JP2002161131A - Flame retardant polyester resin - Google Patents

Abstract

(57) [Summary] [Object] To provide a flame-retardant polyester resin which is excellent in environmental suitability without using a halogen-based flame retardant and does not cause a decrease in heat resistance. [Constitution] The following general formula (I) derived from a dicarboxylic acid component
And the following general formula (II) derived from the diol component
And (III), and the mole fractions [I], [II], and [II] of the respective structural units of the general formulas (I), (II), and (III).
I] is a flame-retardant polyester resin satisfying the following formulas (1) and (2). Embedded image [In the formula (I), R ¹ represents an arylene group. [Chemical formula 2] [In the formula (II), R ² is an alkylene group having 2 to 10 carbon atoms,
Or a cycloalkylene group. [Chemical formula 3] [In the formula (III), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and n is an integer of 1 to 5. (1) 0.9 ≦ ([II] + [III]) / [I] ≦ 1.5 (2) 0.01 ≦ [III] / [I] ≦ 0.5

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyester resin obtained by copolymerizing a flame-retardant component, which is excellent in environmental suitability without using a halogen-based flame retardant and which is not accompanied by a decrease in heat resistance.

[0002]

2. Description of the Related Art Among polyester resins, polybutylene terephthalate resin has a higher crystallization rate than polyethylene terephthalate resin and has excellent moldability, and furthermore has excellent mechanical and electrical properties. More widely used as engineering plastics in the fields of electric / electronic parts, automobile parts, mechanical structural parts and the like.

[0003] When flame retardancy is required among these, a method of adding a halogen-based flame retardant and an antimony-based flame retardant auxiliary has been conventionally employed. Due to corrosion of metal members and concerns about environmental effects at the time of disposal, alternatives to organic phosphorus-based flame retardants such as triphenyl phosphate are being studied as non-halogen flame retardants. However, those phosphorus-based flame retardants have drawbacks such as causing bleed-out during molding and lowering heat resistance with respect to the resin.Also, alternatives to phosphorus such as red phosphorus have been studied. Phosphorus has drawbacks in that the resin is easily colored, in addition to concerns about problems in the working environment. On the other hand, as a flame-retardant method for solving those drawbacks, bis (3,3 5-
Although a method of copolymerizing dimethyl-4-hydroxyphenyl) methane [tetramethylbisphenol F] has been proposed (for example, see Japanese Patent Application Laid-Open No. 60-186528), a flame-retarding method for polyester resin is still established. It has not been done yet.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art. Therefore, the present invention is excellent in environmental suitability without using a halogen-based flame retardant and is accompanied by a decrease in heat resistance. Aims to provide a non-flammable polyester resin.

[0005]

Means for Solving the Problems The present invention has been made to achieve the above object, that is, the present invention relates to a structural unit of the following general formula (I) derived from a dicarboxylic acid component:
Consisting of the structural units of the following general formulas (II) and (III) derived from the diol component, the mole fractions [I] and [II] of the structural units of the general formulas (I), (II) and (III) And [III] are flame-retardant polyester resins satisfying the following formulas (1) and (2):
Is the gist.

[0006]

Embedded image

[In the formula (I), R ¹ represents an arylene group. ]

[0008]

Embedded image

[In the formula (II), R ² represents an alkylene group having 2 to 10 carbon atoms or a cycloalkylene group. ]

[0010]

Embedded image

[In the formula (III), R ³ , R ⁴ , R ⁵ and R
⁶ independently represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and n is an integer of 1 to 5. ]

(1) 0.9 ≦ ([II] + [III]) / [I] ≦ 1.5 (2) 0.01 ≦ [III] / [I] ≦ 0.5

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the structural unit of the above general formula (I) derived from the dicarboxylic acid component in the flame-retardant polyester resin of the present invention, the arylene group for R ¹ may be a monocyclic, ring-assembled, or polycyclic group. It may be any of cyclic, and specifically, for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4,4′-biphenylene group, 1,5- Examples thereof include a naphthalene group and a 2,6-naphthalene group, which may have an alkyl group or the like as a substituent, or may be composed of two or more kinds. It is preferable that the main component be a group or a 2,6-naphthalene group, and it is particularly preferable that the main component be a 1,4-phenylene group.

Further, the above-mentioned general formula (I) derived from the diol component
In the structural unit of I), examples of the alkylene group or cycloalkylene group of R ² include, for example, ethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, octamethylene group, , 2
-Cyclohexylene group, 1,4-cyclohexylene group,
A 1,2-dimethylenecyclohexylene group, a 1,4-dimethylenecyclohexylene group, etc., which may have an alkyl group or the like as a substituent, or may be composed of two or more kinds. Of these, it is preferable to mainly use an ethylene group, a tetramethylene group, or a 1,4-dimethylenecyclohexylene group, and particularly preferable to use a tetramethylene group as a main component.

Further, the above-mentioned general formula (I) derived from the diol component
In the structural unit of II), R^Three~ R ⁶As an alkyl group
Specifically, for example, a methyl group, an ethyl group,
A pill group and the like;^Three, R^Four, R^Five, And R
⁶Are preferably methyl groups, and n is
Is preferably 1 to 3.

The flame-retardant polyester resin of the present invention comprises the structural unit represented by the general formula (I) derived from a dicarboxylic acid component and the general formulas (II) and (I) derived from a diol component.
II) comprising the structural units of the general formulas (I), (II), and
The molar fraction [I], [II], and [III] of each structural unit of (III)
Satisfies the following expressions (1) and (2), and preferably satisfies the following expressions (3) and (4), and satisfies the following expressions (5) and (6). Particularly preferred.

(1) 0.9 ≦ ([II] + [III]) / [I] ≦ 1.5 (2) 0.01 ≦ [III] / [I] ≦ 0.5

(3) 1.0 ≦ ([II] + [III]) / [I] ≦ 1.3 (4) 0.03 ≦ [III] / [I] ≦ 0.3

(5) 1.1 ≦ ([II] + [III]) / [I] ≦ 1.2 (6) 0.05 ≦ [III] / [I] ≦ 0.2

Here, regardless of whether ([II] + [III]) / [I] is less than the above range or more than the above range, it is difficult to produce a polyester resin having a sufficient degree of polymerization.
If the ratio [III] / [I] is less than the above range, the flame retardancy of the polyester resin will be insufficient. On the other hand, if the ratio [III] / [I] exceeds the above range, the polyester resin will be colored and a practical problem will occur. .

The flame-retardant polyester resin of the present invention comprises:
Basically, it is produced by a conventional method for producing a polyester resin from a dicarboxylic acid component and a diol component.
That is, a mixture of a dicarboxylic acid or an ester-forming derivative thereof as a dicarboxylic acid component and an ester-forming derivative thereof and a diol component is subjected to an esterification reaction or a transesterification reaction under normal pressure to pressure under heating, and subsequently, the obtained reaction product is obtained. It is produced by carrying out a melt polycondensation reaction under heating and under reduced pressure as a gradually reduced pressure from normal pressure, and these are performed in a continuous system or a batch system.

Here, as the dicarboxylic acid or the ester-forming derivative thereof as the dicarboxylic acid component, the dicarboxylic acid forming the structural unit of the general formula (I) derived from the dicarboxylic acid component in the flame-retardant polyester resin of the present invention is used. Acid or an ester-forming derivative thereof, specifically, for example, phthalic acid, isophthalic acid, terephthalic acid, 4,4 ′
-Biphenyldicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, or an alkyl ester having about 1 to 4 carbon atoms or a halide thereof is essential. Further, as other copolymerization components, for example, phenylenedioxydicarboxylic acid, 4,
Aromatic dicarboxylic acids such as 4'-diphenyl ether dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, 4,4'-diphenoxyethane dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, and 1,2-cyclohexane dicarboxylic acid Alicyclic dicarboxylic acids such as acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, Aliphatic dicarboxylic acids such as decadicarboxylic acid and dodecadicarboxylic acid, or one of these aromatic dicarboxylic acids, alicyclic dicarboxylic acids, alkyl esters of aliphatic dicarboxylic acids having about 1 to 4 carbon atoms, and halides; The above may be used.

As the diol component, a diol which forms the structural units of the general formulas (II) and (III) derived from the diol component in the flame-retardant polyester resin of the present invention, specifically, for example, ethylene Aliphatic diols such as glycol, trimethylene glycol, tetramethylene glycol, pentamethylene glycol, hexamethylene glycol, octamethylene glycol, neopentyl glycol, 1,2-cyclohexanediol,
Alicyclic diols such as 4-cyclohexanediol, 1,2-cyclohexanedimethylol, and 1,4-cyclohexanedimethylol, and ethylene oxide adducts of bis (4-hydroxyphenyl) methane [bisphenol F], bis (3 -Methyl-4-hydroxyphenyl)
An ethylene oxide adduct of methane [dimethylbisphenol F], an ethylene oxide adduct of bis (3,5-dimethyl-4-hydroxyphenyl) methane [tetramethylbisphenol F], and the like are essential. Further, as other copolymerization components, for example, xylylene glycol,
4,4'-dihydroxybiphenyl, bis (4-hydroxyphenyl) methane [bisphenol F], bis (3
-Methyl-4-hydroxyphenyl) methane [dimethylbisphenol F], bis (3,5-dimethyl-4-hydroxyphenyl) methane [tetramethylbisphenol F], 2,2-bis (4′-hydroxyphenyl) propane [ Bisphenol A], 2,2-bis (4′-β
-Hydroxyethoxyphenyl) propane, bis (4-
Hydroxyphenyl) sulfone [bisphenol S],
Aromatic diols such as bis (4-β-hydroxyethoxyphenyl) sulfonic acid, or 1 such as ethylene oxide adduct or propylene oxide adduct of 2,2-bis (4′-hydroxyphenyl) propane [bisphenol A] More than one species may be used.

Further, for example, hydroxycarboxylic acids and alkoxycarboxylic acids such as glycolic acid, p-hydroxybenzoic acid and p-β-hydroxyethoxybenzoic acid, and stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, t- Monofunctional components such as butylbenzoic acid and benzoylbenzoic acid, and trifunctional or higher functionalities such as tricarballylic acid, trimellitic acid, trimesic acid, pyromellitic acid, gallic acid, trimethylolethane, trimethylolpropane, glycerol and pentaerythritol. One or more of the functional components may be used as a copolymer component.

Examples of the polycondensation catalyst used in the melt polycondensation include titanium compounds such as tetrapropyl titanate, tetrabutyl titanate, titanium oxalate, and potassium titanium oxalate, magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate. , Magnesium compounds such as magnesium carbonate, cobalt formate, cobalt acetate, cobalt stearate, cobalt oxalate, cobalt carbonate, cobalt bromide, cobalt compounds such as cobalt acetylacetonate, germanium dioxide,
Germanium tetroxide, germanium hydroxide, germanium oxalate, germanium compounds such as germanium tetraethoxide, germanium tetrabutoxide, antimony trioxide, antimony acetate, antimony compounds such as methoxyantimony, and the like, the amount of which is used, the amount of polyester resin 10 to 1 as compound used for theoretical yield
It is preferable to set the amount to be 0.00000 ppm.
It is particularly preferred that the amount is 1,000 ppm.

In the present invention, it is preferable that a titanium compound is used as the polycondensation catalyst, because a titanium compound and a magnesium compound are used, since the effects of the present invention can be remarkably exhibited. Is particularly preferred. In this case, the amount ratio of the titanium compound to the magnesium compound is 1/10 to 10/1 by the equivalent ratio of Ti / Mg.
Is preferably, and particularly preferably 1/3 to 3/1.

In the melt polycondensation, a stabilizer may be used. Examples of the stabilizer include orthophosphoric acid, tris (triethylene glycol) phosphate, ethyl diethylphosphonoacetate, ethyl acid phosphate and triacid. Phosphorus compounds such as ethylene glycol acid phosphate and phosphorous acid, and the like, are used in an amount of 20 to 5 as a phosphorus compound based on the theoretical yield of the polyester resin.
Preferably, the amount is 00 ppm, and 40 to 400 ppm.
It is particularly preferable to set the amount to be ppm.

The temperature in the melt polycondensation is 150 ° C.
The temperature is gradually increased from about 200 ° C. and finally to 275 ° C. or less from the viewpoint of polymerization rate and the like and from the viewpoint of prevention of coloring and the like.
The pressure is reduced to 33 to 13.3 Pa and the stirring is performed for 1 to 20 Pa.
The melt polycondensation reaction takes place in a short time.

The polyester resin melt-polycondensed by the above-mentioned production method is usually withdrawn in the form of a strand from an extraction port provided at the bottom of the reaction tank, and then cooled or cooled with water, and then cut with a cutter into pellets, chips, or the like. The melt-polycondensed granules are usually obtained under an inert gas atmosphere such as nitrogen, carbon dioxide, argon, or the like, or a steam atmosphere, or a steam-containing inert gas atmosphere. After heating at a temperature of 60 to 180 ° C. to crystallize the surface of the resin granule, immediately below the adhesive temperature of the resin under an inert gas atmosphere or / and under a reduced pressure of 1333 to 13.3 Pa. It is preferable to carry out a heat treatment for a period of 100 hours or less to carry out solid-phase polycondensation at a temperature lower by about 80 ° C. while flowing the granules so as not to adhere to each other. It can be further high degree of polymerization by condensation.

The flame-retardant polyester resin of the present invention preferably has an intrinsic viscosity of 0.5 to 2.0 dl / g,
Also, if necessary, antioxidants, ultraviolet absorbers, light stabilizers, antistatic agents, lubricants, antiblocking agents, antifogging agents, nucleating agents, plasticizers, coloring agents, dispersants, and infrared rays that are normally used Additives such as an absorbent and a filler are added, and the mixture is subjected to ordinary molding.

[0031]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to the following examples unless it exceeds the gist.

Example 1 113 g of dimethyl terephthalate, 63 g of 1,4-butanediol and tetramethylbisphenol F were placed in a glass polymerization tube equipped with a stirring blade and having a nitrogen inlet and a decompression port.
Of ethylene oxide adduct (a mixture of n = 1 to 3 in the above general formula (III)) was charged, and the inside of the system was replaced with nitrogen. Then, the temperature was raised to 150 ° C. with stirring, and after 30 minutes, all the raw materials were dissolved. Then, tetrabutyl titanate was added.
After adding 032 g and keeping at 150 ° C. for 1 hour, the temperature was raised to 215 ° C. over 2 hours, and 0.075 g of tetrabutyl titanate and 0.066 g of magnesium acetate were added, and the temperature was raised to 240 ° C. over 1 hour. While heating, the pressure was gradually reduced to 66.6 Pa over one and a half hours,
The flame-retardant polyester resin was produced by terminating the polycondensation reaction 2 hours after the temperature reached 240 ° C.

The obtained polyester resin is prepared by the following method by the following general formulas (I), (II) and (III):
Calculate the molar fractions [I], [II], and [III] of each structural unit of (I), ([II] + [III]) / [I], and [III] / [I]
When the values were determined, they were 1.18 and 0.09, respectively.
Met.

Calculation of molar fractions [I], [II], and [III] of each structural unit Nuclear magnetic resonance apparatus (500 MHz-NMR, Varian
Using “Inova500” (manufactured by the company), a sample solution dissolved in a mixed solvent of D-hexafluoroisopropanol / D-chloroform and a peak derived from terephthalic acid appearing at 8.13 ppm and 1,4-appearing at 2.04 ppm. 1. a peak derived from butanediol, and
Peaks derived from tetramethylbisphenol F appearing at 30 ppm were measured, and from the integrated values of these peaks,
The molar fractions [I], [II] and [III] of the respective structural units of the general formulas (I), (II) and (III) were calculated.

In addition, regarding the obtained polyester resin,
The intrinsic viscosity measured by the method described below is 0.86 dl /
g, the melting point was 211 ° C., and the flame retardancy evaluated by the following method was 24.3% in terms of oxygen index OI.

Intrinsic Viscosity The viscosity of a solution obtained by dissolving the obtained resin in a mixed solvent of phenol / tetrachloroethane (weight ratio 1/1) at a concentration of 0.5 g / dl was measured at 30 ° C. using an Ubbelohde viscometer.
It was determined by measuring with. Using a melting point differential scanning calorimeter, the temperature was raised at a rate of 16 ° C.
Measured in minutes. Flame retardancy From the obtained resin, hot press, width 6mm, length 1
A test piece having a thickness of 20 mm and a thickness of 3 mm was prepared and subjected to JIS K7
The oxygen index OI (%) was measured using a candle method combustion tester D (manufactured by Toyo Seiki Seisaku-sho, Ltd.) in accordance with 201-2.

Example 2 The amount of 1,4-butanediol charged was 32 g, the amount of ethylene oxide adduct of tetramethylbisphenol F was 46 g, and the polycondensation reaction was terminated three and a half hours after reaching 240 ° C. Other than that, a flame-retardant polyester resin was produced in the same manner as in Example 1, and the obtained polyester resin was evaluated for ([II] + [III]) / [I] value, and
When [III] / [I] values were determined, they were 1.28,
And 0.16. The intrinsic viscosity measured in the same manner was 0.96 dl / g and the melting point was 203 ° C. The flame retardancy evaluated in the same manner was 26.3% in terms of oxygen index OI.
Met.

Comparative Example 1 The amount of dimethyl terephthalate charged was 132 g,
A polyester resin was produced in the same manner as in Example 1 except that the charged amount of butanediol was 74 g, and the ethylene oxide adduct of tetramethylbisphenol F was not used, and the obtained polyester resin was measured in the same manner. Intrinsic viscosity is 0.96 dl / g, melting point is 216
° C, and the flame retardancy evaluated in the same manner was 21.6% in oxygen index OI.

[0039]

According to the present invention, it is possible to provide a flame-retardant polyester resin which is excellent in environmental suitability without using a halogen-based flame retardant and which is not accompanied by a decrease in heat resistance.

 ──────────────────────────────────────────────────続 き Continued on front page F term (reference) 4J029 AA01 AA03 AB01 AC02 AE01 BA02 BA05 BB12A BB12B BD02 BD03A BD04A BD05A BD06A BD07A CB03A CB06A HA01 HA02 HA07 HB01 JA091 JB131 JB171 JF131 JF321 JF361 JF471

Claims (5)

[Claims] 1. The following general formula derived from a dicarboxylic acid component:
The following general formula derived from the structural unit of (I) and the diol component
Consisting of the structural units of (II) and (III), the general formulas (I) and (I
A flame-retardant polyester resin characterized in that the molar fractions [I], [II], and [III] of the structural units of (I) and (III) satisfy the following formulas (1) and (2): . Embedded image [In the formula (I), R ¹ represents an arylene group. [Chemical formula 2] [In the formula (II), R ² is an alkylene group having 2 to 10 carbon atoms,
Or a cycloalkylene group. [Chemical formula 3] [In the formula (III), R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and n is an integer of 1 to 5. (1) 0.9 ≦ ([II] + [III]) / [I] ≦ 1.5 (2) 0.01 ≦ [III] / [I] ≦ 0.5 2. The compound of the formula (I) wherein R ¹ is 1,4-
The flame-retardant polyester resin according to claim 1, which is a phenylene group. 3. The flame-retardant polyester resin according to claim 1, wherein R ² in the general formula (II) is a tetramethylene group. 4. A method according to claim 1, wherein R ³ , R ⁴ ,
R ^5, and also R ⁶ are both a methyl group, and, a flame retardant polyester resin according to any one of claims 1 to 3 n is an integer of 1 to 3. 5. The molar fraction of each structural unit [I], [II], and
The flame-retardant polyester resin according to any one of claims 1 to 4, wherein [III] satisfies the following formulas (5) and (6). (5) 1.1 ≦ ([II] + [III]) / [I] ≦ 1.2 (6) 0.05 ≦ [III] / [I] ≦ 0.2