JP2001131272A - Polyester resin and flame resisting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame resisting resin which does not cause a die pollution at an injection molding, can improve a compatibility with a blended resin, does not reduce mechanical properties such as impact resistance and the like and exhibits an excellent flame retardance, and to provide a flame retardant resin composition containing it. SOLUTION: This flame retardant resin is a polyester resin which has a specific molecular weight and to the molecular structure of which an oxoacid metal based and a polysiloxane structure are introduced.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel and useful polyester resin and a flame-retardant resin containing the same in various uses such as housing materials for electric products, electric component materials, automobile parts and packaging materials. The present invention relates to a composition, and more particularly, to a polyester resin exhibiting excellent flame retardancy without causing mold contamination, and a flame retardant resin composition containing the same.

[0002]

2. Description of the Related Art Thermoplastic resins are generally lightweight and excellent in moldability, and are also excellent in heat resistance, mechanical properties, electrical properties and aesthetics. It is frequently used for various purposes such as packaging materials and furniture. However, thermoplastic resins have the disadvantage that they become ignitable when the molded article is ignited due to short-circuiting of an electric circuit or the like because of the flammability. Is added.

[0003] Since flame retardancy can be imparted without generating harmful halogen-based gas during combustion, phosphorus-based flame retardants and silicone-based flame retardants which are non-halogen flame retardants have been studied. Is underway.

[0004] Of these, phosphorus-based flame retardants have insufficient flame retarding effects themselves, and JP-A-10-152610 discloses halogenated organic phosphoric acid esters in order to exhibit good flame retardancy. It is disclosed that it is useful to use together with a metal salt of an aromatic sulfonic acid.

[0005] In addition, when the silicone compound is used alone, the flame retardant effect is insufficient, and when the compounding amount of the silicone compound is increased for the purpose of exhibiting good flame retardancy,
Alloying is not possible due to poor compatibility between the compounding resin and the silicone compound, or even if alloying is possible, the mechanical properties of the obtained resin composition are significantly reduced as compared with the compounding resin, There was a problem that it could not be put to practical use.

Therefore, Japanese Patent Application Laid-Open No. 11-217494 discloses that a silicone compound having a branched main chain and an aromatic group is used to suppress the compounding amount, prevent the mechanical properties of the resin composition from deteriorating, and It is disclosed that flame retardancy can be imparted.

[0007]

However, the above-mentioned Japanese Patent Application Laid-Open No.
The silicone compounds disclosed in JP-A-152610 and JP-A-11-217494 are not sufficient in flame retardancy by themselves, and in order to exhibit a predetermined flame retardancy, a low molecular weight such as a metal salt of an aromatic sulfur compound is required. Compounds need to be used together,
There were problems such as occurrence of bleeding and significant mold contamination during injection molding.

The problem to be solved by the present invention is that the flame retardant exhibits excellent flame retardancy even when used alone, and it is not necessary to use a low molecular weight compound such as a metal salt of an aromatic sulfur compound. A polyether resin that does not cause mold contamination, and that can further improve the compatibility with the resin to be compounded and that does not reduce mechanical properties such as moldability and impact resistance of a molded product; And a flame-retardant resin composition.

[0009]

The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by introducing an oxo acid metal base and a polysiloxane skeleton into the molecular structure of the polyester resin, the present inventors have achieved excellent results. It has flame retardancy, does not cause significant mold contamination during injection molding, and has improved compatibility with the compounded resin. Excellent flame retardancy, molding processability, and impact resistance in resin compositions The present inventors have found that they exhibit properties and the like, and have completed the present invention.

That is, the present invention provides a compound represented by the following structural formula (1):

[0011]

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Wherein Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group containing one or more atoms other than carbon atoms in a ring; R is a polyester residue), a oxo acid metal base and a polysiloxane skeleton, and a number average molecular weight of 5,000 to 5,000,000.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.

The polyester resin used as the flame-retardant resin of the present invention has the following structural formula (1) in its molecular structure.

[0015]

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(Where Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group containing one or more atoms other than carbon atoms in a ring, R is a polyester residue), an oxo acid metal base and a polysiloxane skeleton, and the number average molecular weight is in the range of 5,000 to 5,000,000.

Here, if the number average molecular weight of the polyester resin is less than 5,000, no mechanical properties are exhibited.
On the other hand, when it exceeds 5,000,000, the compatibility and dispersibility with the resin to be compounded are inferior, and the moldability decreases.
Among them, the number average molecular weight is 10,000 to 1,000,
000 is particularly preferable in view of the manifestation of the flame retardant effect.

Here, the number-average molecular weight is determined by using a gel permeation chromatography (hereinafter abbreviated as GPC) measuring device [mobile phase: 5 mmol / dm ³ CF ₃ COON.
a / HFIP solution, column bath: 40 ° C, detector: U
V (220 nm), flow rate 1.0 cm ³ / min, column: Shod
ex HFIP-805 + HFIP-806 + HF-8
07], and converted to PMMA.

The content of the oxo acid metal base in the polyester resin is not particularly limited, but is a measured value of the amount of metal ions by an inductively coupled plasma emission spectrometry (ICP) method after the pretreatment with acid decomposition. As 0.01% to 10%
% Is preferable. That is, when the content is 0.01% or more, the flame retardant effect of the polyester resin is significantly improved. On the other hand, when the content is 10% or less, the mechanical properties of the obtained polyester resin are good.

Here, the oxo acid metal base to be introduced into the polyester resin is not particularly limited, but an aromatic oxo acid metal base is preferred from the viewpoint of improving flame retardancy. Specifically, the following structural formula (2)

[0021]

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Wherein Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group containing one or more atoms other than carbon atoms in a ring; ^Bm- is an oxoacid anion, and ^{Mn +} is a monovalent, divalent or trivalent metal cation).

It is preferable that the metal salt of an aromatic oxo acid in the molecular structure is a metal salt of a sulfonic acid or a metal salt of a phosphonate, from the viewpoint of exhibiting the flame retardant effect.

Ar in the structural formula (2) is an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heterocyclic group containing one or more atoms other than carbon atoms in the ring. Include a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, and the like. Among them, a phenyl group is preferable because of low raw material cost and easy availability.

M ^{n +} is a monovalent, divalent or trivalent metal cation, among which Na ⁺ , K ⁺ , Li ⁺ , Mg ²⁺ , Ca
^{2+ and the} like are preferable in terms of mechanical properties.

The polysiloxane skeleton introduced into the polyester resin is not particularly limited, but may be, for example, any of the following structural formulas (3) to (7)

[0027]

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(Where m is 1 to 5)
1,000,000, n is 1 to 1,000,000, R
_{1 to} R ₉ are each independently a chemical structure containing a hydrogen atom, an alkyl group, or an aryl group).

Such a polyester resin is, for example,
(A1) a polysiloxane compound having a functional group reactive with a hydroxyl group or a carboxyl group, (a2) an aromatic polycarboxylic acid or an alkyl ester thereof (a3) a diol compound, and (a4) an oxo acid metal base. It is preferable to polymerize an aromatic dicarboxylic acid or an alkyl ester thereof as an essential component.

The polysiloxane compound (a1) having a functional group reactive with a hydroxyl group or a carboxyl group, which constitutes the polyester resin in the present invention, is not particularly limited. It is preferable because the melt viscosity of the target polyester resin can be easily increased.

Further, the polysiloxane compound (a1)
Those having a number average molecular weight of 500 to 1,000,000 are preferred because the effect of improving flame retardancy becomes more remarkable.

Here, the number average molecular weight is defined as [mobile phase: 5
mmol / dm ³ CF ₃ COONa / HFIP solution, column thermostat: 40 ° C., detector: UV (220 nm), flow rate 1.0 cm ³ / min, column: Shodex HFIP-80
5 + HFIP-806 + HF-807] GP
This is a value obtained by measuring C and converting to PMMA.

First, the monofunctional compound can be adjusted so that the mechanical properties of the polyester resin do not deteriorate by being incorporated into the terminal structure of the polyester resin, and the substituents are independently hydrogen atoms as described above. Atom, an alkyl group, a chemical structure containing an aryl group, for example,
Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an alkyl group having 4 to 18 carbon atoms, and examples of the aryl group include a phenyl group, a benzyl group, a naphthyl group, and a pyridyl group. Among them, a methyl group or a phenyl group is preferable because the raw material cost is low.

Further, it has a functional group reactive with one hydroxyl group or carboxyl group per molecule as a substituent, and this chemical structural part reacts with a hydroxyl group or carboxyl group in another raw material compound, Is incorporated into the molecular structure of the polyester resin. Such a chemical structure having reactivity with a hydroxyl group or a carboxyl group includes 1)
Alcoholic hydroxyl group, carboxyl group, carboxylic acid ester group, alkyl group having 3 to 20 carbon atoms or aromatic group containing epoxy group or phenolic hydroxyl group at the terminal, 2) alcoholic hydroxyl group, carboxyl group, carboxylic acid ester group , An epoxy group or a phenolic hydroxyl group at the terminal, and a heterocyclic group containing one or more atoms other than carbon atoms in the ring. Examples of the polysiloxane compound (a1) include: And alcohols having a polysiloxane skeleton, carboxylic acids and their alkyl esters, epoxy compounds and phenol compounds.

As the monohydric alcohol having a polysiloxane skeleton, the total number of carbon atoms constituting the alcohol is 2
It is preferably from 200 to 200 in terms of improving flame retardancy and the like,
Specifically, (alkyl) polysiloxane having a propanol skeleton, (alkyl) polysiloxane having a butanol skeleton, (alkyl) having a pentanol skeleton
Examples include polysiloxane, (alkyl) polysiloxane having a cyclononanol skeleton, (alkyl) polysiloxane having an allyl alcohol skeleton, and the like.

As the monovalent carboxylic acid having a polysiloxane skeleton, the total number of carbon atoms constituting the carboxyl group is preferably from 2 to 200 from the viewpoint of improving flame retardancy and the like. Propionic acid, methacrylic acid,
Acrylic acid, benzoic acid, adipic acid and the like can be mentioned. As the monoester of a carboxylic acid having a polysiloxane skeleton, an alkyl ester having 18 or less carbon atoms is preferable from the viewpoint of simplicity of the production of the polyester resin. It is preferable from the viewpoint of properties. Specifically, (alkyl) polysiloxane containing a methyl propionate skeleton, (alkyl) polysiloxane containing a butyl acetate skeleton, (alkyl) polysiloxane containing a methyl methacrylate skeleton, (alkyl) polysiloxane containing a butyl acrylate skeleton, benzoic acid Examples thereof include (alkyl) polysiloxane having an ethyl skeleton, and (alkyl) polysiloxane having a hexyl adipate skeleton in a molecular side chain.

As the monofunctional epoxy compound having a polysiloxane skeleton, the total number of carbon atoms constituting the epoxy group is preferably from 3 to 200 from the viewpoint of mechanical properties. For example, a 1,3-epoxypropane structure , 1,3-
(Alkyl) polysiloxanes having an epoxy octane structure, a 1,4-epoxycyclohexane structure, a 1,4-epoxycyclooctane structure, and the like can be given.

As the monohydric phenol compound having a polysiloxane skeleton, the total number of carbon atoms constituting the phenol skeleton is preferably from 6 to 200 from the viewpoint of improving the flame retardancy and the like. 4,
(Alkyl) polysiloxane having a 4'-diol skeleton, 1,2,4-benzenetriol skeleton, 8-quinolinol skeleton, or the like can be used.

Next, the bifunctional compound has 1 as a substituent.
A compound having two hydroxyl groups or carboxyl groups and a functional group reactive with each other, a compound having functionalities at both ends, a compound having two functionalities at one end, and a functionality at any position other than the end. And the like. As the functional group and other substituents, those similar to the monofunctional compound can be mentioned.

As such a polysiloxane compound (a1), specifically, a dihydric alcohol having a polysiloxane skeleton, a divalent carboxylic acid and an alkyl ester thereof,
Examples include a divalent epoxy compound and a dihydric phenol compound.

As the dihydric alcohol having a polysiloxane skeleton, the total number of carbon atoms constituting the alcohol is 2
It is preferably from 200 to 200 in terms of flame retardancy, and these dihydric alcohols may be used alone or in combination of two or more. Specifically, (alkyl) polysiloxane having a propanol skeleton, (alkyl) polysiloxane having a butanol skeleton, (pentyl) having a pentanol skeleton at both ends of a molecule, at one end of a molecule, and at an arbitrary position A) polysiloxane, (alkyl) polysiloxane having a cyclononanol skeleton, (alkyl) polysiloxane having an allyl alcohol skeleton, and the like.

As the divalent carboxylic acid having a polysiloxane skeleton, the total number of carbon atoms constituting the carboxyl group is preferably from 2 to 200 from the viewpoint of improving flame retardancy and the like. Or two or more of them are used in combination. Specifically, (alkyl) polysiloxane containing a propionic acid skeleton, (alkyl) polysiloxane containing an acetic acid skeleton, and valeric acid skeleton at both ends of a molecule, at one end of a molecule, and at an arbitrary position. (Alkyl) polysiloxane containing, (alkyl) polysiloxane containing dodecanoic acid skeleton, (alkyl) polysiloxane containing methacrylic acid skeleton, (alkyl) polysiloxane containing acrylic acid skeleton, containing benzoic acid skeleton (Alkyl) polysiloxanes, and dicarboxylic anhydrides thereof.

The above-mentioned ester compound of a dicarboxylic acid having a polysiloxane skeleton is a monoester or diester in which a part or all of the divalent carboxylic acid is esterified, and has 18 or less carbon atoms. Alkyl esters are preferred from the viewpoint of simplicity in producing the polyester resin. Specifically, a methyl propionate skeleton-containing (alkyl) polysiloxane, a butyl acetate skeleton-containing (alkyl) polysiloxane, a nonyl valerate nonyl skeleton-containing (alkyl) polysiloxane, a methyl methacrylate skeleton-containing (alkyl) polysiloxane, (Alkyl) polysiloxane containing butyl acrylate skeleton, (alkyl) polysiloxane containing ethyl benzoate skeleton, (alkyl) polysiloxane containing hexyl adipate skeleton in molecular side chain, butyl butyrate skeleton and octyl malonate skeleton (alkyl ) Modified polysiloxane, nonadecyl dodecanoate skeleton and eicosylbenzyl glutarate skeleton containing (alkyl)
Polysiloxane, didecyl mesityl octadecanoate skeleton and nonyl decyl octane diacid skeleton-containing (alkyl) polysiloxane, nonadecyl docosyl dimer skeleton and butyl propionate skeleton (alkyl) polysiloxane, dihexyl dodecane diacid skeleton and dibutyl glutarate (Alkyl) polysiloxane, (heptylphenethyl octadecane diacid skeleton and (alkyl) polysiloxane containing docosylstyryl octane diacid skeleton, dicinnamyl dimer acid skeleton, and (alkyl) polysiloxane containing diethyl dimer acid skeleton, and the like.

As the divalent epoxy compound having a polysiloxane skeleton, the total number of carbon atoms constituting the epoxy group is preferably from 3 to 200 from the viewpoint of mechanical properties. 1,3-epoxypropane structure, 1,3-epoxyoctane structure, 1,4-
(Alkyl) polysiloxanes having an epoxycyclohexane structure, a 1,4-epoxycyclooctane structure and the like can be mentioned.

As the dihydric phenol compound having a polysiloxane skeleton, the total number of carbon atoms constituting the phenol skeleton is preferably from 6 to 200 from the viewpoint of improving the flame retardancy and the like. A phenol skeleton, a biphenyl-4,4′-diol skeleton, 1,2,
(Alkyl) polysiloxanes having a 4-benzenetriol skeleton, an 8-quinolinol skeleton, and the like are included.

The polyfunctional compound having three or more functionalities has, as a substituent, at least three functional groups having reactivity with a hydroxyl group or a carboxyl group per molecule. As the functional group and other substituents, those similar to the monofunctional compound can be mentioned.

Specific examples of the polysiloxane compound (a1) include a trihydric or higher polyhydric alcohol having a polysiloxane skeleton, a trihydric or higher polycarboxylic acid and an alkyl ester thereof, and a trihydric or higher polyhydric epoxy compound. Or polyhydric phenol compounds having three or more valences.

As the trihydric or higher polyhydric alcohol having a polysiloxane skeleton, the total number of carbon atoms constituting the alcohol is preferably from 2 to 200 from the viewpoint of improving the flame retardancy and the like. It may be present at either end or at the molecular side chain.

As the trihydric alcohol, (alkyl) having a butanol skeleton and a propanediethanol skeleton
Examples include polysiloxane, (alkyl) polysiloxane having a cyclohexynedihexanol skeleton and a propanol skeleton, (alkyl) polysiloxane having an octanedipropanol skeleton and a hexylhexanol skeleton, and (alkyl) polysiloxane having a dimerdiol skeleton and a propanol skeleton. Can be

The polyhydric alcohols having four or more valences include (alkyl) polysiloxanes having a butanediol skeleton and an undecanediethanol skeleton, (alkyl) polysiloxanes having a cyclohexynedioctanol skeleton and a nonadecanedipropanol skeleton, and octanedisiloxane. (Alkyl) polysiloxane having a propanol skeleton and a hexanedihexanol skeleton, and (alkyl) polysiloxane having a dimer diol skeleton are exemplified.

Examples of the above-mentioned trivalent or higher polyvalent carboxylic acid ester compounds having a polysiloxane skeleton include monoesters, diesters, and triesters in which a part or all of the trivalent or higher polycarboxylic acid is esterified. Alkyl esters having 18 or less carbon atoms, such as esters and tetraesters, are preferred from the viewpoint of simplicity in producing the polyester resin. The carboxylic acid alkyl ester structure site may be present at either terminal of the molecule or at the side chain of the molecule.

Specific examples of the ester compound of a trivalent or higher polyvalent carboxylic acid include a (alkyl) polysiloxane having a methyl propionate skeleton, an (alkyl) polysiloxane having a butyl acetate skeleton, and a nonyl valerate skeleton having both terminals ( (Alkyl) polysiloxane, methyl methacrylate skeleton-containing (alkyl) polysiloxane, butyl acrylate skeleton-containing (alkyl) polysiloxane, ethyl benzoate skeleton-containing (alkyl) polysiloxane, containing a hexyl adipate skeleton in the molecular side chain ( Alkyl) polysiloxane, butyl butyrate skeleton and octyl malonate skeleton (alkyl) -modified polysiloxane, nonadecyl dodecanoate skeleton and eicosylbenzyl glutarate skeleton (alkyl) polysiloxane, didecyl mesityl octadecanoate skeleton, and octanediacid Nyldecyl skeleton-containing (alkyl) polysiloxane, nonadecyl docosyl skeleton dimerate and butyl propionate skeleton (alkyl) polysiloxane, dodecane diacid dihexyl skeleton and dibutyl glutarate skeleton (alkyl) polysiloxane, octadecane heptyl phenethyl (Alkyl) polysiloxane having a skeleton and a docosylstyryl octane diacid skeleton,
A dicinnamyl dimer skeleton and a (alkyl) polysiloxane containing a diethyl dimer skeleton are exemplified.

As the trivalent or higher polyvalent epoxy compound having a polysiloxane skeleton, the total number of carbon atoms constituting the epoxy group is preferably 3 to 200 from the viewpoint of mechanical properties. Both ends of the molecule and one end of the molecule,
Or a 1,3-epoxypropane structure, a 1,3-epoxyoctane structure at both molecular ends or one molecular end,
(Alkyl) polysiloxanes having a 1,4-epoxycyclohexane structure, a 1,4-epoxycyclooctane structure, or the like can be given.

As the trivalent or higher polyhydric phenol compound having a polysiloxane skeleton, the total number of carbon atoms constituting the phenol skeleton is preferably from 6 to 200 from the viewpoint of flame retardancy and the like. At both ends of the molecule and one end of the molecule, or at both ends of the molecule or one end of the molecule,
(Alkyl) polysiloxanes having a phenol skeleton, biphenyl-4,4'-diol skeleton, 1,2,4-benzenetriol skeleton, 8-quinolinol skeleton, or the like can be given. Although the content of the polysiloxane compound (a1) described in detail above is not particularly limited,
It is preferably used in a range of 3% to 80% as a ratio to the weight of the polyester resin when converted to the weight of the raw material compound. That is, when the content is 3% or more, the flame retardant effect of the polyester resin becomes remarkable. On the other hand, when the content is 80% or less, the resulting polyester resin has remarkably good physical properties such as mechanical properties and heat resistance. In particular, it is preferably in the range of 10% to 40% from the viewpoint of excellent balance between them.

The aromatic polycarboxylic acid or its alkyl ester (a2) used in the present invention is not particularly limited, but is a divalent or higher aromatic carboxylic acid or its carboxylic anhydride, And these alkyl esters of aromatic polycarboxylic acids are used alone or in combination of two or more. The total number of carbon atoms constituting these polycarboxylic acids is preferably in the range of 4 to 200 from the viewpoint of mechanical properties and the like.

First, as the aromatic divalent carboxylic acid, for example, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4'- Dicarboxylic acid, diphenoxyethane dicarboxylic acid, indene-4,7-dicarboxylic acid, naphthalene-2,5-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, azulene-2,5-dicarboxylic acid, heptalen-1,7 -Dicarboxylic acid, biphenylene-1,5-dicarboxylic acid, as-indacene-
2,6-dicarboxylic acid, s-indacene-1,7-dicarboxylic acid, acenaphthylene-3,8-dicarboxylic acid, fluorene-1,8-dicarboxylic acid, phenalene-4,8-
Dicarboxylic acid, phenanthrene-1,6-dicarboxylic acid, anthracene-1,8-dicarboxylic acid, fluoranthene-6,7-dicarboxylic acid, acephenanthrylene-
3,8-dicarboxylic acid, aceanthrylene-3,7-dicarboxylic acid, triphenylene-2,10-dicarboxylic acid, pyrene-1,6-dicarboxylic acid, chrysene 1,7-
Dicarboxylic acid, naphthacene-1,5-dicarboxylic acid, preyandene 2,5-dicarboxylic acid, picene-2,8-
Dicarboxylic acid, perylene-2,8-dicarboxylic acid, pentaphen-5,11-dicarboxylic acid, pentacene 2,6
-Dicarboxylic acids, aromatic carboxylic acids such as these alkyl nucleus-substituted carboxylic acids, halogen nucleus-substituted carboxylic acids, and anhydrides of the above dicarboxylic acids.

As the aromatic trivalent carboxylic acid, for example,
1,2,4-trimellitic acid, 1,2,5-naphthalenetricarboxylic acid, 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-diphenyltricarboxylic acid, benzophenone 3,3 ′, 4-tricarboxylic acid Acid, diphenyl ether-3,3 ', 4-tricarboxylic acid, indene-
3,4,7-tricarboxylic acid, naphthalene-2,5,7
-Tricarboxylic acid, naphthalene-2,4,6-tricarboxylic acid, azulene-2,5,7-tricarboxylic acid, heptalen-1,3,7-tricarboxylic acid, biphenylene-
1,3,5-tricarboxylic acid, as-indacene-2,
4,6-tricarboxylic acid, s-indacene-1,3,7-
Tricarboxylic acid, acenaphthylene-3,6,8-tricarboxylic acid, fluorene-1,5,8-tricarboxylic acid,
Phenalene-2,4,8-tricarboxylic acid, phenanthrene-1,6,8-tricarboxylic acid, anthracene-
1,5,8-tricarboxylic acid, fluoranthene-4,
6,7-tricarboxylic acid, acephenanthrylene-3,
6,8-tricarboxylic acid, aceanthrylene-3,5
7-tricarboxylic acid, triphenylene-2,6,10-
Tricarboxylic acid, pyrene-1,3,6-tricarboxylic acid, chrysene 1,4,7-tricarboxylic acid, naphthacene-1,3,5-tricarboxylic acid, preyandene 2,
5,8-tricarboxylic acid, picene-2,5,8-tricarboxylic acid, perylene-2,4,8-tricarboxylic acid, pentaphen-5,11,14-tricarboxylic acid, pentacene 2,6,14-tricarboxylic acid, And aromatic tricarboxylic acids such as substituted alkyl nuclei and halogen nuclei thereof, and anhydrides of the above tricarboxylic acids.

As the aromatic tetravalent carboxylic acid, for example,
Pyromellitic acid, diphenyl-2,2 ', 3,3'-tetracarboxylic acid, benzophenone-2,2', 3,3 '
-Tetracarboxylic acid, diphenylsulfone-2,2 ',
3,3'-tetracarboxylic acid, diphenyl ether-
2,2 ′, 3,3′-tetracarboxylic acid, 2,3,6
7-naphthalenetetracarboxylic acid, indene-2,3,
4,7-tetracarboxylic acid, naphthalene-2,3,5
7-tetracarboxylic acid, naphthalene-2,4,6,7-
Tetracarboxylic acid, azulene-2,3,5,7-tetracarboxylic acid, heptalene-1,3,4,7-tetracarboxylic acid, biphenylene-1,3,5,7-tetracarboxylic acid, as-indacene- 2,4,6,7-tetracarboxylic acid, s-indacene-1,2,3,7-tetracarboxylic acid, acenaphthylene-3,4,6,8-tetracarboxylic acid, fluorene-1,2,5,5 8-tetracarboxylic acid,
Phenalene-2,3,4,8-tetracarboxylic acid, phenanthrene-1,2,6,8-tetracarboxylic acid, anthracene-1,5,6,8-tetracarboxylic acid, fluoranthene-4,5,6, 7-tetracarboxylic acid, acephenanthrylene-2,3,6,8-tetracarboxylic acid, acetantetralen-3,4,5,7-tetracarboxylic acid, tetraphenylene-2,3,6,10 -Tetracarboxylic acid, pyrene-1,3,6,7-tetracarboxylic acid, chrysene 1,4,7,8-tetracarboxylic acid, naphthacene-1,2,5,7-tetracarboxylic acid, preyandene 2, 5,8,9-tetracarboxylic acid, picene-
2,5,7,8-tetracarboxylic acid, perylene-2,
4,5,8-tetracarboxylic acid, pentaphen-5,1
1,12,14-tetracarboxylic acid, pentacene 2,
Aromatic tetracarboxylic acids such as 3,6,14-tetracarboxylic acid and the like, and tetracarboxylic monoanhydrides and tetracarboxylic dianhydrides of the above-mentioned compounds can be mentioned.

As the aromatic polycarboxylic acid or its alkyl ester (a2), terephthalic acid, isophthalic acid, sebacic acid and naphthalene-2,6-dicarboxylic acid among the above aromatic carboxylic acids are polymerizable and have a color tone. In addition, terephthalic acid and naphthalene-2,6-dicarboxylic acid are particularly preferable. Further, these terephthalic acid, isophthalic acid, sebacic acid, naphthalene-
It is preferable to partially use a polyhydric carboxylic acid having a valency of 3 or more with 2,6-dicarboxylic acid since the melt viscosity of the target polyester resin can be easily increased.

The polycarboxylic acid esters include monoesters, diesters and tri- and tetraesters of the above-mentioned polycarboxylic acids, and are compounds in which a part or all of the polycarboxylic acid is esterified. Can be used.

The amount of the aromatic polycarboxylic acid or its alkyl ester (a2) to be used is not particularly limited, but the amount of each of the raw material compounds constituting the polyester resin is converted to the weight of the polyester resin. It is preferable in terms of mechanical properties that the ratio be in the range of 5 to 95% by weight.

The diol compound (a3) constituting the polyester resin in the present invention includes, for example, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1, 2-butylene glycol, trimethylene glycol, neopentyl glycol, diethylene glycol, 2-methyl-1,3-propylene glycol, triethylene glycol, octamethylene glycol,
1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,6-hexaneglycol and 3
And alkylene glycols such as -methyl-1,5-pentanediol. The diol compound (a3) may be used alone or in combination of two or more. Among them, diols having 2 to 8 carbon atoms are preferable because of excellent mechanical properties, and particularly, ethylene glycol and 1,3-propanediol are preferable.

As described above, the oxo acid metal group contained in the molecular structure of the polyester resin of the present invention has the following structural formula (2)

[0064]

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A compound having a structural unit represented by the following formula is preferable. In order to incorporate the structural unit into the molecular structure of the polyester resin, a functional group having reactivity with a hydroxyl group or a carboxyl group at both ends of the structural unit is preferred. A method in which a compound containing a group is reacted with the above (a1) to (a3).

Here, the functional group reactive with a hydroxyl group or a carboxyl group includes an alcoholic hydroxyl group, a carboxyl group or its alkyl ester group, an epoxy group,
Alternatively, a phenolic hydroxyl group or the like may be mentioned, and among them, a carboxyl group or an alkyl ester thereof is preferable from the viewpoint of excellent dispersibility and mechanical strength in the resin to be compounded. Specific examples of such a compound include an aromatic dicarboxylic acid having an oxo acid metal base or an alkyl ester thereof (a
4) is preferred.

As described above, Ar in the structural formula (2) is an aromatic hydrocarbon group having 6 to 20 carbon atoms or a heterocyclic group containing one or more atoms other than carbon atoms in the ring. Specific examples include a phenyl group, a benzyl group, a naphthyl group, a pyridyl group, and the like. Particularly, a phenyl group is preferable, and isophthalic acid and terephthalic acid are particularly preferable in terms of low raw material cost.

It is preferable that the oxo acid metal base in the molecular structure is a sulfonic acid metal base or a phosphonate metal base from the viewpoint of exhibiting a flame retardant effect. In the formula, B ^m- is an oxo acid anion. , A sulfonate anion or a phosphonate anion is preferred.

In the formula, M ^{n +} is a monovalent, divalent or trivalent metal cation, and specifically, sodium salt, potassium salt, magnesium salt, calcium salt, zinc salt, phosphonium salt, ammonium salt, ammonium salt Salt, monomethyl sodium salt, monomethyl potassium salt, monomethyl magnesium salt, monomethyl calcium salt, monomethyl zinc salt, monomethyl phosphonium salt, monomethyl ammonium salt, dimethyl sodium salt, dimethyl potassium salt, dimethyl magnesium salt, dimethyl calcium salt, dimethyl zinc salt, Dimethylphosphonium salts, or dimethylammonium salts and the like, particularly preferably an alkali metal or an alkaline earth metal, among which sodium, potassium, lithium, magnesium, calcium and the like,
It is preferable from the viewpoint of moldability.

As described above, an aromatic dicarboxylic acid having an oxo acid metal base or an alkyl ester thereof (a4)
As the aromatic dicarboxylic acid having a sulfonic acid metal base or an alkyl ester thereof, for example, a sulfonated metal phthalate, a sulfonated phosphonium salt, a sulfonated ammonium phthalate, or a monoester thereof, Examples thereof include compounds in which a part or all of a sulfonated phthalate such as a diester is esterified, and specifically, sodium, potassium, lithium, and magnesium salts of sulfonated isophthalic acid or sulfonated terephthalic acid. And a calcium salt is particularly preferable, and a lower alkyl ester having 6 or less carbon atoms such as a methyl ester and an ethyl ester is preferable from the viewpoint of simplicity in producing the polyester resin.

Next, as the aromatic dicarboxylic acid having a phosphonate metal base or an alkyl thereof, for example, a phosphonated phthalic acid metal salt, a phosphonated ammonium phthalate salt, or a phosphonated such as a monoester or diester thereof is used. Examples include compounds in which part or all of the phthalate is esterified.Specifically, phosphonated isophthalic acid, or sodium, potassium, lithium, magnesium, and calcium salts of phosphonated terephthalic acid are particularly preferable. Preferably, lower alkyl esters having 6 or less carbon atoms, such as methyl ester and ethyl ester, are preferable from the viewpoint of simplicity in producing the polyester resin.

Among the above-mentioned aromatic dicarboxylic acids having a sulfonic acid metal base and a phosphonate metal base or an alkyl thereof, when a plastic containing a flame retardant is discarded,
It is more preferable to use an aromatic metal sulfonate base because the phosphorus compound pollutes water and soil. These aromatic dicarboxylic acids having an oxo acid metal base or the alkyl (a4) thereof may be used alone, or
Two or more kinds may be used in combination.

The amount of the aromatic dicarboxylic acid having an oxo acid metal base or its alkyl ester (a4) is not particularly limited, but as described above, the oxo acid metal base contained in the molecular structure is used as described above. Is preferably in the range of 0.01% to 10% as the amount of metal ions.

The method of polymerizing each of the above-mentioned raw materials (a1) to (a4) is not particularly limited.
For example, an aromatic polycarboxylic acid or an alkyl ester thereof (a2), a diol compound (a3), and an aromatic dicarboxylic acid having an oxo acid metal base or an alkyl ester thereof (a4) are subjected to a first step under normal pressure. 100-2
The reaction was carried out at 00 ° C., and it was confirmed that the ester was formed quantitatively. From the observation, it was further confirmed that the polysiloxane compound (a) having a functional group reactive with a hydroxyl group or a carboxyl group (a
1) and as a second step under reduced pressure 200-330
A method in which a polycondensation reaction is carried out while raising the temperature to ° C to obtain a target polyester resin is preferred from the viewpoint of simple reaction.

As the catalyst used in the above method, a large number of compounds are effective. Particularly, in the first stage, an alkali metal or alkaline earth metal acetate is used, and in the second stage, zinc, manganese, cobalt, antimony is used. , Germanium, titanium, tin, and zirconium compounds. In particular, tetraalkyl titanate, tin oxalate, and potassium oxalate titanate are preferably used as a catalyst effective for all of the transesterification reaction and the polycondensation reaction. It is preferable that the catalyst is used in the range of 0.005% to 3% with respect to the total raw material of the polyester in terms of good physical properties of the polyester resin.

In the above method for producing a polyester resin, an antioxidant can be added during the production or at any time after the production. In particular, it is effective to add an antioxidant which does not inhibit the polycondensation reaction in order to prevent the polyester resin from being oxidized and deteriorated at the time of entering the second stage polycondensation step. These antioxidants include phosphoric acid,
Examples thereof include aliphatic and aromatic esters of phosphorous acid, or phenol derivatives, particularly so-called hindered phenols having a group showing a high degree of steric hindrance. Further, it is preferable to use several kinds of stabilizers such as antioxidants and ultraviolet absorbers.

Further, in the polyester resin of the present invention, it is preferable to introduce an imide skeleton or a triazine skeleton into the molecular structure from the viewpoint of further improving the flame retardancy.

The compounds having an imide skeleton introduced into the molecular structure include N, N′-ethylenebis (trimellitimide), N, N′-tetramethylenebis (trimellitimide), N, N '-Hexamethylenebis (trimellitimide), N, N'-decamethylenebis (trimellitimide), N, N'-dodecamethylenebis (trimellitimide), 3,4'-diphenyletherbis (trimellitimide) ) And the like. In order to incorporate the compound having an imide skeleton into the molecular structure of the polyester resin, a compound having a functional group having reactivity with a hydroxyl group or a carboxyl group at both ends of the imide skeleton may be added at any time in the polymerization reaction. May be added.

Compounds having a triazine skeleton introduced into the molecular structure include bis (2-carboxyethyl) isocyanurate, tris (2-carboxyethyl) isocyanurate, bis (2-hydroxyethyl)
Cyanuric acid derivatives such as isocyanurate and tris (2-hydroxyethyl) isocyanurate are exemplified.
In order to incorporate the compound having the triazine skeleton into the molecular structure of the polyester resin, in the polymerization reaction,
A compound having a functional group reactive with a hydroxyl group or a carboxyl group at both ends of the triazine skeleton may be added at any time.

The polyester resin of the present invention has excellent flame retardancy and does not cause significant mold contamination during injection molding. Therefore, the housing material, electric component material, automobile component, and packaging material of electric products are used alone. It is used for such purposes.

The flame-retardant resin composition of the present invention is characterized by comprising the above-described polyester resin and thermoplastic resin of the present invention as essential components. Here, the silicone-based flame retardant disclosed in JP-A-11-217494 has a low flame retardancy, and therefore uses a polycarbonate resin having a high flame retardant effect. On the other hand, the polyester resin of the present invention has excellent flame retardancy as described above, and can further control the compatibility with the compounded resin. The flame-retardant resin composition also exhibits excellent flame retardancy, moldability, impact resistance, and the like.

The content of the polyester resin in the flame-retardant resin composition of the present invention is not particularly limited, but may be 1%.
It is preferably in the range of 30% to 30%. That is, at 1% or more, the flame retardancy of the resin composition becomes good, while
When the content is 30% or less, the mechanical properties of the flame-retardant resin composition are improved, which is preferable. It is preferable that the content be in the range of 2 to 25% from the viewpoint of excellent balance between them.

The thermoplastic resin used in the present invention includes:
Although not particularly limited, for example, polystyrene resin, polymethylstyrene resin, rubber-modified polystyrene resin (HIPS resin), acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin) Acrylonitrile-acryl rubber-styrene copolymer (AAS resin), acrylonitrile-ethylene propylene rubber-styrene copolymer (AES resin), alloy of ABS resin and polycarbonate, alloy of ABS resin and polyester resin, AB
Styrene-based resins such as alloys of S-resin and polyamide-based resin, and alloys of polystyrene and polyphenylene oxide;
Polycarbonate resins such as polycarbonate resins, alloys of polycarbonate resins and polyester resins, alloys of polycarbonate resins and polyamide resins; polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polyethylene naphthalene dicarboxylate, poly Polyester resins such as butylene naphthalene dicarboxylate and polyhexamethylene naphthalene dicarboxylate; polyolefin resins such as polyethylene, polypropylene and polybutene; polyamide resins such as nylon 6 and nylon 66; polyphenylene oxide resins; acrylic resins. .

Among the above thermoplastic resins, a transparent thermoplastic resin, ie, a polystyrene resin, is excellent in compatibility with the polyester resin and can suppress a remarkable decrease in the transparency of the flame-retardant resin composition. Polystyrene resin such as polymethylstyrene resin, acrylonitrile-styrene copolymer (AS resin), alloy of polystyrene and polyphenylene oxide; polycarbonate resin, alloy of polycarbonate resin and polyester resin, polycarbonate such as alloy of polycarbonate resin and polyamide resin Resin: polyethylene terephthalate (PE
T), polyester resins such as polybutylene terephthalate (PBT), polyhexamethylene terephthalate, polyethylene naphthalenedicarboxylate, polybutylene naphthalenedicarboxylate, polyhexamethylene naphthalenedicarboxylate; polyolefin resins such as polyethylene, polypropylene and polybutene Preferred are resins; polyamide resins such as nylon 6 and nylon 66; polyphenylene oxide resins. Further, styrene-based resins, polyester-based resins, and polycarbonate-based resins are preferred in that the flame-retardant effect is remarkable, and polycarbonate-based resins are particularly preferred for the same reason.

Further, for the purpose of improving flame retardancy, it is preferable to use a polyamide resin, a wholly aromatic polyester resin, polybutylene terephthalate, polyphenylene oxide, polyoxymethylene, chlorinated polyethylene resin or the like in combination.

The polyester resin and the flame-retardant resin composition of the present invention have sufficient flame retardancy and do not use a halogen-based compound such as a metal salt of perfluoroalkanesulfonic acid or a fluorine-containing polymer. It can be used in space and inside buildings, and has a low environmental load. But,
Depending on the use, known flame retardants and flame retardant auxiliaries containing halogen compounds such as perfluoroalkanesulfonic acid metal salts and fluorine-containing polymers may be mixed at any time.

As these known flame retardants and flame retardant auxiliaries,
Silicone powder, antimony oxide, aluminum hydroxide, zinc borate, platinum powder, ferrocene, tricresyl phosphate, tris (dichloropropyl) phosphate, chlorinated paraffin, tetrabromobutane, hexabromobenzene, tetrabromobisphenol A, polytetrafluoro Ethylene, tetrafluoroethylene-based copolymers such as tetrafluoroethylene and hexafluoropropylene copolymers, polycarbonates prepared from fluorinated diphenols, metal salts of aromatic sulfonamides or metal salts of aromatic sulfonic acids, and the like. And, above all,
Metal salts of aromatic sulfonic acids are preferred from the viewpoint of improving the flame retardant effect. Examples of the metal of the metal salt of aromatic sulfonic acid include alkali metals such as sodium and potassium, alkaline earth metals, copper, and aluminum.

The content of the flame retardant and the flame retardant aid in the whole flame retardant resin composition of the present invention is not particularly limited, but is preferably in the range of 1% to 10%. It is preferable because flame retardancy can be imparted without deteriorating properties.

The polyester resin and the flame-retardant resin composition of the present invention may further contain known additives. Known additives include, for example, 2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol and 2,2-methylenebis- as antioxidants. (4-ethyl-6-t-methylphenol), 4,4'-thiobis-
(6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di-nonylphenyl) phosphite, and the like.
-T-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, etc., and paraffin wax and stearic acid as lubricants. , Hydrogenated oil, stearoamide, methylene bis-stearamide, ethylene bis-stearamide, n
-Butyl stearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, etc., as a coloring agent, titanium oxide, carbon black, etc., as a filler, calcium carbonate, clay, silica, glass fiber, glass. ball,
And carbon fibers.

The thermoplastic resin composition of the present invention may further contain a known compatibilizer. Known compatibilizers include, for example, styrene-ethylene-butadiene block copolymer, polyethylene-
Polymethyl methacrylate block copolymer, polyethylene-polystyrene graft copolymer, polyethylene-
Polymethyl methacrylate graft copolymer, polypropylene-acrylonitrile graft copolymer, and the like.Examples of the reactive compatibilizer include maleic anhydride-grafted polypropylene, styrene-maleic anhydride copolymer,
Ethylene-glycidyl methacrylate copolymer, styrene graft copolymer to ethylene-glycidyl methacrylate copolymer, methyl methacrylate graft copolymer to ethylene-glycidyl methacrylate copolymer,
Examples include a polypropylene-β-hydroxyethyl methacrylate graft copolymer and a polypropylene-glycidyl methacrylate graft copolymer.

The method of preparing the resin composition of the present invention is not particularly limited. For example, the polyester resin of the present invention, a thermoplastic resin, and, if necessary, the above-mentioned other additive components in a predetermined amount. Blend, Henschel mixer,
It can be easily produced by premixing with a mixer such as a tumbler mixer and then melt-mixing with an extruder, a kneader, a hot roll, a Banbury mixer or the like.

[0092]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. still,
In each of the following examples, “parts” indicates “parts by weight”.

The physical properties in the examples were measured as follows. (1) Number average molecular weight [Mobile phase: 5 mmol / dm ^3]
CF ₃ COONa / HFIP solution, column bath: 4
0 ° C., detector: UV (220 nm), flow rate 1.0 cm ³ / min,
Column: Shodex GPC measurement HFIP-805
+ HFIP-806 + HF-807] and is a value converted into PMMA. (2) Content of sulfonic acid metal salt After pretreatment with acid decomposition, inductively coupled plasma emission spectrometry (IC
This is a value obtained by quantifying the amount of metal ions using the P) method.

Example 1 A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 726 parts of dimethyl naphthalene-2,6-dicarboxylate, 21 parts of dimethyl potassium 5-sulfoisophthalate, Ethylene glycol 900
Parts and 2.4 parts of calcium acetate as a catalyst,
Stirring was continued at 180 ° C. for 2 hours while removing methanol while flowing nitrogen. Next, 440 parts of a modified polysiloxane (KF-6003 manufactured by Shin-Etsu Chemical Co., Ltd.) and 1.0 part of tetrabutyl titanate as a catalyst were added. The reaction was further allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 130 Pa. Then, while slowly raising the temperature to 300 ° C.,
The pressure was reduced to 3 Pa, and the reaction was performed for 3 hours. After completion of the reaction, the resultant was taken out into a strand under nitrogen pressure and pelletized to obtain a pellet-like polyester. Hereinafter, this is referred to as Sample A. Sample A had a number average molecular weight of 9.1 × 10 ⁵ and a potassium content of 0.2%.

Example 2 A flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade) was charged with 277 parts of dimethyl naphthalene-2,6-dicarboxylate, 89 parts of dimethyl potassium 5-sulfoisophthalate, Ethylene glycol 374
Parts and 2.0 parts of calcium acetate as a catalyst,
Stirring was continued at 180 ° C. for 2 hours while removing methanol while flowing nitrogen. Then, 243 parts of modified diphenylpolysiloxane (alcoholic hydroxyl group at both ends, number average molecular weight 3,000) was added, and while removing excess distillate such as ethylene glycol under a reduced pressure of 130 Pa,
The reaction was allowed to proceed at 210 ° C. for 2 hours. Further, 1.5 parts of tetrabutyl titanate was added as a catalyst, and the temperature was raised to 295 ° C. Next, the mixture was reacted under a reduced pressure of 13 Pa for 3 hours, then taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyester. Hereinafter, this is referred to as Sample B. This sample B had a number average molecular weight of 6.8 × 10 ⁵ and a potassium content of 1.
8%.

Example 3 A flask equipped with a temperature controller, a nitrogen inlet tube and a stirrer (double helical blade) was charged with 343 parts of dimethyl naphthalene-2,6-dicarboxylate, 45 parts of dimethyl potassium 5-sulfoisophthalate, Ethylene glycol 478
Parts and 2.8 parts of calcium acetate as a catalyst,
Stirring was continued under a nitrogen atmosphere at 180 ° C. for 2 hours while removing methanol. Next, 380 parts of modified diphenylpolysiloxane (alcoholic hydroxyl group at both ends, number average molecular weight 3,000) was added, and at 210 ° C. while removing excess distillate such as ethylene glycol under a reduced pressure of 130 Pa. The reaction was allowed to proceed for 2 hours. Further, 1.8 parts of tetrabutyl titanate was added as a catalyst, and 285
The temperature was raised to ° C. Next, the mixture was reacted for 4 hours under a reduced pressure of 14 Pa, taken out into a strand under nitrogen pressure, and pelletized to obtain a pellet-like polyester. Hereinafter, this is referred to as Sample C. This sample C
Had a number average molecular weight of 4.1 × 10 ⁵ and a potassium content of 0.8%.

Example 4 A flask equipped with a temperature controller, a nitrogen inlet tube, and a stirrer (double helical blade) was charged with 394 parts of dimethyl naphthalene-2,6-dicarboxylate, 29 parts of dimethyl potassium 5-sulfoisophthalate, 58 parts of N, N'-ethylenebis (trimeritimide), ethylene glycol 4
96 parts and 2.8 parts of calcium acetate were charged as a catalyst, and stirring was continued while removing methanol over 2 hours at 180 ° C. under a flow of nitrogen. Then, the reaction was allowed to proceed at 210 ° C. for 2 hours while removing excess distillate such as ethylene glycol under a reduced pressure of 850 Pa. Further, modified dimethylpolysiloxane (KF manufactured by Shin-Etsu Chemical Co., Ltd.)
-6003) 250 parts and 1.5 parts of tetrabutyl titanate as a catalyst were added, and the temperature was raised to 295 ° C. Then 1
After reacting under a reduced pressure of 3 Pa for 3 hours, the reaction mixture is taken out in a strand shape under nitrogen pressure, and pelletized.
A pellet-shaped polyester was obtained. Hereinafter, this is referred to as sample D. The number average molecular weight of this sample D was 4.1 ×
10 ⁵ , the potassium content was 0.5%.

Examples 5 to 16 and Comparative Examples 1 to 3 The components were mixed in the proportions shown in Tables 1 to 4 below.
Using a 25 mm twin screw extruder manufactured by Toyo Seiki Seisaku-sho, Ltd.
The mixture was kneaded and extruded at 270 ° C. Each test piece was prepared from the obtained pellet at 265 ° C. using a 1-oz injection molding machine manufactured by Yamashiro Seiki Co., Ltd., and the following evaluations were made. The evaluation results are shown in Tables 1 to 4. (1) Flame retardancy test A 125 x 13 x 3.2 mm flat plate was conditioned for 48 hours at a temperature of 23 ° C and a relative humidity of 50%.
The flame retardancy was evaluated based on the UL94 test (flammability test of plastic materials for equipment parts) specified by Laboratories. UL94V is a method for evaluating the flame retardancy from the residual flame time and drip property after indirectly igniting a burner flame for 10 seconds on a test piece of a predetermined size held vertically, and is classified into the following classes. .

[0099]

[Table 1]

The afterflame time shown above is the length of time that the test piece continues flaming combustion after the ignition source is moved away, and the ignition of the cotton by the drip is approximately from the lower end of the test piece. 300
The determination is made based on whether or not the marking cotton below mm is ignited by a drip from the test piece. (2) Drop weight impact test In accordance with ASTM D-3763, an instrumented drop weight impact tester Dynatup (GR manufactured by General Research Corporation)
C 730-I) using a flat plate of 80 × 80 × 3 mm as a test plate. (3) Mold Contamination Property The obtained pellets were subjected to a 1-oz injection molding machine manufactured by Yamashiro Seiki Co., Ltd., and the mold contamination was evaluated by a two-step sensory evaluation of ○ no contamination and × contamination.

In the table, PC is "S-3000" manufactured by Mitsubishi Engineering-Plastics Corporation, and PC / ABS
In addition, the is manufactured by Sumitomo Dow Ltd. "IM-6100", the additive 1 Dainippon Ink and Megafac F114 (C ₄ F ₉ S
O ₃ K), additive 2 was potassium diphenylsulfonate, and additive 3 was CR-741 manufactured by Daihachi Chemical Industry Co., Ltd.
(Phosphorus flame retardant).

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

[0106]

Industrial Applicability The novel polyester resin of the present invention exhibits excellent flame retardancy, and the flame retardant resin containing the same provides excellent flame retardancy without causing mold contamination during injection molding. It has good compatibility with the resin to be compounded, and does not cause a significant decrease in mechanical strength, especially impact resistance.

[0107]

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR chart of the polyester resin obtained in Example 1.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J002 AA011 CF11X CF13X CF14X CF15X CG001 4J029 AA01 AA03 AB01 AB07 AC02 AC03 AD01 AD10 AE01 BA02 BA03 BA04 BA05 BA07 BA08 BA09 BA10 BD04A BD07A BH01 CB04A CB05 CC05ACB06 CH03 DA15 DA17 DB01 DC03 DC06 EF04 FC35 HB01 HB02 JE222

Claims (12)

[Claims] In the molecular structure, the following structural formula (1): (Where Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group containing one or more atoms other than carbon atoms in a ring, R is a polyester) Residue), an oxo acid metal base and a polysiloxane skeleton, and having a number average molecular weight of 5,
A polyester resin having a range of 000 to 5,000,000. 2. The polyester resin according to claim 1, wherein the metal oxoacid base contained in the molecular structure is contained in a range of 0.01% to 10% as a metal ion amount. 3. The oxo acid metal base contained in the molecular structure is represented by the following structural formula (2): (Where Ar is an aromatic hydrocarbon group having 6 to 20 carbon atoms, or a heterocyclic group containing one or more atoms other than carbon atoms in the ring, ^Bm- is an oxoacid anion, ^{Mn +} The polyester resin according to claim 1 or 2, which is present in the molecular structure as a structural unit represented by the following formula: 4. The polyester resin according to claim 1, wherein the oxo acid metal base in the molecular structure is a sulfonic acid metal base. 5. The polyester resin according to claim 1, wherein the oxo acid metal base in the molecular structure is a phosphonate metal base. 6. The polyester resin according to claim 1, wherein the polysiloxane skeleton in the polyester resin has a number average molecular weight of 500 to 1,000,000. 7. A polysiloxane compound having a functional group reactive with a hydroxyl group or a carboxyl group.
2) aromatic polycarboxylic acids or alkyl esters thereof,
The compound according to any one of claims 1 to 6, which is obtained by reacting (a3) a diol compound and (a4) an aromatic dicarboxylic acid having an oxo acid metal base or an alkyl ester thereof as an essential component. Polyester resin. 8. The polyester resin according to claim 1, which has an imide skeleton in its molecular structure. 9. The polyester resin according to claim 1, which has a triazine skeleton in a molecular structure. 10. A flame-retardant resin composition comprising the polyester resin according to claim 1 and a thermoplastic resin as essential components. 11. The polyester resin content is from 1% to 1%.
The flame-retardant resin composition according to claim 10, which is 30%. 12. The flame-retardant resin composition according to claim 10, wherein the thermoplastic resin is a polycarbonate resin.