JPH09296120A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a resin composition having high frame-retardancy and causing little bleed-out of the flame-retardant and lowering of the deflection temperature under load caused by the flame-retardant by adding a phosphorus- containing phenolic resin in combination with a specific compound to a thermoplastic resin. SOLUTION: This composition is produced by compounding (A) 100 pts.wt. of a thermoplastic resin (preferably a polyester resin) with (B) 1-100 pts.wt. of a phosphorus-containing phenolic resin and (C) 1-100 pts.wt. of a cyanuric acid salt or an isocyanuric acid salt of a triazine compound (preferably melamine, benzoguanamine or acetoguanamine). The component B is preferably a phenolic resin composed of the unit of formula I or formula II (R<1> and R<2> are each H or a 1-5C alkyl; (x) and (y) are each mol% of each of the unit of formula I and formula II in the polymer and x+y is 100). The resin can be produced e.g. by adding a phosphoric acid ester monohalide to a phenolic resin and subjecting the mixture to dehydrohalogenation reaction. The composition is preferably further incorporated with a non-halogenic flame-retardant to improve the flame-retardancy.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition using a non-halogen flame retardant. More specifically, it has a high degree of flame retardancy, little bleed out of the flame retardant, and little plasticizing effect of the flame retardant, and electrical / electronic equipment such as connectors, relays, switches, case members, transformer members, coil bobbins, The present invention relates to a flame-retardant thermoplastic resin composition suitable for parts, automobile parts and machine parts.

[0002]

2. Description of the Related Art Polyesters represented by polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polycyclohexane dimethylene terephthalate, etc., or thermoplastic resins such as polycarbonate, polyamide, polyphenylene oxide, etc. make full use of their excellent characteristics. As an injection molding material, it is being used in a wide range of fields such as mechanical parts, electric parts, and automobile parts. On the other hand, since these thermoplastic resins are inherently flammable, in order to be used as industrial materials, in addition to the general balance of chemical and physical properties, fire safety, that is, flame retardancy is required. Often.

As a method of imparting flame retardancy to a thermoplastic resin, a method of compounding a halogen-based organic compound as a flame retardant and an antimony compound as a flame retardant auxiliary into the resin is generally used. However, this method has a problem that a large amount of smoke is generated during combustion.

Accordingly, in recent years, it has been strongly desired to use a flame retardant containing no halogen in order to overcome the disadvantages of these halogen-based flame retardants.

Heretofore, blending of phosphorus compounds has been widely known as a method of flame-retarding a thermoplastic resin without using a halogen-based flame retardant. For example, European Published Patent EP4
No. 91986 discloses a method of adding a resorcin type aromatic phosphate oligomer to a flame-retardant PBT alloy molded article, and in JP-A No. 05-70671, there is a resorcin type aromatic bisphosphate or melamine cyanate for polyalkylene terephthalate. A method of adding nurate and inorganic filler is disclosed. In addition, JP-A-7-292
Japanese Patent Publication No. 050 discloses a method of adding a novolac type phenol resin containing phosphorus to a thermoplastic resin.

[0006]

The flame-retardant thermoplastic resin composition for injection molding, particularly for machine parts, electric / electronic parts and automobile parts, has not only excellent flame retardancy of molded products but also load resistance. It is required that the heat resistance represented by the deflection temperature and the bleed-out that the flame retardant contained in a large amount in the resin composition exude to the surface of the molded product are suppressed. However, when a resin composition containing a conventional resorcin-type aromatic bisphosphate or resorcin-type aromatic phosphate oligomer is formed into a molded article, the heat resistance of the resin composition is reduced by the plasticizing effect of these compounds and a flame retardant. The bleed-out phenomenon that oozes on the surface of the molded product became a problem.

The flame-retardant resin composition containing a novolac-type phenol resin containing phosphorus has a problem that the bleed-out phenomenon and the plasticizing effect of the flame retardant are suppressed, but the flame retardancy is not sufficient. Was.

Therefore, the present invention uses a non-halogen flame retardant to impart a high degree of flame retardancy to a thermoplastic resin, and at the same time, has a small bleed out of the flame retardant and a small plasticizing effect by the flame retardant. An object is to obtain a resin injection molded product.

[0009]

Means for Solving the Problems In view of the above situation, the inventors of the present invention have conducted extensive studies and, as a result, have used a salt of a phenol resin containing phosphorus, a triazine compound and cyanuric acid or isocyanuric acid in combination. As a result, it has been found that high flame retardancy, suppression of the plasticizing effect of the flame retardant and suppression of bleed-out of the flame retardant can be achieved, and the present invention has been achieved.

That is, the present invention relates to (A) thermoplastic resin 1
1 to 100 parts by weight of (B) phosphorus-containing phenol resin to 100 parts by weight of (C) triazine compound and salt 1 to 100 of cyanuric acid or isocyanuric acid
It is intended to provide a flame-retardant resin composition containing parts by weight and a molded article made of the same.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The thermoplastic resin (A) used in the present invention is a synthetic resin which exhibits fluidity when heated and can be molded using this. Specific examples thereof include polyester, liquid crystal polyester, polycarbonate, polyamide, wholly aromatic polyamide, wholly aromatic polyester, polyimide, polybenzimidazole, polyketone, polyether ether ketone, polyether ketone, polyether sulfone, and polyphenylene oxide. , Phenoxy resin, polyphenylene sulfide, phenol resin other than component (B) described later, phenol-formaldehyde resin, olefin polymers such as polypropylene, polyethylene and polystyrene, ethylene / propylene copolymer, ethylene / 1-butene copolymer , Ethylene / propylene / non-conjugated diene copolymer,
Ethylene / ethyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / vinyl acetate /
One or more selected from glycidyl methacrylate copolymer and ethylene / propylene-g-maleic anhydride copolymer, olefin copolymer such as ABS, elastomer such as polyester polyether elastomer and polyester polyester elastomer. Examples thereof include a mixture, but one or a mixture of two or more selected from polyester, polyethylene, polypropylene, ABS, polyamide, polycarbonate, phenoxy resin, polyphenylene sulfide and phenol resin is preferable, and polyester is more preferable.

The phosphorus-containing phenol resin used in the present invention is a phenol resin containing one or more phosphorus atoms in the polymer constituting the resin and has the following structural unit (a) or (a) Phenol resin consisting of) and (b) is preferably used.

[0013]

Embedded image (However, the above formulas R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. X and y represent mol% in the polymer, and x + y = 100.) In the unit, R ¹ represents the same or different hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms. 1 to 5 carbon atoms
Specific examples of the alkyl group of methyl, ethyl, n-
Examples thereof include propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, etc., among which methyl, ethyl, n-propyl and isopropyl are preferable, and methyl is more preferable.

In the above formula, x and y are mol% in the polymer.
And x + y = 100.

The mol% of x in the polymer of the phenolic resin comprising the above structural unit (a) or (a) and (b) preferably used in the present invention is the flame retardant aspect of the resulting thermoplastic resin composition. To 50 mol% or more and 100 mol% or less, and more preferably 60 mol% or more and 100 mol% or less.
Mol% or less.

Such a phenol resin can be manufactured by the following methods, but the method is not limited to these methods.

For example, it can be produced by the method represented by the following general formula (1).

[0018]

Embedded image (However, the above formulas R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. X and y represent mol% in the polymer, and x + y = 100.) That is, phenol It can be produced by adding a phosphoric acid ester compound to the resin and carrying out a transesterification reaction. The addition amount of the phosphoric acid ester is preferably 0.1 or more and 10 times or less, more preferably 0.5 or more and 8 times or less the mole of the hydroxyl group in the phenol resin. In this case, the reaction temperature is 100 ° C or higher and 30
It is preferably 0 ° C or lower, more preferably 150 ° C or higher 2
It is 50 ° C or lower. Further, it is preferable to carry out the reaction under reduced pressure because the reaction proceeds rapidly. The degree of pressure reduction in this case is not particularly limited, but is preferably 0.1 mmHg or more and 500 mmHg or less, and more preferably 0.1 mmHg or more 10
0 mmHg or less. The reaction time is not particularly limited, but is preferably 0.5 hours or more and 20 hours or less, more preferably 1 hour or more and 10 hours or less, from the viewpoint of completing the reaction.

It is preferable to carry out the esterification reaction in the presence of a catalyst because the reaction proceeds rapidly. As such a catalyst, tetra (n-butyl) titanate, titanium tetrachloride, antimony oxide or the like can be preferably used.

The amount of the catalyst used is 0.001% by weight or more and 5% by weight or less based on the total amount of the phenol resin and the phosphoric acid ester.
The following is preferred, and more preferably 0.05% by weight or more and 1% by weight or less.

In the above transesterification reaction, a solvent may be used or a reaction solvent may be used if necessary,
It is preferable not to use a solvent in terms of rapid reaction and manufacturability.

The phenol resin preferably used in the present invention can be produced by the method represented by the following general formula (2).

[0023]

Embedded image (Wherein the above formulas R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, Z represents a halogen atom, x and y represent mol% in the polymer, and x + y That is, it can be produced by a dehydrohalogenation reaction by adding a monohalide of a phosphoric acid ester to a phenol resin. The addition amount of the monohalide of the phosphoric acid ester is preferably 0.1 or more and 10 times or less, and more preferably 0.5 or more and 8 times or less the mole of the hydroxyl group in the phenol resin. In this case, the reaction temperature is preferably 100 ° C or higher and 300 ° C or lower, more preferably 150 ° C or higher and 250 ° C or lower. Further, it is preferable to carry out the reaction under reduced pressure because the reaction proceeds rapidly. The degree of pressure reduction in this case is not particularly limited, but is usually 0.1.
It is preferably mmHg or more and 500 mmHg or less, and more preferably 0.1 mmHg or more and 100 mmHg or less. The reaction time is not particularly limited, but is preferably 0.5 hours or more and 20 hours or less, more preferably 1 hour or more and 10 hours or less, from the viewpoint of completing the reaction.

The dehydrohalogenation reaction is preferably carried out in the presence of a catalyst because the reaction proceeds rapidly. As such a catalyst, magnesium chloride, aluminum chloride, zinc chloride and the like can be preferably used.

The amount of the catalyst used is 0.001 with respect to the total amount of the phenol resin and the monohalide of the phosphoric acid ester.
The amount is preferably 5% by weight or more and 5% by weight or less, and more preferably 0.05% by weight or more and 1% by weight or less.

In the above dehydrohalogenation reaction, a solvent may be used or a reaction solvent may be used if necessary, but it is preferable not to use a solvent from the viewpoints of rapid reaction and productivity. .

The molecular weight of the phosphorus-containing phenol resin (B) used in the present invention is preferably 1,000 or more and 100,000 or less, more preferably 1,000 or more and 50,000 or less, further preferably 1,000 or more and 100 or less in terms of number average molecular weight.
00 or less.

The amount of the phosphorus-containing phenol resin (B) used in the present invention is 1 to 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 100 parts by weight of the thermoplastic resin (A). 3 to 70 parts by weight. When the amount of the phosphorus-containing phenol resin (B) used is less than 1 part by weight, the flame retardancy-improving effect is not observed.
If the amount exceeds 0 parts by weight, the mechanical properties and surface appearance of the molded product will be impaired, which is not preferable.

The salt (C) of cyanuric acid or isocyanuric acid used in the present invention is an adduct of cyanuric acid or isocyanuric acid and a triazine compound,
Usually 1 to 1 (molar ratio), sometimes 1 to 2 (molar ratio)
It is an adduct having a composition of. Of the triazine compounds, those that do not form a salt with cyanuric acid or isocyanuric acid are excluded.

Examples of the triazine-based compound include compounds represented by the following general formula (3).

[0031]

Embedded image (However, in the above formula, R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different hydrogen alkyl groups, aralkyl groups, cycloalkyl groups, or -CONH _2. Also, R is -NR ₃ in the above formula. R ₄ or -NR ₅ R ₆ the same groups or independently hydrogen and those, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, --NH2 or -CO,
It is a group selected from NH2. In the general formula (3), R ³ , R ⁴ , R ⁵ , and R ⁶ are the same or different hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, or —CONH ₂ . Here, the aryl group has 6 to 15 carbon atoms,
The alkyl group is preferably one having 1 to 10 carbon atoms, the aralkyl group is preferably one having 7 to 16 carbon atoms, and the cycloalkyl group is preferably one having 4 to 15 carbon atoms. R is the same group as —NR ₃ R ₄ or —NR ₅ R ₆ in the above formula, or independently of these, hydrogen, an aryl group, an alkyl group, an aralkyl group, a cycloalkyl group, —NH ₂ , or — CONH
A group selected from ₂ , wherein the aryl group has 6 to 15 carbon atoms and the alkyl group has 1 to 1 carbon atoms.
Preferred are those having 0, aralkyl groups having 7 to 16 carbon atoms, and cycloalkyl groups having 4 to 15 carbon atoms.

Specific examples of R ₃ , R ₄ , R ₅ and R ₆ are hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β-naphthyl group, methyl group, ethyl group and n-propyl group. Group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, hydroxymethyl group, methoxymethyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-pentyl group, Examples thereof include 4-methyl-1-cyclohexyl group and amide group, and among them, hydrogen, phenyl group, methyl group, hydroxymethyl group, methoxymethyl group, benzyl group and amide group are preferable.

A specific example of R is an amino group,
Amide group, methylamino group, dimethylamino group, ethylamino group, diethylamino group, mono (hydroxymethyl) amino group, di (hydroxymethyl) amino group, mono (methoxymethyl) amino group, di (methoxymethyl) amino group, Phenylamino group, diphenylamino group, hydrogen, phenyl group, p-toluyl group, α-naphthyl group, β
-Naphthyl group, methyl group, ethyl group, n-propyl group,
Isopropyl group, n-butyl group, sec-butyl group, t
tert-butyl group, benzyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 2-methyl-1-
Examples thereof include a pentyl group and a 4-methyl-1-cyclohexyl group, among which hydrogen, an amino group, an amide group, a methyl group, a mono (hydroxymethyl) amino group, a di (hydroxymethyl) amino group, and a mono (methoxymethyl) group An amino group, a di (methoxymethyl) amino group, a phenyl group, and a benzyl group are preferred.

Of the salts of the above triazine compounds with cyanuric acid or isocyanuric acid, particularly preferred examples are melamine, mono (hydroxymethyl) melamine,
Examples include salts of di (hydroxymethyl) melamine, tri (hydroxymethyl) melamine, benzoguanamine, acetoguanamine, 2-amido-4,6-diamino-1,3,5-triazine with cyanuric acid or isocyanuric acid, Particularly, salts of melamine, benzoguanamine, acetoguanamine and cyanuric acid or isocyanuric acid are preferable.

As the component (C) used in the present invention, a mixture of a triazine compound and cyanuric acid or isocyanuric acid is made into a water slurry, which is well mixed to form a salt of both particles and then the slurry is filtered. , A powder obtained by drying, which is different from a mere mixture. The salt does not need to be completely pure, and a somewhat unreacted triazine-based compound or cyanuric acid or isocyanuric acid may remain. The form of the salt is not particularly limited, but it is preferable to use a powder obtained as fine powder as possible from the viewpoint of mechanical strength and surface properties of a molded product obtained from the composition of the present invention. Particularly, those having an average particle size of 100 μm or less before being blended with the resin are particularly preferable. If the salt has poor dispersibility, a dispersant such as tris (β-hydroxyethyl) isocyanurate may be used in combination.

In the present invention, a salt consisting of such a triazine compound and cyanuric acid or isocyanuric acid can be added if necessary, and the amount of the above salt used is 100 parts by weight of the thermoplastic resin. For 1 to
The amount is 100 parts by weight, preferably 2 to 80 parts by weight, more preferably 3 to 70 parts by weight. If the amount of the above salt used is less than 1 part by weight, the flame retardancy-improving effect is not recognized.
If it exceeds 100 parts by weight, the mechanical properties and surface appearance of the molded product are impaired, which is not preferable.

The flame-retardant resin composition of the present invention can be further improved in flame retardancy by adding a non-halogen flame retardant.

As such a non-halogen flame retardant,
There is no particular limitation as long as it is a flame retardant containing no halogen, but a flame retardant containing phosphorus is preferable, and specifically, those represented by the following general formulas (4) and (5) can be preferably mentioned.

[0039]

[Chemical 6] (However, the above formulas R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² ,
R ¹³ and R ¹⁴ represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. In addition, Ar ¹ , Ar ² and A
r ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ represent the same or different phenyl groups or phenyl groups substituted with halogen-free organic residues. Z is a direct bond, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHP.
h and Ph represents a phenyl group. N represents an integer of 1 or more. ) First, the structure of the flame retardant represented by the formula (4) will be described. In the formula (4), R ^{7 to} R ¹³ represent the same or different hydrogen or an alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, sec-butyl group, tert-butyl group,
Examples thereof include n-pentyl group, 2-pentyl group, 3-pentyl group and neopentyl group, with hydrogen, methyl group and ethyl group being preferable, and hydrogen being particularly preferable.

Ar ¹ , Ar ² , Ar ³ and Ar ⁴ represent the same or different phenyl groups or phenyl groups substituted with a halogen-free organic residue. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

Z is a direct bond, O, S, SO ₂ , C
(CH ₃ ) ₂ , CH ₂ and CHPh are represented, and Ph represents a phenyl group.

Further, n represents an integer of 1 or more.

The flame retardant represented by the above formula (4) is generally manufactured according to the following chemical formula (6).

[0044]

[Chemical 7] Next, the flame retardant represented by the formula (5) will be described. In the above formula (5), Ar ⁵ , Ar ⁶ and Ar ⁷ represent the same or different phenyl groups or phenyl groups substituted with a halogen-free organic residue. Specific examples thereof include a phenyl group, a tolyl group, a xylyl group, a cumenyl group, a mesityl group, a naphthyl group, an indenyl group, and an anthryl group, and a phenyl group, a tolyl group, a xylyl group, a cumenyl group, and a naphthyl group are preferable. Especially, a phenyl group, a tolyl group and a xylyl group are preferable.

The flame retardant represented by the above formula (5) can be generally produced according to the following chemical formula (7).

[0046]

Embedded image In the present invention, such a non-halogen flame retardant can be added, if necessary, within a range that does not impair the effects of the present invention. The addition amount at that time is usually 100 parts by weight of the thermoplastic resin. On the other hand, it is 1 to 100 parts by weight, preferably 2 to 50 parts by weight, and more preferably 3 to 20 parts by weight.

When the resin composition of the present invention is further added with a fluorine-based resin, the drop (drip) of droplets during combustion is suppressed. Examples of such fluororesins include polytetrafluoroethylene, polyhexafluoropropylene, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / perfluoroalkylvinyl ether) copolymer, and (tetrafluoroethylene / Ethylene) copolymer, (hexafluoropropylene / propylene) copolymer, polyvinylidene fluoride, (vinylidene fluoride / ethylene) copolymer and the like. Among them, polytetrafluoroethylene, (tetrafluoroethylene / (Perfluoroalkyl vinyl ether) copolymer, (tetrafluoroethylene / hexafluoropropylene) copolymer, (tetrafluoroethylene / ethylene) copolymer, and polyvinylidene fluoride are preferred. Polytetrafluoroethylene, (tetrafluoroethylene / ethylene) copolymer are preferable.

In the present invention, a fluororesin can be added if necessary, but the addition amount in this case is usually 0.01 to 10 relative to 100 parts by weight of the thermoplastic resin from the viewpoint of moldability. Parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.2 to 3 parts by weight.

It has also been found that the flame-retardant resin composition of the present invention, when further combined with a hindered phenol stabilizer, maintains extremely good heat resistance even when exposed to high temperatures for a long period of time. Examples of such stabilizers include triethylene glycol-bis [3- (3-t-butyl-5)
-Methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5
-Di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate], 2,2-thio-diethylenebis [3
-(3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-
Di-t-butyl-4-hydroxyphenyl) propionate, 3,5-di-t-butyl-4-hydroxybenzylphosphonate diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3,5 -Di-t-butyl-4-hydroxybenzyl) benzene, bis or tris (3-t-butyl-6-methyl-4-hydroxyphenyl) propane, N, N'-hexamethylenebis (3,5-di- t-butyl-4-hydroxy-hydrocinnamamide), N, N'-trimethylenebis (3,5-
Di-t-butyl-4-hydroxy-hydrocinnamide) and the like.

In the present invention, such a hindered phenol-based stabilizer can be added if necessary, and the amount of the hindered phenol-based stabilizer added is usually 100 parts by weight of the thermoplastic resin. Against 0.01-3
The amount is preferably 0.01 to 1 part by weight, more preferably 0.03 to 0.5 part by weight.

Further, the resin composition of the present invention has periodic table II to
Addition of a hydrate of a metal oxide, a metal hydroxide or a metal hydroxide containing a group V metal as a central atom can improve flame retardancy. Specific examples of such compounds include aluminum hydroxide, aluminum hydroxide hydrate, magnesium hydroxide, magnesium hydroxide hydrate, zinc hydroxide, zinc hydroxide hydrate, boric acid, and antimony oxide. , Zinc tin hydroxide, hydrate of zinc tin hydroxide, zinc tin oxide, hydrotalcite, dawsonite and the like.

The amount of the metal oxide, metal hydroxide or metal hydroxide hydrate added is usually 1 to 100 parts by weight, preferably 2 parts by weight, relative to 100 parts by weight of the thermoplastic resin.
The amount is from 80 to 80 parts by weight, more preferably from 3 to 70 parts by weight.

With respect to the resin composition of the present invention, phosphorus-based or sulfur-based antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, release agents, and dyes, etc. One or more conventional additives such as colorants including pigments can be added.

Although not particularly required, strength, rigidity, heat resistance, etc. can be significantly improved by adding a fibrous and / or granular filler to the composition of the present invention. .

Specific examples of such fillers include glass fiber, carbon fiber, metal fiber, aramid fiber, asbestos, potassium titanate whiskers, wallastonite, glass flakes, glass beads, talc, mica, clay,
Examples thereof include calcium carbonate, barium sulfate, titanium oxide and aluminum oxide, and among them, chopped strand type glass fiber is preferably used. The addition amount of these is 5 to 1 with respect to 100 parts by weight of the thermoplastic resin.
It is preferably 40 parts by weight, particularly preferably 5 to 100 parts by weight.

The resin composition of the present invention is usually produced by a known method. For example, thermoplastic resin, polyphosphate,
A method of melt-mixing a triazine-based compound with a salt of cyanuric acid or isocyanuric acid and other necessary additives in an extruder, or after mechanically mixing particulates evenly and mechanically and simultaneously with an injection molding machine. Examples of the method include molding.

The resin composition of the present invention is a generally known method,
For example, it can be molded by injection molding, extrusion molding, compression molding, etc., and is extremely practical as a connector, relay, switch, case member, transformer member, coil bobbin and other electrical / electronic equipment parts, automobile parts, machine parts. Can be used.

[0058]

The effects of the present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.

Each measurement item described in Examples and Comparative Examples was according to the following method.

The effects of the present invention will be described in more detail with reference to the following examples. Here, all parts are parts by weight. The measuring method of each characteristic is as follows.

(1) Number average molecular weight (Mn) A differential refractometer WATERS410 manufactured by WATERS was used as a detector.
And using MODEL510 high performance liquid chromatography. The measurement conditions are THF as an eluent,
0.1 ml of a solution having a column temperature of 39 ° C. and a sample concentration of 1 to 2 mg / ml was injected. As the column, Ultrastyra Gel 100A filled with polystyrene porous swelling gel manufactured by WATERS was connected in series, and the eluent was 0.5 ml / mi.
n and the column pressure was 500 psi. The polymer molecular weight was converted by comparison with a calibration curve using standard polystyrene.

(2) 1H-NMR measurement A 90 MHz 1H-NMR manufactured by JEOL Datum was used. A sample (30 mg) was dissolved in deuterated DMSO, and measurement was performed at an integration count of 5000 times.

(3) Production of flame-retardant resin composition and preparation of test piece Phenol resin copolymer containing phosphorus in thermoplastic resin, salt of cyanuric acid or isocyanuric acid, and phenol resin containing phosphorus A non-halogen flame retardant other than the polymer and other additives were mixed and melt-kneaded at a resin temperature of 260 ° C. using a 10 mmΦ single screw extruder. After drying the obtained pellets, they were supplied to a Sumitomo Nestal injection molding machine, Promat 40/25 (manufactured by Sumitomo Heavy Industries, Ltd.), and ASTM D-638 under the conditions of a cylinder temperature of 290 ° C and a mold temperature of 80 ° C. A specified tensile test piece was prepared and the deflection temperature under load at a load of 1.82 MPa was measured. Further, press molding was performed to obtain a flame retardant evaluation sample and a flame retardant bleed-out evaluation sample based on UL94.

(4) Bleed-out Evaluation of Flame Retardant Tensile Test Dumbbells were treated in a gear oven at 100 ° C. for 24 hours. The P content of the dumbbell surface before and after the treatment was determined by fluorescence X
It measured by the line and the peak intensity of P was measured. The peak intensity ratio before and after the treatment was taken as the rate of increase in P content and used as an index of bleed-out.

(5) The phenol resin containing phosphorus used in the present invention was synthesized by the following method.

Reference Example 1 Phenol novolac resin (PR50 manufactured by Sumitomo Durez Co., Ltd.
731) 200 g (the number of moles of hydroxyl group: 0.75 mol) was put into a polycondensation test tube equipped with a three-one motor, and phenylphosphoric acid monochloride (0.75 mol) was added.
Then, 0.1 mmol of magnesium chloride was added as a catalyst, the temperature was raised from 100 ° C. to 150 ° C. over 1 hour, and then the reaction was performed for 1 hour. Thereafter, the degree of vacuum was 10 mmHg, and the polymerization temperature was changed from 150 ° C to 200 ° C over 1 hour to 200 ° C to react for 4 hours, and the polymer was discharged from the navel portion of the lower part of the test tube (yield 95%).

When ¹ H-NMR was measured using deuterated dimethyl sulfoxide as a measuring solvent, absorption of phenolic hydrogen of 9.0 to 9.5 ppm found in the phenol resin completely disappeared, and 6.3 was newly added. It was found that the phosphoric acid esterified phenol unit mol% (x) = 100 mol% because the absorption of aromatics at ˜7.2 ppm increased. This polymer was designated as A-1.

Reference Example 2 Example 1 was repeated except that 0.5 mol of 2,6-dimethylphenylphosphoric acid monochloride was used instead of phenylphosphoric acid monochloride. ^The composition of the phenolic resin in the polymer obtained from ¹ H-NMR measurement was x: y = 60: 40 (mol%). This polymer was designated as A-2.

Reference Example 3 200 g of phenol novolac resin (PR50731) manufactured by Sumitomo Durez Co., Ltd. (PR mole number: 0.75 mol) was placed in a test tube with a navel for polycondensation equipped with a three-one motor, and triphenyl phosphate (0.75 mol). And 0.1m as catalyst
mol tetra (n-butyl) titanate was added, 1
The temperature was raised from 00 ° C to 150 ° C over 1 hour, and then reacted for 1 hour. After that, the degree of vacuum is 0.5 mmHg and the polymerization temperature is 15
From 0 ° C to 230 ° C over 1 hour, react for 4 hours,
The polymer was discharged from the test tube (yield 90%).

The composition of the phenolic resin containing phosphorus obtained from ¹ H-NMR measurement in the polymer is x: y = 70:
It was 30 (mol%). This polymer was designated as A-3.

(6) Non-Halogen Flame Retardant Other than Polyphosphate The abbreviations and structures of the non-halogen flame retardants used in Examples and Comparative Examples other than the polyphosphates synthesized above are shown below.

[0072]

Embedded image

(7) Cyanuric acid salt When the cyanuric acid salt used in this example was observed with an electron microscope, the average particle size (average value of the number of solids 100) was smaller than 100 μm in all cases.

Examples 1 to 7 and Comparative Examples 1 to 3 have a limiting viscosity of 0.85 (25 ° C., o-
Chlorophenol solution) polybutylene terephthalate (hereinafter abbreviated as PBT) is used, and a phosphorus-containing phenol resin produced in Reference Example, a salt of cyanuric acid or isocyanuric acid, and a non-halogen system other than phosphorus-containing phenol resin Mix flame retardant and other additives,
Melt kneading was carried out at a resin temperature of 260 ° C. using a 0 mmΦ single screw extruder. The compounding recipe and the results are shown in Table 2.

[0075]

[Table 1]

Examples 1 to 6 and Comparative Examples 1, 2, 3, 4
From the comparison of the combination of the phosphorus-containing phenol resin of the present invention, the triazine-based compound and a salt of cyanuric acid or isocyanuric acid, a high degree of flame retardancy is obtained, the deflection temperature under load is lowered, and the flame retardant It can be seen that bleed-out is suppressed (Examples 1, 2, 3).
On the other hand, only a phenol resin containing phosphorus (Comparative Example 3),
Alternatively, it can be seen that the flame retardant effect is not sufficient only with a salt composed of a triazine compound and cyanuric acid or isocyanuric acid (Comparative Example 2). In addition, when a low molecular weight type aromatic bisphosphate (B-1), a triazine compound and a salt of cyanuric acid or isocyanuric acid are used in combination instead of the phosphorus-containing phenol resin of the present invention It can be seen that although the flame retardancy can be imparted, the deflection temperature under load is lowered and the flame retardant bleeds out (Comparative Example 4). Further, from Examples 4 to 6, a low molecular weight type aromatic phosphate other than the phenol resin containing phosphorus is further added to the combination of the phosphorus-containing phenol resin of the present invention, the triazine compound and the salt of cyanuric acid or isocyanuric acid ( It can be seen that the effects of the present invention can be obtained even when B-1 and B-2) or an antioxidant is used in a small amount.

Further, from the comparison of Example 7 and Comparative Example 5, even when glass fiber (GF) or polytetrafluoroethylene was added as a filler, the phosphorus-containing phenol resin and triazine-based compound of the present invention were added. It can be seen that the combination of a salt consisting of and cyanuric acid or isocyanuric acid makes it possible to impart flame retardancy, further reduces impact strength and deflection temperature under load, and less bleed out of the flame retardant.

Examples 8 to 15 and Comparative Examples 6 to 11 As the thermoplastic resin, the intrinsic viscosity was 0.8 instead of PBT.
5 (25 ° C, o-chlorophenol solution) polyethylene terephthalate (hereinafter abbreviated as PET), poly (1,4)
-Cyclohexane dimethylene terephthalate) (PC
T, "Ector" GN002 manufactured by Toray Industries, Inc., bisphenol A type polycarbonate (PC, "Upilon" S-200 manufactured by Mitsubishi Engineering Plastics Co., Ltd.)
0), ABS resin (“Toyolac” 50 manufactured by Toray Industries, Inc.)
0), PC // ABS resin (90 // 10 weight ratio) (P
It means that C and ABS resin are blended at 90:10 (parts by weight)), nylon 6 (PA6, CM1011 manufactured by Toray Industries, Inc.), nylon 66 (PA66, Toray Industries, Inc.).
The same procedure as in the above-described example was performed except that CM3001) manufactured by CM was used. A series of formulation and results are shown in Table 2.

[0079]

[Table 2]

Comparing Examples and Comparative Examples of each resin, PET, PCT, PC, PA6, PA66, AB
Similarly, in the case of S and PC // ABS, the combination of the phosphorus-containing phenol resin and the triazine-based compound of the present invention and the salt of cyanuric acid or isocyanuric acid does not reduce the deflection temperature under load, and flame retardancy is improved. It can be seen that the flame retardant can be applied and the bleed out of the flame retardant is small. On the other hand, when an aromatic phosphate (B-1, 2) other than the phosphorus-containing phenol resin of the present invention is used, flame retardancy can be imparted, but the deflection temperature under load is significantly lowered, and these compounds are bleed out. I understand that

From the above results, flame retardancy was improved by blending a thermoplastic resin with a phosphorus-containing phenol resin copolymer of the present invention containing phosphorus, a triazine compound and a salt of cyanuric acid or isocyanuric acid. It can be seen that a resin composition can be obtained in which the deflection temperature under load and the bleed-out of the flame retardant are reduced. The same applies when GF is added as a filler.

[0082]

The flame-retardant resin composition obtained by blending a phosphorus-containing phenol resin containing phosphorus and a triazine compound and a salt of cyanuric acid or isocyanuric acid in a thermoplastic resin is a conventionally known aromatic phosphate. Higher flame retardancy than resin compositions containing phosphorus-based flame retardants such as aromatic phosphate oligomers, less bleed-out of flame retardants, and less decrease in deflection temperature under load due to addition of flame retardants, A flame-retardant thermoplastic resin composition suitable for electrical / electronic device parts such as connectors, relays, switches, case members, transformer members, coil bobbins, automobile parts, and machine parts.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 61/04 LMR C08L 61/04 LMR 61/14 LMU 61/14 LMU 67/02 LPF 67/02 LPF 71/10 LQK 71/10 LQK 81/02 LRG 81/02 LRG H01B 3/30 H01B 3/30 P

Claims (12)

[Claims] 1. A salt of 1 to 100 parts by weight of (B) a phenol resin containing phosphorus and (C) a triazine compound and a salt of cyanuric acid or isocyanuric acid to 100 parts by weight of a thermoplastic resin (A). A flame-retardant resin composition containing 100 parts by weight. 2. The flame-retardant resin composition according to claim 1, wherein the phenol resin containing phosphorus (B) is a phenol resin comprising the following structural unit (a) or (a) and (b). Embedded image (However, the above formulas R ¹ and R ² represent the same or different hydrogen atoms or alkyl groups having 1 to 5 carbon atoms. X and y represent mol% in the polymer, and x + y = 100.) 3. In a phenolic resin containing phosphorus, x
Is 50 mol% or more, the flame-retardant resin composition according to claim 2. 4. The flame-retardant resin composition according to claim 1, which further comprises 1 to 50 parts by weight of a non-halogen flame retardant with respect to 100 parts by weight of the thermoplastic resin. 5. The flame retardant resin composition according to claim 4, wherein the halogen-free flame retardant is a flame retardant containing phosphorus. 6. The flame-retardant resin composition according to claim 1, which further comprises 0.01 to 10 parts by weight of a fluororesin to 100 parts by weight of the thermoplastic resin. 7. The flame-retardant resin composition according to claim 1, further comprising 0.01 to 3 parts by weight of a hindered phenolic stabilizer based on 100 parts by weight of the thermoplastic resin. 8. The flame-retardant resin composition according to claim 1, further comprising 5 to 140 parts by weight of a filler with respect to 100 parts by weight of the thermoplastic resin. 9. The flame retardant according to claim 1, wherein the thermoplastic resin is one kind or a mixture of two or more kinds selected from polyester, polyethylene, polypropylene, ABS, polyamide, polycarbonate, phenoxy resin, polyphenylene sulfide and phenol resin. Resin composition. 10. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin is polyester. 11. A molded article comprising the flame-retardant resin composition according to claim 1. 12. The molded article according to claim 11, which is an electric / electronic device part, an automobile part or a mechanical part.