JPS61268752A - Flame-retardant polyester resin composition - Google Patents

Abstract

PURPOSE:To obtain the titled composition of high crystallization rate, free from bleedout of the flame-retardant contained, excellent in the surface gloss and mechanical properties of the molded articles therefrom, by incorporating a polyester with specific flame-retardant, flame-retarding aid, specific nucleating agent and ester-based plasticizer. CONSTITUTION:The objective composition can be obtained by incorporating 100pts.wt. of a polyester having ethylene terephthalate recurring unit with polyethylene terephthalate accounting for >=80mol%, with (A) 0.01-10pts.wt. of at least one kind of compound selected from inorganic compound with an average particle size <=50mu and either organic or polymeric compounds having carboxyl group metal salt, (B) 5-40pts.wt. of a halogenated bisphenol type epoxy compound of formula (X is Br or Cl; Y is H, glycidyl, etc.; R is alkylene, etc.; n is integer corresponding to >=2,500 in epoxy equivalent; p is 1-4), (C) 1-15pts.wt. of either organic or inorganic antimony-contg. compound and (D) 0-175pts.wt. of fibrous reinforcer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flame-retardant polyester composition that has good moldability and provides a molded article with good surface gloss and mechanical properties. More specifically, it has a high crystallization rate, provides an excellent molded product even at a mold temperature of about 120°C or less during injection molding, has excellent mechanical properties, and has low oozing of N fuel. suppressed. That is, the present invention relates to a flame-retardant polyester resin composition in which bleed-out of flame retardant is suppressed.

(Prior Art) Polyethylene terephthalate has excellent mechanical properties, electrical properties, heat resistance, chemical resistance, etc., and is used in many industrial products as fibers and films.

In this way, when used as fiber or film, 1
Normally, stretched products are used, but if the product is to be used as an injection molded product in plastic applications, for example, the stretching process described above has not been applied.
It is known that some problems occur in terms of molding and physical properties. In other words, because polyethylene terephthalate has a low crystallization rate at low temperatures,2 the mold temperature normally used when injection molding other plastics is approximately 120°C.
In the following, the crystallization rate is insufficient, and the resulting molded product has a difference in crystallinity between the surface and the inside, resulting in uneven mechanical properties (1) dimensional stability and shape stability,
It is extremely difficult to obtain molded products that can withstand practical use.

Many methods have been proposed to solve these problems, such as using a high-temperature mold and adding a crystallization nucleating agent or crystallization accelerator.

The present inventors have also proposed polyethylene terephthalate resin compositions having a high crystallization rate in Japanese Patent Application No. 163821/1982, Japanese Patent Application No. 194003/1982, and Japanese Patent Application No. 10647/1982.

In addition, in recent years, polyethylene terephthalate reinforced with glass fiber, etc. has been used in large quantities as an engineering plastic in the field of industrial parts such as electrical parts, automobile parts, and mechanical parts. It is essential that the flame retardant does not seep out onto the surface of the molded product, that is, it does not bleed out.

(Problem to be solved by the invention) Conventionally, halogen compounds, organic phosphorus compounds, halogen-containing phosphorus compounds, etc. have been used to make resins flame retardant, and the purpose has been largely achieved. It is said that a combination of a halogen compound or an organic halogen compound and an antimony-containing compound is effective. However, these organic halogen compounds cannot be said to have sufficient compatibility with thermoplastic polyester, and even if they appear to be well compatible with the resin at room temperature, if they are left in an atmosphere at high temperatures (e.g., 80°C or higher), The organic halogen compound bleeds out onto the surface of the molded product, which not only deteriorates the appearance of the molded product, but also often poses a major problem especially when used as an electrical component. Furthermore, when the above-mentioned flame retardant is blended into a polyethylene terephthalate resin composition that has been improved to have a high crystallization rate, the crystallization rate of the polyethylene terephthalate resin composition decreases, resulting in poor moldability. A problem may arise in which the condition worsens.

(Means for Solving the Problems) As shown above, the present inventors have conducted intensive research to solve the problems of flame-retardant polyethylene terephthalate compositions, and found that molded products with a high crystallization rate. Surface gloss 9 Excellent mechanical properties.

As a result of intensive research to obtain a flame-retardant polyethylene terephthalate resin composition with suppressed flame retardant bleed-out, we found that polyethylene terephthalate resin contains a specific flame retardant, a flame retardant aid, a specific nucleating agent, and an ester plasticizer. The present inventors have discovered that the above object can be achieved by blending the agent with the agent, and have thus arrived at the present invention. That is, the present invention relates to polyethylene terephthalate or polyester having at least 80 mol% of ethylene or terephthalate repeating units (hereinafter referred to as PET).
100 parts by weight (referred to as resin), (a) average particle size 5
0.01 to 10 parts by weight of at least one of an inorganic compound having a size of 0μ or less, an organic compound having a metal salt of a carboxyl group, and a polymer compound having a metal salt of a carboxyl group; (b) 0.3 parts by weight of an ester plasticizer; ~15 parts by weight.

(c) 5 to 40 parts by weight of a halogenated bisphenol type epoxy compound represented by the following general formula (I).

X: Bromine or chlorine atom Y: Hydrogen, a group selected from a glycidyl group, an alkyl group, a phenyl group, a benzyl group, or a derivative thereof R: Direct bond, alkylene group, carbonyl group.

Group selected from ether group, thioether group, and sulfone group n: An integer necessary to make the epoxy equivalent 2,500 or more p: An integer from 1 to 4 (to) an organic or inorganic antimony-containing compound 1 to 1
5 parts by weight, and (e) 0-175 parts by weight of a fibrous reinforcing material.

(Function) The present invention provides specific amounts of component (a) and component (b) in PET resin.
By blending, the crystallization rate of PET is increased and moldability is improved, and surface properties such as surface gloss are improved. , imparts flame retardancy while maintaining excellent moldability,
In addition, flame retardant bleed-out was suppressed. The present invention provides a composition useful as a molding material.

The polyethylene terephthalate used in the present invention is obtained from terephthalic acid or an ester of terephthalic acid and ethylene glycol by a conventional melt polymerization method, or is obtained by solid phase polymerization. Polyester having at least 80 mol% or more of ethylene terephthalate repeating units means a copolymer consisting of 80 mol% or more of ethylene terephthalate repeating units and other repeating units, that is, other copolymer components, and As other copolymerization components, nine different acid components and glycol components can be used. For example, acid components include isophthalic acid, naphthalene dicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylmethane dicarboxylic acid, diphenylsulfone dicarboxylic acid, p-(2-hydroxyethoxy)benzoic acid, 5-sodium sulfoisophthalic acid, adipic acid, azelaic acid, and sebacin. acid, decane-1
, 10-dicarboxylic acid, undecane-1,11-dicarboxylic acid.

Dodecane-1,12-dicarboxylic acid, tridecane-1゜13-dicarboxylic acid, tetradecane-1,14-dicarboxylic acid, pentadecane-1,15-dicarboxylic acid, hexadecane-1,16-dicarboxylic acid, heptadecane-1
, 15-dicarboxylic acid, hexadecane-1,16-dicarboxylic acid, heptadecane-1,17-dicarboxylic acid.

Octadecane-1,18-dicarboxylic acid, nonadecane-
1,19-dicarboxylic acid, eicosane-1,20-dicarboxylic acid, heneicosane-1,21-dicarboxylic acid.

Tocosan-1,22-dicarboxylic acid, Tetracosan-1
, 24-dicarboxylic acid, decane-1,6-dicarboxylic acid, 6-ethyl-hexadecane-1,16-dicarboxylic acid, 6-ethyl-dodecane-1,12-dicarboxylic acid, and the like.

In addition, glycol components include polyalkylene glycols such as propylene glycol, diethylene glycol, pentyl glycol, neopentyl glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, etc.
．． 2-bis(p-hydroxyphenyl)propane, bis(p-hydroxyphenyl)sulfone, I)+1)'-
Obtained by addition condensation of alkylene oxides such as ethylene oxide and propylene oxide to bisphenols such as dihydroxybiphenyl, bis(p-hydroxyphenyl)methane, bis(p-hydroxyphenyl)ether, and bis(p-hydroxyphenyl)ketone. Examples include polyalkylene glycols containing bisphenols.

The inorganic compound used as component (a) of the present invention is as follows.

The effect as a crystal nucleating agent varies depending on the particle size, and if the average particle size exceeds about 50 μm, the effect decreases, so inorganic compounds with an average particle size of 50 μm or less are generally useful.

Specific examples of inorganic compounds with an average particle size of 50μ or less used in the present invention include carbon black, silica, calcium carbonate, synthetic silicic acid and silicates, zinc white, hallosite clay, kaolin, basic carbonate, etc. Magnesium, mica.

Examples include talc, quartz powder, diatomaceous earth, dolomite powder, titanium oxide, zinc oxide, antimony oxide, barium sulfate, calcium sulfate, alumina, calcium silicate, etc., and one or more of these inorganic compounds are used. Although you can.

Among them, mica, kaolin, talc, and silica are useful in the present invention.

In addition, as the organic compound having a metal salt of a carboxyl group used in the present invention, any compound having a metal salt of a carboxyl group can be used, but usually has about 7 to 3 carbon atoms. 30 higher fatty acids, metal salts of aromatic acids are used, such as heptanoic acid,
pelargonic acid.

Lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, cerotic acid, montanic acid.

Metal salts of higher fatty acids such as melisic acid, benzoic acid.

Terephthalic acid, terephthalic acid monomethyl ester.

Specific examples include metal salts of aromatic acids such as isophthalic acid and monomethyl ester of isophthalic acid.

Further, the polymer compound having a metal salt of a carboxyl group is not particularly limited as long as it has a metal salt of a carboxyl group at the terminal or side chain of the polymer, but for example, a carboxyl group obtained by oxidation of polyethylene is used. Containing polyethylene, carboxyl group-containing polypropylene obtained by oxidizing polypropylene, copolymers of olefins such as ethylene, propylene, butene-1, and (meth)acrylic acid, copolymers of olefins and maleic anhydride, styrene and ( Specific examples include copolymers of meth)acrylic acid and metal salts of copolymers of styrene and maleic anhydride5.Usually, copolymers of olefin and (meth)acrylic acid or styrene and (meth)acrylic acid are used. Coalescent metal salts are used. As the metal that forms a salt with a carboxyl group, alkaline earth metals, alkali metals, etc. are usually used, and alkali metals are excellent in their effectiveness as crystal nucleating agents, with sodium and potassium being particularly useful.

In the present invention, nine different compounds can be used as the ester plasticizer which is the component (b).
Among them, the following general formula (n), (I[[).

Ester compounds represented by CN'') are useful.

RI: an alkylene group Rm, R2: a group selected from an alkyl group, a benzyl group, and a phenyl group, +R *Ra are the same or different groups.

m, n: Integer greater than or equal to 1 (I[) 〇 15O! - is a group selected from.

R4, Rs: A group selected from an alkyl group, a benzyl group, a phenyl group, or a derivative thereof, and R4 and R8 are the same or different groups.

Rs l l? ? : Hydrogen, an alkyl group, or a halogen, and Rs and Ry are the same or different groups.

ra, n: integers of 1 or more Re, Rs: hydrogen, alkyl group, benzyl group.

A group selected from a phenyl group or a derivative thereof, and R8°Rs and R11 are the same or different groups.

Rso: A group selected from a phenyl group, a benzyl group, or a derivative thereof.

R1: A group selected from hydrogen, an alkyl group, and a group defined by Rso.

n: An integer of 4 or more.

In the ester plasticizer represented by the general formula (If), RI represents an alkylene group, and usually a straight alkyl group having 1 to 20 carbon atoms or a branched alkyl group having molecular symmetry is used. is desirable.

R1+Ra is methyl, ethyl, propyl.

Specific examples include butyl, pentyl, hexyl, heptyl, octyl, benzyl, phenyl and the like. Regarding mtn, there is a tendency that the larger 1llIn, the greater the effect as a crystallization promoter, but conversely, P
Since the compatibility with the INT resin and the heat resistance decrease, 1llIn is usually 1 to about 20. Preferably it is 1 to about 10.

In general formula (I[I), X is usually an alkylene group such as methylene, ethylene, propylene, or 10-
is useful, and R4+'' is usually an alkyl group having 5 or more carbon atoms, a benzyl group, or a phenyl group, m,
Desirably, n is 1 to about 10.

In general formula (IV), Re and Rs are hydrogen and alkyl groups, and I? A benzyl group is useful as +o +Rn. If n is 3 or less, it will easily volatilize during heating and the effect as a crystallization promoter will be small, so n is 4 or more. For example, adipic acid, azelaic acid, sebacic acid, decane-1,10-dicarboxylic acid, Dibenzyl ester of octadecane-1,18-dicarboxylic acid is useful.

In the present invention, the flame retardant used as component (i) is -m
Since it is a halogenated bisphenol-type poxy oligomer or polymer-type flame retardant shown in formula (I), it is well compatible with PET resin and has the property of being resistant to bleed-out. X is a group consisting of bromine or chlorine, but bromine is more preferable than chlorine from the viewpoint of imparting flame retardancy.In general formula (I), when the epoxy equivalent is less than 2.500, If the amount of epoxy groups in 9 increases, gel etc. may occur during production of the resin composition of the present invention, making it difficult to operate, so the epoxy equivalent is preferably 2.500 or more.
Furthermore, if the epoxy equivalent becomes too large, n becomes too large and the compatibility with PET resin decreases. Those having an epoxy equivalent weight of .000 are desirable.

In addition, the component used as a flame retardant aid in the present invention is an organic or inorganic antimony-containing compound such as antimony dioxide and antimony phosphate.

Examples include triphenylantimony.

Antimony trioxide is particularly preferred.

Specific examples of the fibrous reinforcing material used in the present invention include glass fibers, carbon fibers, aromatic polyamide fibers, silicon carbide fibers, titanate fibers, etc.2 Glass fibers are usually used. Ru. There are no particular restrictions on the diameter and length of the various fibers, but if the fiber length is too long, the PUT resin or other compounding agents may be used.

In other words, it is difficult to mix and disperse the fibers uniformly with the components in
Particularly when the fibrous reinforcing material is glass fiber, the fiber length is preferably from 0.1 to 71, more preferably from 0.3 to 411 II.

In addition, the fibrous reinforcing material can be treated with various compounds as necessary in order to improve the interfacial adhesion with the PET resin and increase the reinforcing effect. When using 2 various surface treatment agents, such as vinyltriethoxysilane, T-methacryloxypropylmethoxysilane, β-(3,4-epoxycyclohexyl)-ethyltrimethoxysilane +
Silane-based processing agents such as T-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropylmethoxysilane, T-mercaptopropyltrimethoxysilane, and chromium-based processing agents such as methacrylate chromic chloride. The processed one is used.

Regarding the blending amount of each component in the flame-retardant polyester resin composition of the present invention, based on 100 parts by weight of PET resin;
(If the component () is less than 0.01 parts by weight, the effect as a crystal nucleating agent will be small; conversely, even if more than 10 parts by weight is added, the effect as a crystal nucleating agent will not improve as the amount is added, and the physical properties This is not preferable because it may cause a decrease in

Therefore, the blending amount of component (a) is ppTItM fat 100
0.01 to 10 parts by weight.

Preferably 0.3 to 7 parts by weight, more preferably 0.5 parts by weight
~5 parts by weight. Next, the amount of component (b), that is, the ester plasticizer, varies depending on the type of ester plasticizer, but in general, if it is less than 0.3 parts by weight, the effect of promoting crystallization will be insufficient; Blending in a larger amount is not preferable because the mechanical and thermal properties of 9 deteriorate. Therefore, the blending amount of component (b) is 100% of PET resin.
0.3 to 15 parts by weight, preferably 1 to 1 parts by weight
0 parts by weight, more preferably 3 to 7 parts by weight. Regarding the blending amount of component (c), that is, the flame retardant represented by the general formula CI), if it is less than 5 parts by weight, the effect of imparting flame retardancy will be insufficient, and if it is more than 40 parts by weight, the mechanical properties will deteriorate. I don't like it because it gets bigger.

Therefore, the amount of component (c) is PI! The amount is 5 to 40 parts by weight, preferably 10 to 30 parts by weight, and more preferably 12 to 25 parts by weight, based on 100 parts by weight of T resin. The amount of the antimony-containing compound (component) blended as a flame retardant aid is 1 to 15 parts by weight, preferably 2 to 10 parts by weight.

Regarding the amount of fibrous reinforcing material that is optionally blended in the present invention, it is usually desirable to keep it to 175 parts by weight or less, since if the amount increases, it becomes difficult to mix and disperse it uniformly in the resin. .

The composition of the present invention further includes an antioxidant, if necessary.
Ultraviolet absorber 1 Various inorganic or organic compounds such as colorants, mold release agents, fillers, etc. can be blended. Particularly in the present invention, when phosphoric acid or phosphorous acid derivatives such as phosphoric acid esters and phosphite esters are blended, a composition with excellent heat resistance stability can be obtained.

The polyester composition of the present invention can be produced by mixing in various methods, and the production method is not particularly limited. It is manufactured by mixing using an extruder or kneader. The composition of the present invention can be in various forms, such as various molded articles.

It can be formed into a sheet, fibrous material, tubular material, etc. and used.

(Example) Next, the present invention will be specifically described with reference to Examples and Comparative Examples. Note that "parts" shown in Examples and Comparative Examples indicate parts by weight.

Example First, polyethylene terephthalate and copolymerized polyethylene terephthalate shown in Table 1 were produced according to a conventional method. However, the relative viscosity ηrelt is in phenol/tetrachloroethane-6/4 solvent, concentration 0.5%, temperature 20°C.
This is the value measured under the following conditions.

Table 1 Various additives in predetermined amounts to polyethylene terephthalate.

and glass fiber [3mm + long chopped strand made by Asahi Fiberglass ■, product number N1429] and structural formula (V
) A predetermined amount of the flame retardant having an epoxy equivalent of 5,000 was blended and melt-extruded using a 65 amφ extruder to produce pellets. A pellet that had been partially quenched during pellet production was collected, and the crystallization temperature THC was determined when the temperature was raised from room temperature at 20°C/min using a differential calorimetry needle (Model DSC-1 manufactured by PerkinElmer). . Furthermore, Ti1e
It can be evaluated that the lower the value, the higher the crystallization rate in the low temperature region. The results are summarized in Table 2.

n: L7 (average value) On the other hand, after drying the obtained pellets, the cylinder temperature was
40-260-270℃, mold temperature 95℃, injection holding time 10 seconds, cooling time 20 seconds, injection pressure 300-600K
1/2 inch x 1/4 inch x 1 under g/cmt condition
A test piece of /3 inch was molded, and the surface of the molded product was observed, and flame retardancy was evaluated according to UL94.

Furthermore, the flexural strength of the 1/2 inch x 5 inch x 174 inch specimen is 8 flexural modulus and the heat distortion temperature (18,56 K
g/cmR under load) was measured. In addition, 130 molded products
It was investigated whether the N fuel agent would bleed out when heat treated at ℃ for 24 hours. The results are summarized in Table 3.

Table 2 H: Adipic acid dibenzyl ester ■; Azelaic acid dibenzyl ester Chilin 1555: Ethylene-acrylic acid copolymer Ha
Salt (manufactured by DuPont) Table 3 Test piece for measuring bending properties; 1/2 inch x 5 inch x l/
4 inch heat distortion temperature measurement test piece: 1/2 inch x 5 inch
1/16 inch flame retardant evaluation test piece: 172 inches x 5 inches
1/32 inch (effect of the invention) From these results, a composition in which 1ml of pEt is blended with a specific nucleating agent, an ester plasticizer, and a halogenated bisphenol type polycarbonate compound has excellent physical properties even when molded in a low-temperature mold. The appearance shows that a flame-retardant polyester resin composition with suppressed bleed-out properties can be obtained.

Patent applicant: Unitika Co., Ltd. 1st word 8th line August 6, 1985 Sein g60-, No. 111147 2. Name of the invention M raw polyester dumplings Address: Jianhun Zhichen Shrine I-chome 50wa

Claims (1)

[Claims] (1) Polyethylene terephthalate or at least 8
For 100 parts by weight of polyester having 0 mol% or more of ethylene terephthalate repeating units, (a) an inorganic compound with an average particle size of 50 μm or less, an organic compound having a metal salt of a carboxyl group, or a polymer having a metal salt of a carboxyl group. At least one of the molecular compounds is 0.01 to 10
parts by weight, (b) ester plasticizer 0.3 to 15 parts by weight,
(c) 5 to 40 parts by weight of a halogenated bisphenol type epoxy compound represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) group, ether group, thioether group, and sulfone group n: an integer necessary to make the epoxy equivalent 2,500 or more p: an integer from 1 to 4 (d) organic or inorganic antimony-containing compound 1 to 1
5 parts by weight, and (e) 0 to 175 parts by weight of a fibrous reinforcing material. The flame-retardant polyester resin composition according to claim 1, which is an ester compound of at least one of the following: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) R_1: alkylene group R_2, R_3: alkyl group, A group selected from a benzyl group and a phenyl group, and R_2 and R_3 are the same or different groups. m, n: Integers of 1 or more ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) - is a group selected from. R_4, R_5: A group selected from an alkyl group, a benzyl group, a phenyl group, or a derivative thereof, and R_4 and R_5 are the same or different groups. R_6, R_7: hydrogen, alkyl group, or halogen, and R_6 and R_7 are the same or different groups. m, n: Integer greater than or equal to 1 ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (IV) R_8, R_9: A group selected from hydrogen, an alkyl group, a benzyl group, a phenyl group, or a derivative thereof, and R_8 and R_9 are They are the same or different groups. R_1_0: A group selected from a phenyl group, a benzyl group, or a derivative thereof. R_1_1: Hydrogen, an alkyl group, or a group selected from the groups defined in R_1_0. n: An integer of 4 or more.