JPH02222445A - Polyarylate resin composition improved in flame retardancy and dripping properties - Google Patents

Abstract

PURPOSE:To obtain the title composition which is suitable for electric or electronic materials, because of its excellent mechanical strength and heat resistance, shortened combustion time and improved dripping properties, by adding specific amounts of specific polymeric flame retarder and a flame retardant auxiliary to a specific polyarylate resin. CONSTITUTION:(A) 100 pts.wt. of a polyarylate resin containing 3 to 30mole% of the units of formula I (R is p-phenylene, m-phenylene), more than 30mole% of formula II units, and more than 30 mole% of formula III (X is formula IV, -CH2), when needed, less than 20 mole% of formula V units are admixed to (B) 1 to 30 pts.wt., preferably 3 to 20 pts.wt. of a polymeric flame retarder bearing halogen atoms on the aromatic nucleus and (C) 0.1 to 10 pts.wt. of a flame retardation auxiliary such as antimony trioxide. The polyarylate resin (A) has an intrinsic viscosity of more than 0.50dl/g.

Description

Detailed Description of the Invention <Industrial Application Field> The present invention relates to a polyarylate resin composition that has excellent mechanical strength and heat resistance, and has improved flame retardancy, that is, shortens combustion time and prevents droplet fall. .

<Prior Art> Aromatic polyester copolymers synthesized from aromatic dicarboxylic acids and bisphenols are hereinafter referred to as polyarylate resins. ) In particular, polyarylate resins synthesized from terephthalic acid and/or isophthalic acid and 2゜2-bis(4-hydroxyphenyl)propane [bisphenol A] have excellent mechanical strength, electrical properties, and flame retardancy. It has heat resistance, dimensional stability, and transparency, and its melt-molded products are widely used for various mechanical parts, films, fibers, etc.

However, in recent years, there has been an even stronger demand for fire safety, especially in the fields of electrical parts and automobile parts, and in addition to nonflammability and self-extinguishing properties, droplet resistance, which serves as a guideline for dispersing fire sources, is extremely important. It has come to have a In this sense, the nonflammability and droplet resistance of polyarylate resins cannot necessarily be said to be sufficient. Especially in thin molded products, the nonflammability and droplet resistance decrease, so it is necessary to have better flame retardancy. There is a demand for polyarylate resins that have the following properties.

As a means of making thermoplastic resins such as polyarylate resins flame retardant, generally an organic phosphorus compound or a halogen-containing compound is used as a flame retardant, or a flame retardant aid such as antimony trioxide is added to the resin together with the flame retardant. The method of containing is widely adopted.

The most common method for incorporating such a flame retardant is to melt and knead a thermoplastic resin, a flame retardant, and a flame retardant aid using an extruder or the like.

However, in the case of polyarylate, the melt viscosity is high and melt-kneading requires a considerably high temperature, e.g. 300°C or higher, so the flame retardant tends to thermally decompose during melt-kneading, which can lead to coloring of molded products or This causes a decrease in strength. Another problem is that if the molded product is left at high temperatures for a long period of time, the flame retardant bleeds out onto the surface.

Therefore, in order to solve these problems, for example, tetrabromobisphenol A such as halogenated polycarbonate
It is known to use polymeric flame retardants having an l-rating. A polyarylate resin made by adding such a polymeric flame retardant alone or together with a flame retardant aid such as antimony trioxide has thermal stability because the flame retardant itself has thermal stability.
Problems such as coloring of the resin and deterioration of physical properties caused by thermal decomposition of flame retardants are solved. It also has good compatibility with polyarylate and solves the problem of bleed-out on the surface.

However, such polymeric flame retardants have little effect on preventing droplets from falling, and if left for a long period of time, they will cause melting and dripping.

On the other hand, many methods for preventing droplets of thermoplastic polyester from falling are also known. For example, glass fiber and polytetrafluoroethylene resin (JP-A-47-42942, etc.),
Or magnesium silicate (JP-A-6L-24624
9), powdered phenolic resin (JP-A-6L-24624
8) A method is known in which a filler such as calcined silica (Japanese Unexamined Patent Publication No. 58-122957) is added in combination, and a flame retardant is added to the coating to prevent droplets from falling. By incorporating these fillers together with polymeric flame retardants, it is possible to shorten the combustion time of polyarylate, prevent droplets from falling, or prevent bleed-out.

However, such glass! L1Il fibers and fillers have poor compatibility with polyarylate, causing problems such as a decrease in mechanical strength, particularly impact strength, a decrease in tensile elongation at break, and poor appearance. Because of this,
There is a need for a polyarylate resin composition that maintains the excellent mechanical strength of polyarylate, shortens combustion time, and prevents droplets from falling.

<Problems to be Solved by the Invention> Therefore, the present invention has been proposed to reduce the disadvantages such as a decrease in mechanical strength, bleed-out, and thermal decomposition of the flame retardant during the processing process due to the mixing of the flame retardant, shorten the combustion time, and reduce the droplet The object of the present invention is to provide a polyarylate resin composition that has improved drop properties.

Means for Solving the Problems The present inventors have conducted intensive research to improve the combustibility and droplet falling properties of polyarylate resin, and as a result, by using a polyarylate resin with the following components and composition, It has been discovered that the flame retardant and droplet drop resistance can be improved without causing problems such as strength reduction, bleed-out, and thermal decomposition of the flame retardant during the processing process, leading to the present invention.

That is, the present invention provides (■) (1) (-0-R-C-) The following units (I) to (III) +00XKn o+ (R is a paraphenylene group, a metaphenylene group,
-biphenylene group, 2,6-naphthalene group, each independently selected in units (I) and (II), and X is t, , 2n5 . 1. , :3F17, in which the hydrogen atom on the aromatic ring of units (1) to (III) is an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 6 carbon atoms;
optionally substituted with an alkoxy group of 6),
Each of the units (I) to (111) contains one or more of the above R or X, and the unit (1)
Unit (I) for the total number of moles of ~(III)
The total amount of 3 to 30 mol%, the total amount of units (I) is 30 to 30 mol%
mol% or more, a polyarylate resin containing a total amount of units (III) of 30 mol% or more, and 1 to 30 parts by weight of a polymeric flame retardant having a halogen atom in the aromatic nucleus per 100 parts by weight of the polyarylate resin. , flame retardant aid 0.1~
10 parts by weight of the polyarylate resin composition.

Further, the present invention provides the following units ('I) to (IV) (R is any group of paraphenylene group, metaphenylene group, 4,4'-biphenylene group, 2,6-naphthalene group, (1), (II), and (rV) are each independently selected, X is either Shiri3 or Shii3, and the hydrogen atom on the aromatic ring of units (1) to ([V) has 1 carbon number. ~6 alkyl group, carbon number 1-6
may be substituted with an alkoxy group. ), and each of the units (I) to (IV) is 1f! of R or X! !
or consists of two or more types, and unit (1)
The total amount of units (I) is 3 to 30 mol%, the total amount of units (II) is 30 mol% or more, and the total amount of units (III) is 30 mol%, based on the total number of moles of ~(rv). % or more, and a total amount of units (IV) is 20 mol% or less, and 1 to 30 parts by weight of a polymeric flame retardant having a halogen atom in the aromatic nucleus per 100 parts by weight of the polyarylate resin, Provided is a polyarylate resin composition with improved flame retardancy and droplet fall properties, which is characterized by containing from 10 parts by weight of flame retardant aids o and i.

And the units (1) to (III) or (I) to
Logarithmic viscosity of polyarylate resin having (rV) (concentration 0.25 g/dl, temperature 23°C, measured value in phenol/tetrachloroethane 60/40 (weight ratio) solvent)
is preferably 0.50 dfL/g or more.

Further, the total amount of the units (IV) is the units (1) to (I
The amount is preferably 2 to 20 mol % based on the total number of moles of V).

The present invention will be explained in detail below.

The improved polyarylate resin of the present invention has the following unit (I)
~(rV) (I) (-0-R-C-) (III) +0<ΣXbe=XO+ (R is paraphenylene group, metaphenylene group, 4.4'
- Biphenylene group, 2,6-naphthalene group, each independently selected by unit (1), (II), (IV), X is any one of, unit (I) - The hydrogen atom on the aromatic ring of (rV) may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. ), each of the units (1) to (IV) contains one or more of the above R or X, and the units (1 to (rV
), the unit (I) is 3 to 3 mol%, the unit (II') is 30 mol% or more, the unit (II') is 30 to 3 mol%, and the unit (II
It contains 30 mol% or more of I) and 20-1-mol% or less of the unit (IV).

Unit (I) is represented by (-C-R-O+) and is an essential component particularly for imparting the effect of preventing droplets from falling.

Examples of raw materials for providing unit (I) include parahydroxybenzoic acid, metahydroxybenzoic acid, 2-hydroxy-6-naphthoic acid, and ester derivatives thereof.

The unit (R) is preferably a divalent group selected from a paraphenylene group, a metaphenylene group, a 4.4'-biphenylene group, and a 2.6-naphthalene group, and in particular, a parahydroxy group in which R is a paraphenylene group. Preferably, benzoic acid (or a derivative thereof) is used.

Unit (1) may be contained in one type or two or more types in the molded article, and the hydrogen atom on the aromatic ring of R is substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. may have been done.

is a divalent functional group selected from paraphenylene group, metaphenylene group, 4,4'-biphenylene group, and 2,6-naphthalene group, and even if the molded product contains one or more types, Often, the hydrogen atom on the aromatic ring of R has 1 to 1 carbon atoms.
6 alkyl group or a C1-6 alkoxy group. Due to the ease of obtaining raw materials, the unit (
II) is preferably terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 4゜4'-diphenyldicarboxylic acid and derivatives thereof, in particular terephthalic acid (and its derivatives) and isophthalic acid (and its derivatives). ) is preferably introduced into the molded product.

The unit (III) is CH.

― CH.

Any of the above, and the hydrogen atom on the aromatic ring has 1 to 6 carbon atoms.
may be substituted with an alkyl group or an alkoxy group having 1 to 6 carbon atoms. Furthermore, the molded product may contain one or more units (m 2 ).

Preferred raw materials for producing the unit (III) include, for example, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)methane, and bis(4-hydroxyphenyl)sulfone due to their ease of availability.
-hydroxy-3-methylphenyl)methane, 1.1-
Bis(4-hydroxyphenyl)ethane, 2.2-bis(4-hydroxy-3-methylphenyl)propane, 1
．． 1-bis(4-hydroxyphenyl)butane, 2,2
-bis(4-hydroxyphenyl)butane, bis(4-
Examples include hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)diphenylmethane, and their acetate ester recognized conductors.

Preference is given to using 2-bis(4-hydroxyphenyl)propane, ie bisphenol A (or a derivative thereof).

Unit (IV) is included for the purpose of improving workability. R is a divalent functional group, such as a paraphenylene group, a metaphenylene group, 4.4
'-biphenylene group or 2,6-naphthalene group, and the hydrogen atom on the aromatic ring of R has 1 to 6 carbon atoms.
may be substituted with an alkyl group or an alkoxy group having 1 to 6 carbon atoms. Moreover, one or more types of unit (IV) may be contained in the product.

Examples of raw materials for providing the unit (l) include polyethylene terephthalate, polyethylene-2,6-naphthalate, etc., but from the viewpoint of easy availability of raw materials, it is preferable to use polyethylene terephthalate as the unit (IV).

Next, the abundance ratio of positions 411 (I) to (IV) will be described.

The unit (I) is 3 to 30 mol%, preferably 5 to 2 mol%, based on the total number of moles of units (I) to (IV) in the molded product.
It is preferable that it be contained in an amount of 0 mol%.

Table 1 specifically shows the reason why the amount of unit (I) is within this range.

That is, a polyarylate resin was synthesized by melt polymerization by changing the amount X of the unit (1) in 5 mol% of the polyarylate resin, and 100 parts by weight of this polyarylate resin and tetrabromobisphenol A as a polymeric flame retardant were added. 3 parts by weight of type polycarbonate ("FR-50" manufactured by Mitsubishi Gas Chemical Co., Ltd.) and 1 part by weight of antimony trioxide as a flame retardant additive were melt-kneaded using an extruder at 300 DEG C. and pelletized.

This pellet was injection molded to obtain a test piece, and its tensile strength, tensile elongation at break, Izod impact strength, flame retardancy test, droplet fall property, and heat denaturation temperature were investigated. The details of the measurement method will be explained later in Examples.
As shown in Table 1, if the unit (I) is less than 3 mol%, droplets fall easily, while if it is more than 30 mol%, droplet falling properties are sufficiently improved, but mechanical It was found that the properties, especially tensile elongation at break and impact strength, were reduced.

The abundance of the unit (II) and the unit (Hl) is both 30 mol% or more of the total amount of the units (I) to (rV), and the abundance ratio of the unit (It) and the unit (III) is preferably is (11) / (III >=0.9~1
．． 1 (molar ratio), more preferably in an equal amount.

If the amount of units (II) and (III) present is less than 30 mol %, the mechanical properties, particularly the Izot impact strength and tensile elongation at break, will decrease, resulting in brittleness, which is not preferred.

Further, the unit (TV) can be present in the molded article in an amount of 20 mol% or less.

Table 2 shows the reason why the amount of units (■) is kept within this range.

That is, a polyarylate resin was synthesized by melt polymerization while changing the amount Y of the unit (IV) in polyarylate resin H3, and 100 parts by weight of this polyarylate resin and tetrabromobisphenol A were synthesized.
Type polycarbonate (“FR-50” manufactured by Mitsubishi Gas Chemical Co., Ltd.)
)-3 parts by weight and 1 part by weight of antimony trioxide as a flame retardant aid were melt-kneaded using an extruder at 300°C,
Pelleted.

This pellet was injection molded to obtain a test piece.

The tensile strength, tensile elongation at break, and Izot impact strength of this test piece were measured, and the flame retardancy test, droplet fall property, and heat denaturation temperature were also investigated.

As shown in Table 2, the abundance ratio of the unit (rV) is
In addition to the above-mentioned moldability and processability, it also affects mechanical strength, combustibility, and heat resistance.

From the viewpoint of flame retardancy, the unit (IV) does not need to be contained, but from the viewpoint of flame retardancy, moldability, Izod impact strength, and tensile elongation at break, it is more preferably 2 mol % or more.

It is also found that when the unit (fV) exceeds 20 mol%, flame retardancy, particularly droplet drop resistance and heat resistance, are poor.

The flame retardant added to the polyarylate resin used in the present invention is a polymeric flame retardant having a halogen atom in its aromatic nucleus. The polymeric flame retardant referred to herein is a flame retardant containing two or more repeating units in its molecule, and examples include flame retardants of the following formula.

(4) Brominated polyglycidyl ether (1) Brominated polycarbonate (2) Brominated polyphosphonate n≧2 (3) Brominated polyester (5) Brominated polyether n2 (6) Brominated polystyrene (non-crosslinked) Note that the terminal groups of the polymeric flame retardants (1), (2), (3), and (5) may be blocked with a phenol compound.

As a specific example of the above flame retardant, for example, as a brominated polycarbonate type flame retardant, FR-50 manufactured by Sanni Gas Kagaku ■ Co., Ltd.
, Teijin Kasei Fire Guard 7000 or 7
500. Examples of the brominated polyglycidyl ether flame retardant include EBR-700, EBR-734 and EBR-107 manufactured by Manac Corporation, and examples of the brominated polystyrene flame retardant include EBR-37.0FK manufactured by Manac Corporation.

Among these, brominated polycarbonates, brominated polyglycidyl ethers, and oligomers thereof are preferred because they have good thermal stability.

Note that low molecular weight flame retardants such as triphenyl phosphate and hexabromobenzene cause problems such as thermal decomposition during melt-kneading, bleeding at high temperatures, and a decrease in mechanical strength. It is not recommended to use it inside.

The flame retardant is preferably contained in an amount of 1 to 30 parts by weight, preferably 3 to 20 parts by weight, per 100 parts by weight of the polyarylate resin of the present invention.

Table 3 shows the reason why the flame retardant was limited to a polymeric flame retardant and the reason why the content of the flame retardant was within the above range. That is, a polyarylate resin having the components and composition of the present invention is melt-kneaded with different flame retardant compositions, test pieces are created by injection molding, and the tensile strength, tensile elongation at break, and Izot impact strength are measured. Also, flame retardancy tests and droplet fall properties were investigated.

If the amount of flame retardant is less than 1 part by weight, the desired flame retardant effect, especially the combustion time shortening effect, will be reduced. On the other hand, if the amount is more than 30 parts by weight, although a sufficient flame retardant effect is exhibited, the mechanical strength, particularly the tensile elongation at break and the Izot impact strength, decrease.

The type of flame retardant aid added to the polyarylate resin used in the present invention is not particularly limited.

Specific examples include antimony trioxide, antimony tetroxide, antimony pentoxide, sodium pyroantimonate, tin dioxide, barium metaborate, zinc borate, aluminum hydroxide, zirconium oxide, and molybdenum oxide. Preferably, antimony trioxide is used because it is easily available.

Incidentally, the term "flame retardant auxiliary agent" as used herein refers to a substance that has a flame retardant effect by itself, but exhibits a remarkable synergistic effect when used in combination with another flame retardant.

If the amount of the flame retardant aid exceeds 10% by weight, the mechanical strength, especially the tensile elongation at break and the Izot impact strength, decreases.

In addition, these flame retardants and flame retardant aids contain the unit (I)
It is preferable to add it at the polymerization stage or molding stage of the polyarylate resin consisting of (IV) and mix uniformly.

The polyarylate resin used in the present invention can be obtained by any polymerization method commonly used for polyester production, such as melt polymerization, solution polymerization, and interfacial polymerization. Furthermore, for example, a polyarylate obtained by copolymerizing the units (I) to (III) may be synthesized, and the unit (IV) may be melt-kneaded therewith using an extruder or the like.

However, from a cost standpoint, it is preferable to synthesize the polyarylate containing units (I) to (IV) by a melt polymerization method using a transesterification method.

An example of the method for producing the polyarylate resin of the present invention by melt polymerization will be described below.

The reaction is started by putting necessary raw materials, namely polyester, aromatic dicarboxylic acid, bisphenol A diacetate, aromatic acetoxycarboxylic acid, and a catalyst as necessary into a polymerization container, heating it, and continuing for a predetermined period of time. Termination occurs through polymerization. The acetylated raw material may be synthesized from the corresponding aromatic hydroxy compound and acetic anhydride in a polymerization vessel.

There is no particular limit to the polymerization temperature, but -180 to 40 for boat fishing.
Conducted at 0°C, more preferably at 200 to 380°C,
If the temperature is lower than 180°C, the reaction will be slow, and if the temperature is higher than 400°C, the resin will be discolored or decomposed violently, which is not preferable.

The pressure during the reaction is not particularly limited, but it is preferable to carry out the reaction at around atmospheric pressure at the initial stage and gradually reduce the pressure as the polymerization progresses.

In order to prevent the coloring and decomposition of the resin due to local overheating, and to facilitate the removal of the acetic acid produced, it is preferable to carry out the reaction with stirring.Also, to prevent the oxidative decomposition of the resin due to oxygen, the reaction system should be kept under aerobic atmosphere. is preferably under an inert gas such as nitrogen or argon.

Furthermore, after synthesizing the polyarylate resin, a polymeric flame retardant and a flame retardant aid are added.

Although the polymerization reaction can be carried out without using a catalyst, a catalyst may be used to accelerate the polymerization reaction. The catalyst may be mixed into the starting materials or may be newly added at the beginning of the reaction.

Examples of catalysts include germanium compounds such as germanium oxide, tin compounds such as stannous oxalate, stannous acetate, dialkyltin oxides, diaryltin oxides, titanium dioxide, titanium alkoxides, and alkoxytitanium silicates. titanium compounds such as, antimony compounds such as antimony trioxide, metal salts of organic acids such as sodium acetate, potassium acetate, calcium acetate, zinc acetate, ferrous oxalate, Lewis acids such as boron trifluoride, aluminum chloride, and amines. Amides,
Examples include inorganic acids such as hydrochloric acid and sulfuric acid.

Preferably, sodium acetate, potassium acetate, calcium acetate, titanium isopropoxide, etc. are preferred because they are relatively inexpensive.

Furthermore, reinforcing agents, fillers, additives, and the like may be added to the polyarylate resin of the present invention at the polymerization stage or molding stage to the extent that the effects of the present invention are not impaired.

However, if these reinforcing agents are used in large amounts, they will be inferior in terms of maintaining mechanical strength, which is a feature of the present invention, so it is preferable that the amount is less than 5 parts by weight based on 100 parts by weight of the polyarylate resin.

Table 4 shows specific examples. In other words, the types and amounts of flame retardants and flame retardant aids are kept constant, and the units (
The effects on flammability and mechanical strength when a commonly used anti-drip agent was added without containing I) was investigated.

It can be seen that the conventional anti-drip agents (Comparative Examples 9, 10, and 11) are inferior in Izot impact strength and tensile elongation at break.

Under the above conditions, examples of reinforcing agents include glass fibers, asbestos fibers, carbon fibers, and the like. These reinforcing agents and reinforcing agents can be added to improve the elastic modulus and further prevent droplets.

Examples of the filler include inorganic fillers such as talc, calcium carbonate, mica, wollastonite, ferrite, and rare earth magnet powder.

Stabilizers or anti-coloring agents include triaryl phosphites, trialkyl phosphites, hydrogen phosphite diesters, pentaerythritol-type dish phosphates, trialkyl phosphates, triaryl phosphates, and phosphones. Phosphorus compounds such as acid derivatives, phosphinite conductors, halogenated alkyl acid phosphates, and alkyl acid phosphates; Epoxy compounds such as monoglycidyl derivatives, diglycidyl derivatives, and halogenated glycidyl derivatives; Sulfur compounds such as hydrosulfides; Examples include phenol derivatives; mercaptobenzothiazoles: ultraviolet absorbers such as benzotriazoles; metal deactivators, and the like. In general, it is preferable to use phosphite esters, hindered phenol derivatives, etc. as stabilizers or anti-coloring agents.

Furthermore, moldability can be improved by adding appropriate amounts of silicone resin, paraffin wax, microcrystalline wax, liquid paraffin, mold release agents such as montanic acid, and plasticizers.

Logarithmic viscosity of the polyarylate resin of the present invention (23°C, concentration 0.25 g/dfL, phenol/l/1,1,2,2.tetrachloroethane = 60:40
(measured in weight ratio) is 0.40d117g or more, preferably 0.50dl/g or more. In particular, if the logarithmic viscosity is less than 0.40 dJ2/g, droplet fall cannot be sufficiently prevented, and mechanical strength, particularly Izot impact strength and tensile elongation at break, decrease.

Melt-molded articles can be made using the polyarylate resin of the present invention. Examples of melt-molded products include fibers, films, sheets, extrusion-molded products, injection-molded products, blow-molded products, and compression-molded products.

<Examples> The present invention will be specifically explained below using examples.
The present invention is not limited only to these examples.

(Example 1) Stirring device with torque meter/tachometer, argon introduction pipe,
16.2 g (0.09 mon, 3.0 mol%) of p-acetoxybenzoic acid was added to a reaction device equipped with a thermometer and a distillation device.
, bisphenol A diacetate 431. tg (1,
38 mail, 46.0 mol%) Terephthalic acid 1 f
4.6g (0.69moj2,23.0mol%),
Isophthalic acid 114. 6g (o, 69moJZ
, 23.0 mol%), polyethylene terephthalate 28
．． 8 g (0.15 mon, 5 mol%) and 0.09 g of sodium acetate as a catalyst were charged.

After the inside of the apparatus was sufficiently purged with argon, the temperature was raised to 300° C. over 1 hour while acetic acid was distilled off under an argon stream.

Stirring was started when the raw materials were sufficiently melted during the temperature rise.

After reacting at 300°C for 30 minutes, the temperature was further raised, and at the same time the pressure was gradually reduced to a final temperature of 340°C and 0.5 mmHg. (This time was approximately 20 minutes). After reacting at this temperature and pressure for 35 minutes, the logarithmic viscosity was 0.62 dfL.
/H polyarylate was obtained.

400g (100 parts by weight) of this polyarylate, FR-5012g (3 parts by weight) manufactured by Mitsubishi Gas Chemical Co., Ltd. as a brominated polycarbonate type flame retardant, and 4g (1 part by weight) of antimony trioxide were uniformly mixed in a mixer for 5 minutes. Mixed.

This mixture was heated to 20 m t mφ manufactured by Thermoplastics.
The mixture was melt-kneaded using a single-screw extruder at a barrel temperature of 340°C to obtain pellets.

This pellet was injection molded using a 5AV-60-52 injection molding machine manufactured by Yamaguchi Seiki Co., Ltd. to obtain a test piece for measuring physical properties.

Physical property tests were conducted using the method described below, and the results are shown in Table 1.

(Examples 2 to 4) Polyarylate was synthesized and flame retardant was mixed in the same manner as in Example 1, except that the raw materials were used in the proportions shown in Table 1, and test pieces were obtained.

Physical property tests were conducted using the method described below, and the results are shown in Table 1.

(Examples 5 to 8) A test piece was obtained by synthesizing polyarylate and mixing a flame retardant in the same manner as in Example 1, except that the raw materials were used in the proportions shown in Table 2.

Physical property tests were conducted using the method described below, and the results are shown in Table 2.

(Examples 9 to 16) Polyarylate was synthesized and flame retardants were mixed in the same manner as in Example 1, except that the type and content of the flame retardant were changed to the proportions shown in Table 3, and test pieces were obtained. Ta.

Physical property tests were conducted using the method described below, and the results are shown in Table 3.

(Comparative Examples 1 to 3) A test piece was obtained by synthesizing polyarylate and mixing a flame retardant in the same manner as in Example 1, except that the raw materials were used in the proportions shown in Table 1.

Physical property tests were conducted using the method described below, and the results are shown in Table 1.

(Comparative Example 4) A test piece was obtained by synthesizing polyarylate and mixing a flame retardant in the same manner as in Example 1 except that the raw materials were used in the proportions shown in Table 2.

Physical property tests were conducted using the method described below, and the results are shown in Table 2.

(Comparative Examples 5 to 8) Synthesis of polyarylate and mixing of flame retardants were carried out in the same manner as in Example 1, except that the types and amounts of flame retardants and flame retardant aids were changed to the proportions shown in Table 3. A test piece was obtained.

Physical property tests were conducted using the method described below, and the results are shown in Table 3.

(Comparative Examples 9 to 11) Test pieces were obtained in the same manner as in Example 1, except that the droplet preventive agent shown in Table 4 was melt-kneaded together with the flame retardant and the flame retardant aid.

Physical property tests were conducted using the method described below, and the results are shown in Table 4.

[Injection molding and physical property measurement method] (1) The test piece for measuring the physical properties of injection molding was 5AV manufactured by Yamaguchi Seiki Co., Ltd.
It was molded using a -60-52 injection molding machine. For injection molding, mold temperature is 130℃, injection pressure is 1200g/cm
”, and the cylinder temperature was set so that the mold was completely filled with resin.

(2) Flame retardancy test A 1/32 x 1/2 x 5 inch test piece obtained by injection molding was subjected to a UL-94 flame test.

The UL-94 grades vo, v-i, and V-2 are determined as follows.

r94V-OJ After 10 seconds of ignition, the ignition flame is removed for one blaze, combustion does not exceed 10 seconds, and none of the samples drips flaming particles that ignite cotton wool placed 12 inches below. .

Total flaming time for all 5 samples (10 ignitions)
shall not exceed 50 seconds.

r94V-IJ After the ignition flame is removed, a single flaming burn does not exceed 30 seconds, and none of the samples drips flaming particles that ignite cotton wool placed 12 inches below.
Total flaming time for all 5 samples (10 ignitions)
shall not exceed 250 seconds.

r94V-2J After the ignition flame is released, one flaming combustion does not exceed 30 seconds. The sample drips flaming particles that briefly scorch and ignite cotton wool placed 12 inches below it. The total flame time (10 ignitions) for all five samples does not exceed 250 seconds.

(3) Droplet fall rate 1/32 x 1/2 x 5 inch test piece using 2
The flame dripping of the resin when ignited for 5 seconds was examined.

Ten tests were performed, and the total number of times the drop was applied and the cotton wool placed 12 inches below ignited, and the number of times the drop was applied but did not ignite the cotton wool was expressed as a percentage. 100%
The closer it is, the easier it is to drip due to combustion.

(4) Izotsu impact strength Measured with a notch according to ASTM D-256.

(5) Tensile yield strength, tensile elongation at break ASTM
Measured according to D-638.

(6) Heat distortion temperature According to ASTM D-648, the load is set to 18.6 g/
I set it to c++++'.

<Effects of the Invention> The polyarylate resin composition of the present invention shortens combustion time and improves droplet fall properties without impairing the excellent mechanical strength and heat resistance that polyarylate resins inherently have. I can do things.

Moreover, since it can be molded using any melt molding method, it is useful as a flame retardant material in fields that require high flame retardancy and complex shapes, such as electrical and electronic materials and automobile parts.

Claims (4)

[Claims] (1) The following units (I) to (III) (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R is any one of paraphenylene group, metaphenylene group, 4,4'-biphenylene group, 2,6-naphthalene group, each independently selected in units (I) and (II), X has ▲mathematical formulas, chemical formulas, tables, etc.▼, -CH_2-, -
SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, Chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-, -S- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and hydrogen on the aromatic ring of units (I) to (III) The atom may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. ), each of the units (I) to (III) contains one or more of the above R or X, and the units (I) to (
The total amount of units (I) is 3 to 30 mol%, the total amount of units (II) is 30 mol% or more, and the total amount of units (III) is 30 mol% or more based on the total number of moles including III). The polyarylate resin contained, and 1 to 30 parts by weight of a polymer flame retardant having a halogen atom in the aromatic nucleus and 0.1 to 10 parts by weight of a flame retardant aid per 100 parts by weight of the polyarylate resin. A polyarylate resin composition with improved flame retardancy and droplet drop resistance. (2) The following units (I) to (IV) (I) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (II) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ Numerical formulas, chemical formulas, tables, etc. There are ▼ (IV) ▲ Numerical formulas, chemical formulas, tables, etc. I), (II), (IV)
are selected independently, and X has ▲mathematical formulas, chemical formulas, tables, etc.▼, -CH_2-, -
SO_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, Chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -O-, -S- or ▲There are mathematical formulas, chemical formulas, tables, etc.▼, and hydrogen on the aromatic ring of units (I) to (IV) The atom may be substituted with an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms. ), each of the units (I) to (IV) contains one or more of the above R or X, and the units (I) to (
The total amount of units (I) is 3 to 30 mol%, the total amount of units (II) is 30 mol% or more, and the total amount of units (III) is 30 mol% or more based on the total number of moles including IV). , unit (IV
), 1 to 30 parts by weight of a polymeric flame retardant having a halogen atom in its aromatic nucleus, and 0.0 to 30 parts by weight of a flame retardant auxiliary agent per 100 parts by weight of the polyarylate resin. 1 to 10 parts by weight of a polyarylate resin composition having improved flame retardancy and droplet fall properties. (3) The units (I) to (III) or (I) to (IV)
) Logarithmic viscosity of polyarylate resin (concentration 0.2
5 g/dl, temperature 23°C, phenol/tetrachloroethane = 60/40 (weight ratio) (measured value in solvent) is 0.
The polyarylate resin composition with improved flame retardancy and droplet fall properties according to claim 1 or 2, which has a polyarylate resin composition of 50 dl/g or more. (4) The total amount of units (IV) is 2 to 20 based on the total number of moles of units (I) to (IV)
The polyarylate resin composition with improved flame retardancy and droplet fall properties according to claim 2 or 3, wherein the polyarylate resin composition is mol %.