JPH0812811A - Flame-retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful for a copper-clad laminate having no problems such as denaturation, evaporation and bleed of a flame- retardant, no discoloration and excellent coating adhesivity, comprising a thermoplastic resin and a mixture of specific phosphoric ester compounds. CONSTITUTION:This composition comprises (A) a thermoplastic resin such as polyphenylene ether resin, polycarbonate resin or a resin composition composed of the resin and PS resin, (B) a compound of formula I (Q1 to Q4 are each a 1-6C alkyl; R1 and R2 are each CH3; R3 and R4 are each H or CH3; (n) >=1; n1 and n2 are each 0-2; m1 to m4 are each 0-3) and (C) a compound of formula II (Q is a 2-14C aliphatic hydrocarbon residue, etc.; Q5 to Q7 are each a 1-6C alkyl; (n) >=0; m5 to m7 are 0-3) and the ratio of the component C to the components B+C is 0.1-40wt.%. The amount of the components of the objective composition is 1-200 pts.wt. of the components B+C based on 100 pts.wt. of the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent coating adhesion, no coloring, and difficulty in molding when obtained by blending a thermoplastic resin with two phosphate ester compounds having a specific structure. The present invention relates to a resin composition which is free from denaturation, smoke generation, volatilization and bleeding of a flame retardant and has excellent flame retardancy.

[0002]

2. Description of the Related Art Synthetic resins are generally light, have excellent water resistance, chemical resistance, electrical insulation, mechanical properties, and are easy to mold and process, so they are used as building materials, electrical equipment materials, automotive materials, fibers. Widely used as a material. However, synthetic resins have a drawback that they are more likely to burn than metal materials and inorganic materials. Therefore, many methods for making the synthetic resin flame-retardant have been proposed. The most widely used of these conventional flame retardant methods is a halogen compound,
A method of blending a phosphorus compound, an inorganic hydrate or the like into a synthetic resin, particularly an organic phosphate compound, such as triphenyl phosphate, cresyl diphenyl phosphate,
Tricresyl phosphate and the like are widely used industrially. However, such additives conventionally used have drawbacks such as smoke and volatilization during molding and during use, and bleeding of the flame retardant on the surface of the molded product.

As a method for solving the above drawbacks, an organic phosphorus compound having a large molecular weight is adopted as a flame retardant for resins,
It is being developed. For example, European Patent Application Publication No. 7460 discloses tri (2,6-dimethylphenyl).
Phosphate compound, European Patent Application Publication No. 129
No. 824, No. 129825 and No. 135726 disclose resorcinol / bisdiphenyl phosphate compounds,
U.S. Pat. No. 4,683,255 discloses tribiphenyl phosphate compounds. Further, we have found in Japanese Patent Application No. 5-189924 that a phosphate compound having a binding structure with bisphenols and a terminal structure with an alkyl-substituted monofunctional phenol at the same time exhibits particularly excellent performance. In addition, Japanese Examined Japanese Patent Sho 62
No. 25706 discloses a technique of imparting an antistatic property to a resin composition by leaving an acid value of 1 or more by leaving a phosphoric acid group in a polyphosphoric acid ester. However, the acidity due to the phosphate group causes mold corrosion of the molding machine, which is a serious industrial problem.

Further, Japanese Patent Publication No. 54-32818 and Japanese Patent Application Laid-Open No. 1-223158 describe the use of a polyphosphoric acid ester having a phenolic hydroxyl group for reacting with a thermosetting resin. Main applications are laminates and copper-clad laminates for printed wiring, which is a technology for fields that do not require painting. Further, it is considered that the phenolic hydroxyl group is consumed by the reaction with the thermosetting resin.

On the other hand, recently, when various thermoplastic resins are used for various structural materials such as exterior materials due to their molding processability and recyclability, a good appearance of the molded article is strongly demanded and coated. Is often used. However,
It has not been possible to provide a flame-retardant resin composition having good coating adhesion and practically durable properties.

[0006]

That is, the object of the present invention has excellent coating adhesion, which is not achieved by the prior art, has no coloration of the resin composition, and has a No flame retardant denaturation, fuming, volatilization or bleeding,
It is to provide an excellent flame-retardant composition.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that (A) a thermoplastic resin, (B) a component of a phosphate ester compound and (C) a component of ) By adding a specific amount of a composition in which a phosphoric acid ester compound in which a hydroxyl group is bonded to the terminal carbon of the component is added, there is no coloring of the resin composition, and modification of the flame retardant during molding, fuming, volatilization, It was found that there is no bleeding and that it has excellent coating adhesion. In particular, the component (C) of the present invention has been found to greatly improve the coating adhesion of the resin composition by using a small amount, and the present invention has been completed.

That is, the present invention includes (A) a thermoplastic resin and (B) a general formula (I).

[0009]

Embedded image

(In the formula, Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms, R1 and R2 are methyl groups,
R3 and R4 represent a methyl group or hydrogen. n is an integer of 1 or more, n1 and n2 are integers of 0 to 2, m1,
m2, m3, and m4 each independently represent an integer of 0 to 3. )
A phosphoric acid ester compound represented by: and (C) the general formula (II)

[0011]

[Chemical 6]

(Wherein Q is an aliphatic hydrocarbon residue having 2 to 14 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an alkyl-substituted aryl group, or a divalent residue corresponding to an aralkyl group. Selected from the group consisting of Q.
5, Q6 and Q7 represent an alkyl group having 1 to 6 carbon atoms.
n represents an integer of 0 or more. m5, m6, m7 are 0 to 3
Indicates an integer. ) Of the phosphoric acid ester compound represented by the formula (B), and the phosphoric acid ester compound of the component (C) is added to the total amount of the phosphoric acid ester compound of the component (B) and the phosphoric acid ester compound of the component (C). A flame-retardant resin composition having a proportion of 0.1 to 40% by weight, thereby having excellent coating adhesion, no coloring of the resin composition, modification of the flame-retardant agent during molding and smoke generation. It provides an excellent flame-retardant composition free from volatile matter and bleeding.

The present invention will be described in detail below. First, the thermoplastic resin (A) used in the present invention will be described. The component (A) of the present invention is not limited as long as it is a thermoplastic resin, but a non-halogen type thermoplastic resin is preferable in view of recent environmental problems. Particularly preferred are polyphenylene ether resin (A ₁ ), polycarbonate resin (A ₂ ), polystyrene, rubber-modified polystyrene, AS
Resin, polystyrene resin (A _3), such as ABS resin, polyethylene, polyolefin resins such as polypropylene (A _4), 6- nylon, 6,6-nylon, 6,10
-Polyamide resin such as nylon and 12-nylon (A
₅ ), a thermoplastic resin comprising one or a combination of two or more selected from the thermoplastic elastomers (A ₆ ). In addition to these resins alone, a resin composition comprising a polyphenylene ether resin and a polystyrene resin, a resin composition comprising a polyphenylene ether resin and a polyolefin resin, a resin composition comprising a polyphenylene ether resin and a polyamide resin, a polycarbonate resin and a polystyrene resin. It is possible to use a resin composition composed of the following, or a resin composition composed of a polyamide resin and a polystyrene resin. Particularly, the polyphenylene ether resin and the aromatic polycarbonate resin are resins having a high flame retarding effect by the phosphoric acid ester compound, and when used as the component (A) of the present invention alone or in combination with other resins, non-halogen flame retardant An optimal composition as a material can be obtained.

The polyphenylene ether resin (A ₁ ) used as the component (A) in the present invention is, for example, a compound represented by the general formula (V-
1) and / or a homopolymer or a copolymer having a repeating unit represented by (V-2).

[0015]

[Chemical 7]

[0016]

Embedded image

(Here, R9, R10, R11, R1
2, R13 and R14 are independently an alkyl group having 1 to 4 carbon atoms,
Represents an aryl group, halogen, hydrogen. However, R13, R
14 is not hydrogen at the same time. ) A typical example of a homopolymer of polyphenylene ether resin is poly (2,6-dimethyl-1,4-phenylene).
Ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4)
-Phenylene) ether, poly (2-ethyl-6-n-)
Propyl-1,4-phenylene) ether, poly (2,
6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-) Examples thereof include phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, and poly (2-methyl-6-chloroethyl-1,4-phenylene) ether.

Among these, poly (2,6-dimethyl-1,
4-phenylene) ether is particularly preferred. The polyphenylene ether copolymer is a copolymer having a phenylene ether structure as a main monomer unit. For example,
Copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and 2,3,6- Examples thereof include copolymers with trimethylphenol and o-cresol.

Further, in the polyphenylene ether resin of the present invention, various other phenylene ether units, which have been proposed to be present in the polyphenylene ether resin, are proposed unless they are contrary to the gist of the present invention. It may be included as a partial structure. As an example of what is proposed to coexist in a small amount, JP-A-1-29 is known.
7-28, and 2- (dialkylaminomethyl) -6 described in JP-A-63-301222.
Examples include -methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether unit.

Further, a polyphenylene ether resin in which a small amount of diphenoquinone or the like is bound in the main chain is also included.
Furthermore, for example, polyphenylene ether modified with a compound having a carbon-carbon double bond described in JP-A-2-276823, JP-A-63-108059, JP-A-59-59724 and the like is also available. Including.

The method for producing the polyphenylene ether resin used in the present invention is not particularly limited, but, for example, in the presence of dibutylamine in the presence of dibutylamine according to the method described in JP-B-5-13966. It can be produced by oxidative coupling polymerization of xylenol. Moreover, the molecular weight and the molecular weight distribution are not particularly limited.

Examples of the polycarbonate resin (A ₂ ) used as the component (A) of the present invention include those represented by the general formula (VI-
1)

[0023]

[Chemical 9]

A polymer having a repeating unit represented by the following can be used. Here, Z represents a mere bond, or is an alkylene having 1 to 8 carbons, or 2 to 8 carbons.
Alkylidene, cycloalkylene having 5 to 15 carbon atoms,
SO ₂ , SO, O, CO, or formula (VI-2)

[0025]

[Chemical 10]

It means a group represented by: X represents hydrogen or a saturated alkyl group having 1 to 8 carbon atoms, and a and b represent an integer of 0 to 4. This polycarbonate resin is, for example, a solvent method, that is, in the presence of a known acid acceptor and molecular weight modifier in a solvent such as methylene chloride,
It can be produced by a reaction between a dihydric phenol and a carbonate precursor such as phosgene, or a transesterification reaction between a dihydric phenol and a carbonate precursor such as diphenyl carbonate.

As the dihydric phenol which can be used here, 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], hydroquinone,
4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) alkane, bis (4-hydroxyphenyl) cycloalkane, bis (4-hydroxyphenyl)
Mention may be made of compounds such as sulphides, bis (4-hydroxyphenyl) sulphone, bis (4-hydroxyphenyl) sulphoxide, bis (4-hydroxyphenyl) ether. Particularly, it is preferable to use bisphenol A alone or in combination with other dihydric phenol. Further, these dihydric phenols may be homopolymers of dihydric phenols or copolymers or blends of two or more thereof. Further, the polycarbonate resin used in the present invention may be a thermoplastic random branched polycarbonate obtained by reacting a polyfunctional aromatic compound with a dihydric phenol and / or a carbonate precursor.

As the thermoplastic resin of the component (A) of the present invention, the polystyrene resin (A ₃ ) itself or a mixture of the polystyrene resin with other resins can be used. As the polystyrene resin (A ₃ ), for example, a vinyl aromatic polymer or a rubber-modified vinyl aromatic polymer can be used. As the vinyl aromatic polymer, in addition to styrene, o-methylstyrene, p-methylstyrene, m
-Methylstyrene, 2,4-dimethylstyrene, ethylstyrene, nuclear alkyl-substituted styrene such as p-tert-butylstyrene, α-methylstyrene, α-methyl-
Examples thereof include polymers such as α-alkyl-substituted styrenes such as p-methylstyrene, copolymers of one or more of these with at least one other vinyl compound, and copolymers of two or more thereof. Examples of the compound copolymerizable with the vinyl aromatic compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate, unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile, and acid anhydrides such as maleic anhydride. . Particularly preferred polymers among these polymers are polystyrene and styrene-acrylonitrile copolymer (AS resin).
Is.

Examples of rubbers used for the rubber-modified vinyl aromatic polymer include polybutadiene, styrene-butadiene copolymer, polyisoprene, butadiene-isoprene copolymer, natural rubber, ethylene-propylene copolymer and the like. Can be mentioned. Especially polybutadiene,
A styrene-butadiene copolymer is preferable, and as the rubber-modified aromatic polymer, rubber-modified polystyrene (HIP
S) and rubber-modified styrene-acrylonitrile copolymer (ABS resin) are preferable.

The phosphoric acid ester compound as the component (B) used in the present invention will be described below. The phosphoric acid ester compound of the component (B) used in the present invention has the general formula (I)

[0031]

[Chemical 11]

(Wherein Q1, Q2, Q3 and Q4 represent an alkyl group having 1 to 6 carbon atoms, R1 and R2 are methyl groups,
R3 and R4 represent a methyl group or hydrogen. n is an integer of 1 or more, n1 and n2 are integers of 0 to 2, m1,
m2, m3, and m4 each independently represent an integer of 0 to 3. )
Is a phosphoric acid ester compound represented by. General formula (I)
N in is an integer of 1 or more, and n is preferably an integer of 1 to 10. The more preferable range of n is an integer of 1 to 5. In the general formula (I), it is preferable that n1 and n2 are 0, and R3 and R4 are methyl groups.

In the general formula (I), m1, m2,
m3 and m4 are 0, that is, there is no substitution of an alkyl group on the terminal phenyl group, or Q1, Q2, Q3 and Q
Most preferably, 4 is a methyl group, that is, the terminal phenyl group is substituted with a methyl group. The phosphoric acid ester compound of the component (B) of the present invention has a binding structure with a specific bifunctional phenol and a terminal structure with a specific monofunctional phenol.

As the bifunctional phenol, 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl) is used. )
Examples include, but are not limited to, bisphenols such as methane, bis (4-hydroxy-3,5-dimethylphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane. Bisphenol A is particularly preferable.

As the monofunctional phenol, unsubstituted phenol, monoalkylphenol, dialkylphenol and trialkylphenol can be used alone or as a mixture of two or more kinds. Especially phenol, cresol,
Dimethylphenol (mixed xylenol) is preferred.
The phosphoric acid ester compound as the component (B) is greatly suppressed in volatility and is excellent in stability and hydrolysis resistance.
Further, it does not cause a problem such as gelation by causing a reaction with a polyphenylene ether resin or a polycarbonate resin, and does not corrode a metal part of a molding machine or the like.

Next, the phosphoric acid ester compound as the component (C) used in the present invention will be explained. The phosphoric acid ester compound of the component (C) used in the present invention has the general formula (II)

[0037]

[Chemical 12]

(Wherein Q is an aliphatic hydrocarbon residue having 2 to 14 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an alkyl-substituted aryl group, or a divalent residue corresponding to an aralkyl group. Selected from the group consisting of Q.
5, Q6 and Q7 represent an alkyl group having 1 to 6 carbon atoms.
n represents an integer of 0 or more. m5, m6, m7 are 0 to 3
Indicates an integer. ) Is a phosphoric acid ester compound.

In the general formula (II), Q is the general formula (I
II)

[0040]

[Chemical 13]

(In the formula, R5 and R6 are methyl groups, R7 and R6 are
8 represents a methyl group or hydrogen, and n5 and n6 each represent an integer of 0 to 2. ) Is a phosphate compound and / or Q is a compound represented by the general formula (IV)

[0042]

Embedded image

A phosphoric acid ester compound represented by the following is preferable. In the general formula (III), n
Preferably, 5 and n6 are 0, and R7 and R8 are methyl groups. The phosphoric acid ester compound of the component (C) of the present invention has a specific bifunctional phenol-bonded structure and a structure in which one of the terminal structures has a hydroxyl group bonded to carbon.

Examples of the bifunctional phenol include 2,2-bis (4-hydroxyphenyl) propane [commonly called bisphenol A], 2,2-bis (4-hydroxy-3-methylphenyl) propane, bis (4-hydroxyphenyl). )
Bisphenols such as methane, bis (4-hydroxy-3,5-dimethylphenyl) methane and 1,1-bis (4-hydroxyphenyl) ethane, and aromatic dihydroxy compounds such as resorcinol and hydroquinone,
Further examples include, but are not limited to, biphenol compounds such as 4,4'-biphenol. Bisphenol A, resorcinol and hydroquinone are particularly preferred.

The phosphoric acid ester compound represented by the general formula (II) has a hydroxyl group bonded to one carbon per molecule. This one hydroxyl group per molecule improves the coating adhesion of the flame-retardant resin composition without impairing the compatibility of the phosphate ester compound as the component (C) and the thermoplastic resin. Further, by limiting the number of hydroxyl groups bonded to carbon to one per molecule, coloring of the flame retardant itself that occurs during heating is suppressed.

The phosphoric acid ester compound as the component (B) and the phosphoric acid ester compound as the component (C) are disclosed, for example, in JP-A-1-223158, and the "specific bifunctional phenol" and the monofunctional phenol. Can be obtained by reacting with phosphorus oxychloride, and if necessary, the product can be purified to obtain a highly pure product. The phosphoric acid ester compound of the component (B) and the phosphoric acid ester compound of the component (C) may be separately synthesized and mixed, or the phosphoric acid ester compound of the component (B) and the phosphoric acid ester compound of the component (C) may be mixed. You may synthesize | combine with a phosphoric acid ester compound simultaneously and may be manufactured as a mixture.

The ratio of the phosphoric acid ester compound as the component (B) and the phosphoric acid ester compound as the component (C) is based on the total amount of the phosphoric acid ester compound as the component (B) and the phosphoric acid ester compound as the component (C). On the other hand, the ratio of the phosphoric acid ester compound as the component (C) is 0.1 to 40% by weight. It is more preferably 0.1 to 15% by weight. If this proportion is less than 0.1% by weight, the effect of improving the coating adhesion will not be obtained, and if it exceeds 40% by weight, the effect of improving the coating adhesion will be adversely affected. Problems such as discoloration and swelling of the material under humidity occur.

In addition to the component (B) and component (C) phosphoric acid ester compounds used in the present invention, phosphoric acid esters generally used within a range that does not impair the effects of the present invention, such as triphenyl phosphate and triphenyl phosphate. Even if it contains phosphoric acid esters such as cresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate and the like, compounds obtained by modifying these with various substituents, various condensation type phosphoric acid ester compounds, etc. Good.

A thermoplastic resin as the component (A) used in the resin composition of the present invention and a phosphoric acid ester compound as the component (B),
The mixing ratio of the phosphoric acid ester compound as the component (C) is not particularly limited as long as the effects of the invention can be sufficiently exhibited, but the phosphoric acid ester compound as the component (B) and the phosphoric acid ester as the component (C) are not limited. If the compounding ratio of the total amount of the compounds is too small, the flame retardancy is insufficient, and if it is too large, the heat resistance of the resin is impaired. The total amount of the phosphoric acid ester compound as the component (B) and the phosphoric acid ester compound as the component (C) is preferably 1 to 2 with respect to 100 parts by weight of the thermoplastic resin (A).
00 parts by weight, more preferably 1 to 100 parts by weight. Most preferably, it is 5 to 50 parts by weight.

The composition of the present invention can be produced by kneading using a generally known kneader such as an extruder, a heating roll, a kneader or a Banbury mixer. In addition, the resin composition of the present invention is known to include other flame retardants such as decabromodiphenyl ether, tetrabromobisphenol A, hexabromobenzene, hexabromocyclododecane, and perchlorocyclodecane as long as the effects of the invention are not impaired. Organic halogen compounds, halogen-containing inorganic compounds such as ammonium bromide, organic phosphorus or inorganic phosphorus compounds such as red phosphorus, polyphosphoric acid, ammonium phosphate, and halogen-containing inorganic compounds such as tris (halopropyl) phosphate and tris (haloethyl) phosphate Phosphorus compounds, phosphonitrile chloride derivatives, nitrogen-containing phosphorus compounds such as phosphonoamides, melamine,
Uric acid, methylol melamine, dicyandiamide, melamine formaldehyde resin, uric acid formaldehyde resin, nitrogen compounds such as triazine compounds, magnesium hydroxide, aluminum hydroxide, inorganic hydrates such as dawsonite, antimony oxide, barium metaborate antimonate, Zirconium oxide, zirconium hydroxide, molybdenum oxide, ammonium molybdate, zinc borate,
Inorganic compounds such as ammonium borate, barium metaborate and tin oxide, and anti-dripping agents such as polytetrafluoroethylene and siloxane compounds may be used in combination.

Further, other additives such as a plasticizer, a release agent, etc. may be added to the resin composition of the present invention within a range not impairing the effects of the invention.
It is possible to contain stabilizers such as ultraviolet absorbers, antioxidants, and light stabilizers, or dyes and pigments, as well as glass fibers, glass chips, glass beads, carbon fibers, wollastonite. Fillers such as calcium carbonate, talc, mica, wood powder, slate powder, and fibrous asbestos can also be added.

Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to the following examples. Table 1 shows the phosphoric acid ester compounds used in the examples.

[0053]

[Table 1]

[0054]

Example 1 Poly-2,6-dimethyl-1,4 having an intrinsic viscosity [η] of 0.47 measured at 30 ° C. in chloroform.
-Phenylene ether (hereinafter abbreviated as PPE) 3
4 parts by weight and impact-resistant polystyrene resin (hereinafter abbreviated as HIPS. Asahi Kasei Kogyo KK: Asahi Kasei Polystyrene 4)
92) 57 parts by weight of polystyrene resin (hereinafter abbreviated as GPPS. Asahi Kasei Kogyo KK: Asahi Kasei Polystyrene 6)
85) 9 parts by weight, 14 parts by weight of phosphate ester B-1
0.5 parts by weight of phosphoric acid ester C-1 and 0.3 parts by weight of octadecyl-3- (3-5-di-t-butyl-4-hydroxyphenyl) propionate are mixed, and the cylinder temperature is set to 300 ° C. Were melt-kneaded with the twin-screw extruder to obtain pellets. Injection molding was performed using the pellets at 280 ° C. to obtain test pieces. Evaluation was performed using this test piece, and the results are shown in Table 2.

The flame retardancy was evaluated by using a 1/8 inch test piece in accordance with the vertical combustion test method specified in UL-94 and ranked. To evaluate the volatility of the composition, the amount of smoke emitted from the nozzle of the injection molding machine was visually observed. The evaluation of the coloring property of the molded piece was performed by visual observation. The hot water immersion test was carried out by immersing the test piece in hot water at 80 ° C. for 600 hours, and the appearance change of the molded piece after the hot water immersion test was visually evaluated.

The coating adhesion was determined by preparing a 75 × 75 × 3 mm test piece, coating it with a commercially available urethane paint, and then conducting a cross-cut test, according to the number of peeled cross-cuts in all cross-cuts (100 pieces). I gave the following ranks. ◎: Peeling number is 0 ◯: Peeling number is 1 to 10 Δ: Peeling number is 11 to 20 ×: Peeling number is 21 to 100

[0057]

Example 2 The same as Example 1 except that the phosphoric acid ester B-2 was used as the phosphoric acid ester of the component (B) and 0.2 part by weight of C-2 was used as the phosphoric acid ester of the component (C). The results are shown in Table 2.

[0058]

Example 3 Example 2 was repeated except that 0.5 part by weight of phosphoric acid ester C-3 was used as the phosphoric acid ester as the component (C), and the results are shown in Table 2.

[0059]

Example 4 Example 2 was repeated except that 0.3 part by weight of phosphoric acid ester C-4 was used as the phosphoric acid ester as the component (C), and the results are shown in Table 2.

[0060]

Comparative Example 1 The same procedure as in Example 2 was carried out except that the phosphoric acid ester as the component (C) was not used, and the results are shown in Table 2.

[0061]

Comparative Example 2 Example except that 6 parts by weight of phosphoric acid ester B-2 was used as the phosphoric acid ester of component (B) and 8 parts by weight of phosphoric acid ester C-2 was used as the phosphoric acid ester of component (C). The same procedure as in Example 2 was performed, and the results are shown in Table 2.

[0062]

[Table 2]

[0063]

Example 5 (Production of ABS Resin) 750 parts by weight of a butadiene latex having an average particle size of 0.30 μm (40% by weight in terms of rubber) and 1 part by weight of an emulsifier (potassium disproportionated rosinate) were charged into a polymerization tank, While stirring, the temperature was raised to 70 ° C. in a nitrogen stream, and a mixture of 200 parts by weight of acrylonitrile, 500 parts by weight of styrene, 0.8 parts by weight of cumene hydroperoxide and 0.7 parts by weight of t-dodecyl mercaptan and distilled. To 500 parts by weight of water, 1.0 part by weight of sodium formaldehyde sulfoxylate, ferrous sulfate (FeSO ₄ ·.
7H ₂ O) 0.10 parts by weight, ethylenediamine tetraacetic acid.
Polymerization was performed by adding an aqueous solution in which 0.2 part by weight of 2Na salt was dissolved over 6 hours.

After the addition was completed, stirring was continued for another 2 hours to complete the polymerization. The polymerization rate was 94%. The produced graft copolymer latex is coagulated with a dilute sulfuric acid aqueous solution,
It was washed, dehydrated and dried to obtain a white ABS resin. (Production of AS resin) To 180 parts by weight of water, 0.4 parts by weight of potassium persulfate and 2.0 parts by weight of potassium rosinate were added and dissolved, and 70 parts by weight of styrene, 30 parts by weight of acrylonitrile and 0 part of dodecyl mercaptan were dissolved in this aqueous solution. 0.2 part by weight was added and the reaction was carried out at 70 ° C. for 4 hours to obtain an aromatic vinyl copolymer. The polymerization rate was 94%. The produced copolymer was coagulated with a dilute sulfuric acid aqueous solution, washed, dehydrated and dried to obtain a white powder AS resin.

50 parts by weight of a polycarbonate resin having a weight average molecular weight of 25,000 and 20 parts by weight of the above ABS resin,
AS resin 30 parts by weight, 10 parts by weight of phosphoric acid ester B-
2, 0.2 parts by weight of phosphoric acid ester C-2 was mixed with a Henschel mixer, and then melt-kneaded with a twin-screw extruder set to a cylinder temperature of 250 ° C. to obtain pellets. Using this pellet, injection molding was performed at 250 ° C. to obtain a test piece. Flame retardancy was evaluated using this test piece, and the results are shown in Table 3.

The flame retardancy was evaluated by using the apparatus of the horizontal combustion test method specified in UL-94, the 1/8 inch molded piece was held horizontally, and the flame was a high blue flame without yellow chips. The thickness was adjusted to 1 inch, and the burning speed after 30 seconds of flame contact with the end of the test piece was measured. The coating adhesion was evaluated in the same manner as in Example 1.

[0067]

Comparative Example 3 The procedure of Example 4 was repeated except that the phosphoric acid ester as the component (C) was not used, and the results are shown in Table 3.

[0068]

[Table 3]

[0069]

Example 6 100 parts by weight of the PPE used in Example 1,
15 parts by weight of phosphoric acid ester B-2, phosphoric acid ester C
-3 was mixed by 1 part by weight and melt-kneaded with a twin-screw extruder set to a cylinder temperature of 320 ° C. to obtain pellets. Using this pellet, injection molding was performed at 300 ° C. to obtain a test piece. The test piece was evaluated in the same manner as in Example 1.

As a result, the flame retardancy was V-0 and no smoke was generated during injection molding. Also, there is no coloring of the molded piece,
There was no change in appearance after the hot water test. Further, the number of peels in the paint adhesion test was zero.

[0071]

Example 7 100 parts by weight of the polycarbonate resin used in Example 5, 35 parts by weight of phosphoric acid ester B-1 and 1 part by weight of phosphoric acid ester C-2 were mixed, and the cylinder temperature was set to 250 ° C. The mixture was melt-kneaded with a shaft extruder to obtain pellets. Injection molding was performed using the pellets at 220 ° C. to obtain test pieces. Using this test piece, flame retardancy and coating adhesion were evaluated in the same manner as in Example 1.

As a result, the flame retardancy was V-0, and the number of peelings in the paint adhesion test was 0.

[0073]

According to the present invention, compared with the conventional flame-retardant resin composition, there are no problems such as denaturation, volatilization and bleeding of the flame-retardant, no coloring, and particularly excellent coating adhesion. A flame-retardant thermoplastic resin composition can be provided.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Junko Kakegawa 5-1 Nakasode, Sodegaura-shi, Chiba Asahi Kasei Industrial Co., Ltd.

Claims (10)

[Claims] 1. A thermoplastic resin (A), a general formula (I): (In the formula, Q1, Q2, Q3, and Q4 represent an alkyl group having 1 to 6 carbon atoms, R1 and R2 represent a methyl group, R3 and R4 represent a methyl group, or hydrogen. N represents an integer of 1 or more, n
1, n2 represents an integer of 0 to 2, m1, m2, m3,
m4 independently represents an integer of 0 to 3. ), And (C) the general formula (II) (Here, Q is an aliphatic hydrocarbon residue having 2 to 14 carbon atoms, or an aryl group having 6 to 20 carbon atoms, an alkyl-substituted aryl group, or a divalent residue corresponding to an aralkyl group. Selected from the group: Q5, Q6, Q7
Represents an alkyl group having 1 to 6 carbon atoms. n represents an integer of 0 or more. m5, m6 and m7 are integers from 0 to 3. ) The phosphoric acid ester compound represented by the formula (4), wherein the phosphoric acid ester compound of the component (C) is added to the total amount of the phosphoric acid ester compound of the component (B) and the phosphoric acid ester compound of the component (C). A flame-retardant resin composition having a ratio of 0.1 to 40% by weight. 2. The proportion of the phosphoric acid ester compound of the component (C) is 0.1 to 15% by weight with respect to the total amount of the phosphoric acid ester compound of the component (B) and the phosphoric acid ester compound of the component (C). The flame-retardant resin composition according to claim 1, which is 3. The total amount of the phosphoric acid ester compound of the component (B) and the phosphoric acid ester compound of the component (C) is 1 to 200 parts by weight with respect to 100 parts by weight of the thermoplastic resin (A). The flame-retardant resin composition according to 2 or 3. 4. In the general formula (II) representing the phosphoric acid ester compound as the component (C), Q is represented by the general formula (III): (In the formula, R5 and R6 represent a methyl group, R7 and R8 represent a methyl group, or hydrogen, and n5 and n6 represent an integer of 0 to 2.) The flame-retardant resin composition according to claim 1. Stuff. 5. In the general formula (II) representing the phosphoric acid ester compound as the component (C), Q is represented by the general formula (IV): The flame-retardant resin composition according to claim 1, represented by: 6. A compound represented by the general formula (I), which represents a phosphoric acid ester compound of the component (B), wherein n1 and n2 are 0, R3 and R4 are methyl groups, and a phosphoric acid ester compound of the component (C) is represented. N in the general formula (III) representing Q in the formula (II)
5. N is 5 and n6 and R7 and R8 are methyl groups.
The flame-retardant resin composition described. 7. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polyphenylene ether resin. 8. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a resin composition comprising a polyphenylene ether resin and a polystyrene resin. 9. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a polycarbonate resin. 10. The flame-retardant resin composition according to claim 1, wherein the thermoplastic resin (A) is a resin composition comprising a polycarbonate resin and a polystyrene resin.