JPH10139996A - Flame-retardant thermoplastic resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition containing no compounds having chlorine or bromine atom, which has not only excellent flame retardancy and excellent chemical resistance, but also has a reduced odor, by compounding a thermoplastic polyester resin and an organic phosphorus compound flame retardant with a polycarbonate resin. SOLUTION: This resin composition contains 100 pts.wt. of a resin component comprising (A) a polycarbonate resin and (B) a thermoplastic polyester resin prepared by the polymerization by use of a germanium compound catalyst, component (A)/component (B) ratio being 99/1 to 20/80 by weight, and (C) 1 to 30 pts.wt. of an organic phosphorus compound flame retardant represented by the formula wherein, each of R<1> to R<3> is a monovalent 1-12C aliphatic group or the like, R<4> is a monovalent 6-20C aromatic group, X is a divalent binding group selected from among a 3-30C alicyclic group and the like, m is 0 or 1, each of n's is 0 to 5, each of p and q is 0 to 2 and r is 1 to 3, with the proviso that p+q+r=3, and (D) 0.5 to 15 pts.wt. of a copolymer containing a unit derived from an olefin and a unit derived from a (meth)acrylate having a 1-10C alkyl group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant thermoplastic resin composition which is excellent in flame retardancy and chemical resistance and has a reduced odor, and does not contain any of chlorine-containing compounds and bromine-containing compounds. Belongs to the technical field of manufacturing and using.

[0002]

2. Description of the Related Art Polycarbonate resin is widely used as a thermoplastic resin having excellent impact resistance, heat resistance and the like in the production of parts for machines, automobiles, electric / electronic devices and the like.

[0003] Among such polycarbonate resins, aromatic polycarbonate resins have a high glass transition temperature and are expected to have high heat resistance. However, in order to obtain sufficient fluidity during processing, relatively high temperatures of around 300 ° C are required. Requires high processing temperatures. In addition, when the polycarbonate resin comes into contact with various organic solvents, gasoline, oil, and the like, cracks or dissolution of the surface of the molded body occur, and thus there are problems in solvent resistance, gasoline resistance, oil resistance, and the like.

[0004] On the other hand, thermoplastic polyester resins are excellent in mechanical properties, electrical properties, solvent resistance, gasoline resistance, oil resistance, and the like. Shows fluidity, traditionally fiber,
Widely used as films, molding materials and the like.

[0005] In order to solve the above-mentioned problems in polycarbonate resin, for example, Japanese Patent Publication No.
JP-A-14035, JP-B-39-20434, JP-A-59-176345, and the like propose a method of adding a thermoplastic polyester resin.

On the other hand, in recent years, especially in applications of electric and electronic parts, in order to ensure fire safety, the resin used conforms to UL-94 (US Underwriters Laboratory Standard) V-0. In many cases, such high flame retardancy is required, and various flame retardants have been studied and developed.

When such a high degree of flame retardancy is imparted to a resin composition, a chlorine-containing flame retardant or a bromine-containing flame retardant is generally used as a flame retardant, if necessary. It is used in combination with auxiliaries. However, although the flame retardant effect of these flame retardants is great, chlorine compounds and bromine compounds generated by the decomposition of the flame retardants during resin processing corrode the surfaces of cylinders of compounding extruders and molding dies. There's a problem. For this reason,
A method for flame retardation without using any chlorine-containing or bromine-containing flame retardant has been studied.

As one of the flame retardants containing no chlorine or bromine, there is an organic phosphorus-based flame retardant, and its use has been studied in various ways. For example, Japanese Patent Application Laid-Open No. 5-179123 discloses flame retardancy in which an organic phosphorus-based flame retardant, a boron compound, a polyorganosiloxane and a fluorine-based resin are mixed with a resin composition comprising a polycarbonate resin and a resin other than the polycarbonate resin. The resin composition is disclosed in JP-A-6-1925.
No. 53 discloses a flame retardant resin obtained by adding a graft copolymer, an organic phosphorus flame retardant which is an oligomer of an organic phosphorus compound and a fluorinated polyolefin to a resin composition comprising a polycarbonate resin and a polyalkylene terephthalate resin. Each composition is disclosed.

[0009]

The resin composition comprising such a polycarbonate resin and a thermoplastic polyester resin or the like and an organic phosphorus-based flame retardant is mixed with the organic phosphorus-based flame retardant during resin processing such as extrusion molding or injection molding. There is a problem in that an unpleasant odor is generated due to decomposition and aromatic hydroxy compounds such as phenol, cresol and xylenol generated as a result. Odor not only reduces the workability during resin processing, but also remains after forming a molded product, so the product value is low despite the fact that a molded product with excellent properties is obtained. There is a problem that it is significantly reduced.

When a molded article made of the above resin composition is used for parts requiring solvent resistance and oil resistance, etc., while maintaining a certain level of strength, it does not come into contact with an organic solvent or oil for a long time. When it is hot or when heat is applied,
When distortion remains during molding, for example, the solvent resistance and oil resistance are not sufficient, and there are problems such as reduced strength and cracks.

As a method for improving the solvent resistance and oil resistance, Japanese Patent Application Laid-Open No. 3-140359 proposes a method in which a polyolefin is further added to a polycarbonate resin and a thermoplastic polyester resin. However, even in this method, the solvent resistance and the oil resistance in the case of prolonged contact or heating are not sufficient.

[0012]

Means for Solving the Problems The present inventors have reduced the odor of a flame-retardant thermoplastic resin composition obtained by adding a thermoplastic polyester resin and an organic phosphorus-based flame retardant to a polycarbonate resin, and have improved the solvent resistance and the like. As a result of intensive studies to improve the oil resistance, a thermoplastic polyester resin polymerized using a specific catalyst was used as the thermoplastic polyester resin, and a specific olefin unit and a specific (meth) acrylic acid were used. By adding a specific amount of a copolymer containing an alkyl ester unit, odor is reduced and chemical resistance (for example, gasoline resistance, oil resistance,
It has been found that a flame-retardant thermoplastic resin composition containing neither a chlorine-containing compound nor a bromine-containing compound having improved plasticizer resistance and the like can be obtained, and the present invention has been completed.

That is, the present invention comprises (A) a polycarbonate resin and (B) a thermoplastic polyester resin polymerized using a germanium compound as a catalyst,
(A) component / (B) component is 99 / 1-20 / 8 by weight ratio.
With respect to 100 parts (parts by weight, hereinafter the same) of the resin composition (I) which is 0, (C) a general formula (I):

[0014]

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(Wherein, R ^{1 to} R ³ are all monovalent groups, each independently being an aliphatic group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, 12 alicyclic groups, R
⁴ is a monovalent aromatic group having 6 to 20 carbon atoms, X is a divalent group, and is an aliphatic group having 2 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or a 3 to 30 carbon atom. A linking group consisting of an alicyclic group or a combination thereof, m is independently 0 or 1, r n are each independently 0 to 5, p
And q are each 0 to 2 and r is 1 to 3, satisfying p + q + r = 3), and 1 to 30 parts of an organophosphorous flame retardant represented by the formula (D): at least one olefin unit; Flame retardant thermoplastic resin composition containing 0.5 to 15 parts of a copolymer containing at least one alkyl (meth) acrylate unit having an alkyl group having 1 to 10 carbon atoms (claim 1) A flame-retardant thermoplastic resin composition obtained by further adding (E) 0.1 to 100 parts of a silicate compound to the flame-retardant thermoplastic resin composition according to claim 1 (claim 2); A flame-retardant thermoplastic resin composition obtained by further adding (F) 0.01 to 5 parts of a fluororesin to the flame-retardant thermoplastic resin composition according to claim 1 or 2 (claim 3). The flame-retardant thermoplastic resin composition according to claim 1, 2 or 3. Further, (G) a reinforcing filler 0.5
To 100 parts by weight of the flame-retardant thermoplastic resin composition (claim 4), the flame-retardant thermoplastic resin composition according to claim 1, 2, 3 or 4, and (H) an epoxy compound. A flame-retardant thermoplastic resin composition containing 0.01 to 15 parts (Claim 5), wherein the thermoplastic polyester resin is a polyalkylene terephthalate resin.
The flame-retardant thermoplastic resin composition according to claim 3, 4, or 5, wherein the thermoplastic polyester resin is a polyethylene terephthalate resin. The resin composition (claim 7) and the organic phosphorus-based flame retardant (C) are represented by the general formula (II):

[0016]

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(Wherein, R ^{5 to} R ¹⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, 4 R ^{15 s} ,
R ¹⁶ may be different; Y is a direct bond;
3 alkylene _{group, -S -, - SO 2 -} , - O -, - C
Or a divalent linking group wherein O- or -N = N-, and t represents 0 or 1). 7. The flame-retardant thermoplastic resin composition according to claim 7, wherein the copolymer (D) has at least one olefin unit and at least one (meth) ene having an alkyl group having 1 to 10 carbon atoms. ) 40/60 acrylic acid alkyl ester units
And a copolymer having a melt index (MI) of 2 to 500 g / 10 min (at 190 ° C., 2
The present invention relates to the flame-retardant thermoplastic resin composition according to claim 1, 2, 3, 4, 5, 6, 7, or 8 (kg claim, based on JIS K6730).

[0018]

DETAILED DESCRIPTION OF THE INVENTION The polycarbonate resin (A), which is the component (A) used in the present invention, comprises one or more dihydric or higher polyhydric phenol compounds and a divalent carbonate such as phosgene or diphenyl carbonate. It is a thermoplastic polycarbonate resin obtained by reacting with at least one ester, and is a component used for improving heat resistance and impact resistance of a thermoplastic polyester resin.

Specific examples of the dihydric phenol compound among the dihydric or higher polyhydric phenol compounds include hydroquinone, 4,4'-dihydroxydiphenyl, 1,1-
Bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, bis (4-hydroxyphenyl) sulfone, , 4'-dihydroxyphenyl ether and the like. Among these, 2,2-bis (4-hydroxyphenyl) propane is preferred from the viewpoint of heat resistance and mechanical properties.

Specific examples of the trivalent or higher polyhydric phenol compound among the above dihydric or higher polyhydric phenol compounds include 1,1,1-tris (4-hydroxyphenyl) ethane.

The polyhydric phenol compounds may be used alone or in combination of two or more.

When a trihydric or higher polyhydric phenol compound is used together with the dihydric phenol compound as the dihydric or higher polyhydric phenol compound, the ratio of dihydric phenol compound / trihydric or higher polyhydric phenol compound is used. Is preferably from 100/1 to 4/1 in terms of molar ratio from the viewpoint of fluidity.

Further, in order to enhance flame retardancy, a polymer obtained by copolymerizing a phosphorus compound or terminal-blocking with a phosphorus compound may be used. In order to enhance weather resistance, a polymer having a benzotriazole group may be used. A polymer obtained by copolymerizing a dihydric phenol compound may be used.

Polycarbonate resin (A) as described above
Has a viscosity average molecular weight of preferably 10,000 to 50,000, more preferably 15,000 to 45,000, particularly 180
00 to 35000. Viscosity average molecular weight 10,000
If it is less than 5,000, the strength and heat resistance of the obtained resin composition tend to decrease. If it exceeds 50,000, the moldability tends to decrease.

The polycarbonate resin (A) as described above
Specific examples include polycarbonate obtained from 2,2-bis (4-hydroxyphenyl) propane and phosgene or diphenyl carbonate.

In the present invention, the thermoplastic polyester resin (B) polymerized by using a germanium compound as a catalyst
(Hereinafter, when the thermoplastic polyester resin (B) is described, it is polymerized using a germanium compound as a catalyst). Since the thermoplastic polyester resin is polymerized using a germanium-based catalyst, the odor due to the aromatic hydroxy compound is reduced even when an organic phosphorus-based flame retardant represented by the following general formula (I) is used. Can be done.

The thermoplastic polyester resin is a saturated polyester resin obtained by polycondensing an aromatic dicarboxylic acid or an ester-forming derivative thereof with a dihydric alcohol or an ester-forming derivative thereof. It is a component used to improve the fluidity, chemical resistance and the like of the polycarbonate resin (A).

Specific examples of the aromatic dicarboxylic acid include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 1,2 -Bis (phenoxy) ethane-
Examples thereof include aromatic dicarboxylic acids having 8 to 22 carbon atoms, such as 4,4'-dicarboxylic acid and 5-sodium sulfoisophthalic acid. Of these, terephthalic acid and naphthalenedicarboxylic acid are preferred because of their excellent heat resistance, chemical resistance and moisture resistance.

Specific examples of the dihydric alcohol include dihydric aliphatic alcohols having 2 to 15 carbon atoms, such as ethylene glycol, propanediol, butanediol, hexanediol, decanediol and neopentylglycol, cyclohexanediol, and the like. C6-20 divalent alicyclic alcohols such as cyclohexanedimethanol and 2,2-bis (4-hydroxycyclohexyl) propane; and C6 carbon atoms such as 2,2-bis (4-hydroxyphenyl) propane and hydroquinone To 40 dihydric aromatic alcohols or dihydric phenol compounds. Of these, ethylene glycol and butanediol are preferred because of their excellent heat resistance and moisture resistance.

Examples of the thermoplastic polyester resin produced from the aromatic dicarboxylic acid and the dihydric alcohol include polyalkylene terephthalate resin, polyalkylene naphthalate resin, polyalkylene isophthalate resin, polyarylate resin and the like. Among these, polyalkylene terephthalate resins and polyalkylene naphthalate resins are preferred because they have a good balance of workability, mechanical properties, electrical properties, heat resistance, and the like, and have high performance.

Specific examples of the polyalkylene terephthalate resin include polyethylene terephthalate resin, polybutylene terephthalate resin, and polyhexamethylene terephthalate resin. Specific examples of the polyalkylene naphthalate resin include polyethylene naphthalate resin and polyalkylene terephthalate resin. Butylene naphthalate resin, polycyclohexane dimethylene naphthalate resin, and the like.
Particularly preferred among these specific examples are:
Polyethylene terephthalate resin is cited because it has a better balance of processability, heat resistance and chemical resistance and has high performance.

The thermoplastic polyester resin preferably contains 20% (% by weight, the same applies hereinafter) as required,
More preferably 15% or less, particularly preferably 10%
At the following ratio, other carboxylic acid components other than aromatic dicarboxylic acid, other alcohol components other than dihydric alcohol, oxyacid components, and copolymer components such as derivatives or cyclic esters thereof having ester forming ability. It may be copolymerized.

Examples of the copolymer component include aliphatic carboxylic acids having 4 to 12 carbon atoms, alicyclic carboxylic acids having 8 to 15 carbon atoms, and aromatic polycarboxylic acids having a tri- or higher moiety, which are the other carboxylic acid components. Examples thereof include carboxylic acids and derivatives thereof having an ester forming ability. Specific examples thereof include aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid and maleic acid, and alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. And aromatic tri- or tetracarboxylic acids such as trimesic acid, trimellitic acid, and pyromellitic acid, and the above-mentioned carboxylic acid derivatives having an ester-forming ability. Examples of the other alcohol component include aliphatic polyalcohols having 3 to 15 carbon atoms or more, alicyclic polyalcohols having 6 to 20 carbon atoms or more, and tri or more alcohols having 6 to 40 carbon atoms. Aromatic polyalcohols or polyphenolic compounds, derivatives thereof having an ester forming ability, and the like can be given. Specific examples thereof include aliphatic tri- or tetra-alcohols such as glycerin and pentaerythritol, and derivatives thereof having ester-forming ability. Specific examples of the oxyacid component include oxyacids such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid, and derivatives thereof having an ester-forming ability. Specific examples of the cyclic ester include: ε-caprolactone and the like.

The thermoplastic polyester resin has a number-average molecular weight of 100 to 10,000, and more preferably 5 to 5 for the purpose of improving moldability, impact resistance, and surface properties of the obtained molded article.
The polyoxyalkylene glycol of 00 to 5000 may be partially copolymerized. Specific examples of the polyoxyalkylene glycol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and random or block copolymers thereof, and general formula (III):

[0035]

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(Wherein, R ¹⁷ is an alkylene group having 2 to 5 carbon atoms, Z is a direct bond or an alkylene group having 1 to 3 carbon atoms,
_{-S -, - SO 2 -,} - O -, - CO- or -N =
A and b are each an integer of 1 or more, and a + b is 3 or more, preferably an integer of 4 to 20, and (a + b) R ¹⁷ may be different. And modified polyoxyalkylene glycols such as an alkylene glycol adduct of a bisphenol compound represented by Of these, bisphenol A adducts of polyethylene glycol are preferred because the thermal stability during copolymerization is good and the heat resistance of molded articles obtained from the resin composition of the present invention is not easily reduced.

The polyalkylene glycol is copolymerized at a ratio of 0.1 to 0.1% in the thermoplastic polyester resin.
It is preferred that the content be 1 to 20%, more preferably 0.1 to 10%, from the viewpoint of heat resistance, chemical resistance, mechanical strength, and flame retardancy.

Examples of the germanium compound used as the polymerization catalyst include germanium oxides such as germanium dioxide, germanium alkoxides such as germanium tetraethoxide and germanium tetraisopropoxide, germanium hydroxide and alkali metal salts thereof, and germanium glycol. And germanium chloride, germanium acetate and the like. These may be used alone or in combination of two or more. Among them, germanium dioxide is preferred because it has excellent reactivity in polymerization and has few by-products.

The amount of the germanium compound used as a polymerization catalyst is preferably 0.005 to 0.1%, more preferably 0.01 to 0.05%, based on the thermoplastic polyester resin.
% Is more preferred. If the amount is less than 0.005%, the progress of the polymerization reaction is slow. If the amount exceeds 0.1%, a side reaction tends to easily occur due to the germanium compound remaining in the resin after the reaction. The addition may be made at any time before the start of the polymerization reaction.

The thermoplastic polyester resin (B) can be produced by a known polymerization method, for example, a melt polycondensation method, a solid phase polycondensation method, a solution polymerization method and the like.

In order to improve the color of the resin during polymerization, phosphoric acid, phosphorous acid, hypophosphorous acid, monomethyl phosphate, dimethyl phosphate, trimethyl phosphate, methyl diethyl phosphate,
Compounds such as triethyl phosphate, triisopropyl phosphate, tributyl phosphate, and triphenyl phosphate may be added. Further, in order to increase the crystallinity of the obtained thermoplastic polyester resin (B), one or more kinds of various kinds of generally known organic or inorganic crystal nucleating agents (for example, talc) may be added at the time of polymerization. .

The intrinsic viscosity of the thermoplastic polyester resin (B) (phenol / tetrachloroethane is 1/1 in weight ratio)
(Measured in a mixed solvent of 25 ° C.) is 0.4 to 1.2 dl /
g, preferably 0.5 to 1.0 dl / g.
It is preferred that If the intrinsic viscosity is less than 0.4 dl / g, mechanical strength and impact resistance tend to decrease,
If it exceeds 1.2 dl / g, the fluidity tends to decrease.

The thermoplastic polyester resin (B) polymerized by using a germanium compound as described above may be used alone or in combination of two or more.

The mixing ratio between the polycarbonate resin (A) and the thermoplastic polyester resin (B) is 99/1 by weight.
20/80, preferably 97/3 to 25/75, more preferably 95/5 to 30/70. When the weight ratio of the component (A) / the component (B) is less than 20/80, the resulting molded article has reduced flame retardancy and generates many burrs. On the other hand, if it exceeds 99/1, chemical resistance (for example, gasoline resistance, oil resistance, plasticizer resistance) and moldability are reduced.

The organophosphorus flame retardant (C) used in the present invention has the general formula (I):

[0046]

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(Wherein, R ^{1 to} R ³ are each a single group, each independently being an aliphatic group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or a group having 3 to 12 carbon atoms. An alicyclic group of R ⁴
Is a monovalent aromatic group having 6 to 20 carbon atoms, X is a divalent group, and is an aliphatic group having 2 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or an aliphatic group having 3 to 30 carbon atoms. A bonding group consisting of a cyclic group or a group obtained by combining them (for example, an aromatic group substituted with an aliphatic group), m is independently 0 or 1, and r n are each independently 0 to 5; , P and q
Are each 0 to 2 and r is 1 to 3, and p + q
+ R = 3), wherein at least one of the substituents on at least one phosphorus atom in one molecule is substituted with an aromatic alkoxy group.
It is a component that does not contain chlorine and bromine atoms and is used as a flame retardant with good heat stability and moisture resistance.

R ^{1 to} R ³ in the general formula (I) each independently represent a monovalent aliphatic group having 1 to 12 carbon atoms (eg, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, n-
Butyl group, n-hexyl group, n-octyl group, n-decyl group, etc., monovalent aromatic group having 6 to 12 carbon atoms (for example, phenyl group, cresyl group, dimethylphenyl group, naphthyl group, etc.), carbon A monovalent alicyclic group of the formulas 3 to 12 (for example, a cyclohexyl group, a cyclopentyl group, a cyclododecane group, etc.), and when R ^{1 to} R ³ are these, the dispersibility in the resin is good. preferable. Of these, R ¹ , R ² , and R ³ are all monovalent aromatic groups having 6 to 12 carbon atoms, specifically, phenyl, cresyl, dimethylphenyl, and naphthyl. It is preferable because of its excellent thermal stability.

R ⁴ in the general formula (I) represents a phenyl group, a cresyl group, a dimethylphenyl group, a naphthyl group, an ethylphenyl group, a propylphenyl group or the like having 6 to 6 carbon atoms.
The monovalent aromatic group of 20 is preferable in this case from the viewpoint of thermal stability. Of these, cresyl, dimethylphenyl, and naphthyl are preferred because they are more excellent in heat stability and moisture resistance.

Further, X in the general formula (I) has 2 carbon atoms.
To 30 divalent aliphatic groups (e.g., ethylene group, propylene group, i-propylene group, butylene group, 1,1-dimethylmethylene group, etc.) and divalent aromatic groups having 6 to 30 carbon atoms (e.g., phenylene Group, methylphenylene group, biphenylene group, etc.), a divalent alicyclic group having 3 to 30 carbon atoms (for example, cyclohexylene group, cyclododecylene group,
A divalent group (eg, cyclopentylene group), a divalent aliphatic group, an aromatic group, or an alicyclic group in combination.
Bisphenol A group), but in these cases,
Heat resistance is improved. Among them, a phenylene group and a divalent bisphenol A group are preferable because they are easy to synthesize and have good heat stability and moisture resistance.

The (p + q + n × r) m in the general formula (I) are each independent and are 0 or 1, and especially when 1, the dispersibility in the resin becomes better.

In the general formula (I), n is from 0 to 5. In this case, the dispersibility in the resin is improved, and it is particularly preferable that n is from 1 to 3.

Further, p and q in the general formula (I) are each 0 to 2, and r is 1 to 3, and p + q + r
= 3, but for this reason, the general formula:

[0054]

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At least one group represented by the formula (1) is present, and the dispersibility in the resin is improved.

Among the organophosphorous flame retardants (C) represented by the general formula (I) as described above, preferred are, for example, those represented by the general formula:

[0057]

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The following can be mentioned.

Specific examples of the organophosphorus flame retardant (C) include phosphates, phosphonates, phosphinates having aromatic alkoxy groups, and condensates thereof. Among these compounds, phosphates having an aromatic alkoxy group and condensates thereof are preferable in terms of good compatibility with the thermoplastic polyester resin (B) and excellent flame retardancy, and furthermore, heat stability of the phosphate itself. From the viewpoint of good properties, a phosphate in which all the substituents on a phosphorus atom are substituted with an aromatic alkoxy group and a condensate thereof are preferable.

Specific examples of the phosphate in which all the substituents on the phosphorus atom are substituted with an aromatic alkoxy group include triphenyl phosphate, tricresyl phosphate, dicresyl phenyl phosphate, cresyl diphenyl phosphate, tricylyl phosphate, Dixylyl phenyl phosphate, xylyl diphenyl phosphate, tri (isopropylphenyl) phosphate,
Tribiphenyl phosphate, trinaphthyl phosphate and condensates thereof, and furthermore, general formula (II):

[0061]

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[0062] (wherein, R ⁵ to R ¹⁶ each independently represent hydrogen atom or an alkyl group (methyl group of 1 to 4 carbon atoms, an ethyl group, a propyl group and a butyl group), four R ^15, R
¹⁶ may be different, Y is a direct bond, an alkylene group having 1 to 3 carbon atoms (methylene group, ethylene group,
1,1-dimethylmethylene group, propylene group, etc.),-
_{S -, - SO 2 -,} - O -, - CO- or -N = N-
And t represents 0 or 1).

Among the organophosphorus flame retardants (C), they themselves have low volatility during molding and good thermal stability, and impair the thermal stability and physical properties of the resin composition (I). From the viewpoint of difficulty, the condensed phosphate represented by the general formula (II) is preferable.

In the general formula (II), at least one of R ^{5 to} R ⁹ is an alkyl group having 1 to 4 carbon atoms and / or
^When at least one of ^{10 to} R ¹⁴ is an alkyl group having 1 to 4 carbon atoms, it is preferable because the thermal stability is further improved. In this case, the molecular weight is increased, so that the volatility is further reduced, which is preferable.

Specific examples of the above-mentioned condensed phosphate ester include, for example, resorcinol bis (diphenyl) phosphate, methylresorcinol bis (diphenyl) phosphate, hydroquinone bis (diphenyl) phosphate, biphenol bis (diphenyl) phosphate,
Bisphenol A bis (diphenyl) phosphate, bisphenol S bis (diphenyl) phosphate, formula (IV):

[0066]

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The resorcinol bis (di-) represented by the formula
2,6-xylyl) phosphate, methylresorcinol bis (di-2,6-xylyl) phosphate, formula (V):

[0068]

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The hydroquinone bis (di-
2,6-xylyl) phosphate, bisphenol bis (di-2,6-xylyl) phosphate, bisphenol A bis (di-2,6-xylyl) phosphate, bisphenol S bis (di-2,6-xylyl) phosphate, resorcinol Bis (dicresyl) phosphate,
Methylresorcinol bis (dicresyl) phosphate, hydroquinone bis (dicresyl) phosphate,
Bisphenol bis (dicresyl) phosphate, formula (VI):

[0070]

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Bisphenol A bis (dicresyl) phosphate, bisphenol S bis (dicresyl) phosphate, resorcinol bis (di-2,
4,6-trimethylphenyl) phosphate, methylresorcinol bis (di-2,4,6-trimethylphenyl) phosphate, hydroquinone bis (di-2,4,
6-trimethylphenyl) phosphate, bisphenol bis (di-2,4,6-phenyl) phosphate, bisphenol A bis (di-2,4,6-trimethylphenyl) phosphate, bisphenol S bis (di-2,
4,6-trimethylphenyl) phosphate, and condensates thereof. Among these, resorcinol bis (di-2,6-xylyl) phosphate, hydroquinone bis (di-2,6-xylyl) phosphate and bisphenol A bis (dicresyl) phosphate have excellent thermal stability and low volatility. Preferred from the point.

These organophosphorus flame retardants (C) may be used alone or in combination of two or more.

The amount of the organic phosphorus-based flame retardant (C) is from 1 to 30 parts, preferably from 1.5 to 27 parts, more preferably from 2 to 25 parts, per 100 parts of the resin composition (I).
Department. If the added amount is less than 1 part, the flame retardancy will be reduced, and if it exceeds 30 parts, the chemical resistance will be reduced, the burr of the molded product will be easily generated, and the odor will be remarkable.

The copolymer (D) used in the present invention is a copolymer containing at least one olefin unit and at least one alkyl (meth) acrylate unit having an alkyl group having 1 to 10 carbon atoms. It is used for the purpose of improving the chemical resistance, and is further used in a resin composition containing a silicate compound for the purpose of improving the rib strength, in order to obtain a greater rib strength improving effect. Component.

The olefin unit constituting the copolymer (D) is for imparting an effect of improving the chemical resistance to the copolymer (D), and specific examples thereof include ethylene, propylene and 1-butene. And units formed when radical polymerization of 1-pentene is performed. One of these olefin groups may be contained in the copolymer (D).
More than one species may be included. Among the olefin groups, an ethylene group is preferred from the viewpoint of improving chemical resistance.

The copolymer (D) has 1 carbon atom.
The (meth) acrylic acid alkyl ester unit having an alkyl group of from 10 to 10 is for dispersing the copolymer (D) in a resin in good condition, and the alkyl group has 1 to 1 carbon atoms.
10 and preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms. If the carbon number of the alkyl group is more than 10, the compatibility with other components is reduced, the dispersion is poor in the resin composition, and the effect of improving the chemical resistance is not preferable.

Specific examples of the (meth) acrylic acid alkyl ester unit include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, t-butyl acrylate, methyl methacrylate, ethyl methacrylate, Examples include units from n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, and the like. These may be contained alone in the copolymer (D) or in combination of two or more. Among the (meth) acrylic acid alkyl ester units, a methyl acrylate unit and an ethyl acrylate unit are preferable from the viewpoint of improving dispersibility in a resin.

At least one of the copolymer (D)
The ratio of the olefin units and the at least one alkyl (meth) acrylate unit having an alkyl group having 1 to 10 carbon atoms is preferably 40/60 by weight.
９５95/5, more preferably 45/55 to 90/1
0, particularly preferably 50/50 to 85/15.
When the ratio of the olefin unit to the alkyl (meth) acrylate unit is more than 95/5, the effect of improving the chemical resistance is reduced, and when the ratio is less than 40/60, the thermal stability at the time of melting (for example, at the time of molding) is reduced. Tend to.

The melt index (M) of the copolymer (D)
I) The value is 190 ° C, 2 kg load condition (JIS K6
730), preferably from 2 to 500 g / 10 min, more preferably from 4 to 400 g / 10 min, especially from 5 to 3 g.
00 g / 10 min. If the MI value is less than 2 g / 10 minutes, poor dispersion tends to occur in the resin composition, and the effect of improving chemical resistance tends to be small. In addition, 500g /
If it exceeds 10 minutes, the thermal stability at the time of melting (at the time of molding) tends to decrease.

The copolymer (D) may be used alone,
Two or more copolymer components having different MI values may be used in combination.

The copolymer (D) is obtained by radical polymerization of one or more olefins and one or more alkyl (meth) acrylates in the presence of a radical polymerization initiator. Is not limited to this method, and can be polymerized using various generally known polymerization methods. Copolymer (D)
May be produced by an arbitrary copolymerization method such as a random copolymerization method, a block copolymerization method, and a graft copolymerization method.

Specific examples of the copolymer (D) include an ethylene-ethyl (meth) acrylate copolymer and an ethylene-methyl (meth) acrylate copolymer.

The copolymer (D) is added in an amount of 0.5 to 100 parts of the resin composition (I) comprising the polycarbonate resin (A) and the thermoplastic polyester resin (preferably polyethylene terephthalate resin) (B). ~ 15 copies,
Preferably 0.7 to 12 parts, more preferably 1.05
To 10 parts. When the addition amount is less than 0.5 part, the effect of improving the chemical resistance is small, and when it exceeds 15 parts,
It is not preferable because flame retardancy is reduced.

The flame-retardant thermoplastic resin composition (II) of the present invention comprising the above components (A) to (D) further contains a silicate compound (E) to reduce the rib strength. An improved flame-retardant thermoplastic resin composition (III) can be obtained. At this time, since the copolymer is used together with the copolymer (D), the rib strength is further improved as compared with the case where the copolymer (D) is not used, so that the moldability can be improved.

The silicate compound (E) is a compound having a chemical composition in the form of a powder, granule, needle, plate or the like containing SiO ₂ units. Aluminum silicate, calcium silicate, talc, mica, wollastonite, kaolin, diatomaceous earth,
And smectite. It may be natural or synthetic, and may be a fired or unfired product, and may be a hydrate or an anhydrate. Among these silicate compounds (E), talc, mica, kaolin, and smectite are preferred from the viewpoint of improving the thermal stability of the resin composition, and mica is particularly preferred.

The preferred average diameter of the silicate compound (E) (particle diameter when converted into a circle determined by image processing of a micrograph) is 0.05 to 40 μm.
m, more preferably 0.1 to 35 μm, especially 0.3 to 30
μm. If the average diameter is less than 0.05 μm, the effect of improving the rib strength is not sufficient, and if the average diameter exceeds 40 μm, the rib strength,
In particular, the toughness tends to decrease.

Further, the silicate compound (E) may be treated with a surface treating agent such as a silane coupling agent or a titanate coupling agent. Examples of the silane coupling agent include an epoxy silane coupling agent, an amino silane coupling agent, and a vinyl silane coupling agent. Examples of the titanate coupling agent include a monoalkoxy type and a chelate type. , And coordinated type.

The method for treating the silicate compound with the surface treating agent is not particularly limited, and can be carried out by a usual method. For example, it can be carried out by adding the surface treatment agent to the layered silicate compound, and stirring or mixing in a solution or while heating.

The addition amount of the silicate compound (E) is 100 parts or less, preferably 60 parts or less, more preferably 40 parts or less based on 100 parts of the resin composition (I). The lower limit is 0.1 part, more preferably 0.5 part, at which the effect of addition can be obtained. Exceeding 100 parts is not preferable because the extrusion processability, the formability, the rib strength, and particularly the toughness are reduced.

The flame-retardant thermoplastic resin composition of the present invention (I
Fluororesin (F) may be added to (I) and (III) to further improve flame retardancy. The flame-retardant thermoplastic resin compositions (II), (III) and the fluororesin (F) added are referred to as flame-retardant thermoplastic resin compositions (IIF), (IIIF).

The fluororesin (F) is a resin containing at least 30%, more preferably at least 40%, of fluorine atoms in the monomer units constituting the fluororesin (F). Examples thereof include polymonofluoroethylene, polydifluoroethylene, polytrifluoroethylene, polytetrafluoroethylene, and tetrafluoroethylene-hexafluoropropylene copolymer. Further, as long as the physical properties such as flame retardancy of the obtained molded article are not impaired, a monomer used for producing the fluororesin and a copolymerizable monomer may be copolymerized as necessary. Polymer may be used. The copolymerization ratio of a monomer containing a fluorine atom and a monomer copolymerizable therewith, which is used in the production of the copolymer, is usually 50/50 to 95/5 by weight.
These fluororesins may be used alone or in combination of two or more.

The molecular weight of the fluororesin (F) is preferably from 1,000,000 to 20,000,000, more preferably from 2,000,000 to 2,000,000.
10 million.

The fluororesin (F) can be produced by a generally known method such as an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method, and a solution polymerization method.

The addition amount of the fluororesin (F) is 0.01 to 5 parts, preferably 0.05 to 4 parts, more preferably 0.1 to 3 parts per 100 parts of the resin composition (I). .5 parts. If the addition amount is less than 0.01 part, the effect of improving the flame retardancy is small, while if it exceeds 5 parts, the moldability and the like deteriorate.

The flame-retardant thermoplastic resin composition of the present invention (I
A reinforcing filler (G) may be further added to (I), (III), (IIF) and (IIIF) in order to improve mechanical properties, heat resistance and the like.

Specific examples of the reinforcing filler (G) include, for example, glass fiber, carbon fiber, potassium titanate fiber, glass beads, glass flake, calcium carbonate, calcium sulfate, barium sulfate and the like. Among them, fibrous reinforcing agents such as glass fibers and carbon fibers are preferable from the viewpoint of the reinforcing effect, and chopped strand glass fibers treated with a sizing agent are preferably used from the viewpoint of workability. Further, in order to enhance the adhesiveness between the resin and the fibrous reinforcing agent, it is preferable that the surface of the fibrous reinforcing agent is treated with a coupling agent, and a material using a binder may be used.

Examples of the coupling agent include γ
Alkoxysilane compounds such as -aminopropyltriethoxysilane and γ-glycidoxypropyltrimethoxysilane are preferably used, and as the binder, for example, epoxy resin and urethane resin are preferably used, but not limited thereto. These may be used alone or in combination of two or more.

The amount of the reinforcing filler (G) used is 0.5 to 100 parts, preferably 1 to 70 parts, more preferably 2 to 50 parts based on 100 parts of the resin composition (I). . If the amount of the reinforcing filler is less than 0.5 part, the effect of improving the mechanical properties and heat resistance is small, and if it exceeds 100 parts, the extrudability and the formability are reduced.

When glass fibers are used as the reinforcing filler, the diameter is preferably about 1 to 20 μm and the length is about 0.01 to 50 mm. If the fiber length is too short, the effect of reinforcement is not sufficient, and if it is too long, on the other hand, the surface properties and extrusion processability of the molded product,
Moldability tends to be poor.

The flame-retardant thermoplastic resin composition of the present invention (I
I), (III), (IIF), (IIIF), and the above four types of compositions each having a reinforcing filler added thereto, have chemical resistance and heat during melting (for example, during molding). To further improve the stability and prevent coloring, an epoxy compound (H) may be added.

The epoxy compound (H) is a compound having at least one epoxy group in the molecule and containing no halogen atom in the molecule. Specific examples thereof include N-glycidylphthalimide, N-glycidyltetrahydrophthalimide, phenyl Glycidyl ether, p-butylphenyl glycidyl ether, neohexene oxide, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tetramethylene glycol diglycidyl ether, polytetramethylene glycol di Glycidyl ether, bisphenol A type epoxy compound,
Bisphenol S epoxy compound, resorcinol epoxy compound, phenol novolak epoxy compound, orthocresol novolak epoxy compound, diglycidyl adipate, diglycidyl sebacate, diglycidyl phthalate, glycidyl methacrylate, glycidyl acrylate, ethylene- Glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-vinyl acetate copolymer and the like can be mentioned. These epoxy compounds may be used singly.
A combination of more than one species may be used. Among these, a bisphenol A type epoxy compound is preferred because it has more excellent coloring property improving effect.

The addition amount of the epoxy compound (H) is preferably 0.01 to 15 parts, more preferably 0.05 to 10 parts, and more preferably 0.1 to 5 parts with respect to 100 parts of the resin composition (I). Particularly preferred. When the addition amount is less than 0.01 part, the effect of improving the thermal stability is small, and when it exceeds 15 parts,
Flame retardancy and chemical resistance decrease.

The flame-retardant thermoplastic resin composition of the present invention comprises:
Still other arbitrary thermoplastic resins or thermosetting resins within a range not impairing the object of the present invention, for example, polyolefin resin, polyamide resin, polystyrene resin, polyphenylene sulfide resin, polyphenylene ether resin, polyacetal resin , A polysulfone-based resin, a polyarylate-based resin, a rubber-like elastic material, or the like may be added alone or in combination of two or more.

In order to improve the performance of the flame-retardant thermoplastic resin composition of the present invention, antioxidants such as phenolic antioxidants and thioether antioxidants, and heat stabilizers such as phosphorus stabilizers. May be used alone or in combination of two or more. Further, if necessary, other well-known stabilizers, lubricants, mold release agents, plasticizers, non-phosphorus-based flame retardants, flame retardant aids, ultraviolet absorbers, light stabilizers, pigments, dyes, Additives such as antistatic agents, conductivity-imparting agents, dispersants, compatibilizers, and antibacterial agents may be added.

The method for producing the composition of the present invention is not particularly limited. For example, it can be produced by a method of drying the above-mentioned components, other additives, resins and the like, followed by melt-kneading with a melt-kneading machine such as a single screw or twin screw extruder.
When the compounding agent is a liquid, the compounding agent can be added to a twin-screw extruder midway using a liquid supply pump or the like to produce the compounding agent.

The method for forming the flame-retardant thermoplastic resin composition of the present invention is not particularly limited, and general methods for forming the thermoplastic resin composition, such as injection molding, blow molding, extrusion molding, and the like. It can be formed by a method such as a vacuum forming method, a press forming method, and a calendar forming method.

As the composition of the present invention, the component (A)
When the composition according to claim 1 comprising the component (D) is used, the odor is reduced and the obtained molded article is excellent in flame retardancy and chemical resistance.

When the composition according to the second aspect, in which the component (E) is added to the composition according to the first aspect, is used, the odor is reduced and the flame retardancy of the obtained molded article is reduced. Excellent chemical resistance and rib strength.

When the composition according to the third aspect, in which the component (F) is added to the composition according to the first aspect, is used, the odor is reduced and the obtained molded article is highly flame-retardant. Excellent in chemical resistance.

When the composition according to the fourth aspect, in which the component (G) is added to the composition according to the first aspect, is used, the odor is reduced and the obtained molded article has flame retardancy, Excellent chemical resistance, mechanical properties and heat resistance.

When the composition according to the fifth aspect, in which the component (H) is added to the composition according to the first aspect, is used, the odor is reduced and the obtained molded article has flame retardancy, Excellent in chemical resistance and heat stability.

[0112] When the composition according to the third aspect is obtained by adding the component (E) and the component (F) to the composition according to the first aspect, the odor is reduced and the molded article obtained is obtained. Has high flame retardancy, excellent chemical resistance and rib strength.

The composition according to claim 1, further comprising:
When the composition according to claim 4 to which the component (F) and the component (G) are added is used, the odor is reduced, and the obtained molded article has high flame retardancy and is resistant to flame. Excellent chemical properties, mechanical properties, heat resistance, and rib strength.

The composition according to claim 1, further comprising:
When the composition according to claim 5 to which the component (F) and the component (H) are added, the odor is reduced, and the obtained molded article has high flame retardancy and is resistant to flame. Excellent chemical properties, thermal stability, and rib strength.

The composition according to claim 1, further comprising:
When the composition according to claim 5 to which the component (G) and the component (H) are added, the odor is reduced, and the obtained molded article has high flame retardancy and is resistant to chemicals. sex,
Excellent heat stability, mechanical properties and heat resistance.

The composition according to claim 1, further comprising (E) a component
In the case of the composition according to claim 5, wherein the component (F), the component (G) and the component (H) are added, the odor is reduced, and the molded article has high flame retardancy; Excellent in chemical resistance, heat stability, mechanical properties, heat resistance and rib strength.

[0117]

EXAMPLES Next, the composition of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

The main raw materials used in the examples and comparative examples are summarized below.

Polycarbonate resin (A) PC (A-1): bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 22,000 PC (A-2): bisphenol A type polycarbonate resin having a viscosity average molecular weight of about 28,800 Thermoplastic polyester resin PET ( B-1): Polyethylene terephthalate having an intrinsic viscosity of 0.75 dl / g obtained by polymerizing germanium dioxide as a catalyst (using 0.03% with respect to the resin) PET (B-2): Using germanium dioxide as a catalyst (with respect to the resin) Polyethylene terephthalate having an intrinsic viscosity of 0.61 dl / g (polymerized as 0.03%) PTE (b-3): intrinsic viscosity of antimony trioxide as a catalyst (0.03% used relative to resin) 0.
75 dl / g polyethylene terephthalate Organophosphorus flame retardant (C) Organophosphorus flame retardant (C-1): bisphenol A bis (dicresyl) phosphate Organophosphorus flame retardant (C-2): Resorcinol bis (di-2, 6-xylyl) phosphate Organophosphorus flame retardant (C-3): Hydroquinone bis (di-2,6-xylyl) phosphate Organophosphorus flame retardant (C-4): Resorcinol bis (diphenyl) phosphate Organophosphorus flame retardant (C-5): tri-2,6-xylyl phosphate copolymer (D) copolymer (D-1): EVAFLEX-EEA A7
09 (Ethylene-ethyl acrylate copolymer manufactured by Du Pont-Mitsui Polychemicals, Inc., ethyl acrylate content 35%, MI value 25 g / 10 min) Copolymer (D-2): EVAFLEX-EEA A7
13 (Ethylene-ethyl acrylate copolymer manufactured by DuPont-Mitsui Polychemicals, Inc., ethyl acrylate content 25%, MI value 20 g / 10 min) Copolymer (D-3): EVAFLEX-EEA A7
04 (Ethylene-ethyl acrylate copolymer, manufactured by Du Pont-Mitsui Polychemicals, Inc., ethyl acrylate content 25%, MI value 275 g / 10 min) Copolymer (D-4): EVAFLEX-EEA A7
07 (ethylene-ethyl acrylate copolymer having 17% ethyl acrylate content and MI value of 25 g / 10 min, manufactured by Du Pont-Mitsui Polychemicals Co., Ltd.) Silicate compound (E) Mica (E-1): A-21S (Yamaguchi Mica Co., Ltd.
Mica (E-2): A-41S (manufactured by Mika Yamaguchi Co., Ltd.)
Talc (E-3): Microace K-1 (manufactured by Nippon Talc Co., Ltd., average diameter 3.2 μm) Kaolin (E-4): SATINTON No. 5
(Manufactured by Engelhard, Inc., average diameter 0.8 μm) Fluorine-based resin (F) PTFE (F-1): polytetrafluoroethylene reinforced filler (G) GF (G-1) having a molecular weight of about 5,000,000: T-195H / PS (glass fiber manufactured by NEC Corporation, fiber diameter 11 μm, fiber length 3 m
m) Epoxy compound (H) Epoxy compound (H-1): pt-butylphenyl glycidyl ether Epoxy compound (H-2): Epicoat 828 (manufactured by Yuka Shell Epoxy Co., Ltd., epoxy equivalent: about 200) Epoxy compound (H-3): ADK STAB EP-22
(Epoxy equivalent of about 200, manufactured by Asahi Denka Kogyo KK) Epoxy compound (H-4): YDCN-704P (Epoxy equivalent of about 210, manufactured by Tobu Kasei Co., Ltd.).

The evaluation of the resin compositions in Examples and Comparative Examples was performed by the following method.

(Preparation of Sample) After the pellets were dried at 110 ° C. for 7 hours, the cylinder temperature was set to 2 using a 75 t injection molding machine.
70 ° C, mold temperature 70 ° C, thickness 1/32 inch, 1/1
6 inch, 1/8 inch, 1/4 inch bars (width 12
mm, 127 mm in length).

(Flame Retardancy) The flame retardancy of a 1/16 inch bar was evaluated according to the UL-94V standard.

(Dripability) According to the UL-94 V standard, a 1/32 inch bar combustion test was performed to evaluate the presence or absence of dripping.

(Gasoline resistance) 1/8 inch bar
Apply 2% bending strain and apply gasoline (Nippon Oil Co., Ltd. regular gasoline) to the center of the bar.
Leave at 23 ° C. for 36 hours, visually observe the surface appearance change,
Evaluation was made according to the following criteria.

：: No change in appearance Δ: Cracks of less than 3.5 mm occurred X: Cracks of 3.5 mm or more occurred

(Oil resistance (salad oil)) A 1.2% bending strain was applied to a 1/8 inch bar, the salad oil was applied to the center of the bar, and then treated in an oven maintained at 85 ° C. for 60 hours. The surface appearance change was visually observed and evaluated according to the following criteria.

：: No change in appearance Δ: Cracks of less than 3.5 mm occurred X: Cracks of 3.5 mm or more occurred

(Plasticizer resistance (dioctyl phthalate))
A 1% bending strain is applied to a 1/8 inch bar, and dioctyl phthalate (reagent) is applied to the center of the bar.
The composition was treated in an oven maintained at 5 ° C. for 20 hours, and the surface appearance was visually observed and evaluated according to the following criteria.

：: No change in appearance Δ: Cracks of less than 3.5 mm occurred X: Cracks of 3.5 mm or more occurred

(Burr) The maximum value of the burr length of a 1/8 inch bar was measured using a factory microscope, and evaluated according to the following criteria.

○: Burr length is less than 0.2 mm ×: Burr length is 0.2 mm or more

(Heat resistance) Using a 1/4 inch bar, AS
The deflection temperature under load was measured at a load of 1.82 MPa according to TM D-648, and the heat resistance was evaluated.

(Mechanical properties) Using a 1/8 inch bar,
The tensile strength was measured according to ASTM D-638.

(Odor) The obtained pellets were heated at 110 ° C. for 7 hours.
After drying for hours, using a 75t injection molding machine, the cylinder temperature was 280 ° C, the mold temperature was 70 ° C, and the size was 120 mm × 120 mm ×
A 2 mm plate-like molded product was molded, and the obtained molded product was examined for odor and evaluated according to the following criteria.

◎: No odor at all ○: Almost no odor ×: Some odor XX: Odor

(Odor during heating residence)
After drying at 10 ° C. for 7 hours, using a 75-t injection molding machine, staying at a cylinder temperature of 280 ° C. for 10 minutes, then forming a plate-shaped molded body of 120 mm × 120 mm × 2 mm at a mold temperature of 70 ° C. Was examined for odor and evaluated according to the following criteria.

◎: No odor at all ○: Almost no odor ×: Some odor XX: Odor

(Thermal Stability) The obtained pellets were heated at 110 ° C.
After drying for 7 hours at a cylinder temperature of 280 ° C. for 10 minutes using a 75-t injection molding machine, a mold temperature of 70
A 120 mm x 120 mm x 2 mm plate-shaped molded body was molded at a temperature of ° C, and the surface appearance of the molded article was visually observed and evaluated according to the following criteria.

◎: Good appearance ○: Slightly discolored to yellow △: Discolored to yellow, poor appearance such as flash, silver, poor surface properties due to gas ×: Large discoloration to yellow, poor surface properties due to flash, silver, gas Large bad appearance

(Evaluation of Rib Strength and Rib Breakage Area) The obtained pellets were dried at 110 ° C. for 7 hours, and then, using a 75t injection molding machine, at a cylinder temperature of 285 ° C. and a mold temperature of 75 ° C., the molded article 1 shown in FIG. Then, the following evaluation was performed.

The rib strength was evaluated by continuing to push the rib portion at a speed of 50 mm / min from the direction of the arrow shown in FIG. 1 at a speed of 50 mm / min and measuring the maximum gauge value (stress value) until breaking.

The broken portion after the measurement of the rib strength was visually observed, and the broken portion was evaluated based on the following criteria.

：: Ductile fracture Δ: Partially ductile fracture ×: Brittle fracture Rib strength has a high stress value, and it is more preferable that the rib fracture portion be evaluated as ductile fracture (evaluation: ○).

Example 1 90 parts of fully dried PC (A-1), 10 parts of fully dried PET (B-1), 6 parts of copolymer (D-1), Adekastab AO-60 (Asahi Denka After dry-blending 1 part of an antioxidant (manufactured by Kogyo Co., Ltd.) in advance, a twin-screw extruder with vent (TEX44 manufactured by Nippon Steel Works, Ltd., hereinafter the same) having a cylinder temperature set at 250 to 270 ° C. Provided to hopper and organic phosphorus flame retardant (C-1)
Seven parts were added in the middle by a liquid addition pump of the same extruder, melt-extruded, and pelletized.

Evaluation was performed using the obtained pellets. Table 1 shows the results.

Examples 2 to 6 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 1 were used in the amounts shown in Table 1. Table 1 shows the results.

Comparative Examples 1 to 8 Resin compositions were obtained and evaluated in the same manner as in Example 1 except that the components shown in Table 2 were used in the amounts shown in Table 2. Table 2 shows the results.

[0148]

[Table 1]

[0149]

[Table 2]

Table 1 for Examples and Table 2 for Comparative Examples
It can be seen from the comparison with the above that the flame-retardant thermoplastic resin composition of the present invention is excellent in flame retardancy, chemical resistance and the like, and has reduced odor.

Example 7 90 parts of PC (A-1), 10 parts of PET (B-1), 5 parts of copolymer (D-1), and 1 part of Adekastab AO-60 were dry-blended in advance, and then the cylinder temperature was reduced. 250
To 270 ° C., and 6 parts of an organic phosphorus-based flame retardant (C-1) was further added to mica (E-) by a liquid addition pump of the extruder.
1) Sixteen parts were melt-extruded by adding each part from the side feeder of the same extruder and pelletized. Table 3 shows the results of evaluation using the obtained pellets.

Examples 8 to 10 Resin compositions were obtained and evaluated in the same manner as in Example 7, except that the components shown in Table 3 were used in the amounts shown in Table 3. Table 3 shows the results.

Comparative Examples 9 to 10 Resin compositions were obtained and evaluated in the same manner as in Example 7, except that the components shown in Table 3 were used in the amounts shown in Table 3. Table 3 shows the results.

[0154]

[Table 3]

Examples 7 to 10 and Example 2, Comparative Examples 9-1
From the comparison with 0, it can be seen that the use of the silicate compound (E) together with the copolymer (D) improves the rib strength and the evaluation of the rib breakage portion.

Example 11 PC (A-1) 85 parts, PET (B-1) 15 parts, copolymer (D-1) 6 parts, PTFE (F-1) 1 part, Adekastab AO-60 1 part Is preliminarily dry-blended, and then supplied to a hopper of a vented twin-screw extruder set at a cylinder temperature of 250 to 270 ° C., and 9 parts of an organic phosphorus-based flame retardant (C-1) is supplied to a liquid addition pump of the extruder. The mixture was further added in the middle, melt-extruded, and pelletized. Table 4 shows the results of evaluation using the obtained pellets.

Comparative Example 11 A resin composition was obtained and evaluated in the same manner as in Example 11, except that the amount of PTFE (F-1) used was changed to the amount shown in Table 4. Table 4 shows the results.

[0158]

[Table 4]

From a comparison between Example 11 and Example 2, it is found that the addition of the fluorine resin (F) further improves the anti-dripping property.

Example 12 PC (A-1) 85 parts, PET (B-1) 15 parts, copolymer (D-1) 6 parts, PTFE (F-1) 1 part, Adekastab AO-60 1 part Is dry-blended in advance, and then supplied to the hopper of a vented twin-screw extruder set at a cylinder temperature of 250 to 270 ° C, and 9 parts of an organic phosphorus-based flame retardant (C-2) is supplied to the extruder by a liquid addition pump. Further, 16 parts of mica (E-2) was further added in the middle from a side feeder of the same extruder, and the mixture was melt-extruded and pelletized. Table 5 shows the results of evaluation using the obtained pellets.

[0161]

[Table 5]

From the comparison between Example 12 and Example 8, it was found that the resin composition using the silicate compound (E) together with the copolymer (D) for the purpose of improving the rib strength showed that the fluororesin (F) It can be seen that the addition of (1) further improves the dripping resistance.

Examples 13 and 14 After 85 parts of PC (A-1), 15 parts of PET (B-1), 6 parts of copolymer (D-1) and 1 part of Adekastab AO-60 were dry-blended in advance, 250 cylinder temperature
To the hopper of a twin-screw extruder with a vent set at ~ 270 ° C, and 9 parts of an organic phosphorus-based flame retardant (C-1) were further fed from the liquid addition pump of the extruder to the amount of GF described in Table 6. (G-1) from the side feeder of the extruder,
Each was added in the middle, melt extruded, and pelletized. Table 6 shows the results of evaluation using the obtained pellets.

Comparative Example 12 A resin composition was obtained and evaluated in the same manner as in Example 13 except that the amount of GF (G-1) was changed to the amount shown in Table 6. Table 6 shows the results.

[0165]

[Table 6]

A comparison between Examples 13 and 14 and Example 2 shows that the addition of the reinforcing filler (G) further improves heat resistance and mechanical properties.

Example 15 After 85 parts of PC (A-1), 15 parts of PET (B-1), 6 parts of copolymer (D-1) and 1 part of Adekastab AO-60 were dry-blended in advance, the cylinder temperature was reduced. 250
To a hopper of a twin-screw extruder with a vent set at ~ 270 ° C, and 9 parts of an organic phosphorus-based flame retardant (C-2) was further fed to a mica (E-
2) 16 parts and 10 parts of GF (G-1) were added respectively from the side feeder of the same extruder, melt-extruded, and pelletized. Table 7 shows the results of evaluation using the obtained pellets.

[0168]

[Table 7]

From a comparison between Example 15 and Example 8, it was found that the resin composition containing the copolymer (D) and the silicate compound (E) in combination with the copolymer (D) for the purpose of improving the rib strength also showed the reinforcing filler (G). ) Indicates that the heat resistance and the mechanical properties are further improved.

Example 16 85 parts of PC (A-1), 15 parts of PET (B-1), 6 parts of copolymer (D-1), 0.4 part of epoxy compound (H-1)
And 1 part of ADK STAB AO-60 in advance, dry-blend and then supply to a hopper of a vented twin-screw extruder set at a cylinder temperature of 250 to 270 ° C. and 9 parts of an organic phosphorus-based flame retardant (C-1) Was added on the way from the liquid addition pump of the extruder to form pellets. Table 8 shows the results of evaluation using the obtained pellets.

Examples 17 to 20 Resin compositions were obtained and evaluated in the same manner as in Example 16 except that the components shown in Table 8 were used in the amounts shown in Table 8. Table 8 shows the results.

[0172]

[Table 8]

A comparison between Examples 16 to 20 and Example 2 shows that the addition of the epoxy compound (H) further improves the thermal stability.

Example 21 PC (A-1) 85 parts, PET (B-1) 15 parts, copolymer (D-1) 6 parts, epoxy compound (H-1) 0.4
And 1 part of Adekastab AO-60 in advance, dry-blend and then supply to a hopper of a vented twin-screw extruder set at a cylinder temperature of 250 to 270 ° C. and 9 parts of an organic phosphorus-based flame retardant (C-2) From the liquid addition pump of the extruder, and 16 parts of mica (E-2) from the side feeder of the extruder, melt extruded, and pelletized. Evaluation was performed using the obtained pellets. Table 9 shows the results.

Examples 22 to 24 Except that the components shown in Table 9 were used in the amounts shown in Table 9, pellets were prepared and evaluated in the same manner as in Example 21. Table 9 shows the results.
Shown in

[0176]

[Table 9]

From a comparison between Examples 21 to 24 and Example 8, it was found that the resin composition using the silicate compound (E) together with the copolymer (D) for the purpose of improving the rib strength shows that the epoxy compound ( It can be seen that the addition of H) improves the thermal stability.

[0178]

The flame-retardant thermoplastic resin composition of the present invention comprises:
It has excellent flame retardancy and chemical resistance, has reduced odor, and contains neither chlorine-containing compounds nor bromine-containing compounds. Therefore, the flame-retardant thermoplastic resin composition of the present invention can be suitably used as a molding material for electric and electronic parts, and is industrially extremely useful.

[Brief description of the drawings]

FIG. 1 is an explanatory view of a molded body for measuring a rib strength.

[Explanation of symbols]

 1 molded body

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 27:12) (C08L 67/02 33:08 27:12) (72) Inventor Yoichi Ohara 2 Kazumichi Torikai, Settsu-shi, Osaka -6-8-103 (72) Inventor Kazufumi Hirobe 3-2-25-307 Honjo Nishi, Kita-ku, Osaka-shi

Claims (9)

[Claims] 1. A thermoplastic resin comprising: (A) a polycarbonate resin; and (B) a thermoplastic polyester resin polymerized by using a germanium compound as a catalyst.
With respect to 100 parts by weight of the resin composition (I) in which the component (B) has a weight ratio of 99/1 to 20/80, (C) the general formula (I): (Wherein, R ^{1 to} R ³ are all monovalent groups, each independently being an aliphatic group having 1 to 12 carbon atoms, an aromatic group having 6 to 12 carbon atoms, or an aliphatic group having 3 to 12 carbon atoms. Cyclic group, R ⁴ has 6 carbon atoms
X is a divalent group, and is an aliphatic group having 2 to 30 carbon atoms, an aromatic group having 6 to 30 carbon atoms, or an alicyclic group having 3 to 30 carbon atoms, or M is independently 0 or 1, r is independently n is 0 to 5, p and q are each 0 to 2, and r is 1 to 3; And p + q +
r = 3) organophosphorus flame retardant 1
0.5 to 15 parts by weight of a copolymer containing 30 parts by weight and (D) at least one olefin unit and at least one alkyl (meth) acrylate unit having an alkyl group having 1 to 10 carbon atoms And a flame-retardant thermoplastic resin composition. 2. A flame-retardant thermoplastic resin composition obtained by further adding 0.1 to 100 parts by weight of (E) a silicate compound to the flame-retardant thermoplastic resin composition according to claim 1. 3. The flame-retardant thermoplastic resin composition according to claim 1 or 2, further comprising:
A flame-retardant thermoplastic resin composition containing 5 parts by weight. 4. The flame-retardant thermoplastic resin composition according to claim 1, further comprising (G) a reinforcing filler of 0.5 to 0.5.
A flame-retardant thermoplastic resin composition containing 100 parts by weight. 5. A flame-retardant thermoplastic obtained by further adding 0.01 to 15 parts by weight of an epoxy compound (H) to the flame-retardant thermoplastic resin composition according to claim 1, 2 or 3. Resin composition. 6. The method according to claim 1, wherein the thermoplastic polyester resin is a polyalkylene terephthalate resin.
6. The flame-retardant thermoplastic resin composition according to 4 or 5. 7. The method according to claim 1, wherein said thermoplastic polyester resin is a polyethylene terephthalate resin.
Or the flame-retardant thermoplastic resin composition according to 5. 8. The organic phosphorus-based flame retardant (C) has the general formula (I)
I): (Wherein, R ^{5 to} R ¹⁶ are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and 4 R ¹⁵ and R ¹⁶ may be different. 3 alkylene _{group, -S -, - SO 2 -} , - O -, - CO- or -
A divalent linking group wherein N = N-, t represents 0 or 1)
The flame-retardant thermoplastic resin composition according to claim 1, which is a condensed phosphate ester flame retardant represented by the formula: 9. The copolymer (D) contains at least one olefin unit and at least one alkyl (meth) acrylate unit having an alkyl group having 1 to 10 carbon atoms in an amount of 40/60 to 95 / 5 weight ratio,
Melt index (MI) of copolymer is 2 to 500 g
/ 10 min (190 ° C, 2kg load, JIS K6730
The flame-retardant thermoplastic resin composition according to claim 1, 2, 3, 4, 5, 6, 7, or 8.