include bis (2,6-di-t-4methylphenyl) pentaerythritol diphosphite, bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite, tetrakis (2,4 -Di-t-butylphenyl) -4,4'-biphenylene phosphite and monobasic calcium phosphate, monobasic sodium phosphate and the like as the metal phosphate.

The phosphorus stabilizer is effective regardless of which is used, but at least one compound selected from the group of phosphites and metal dihydrogen phosphates is preferable from the viewpoint of suppression of mold deposit. Particularly preferred are bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite and tetrakis (2,4-di-t-butylphenyl) -4,4'-biphenylene phosphite.

The compounding quantity of a phosphorus stabilizer is 0.001-3 weight part with respect to 100 weight part of (A) thermoplastic polyester, Preferably it is 0.02-1 weight part. If it is less than 0.01 parts by weight, the improvement effect by addition is low, and if it exceeds 3 parts by weight, it is not preferable because it promotes deterioration of appearance and hydrolysis due to oozing into the molded product.

Moreover, you may add the compound which suppresses dripping of the molten grain at the time of combustion. As such a compound, for example, polytetrafluoroethylene produced by emulsion polymerization can be used.

The flame retardant polyester resin composition of the present invention can be used in combination with other thermoplastic resins in addition to the above components depending on the purpose. The other thermoplastic resin used here may be any resin as long as it is stable at high temperatures. For example, polyamide, polyphenylene oxide, polystyrene resin, polyphenylene sulfide ethylene, polysulfone, polyethersulfone, polyether Examples include imides, polyether ketones, and fluororesins. These thermoplastic resins can be used in combination of two or more. Furthermore, elastomers that are impact resistance improvers can also be blended.

The flame-retardant thermoplastic polyester resin composition of the present invention is easily prepared by equipment and methods generally used as a conventional resin composition preparation method. For example, 1) After mixing each component, kneading and extruding with a single or twin screw extruder to prepare pellets, and then preparing the pellets, 2) once preparing pellets having different compositions, placing the pellets in place Any method can be used, such as a method of quantitatively mixing and subjecting to molding to obtain a molded product of the desired composition after molding, or 3) a method of directly charging one or more of each component into a molding machine. In addition, mixing a part of the resin component as a fine powder with other components and adding it is a preferable method for uniformly blending these components.

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. In addition, the measuring method of characteristic evaluation is as follows.

(1) Tensile strength / tensile elongation The tensile strength / tensile elongation was measured according to ISO527-1,2.

(2) Flammability test (UL94)
In accordance with the method of Subject 94 (UL94) of Underwriters Laboratories, flame retardancy was tested using five test pieces (thickness: 0.8 mm). The flame retardancy is classified into V-0, V-1, V-2, and HB according to the evaluation method described in UL94, and the V-0 notation indicates that the flame retardance level is the highest.

(3) 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 of 25 V in increments of 100 V to 600 V when wet-contaminated with an electric field applied to the surface of a solid electrical insulating material. The higher the value, the better. Is 600V or higher.

(4) Evaluation of hydrolysis resistance The ISO dumbbell pieces were wet-heat treated at 203 KPa in 121 ° C. and saturated steam for 50 hours. Measure the tensile strength before and after treatment according to ISO527-1,2,
The strength retention was determined according to the following formula.
Strength retention (%) = (Tensile strength after treatment / Tensile strength before treatment) × 100

The raw materials used in Examples and Comparative Examples are as follows.

(A) Thermoplastic polyester resin (A-1) Polybutylene terephthalate resin NOVADURAN (registered trademark) 5020 manufactured by Mitsubishi Engineering Plastics Co., Ltd. Intrinsic viscosity 1.20 dl / g (1 of phenol and 1,1,2,2-tetrachloroethane) (Measured at 30 ° C. in a mixed solvent of 1 (weight ratio))

(A-2) Polybutylene terephthalate resin NOVADURAN (registered trademark) 5008 manufactured by Mitsubishi Engineering Plastics Co., Ltd. Inherent viscosity 0.85 dl / g (1: 1 (weight ratio) of phenol and 1,1,2,2-tetrachloroethane) (Measured at 30 ° C in a mixed solvent)

(A-3) Polybutylene terephthalate resin NOVADURAN (registered trademark) 5510 (polytetramethylene glycol (PTMG) copolymerized polybutylene terephthalate resin) manufactured by Mitsubishi Engineering Plastics Co., Ltd. Intrinsic viscosity 1.03 dl / g (phenol and 1,1, (Measured at 30 ° C. in a 1: 1 (weight ratio) mixed solvent of 2,2-tetrachloroethane)

(B) Phosphinic acid salt (B-1) Aluminum salt of phenylphosphinic acid: Fang Qiang, Nanjing Science and Technology Development Co., Ltd. Product CJ-1002
In the chemical formula (1), R ¹ is hydrogen, R ² is phenyl, M is aluminum, m is 3 phenylphosphinic acid aluminum salt (C ₁₈ H ₁₈ O ₆ P ₃ Al) Molecular weight 450 Average particle size 40 μm

(B-2) Aluminum salt of diethylphosphinic acid: product name OP1240, molecular weight 390, average particle size 40 μm, manufactured by Clariant

(C) Flame retardant aid
(C-1) Amino group-containing compound (C-1-1) Melamine polyphosphate: manufactured by Ciba Special, Inc. 200/70

(C-1-2) Melamine cyanurate: MCA manufactured by Sun Chemical Co., Ltd.

(C-2) Silicon-containing compound (C-2-1) manufactured by Toray Dow Corning Co., Ltd., trade name DC4-7081 (60% by weight of polydimethylsiloxane having a methacryl group supported on 40% by weight of silica and powdered) .

(C-2-2) manufactured by Toray Dow Corning Co., Ltd. Product name DC4-7051 (60% by weight of polydimethylsiloxane having an epoxy group supported on 40% by weight of silica and powdered).

(C-2-3) manufactured by Toray Dow Corning Co., Ltd. Trade name Trefil F202 (60% by weight of linear polydimethylsiloxane having a viscosity of 60000 centistokes supported on 40% by weight of silica and powdered).

(C-2-4) Product name: 217 Flake (phenyl silicone resin, softening point 86 ° C.) Mw: 2000, manufactured by Toray Dow Corning
Hydroxyl group content: 7 wt% Phenyl group content: 100 mol%
Average molecular formula: (PhSiO _3/2 ) _1.0 (HO _1/2 ) _0.57

(C-2-5) manufactured by Toray Dow Corning Co., Ltd. Trade name Trefil E601 (containing silicone elastomer epoxy group)

(C-2-6) Product name Metabrene S2200 (polyorganosiloxane core graft copolymer) manufactured by Mitsubishi Rayon Co., Ltd.

(C-3) Boron-containing compound (C-3-1) Zinc borate Product name Fire Break 500 manufactured by BORAX, B ₂ O ₃ : 56.2%, ZnO 43.8%, particle size: 10 μm

(D) Reinforcement filler glass fiber: Asahi Fiber Glass Co., Ltd. Trade name Chopped Strand 03JA-FT592

(E) Phosphorus stabilizer: manufactured by Asahi Denka Co., Ltd., trade name: ADK STAB PEP36 cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite

(Other additives)
Fluorine-based resin: manufactured by Sumitomo 3M Co., Ltd. Product name: DYNION TF1750

Phenol-based antioxidant: Product name Irganox 1010 Pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] manufactured by Ciba Specialty Chemicals

Mold release agent: Nippon Seiwa Co., Ltd. Product name: Paraffin wax FT100

Lubricant: Calcium stearate manufactured by NOF Corporation

[Examples 1 to 18 and Comparative Examples 1 to 8]
As shown in Table 1, components other than glass fibers are mixed together with a super mixer (SK-350 type, manufactured by Shinei Machinery Co., Ltd.), and a L / D = 42 twin screw extruder (manufactured by Nippon Steel Works, TEX30XCT). (C) The glass fiber was side-feeded and extruded under conditions of a discharge rate of 20 kg / hr, a screw rotation speed of 200 rpm, and a barrel temperature of 260 ° C. to obtain pellets of a polybutylene terephthalate resin composition. In Examples 1 to 8 and Comparative Examples 1 and 2 which are non-reinforced systems, the obtained pellets and a predetermined amount of calcium stearate were after-blended to obtain resin composition pellets.

For the resin composition pellets, using the injection molding machine (manufactured by Sumitomo Heavy Industries, Model SH-100), the test pieces of (2) and (3) above under the conditions of a cylinder temperature of 270 ° C. and a mold temperature of 80 ° C. (Vertical and horizontal 10 cm, 3 mm thick flat plate test pieces, and 0.8 mm thick UL-94 standard combustion test pieces) were manufactured. Moreover, as a test piece of (1), an ISO tensile test piece (ISO 3167) was molded at 265 ° C. using an injection molding machine (model S-75 MIII manufactured by Sumitomo Heavy Industries, Ltd.). The evaluation results are shown in Table 1.

The resin composition blended with phenylphosphinate used in the examples is remarkably superior in hydrolysis resistance compared to the resin composition blended with diethylphosphinate used in the comparative examples. I understand. In addition, the resin composition was excellent in flame retardancy and insulation characteristics (CTI: tracking resistance characteristics).

The molded product obtained from the flame-retardant thermoplastic polyester resin composition of the present invention has excellent hydrolysis resistance, flame retardancy, CTI and mechanical properties, and is particularly suitable for electrical and electronic parts such as connectors. It can be applied to a wide range of parts such as terminals, and can also be applied to automobile parts and building material parts.

Claims (5)

(A) 5 to 40 parts by weight of the phosphinic acid salt represented by the formula (1) and / or a polymer thereof, and (C) 0 to 35 parts by weight of a flame retardant aid with respect to 100 parts by weight of the thermoplastic polyester resin. Flame retardant thermoplastic polyester resin composition, comprising (D) 0 to 150 parts by weight of reinforcing filler, and (E) 0 to 5 parts by weight of phosphorus stabilizer.

(In the formula, ^one of R ¹ and R ² represents a hydrogen atom, the other represents an aryl group having 6 to 12 carbon atoms, M represents Ca, Mg, Al and / or Zn, and m represents a valence of M. Represents a number.) (C) The flame retardant aid is at least one compound selected from (C-1) an amino group-containing compound, (C-2) a silicon-containing compound, and (C-3) a boron-containing compound. The flame-retardant thermoplastic polyester resin composition according to claim 1. (C) The flame retardant aid is at least one compound selected from the group consisting of melamine cyanurate, melamine polyphosphate, melamine phosphate, silicone resin, and zinc borate. The flame-retardant thermoplastic polyester resin composition as described. 4. The difficulty according to claim 1, wherein the amount of the (E) phosphorus stabilizer is 0.01 to 5 parts by weight with respect to 100 parts by weight of the (A) thermoplastic polyester resin. A flame-retardant thermoplastic polyester resin composition. (E) The flame retardant thermoplastic polyester resin composition according to claim 1, wherein the phosphorus stabilizer is a phosphite stabilizer.