JPH0834926A - Flame-resistant resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition excellent in flame-resistance and having high safety by compounding a thermoplastic resin with a phosphorus compound, a silicon-containing compound and a phenolic polymer. CONSTITUTION:This composition contains (A) a thermoplastic resin (e.g. a polycarbonate resin or a polystyrene resin), (B) a phosphorus compound [preferably, a phosphorus compound of the formula (R1 to R4 are each independently H or an organic group, excluding the case of R1=R2=R3=R4=H; X is an organic group of divalent or higher valent; p=0, 1; q is an integer of >=1; r is an integer of >=0)], (C) a silicon-containing compound and (D) a phenolic polymer (e.g. a phenolic resin or a hydroxystyrene polymer) as essential components. Further, preferable compounding ratios of each component are as follows: the component A is 100 pts.wt.; the component B is 1-30 pts.wt.; the component C is 0.05-10 pts.wt. in terms of silicon atom; and the component D is 1-30 pts.wt.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a flame-retardant resin composition. More specifically, it relates to a flame-retardant resin composition obtained by blending a thermoplastic resin with a phosphorus compound, a silicon-containing compound and a phenolic polymer.

[0002]

2. Description of the Related Art Conventionally, flame retardation of thermoplastic resins has been achieved mainly by using halogen-based flame retardants, phosphorus-based flame retardants and antimony trioxide alone or in combination, but especially halogen-based flame retardants. It is known that the flame retardancy is synergistically improved when the above is combined with a phosphorus-based flame retardant. However, when a halogen-based flame retardant or antimony trioxide is used, a highly toxic gas such as hydrogen halide or antimony halide is generated during combustion.

In recent years, many home electric appliances using flame-retardant resin have been popularized in general households, but a flame-retardant resin having high flame-retardant property and high safety that does not generate toxic gas is required. As a halogen-free flame retardant,
For example, attention has been paid to silicone oil or silicone resin. This is because the silicone oil and the silicone resin are not only flame-retardant by themselves, but also do not generate toxic gas during combustion.

Examples of utilizing the properties of silicone include:
For example, the surface of the metal hydroxide is treated with a silane coupling agent to improve the heat resistance of the flame retardant, and halogen-free is achieved by using a crosslinkable silicone oil and a silicone resin called MQ resin. In addition to those reported, those used in combination with phosphorus-based flame retardants have also been reported.

However, these flame retardants also have a drawback in that they are ineffective against styrene resins having a low melt viscosity and cannot prevent dripping during burning. The silicon-containing compound used in the present invention is
It is known as a flame retardant for a thermoplastic resin together with a compound containing phosphorus or nitrogen, but an example using a silicon-containing compound and a phenolic polymer at the same time has not been known so far.

When a chlorine- or bromine-containing compound is used to make a thermoplastic resin flame-retardant, the flame-retardant effect is relatively large, but a toxic or toxic substance is generated when a fire occurs or when incinerated. Since it occurs, it has problems such as making emergency activities and fire fighting activities difficult or causing environmental pollution. Therefore, it is desired to develop a flame-retardant resin containing no chlorine or bromine-containing compound or containing a small amount of chlorine or bromine-containing compound. Further, when an inorganic substance such as antimony trioxide is used as the flame retardant component, there is a problem that the mechanical properties of the flame retardant resin are deteriorated.

As a means for solving these problems, the technique disclosed in JP-A-6-49302 is known.
However, in this technique, the mechanical properties of the resin are deteriorated due to the fact that the halogen-based flame retardant is required in a small amount and that other flame-retardant components are added to reduce the amount of the halogen-based flame retardant used. Are forced to. Further, in the technique disclosed in JP-A-5-302013, a halogen-based flame retardant is not used, but it is necessary to add a phosphorus compound and a char-forming component to the thermoplastic resin in an amount of about 30% by weight. It has a problem of impairing the original performance.

[0008]

SUMMARY OF THE INVENTION The present invention is intended to solve these conventional problems, and an object thereof is to use a flame retardant containing substantially no chlorine or bromine and to have excellent flame retardancy. To provide a resin composition having

[0009]

The inventors of the present invention have shown that a particularly excellent flame retardant effect is exhibited by the combined use of a phosphorus compound, a silicon-containing compound and a phenolic polymer in a thermoplastic resin. The present invention has been found.

That is, the present invention provides (A) a thermoplastic resin,
It is a flame-retardant resin composition in which each component of (B) a phosphorus compound, (C) a silicon-containing compound and (D) a phenolic polymer is essential. In addition, the present invention provides the component (A) 1 described above.
1 to 30 parts by weight of the component (B) per 100 parts by weight,
It is a flame-retardant resin composition obtained by mixing component (C) at a content of 0.05 to 10 parts by weight and component (D) at a ratio of 1 to 30 parts by weight.

The present invention will be described in detail below. The thermoplastic resin used in the present invention can be appropriately selected from known ones. Typical examples among them are polycarbonate resin, polystyrene resin,
ABS resin, polyester resin (PBT, PET)
And (modified) polyethylene, (modified) polypropylene, (modified) ethylene / propylene copolymer resin, polyphenylene ether, polyamide resin, polyacetal, polymethyl methacrylate, etc. It is also possible to use them in combination.

The phosphorus compound (B) used in the present invention is not particularly limited as long as it is a compound having a phosphorus atom, but preferably the following general formula (I),

Embedded image (In the formula, R 1, R 2, R 3 and R 4 are independently of each other,
Representing a hydrogen atom or an organic group, R1 = R2 = R3 = R
Except when 4 = H. X represents a divalent or higher valent organic group, and p
Is 0 or 1, q is an integer of 1 or more, and r is an integer of 0 or more. ) Is an organic phosphorus compound represented by.

In the above formula, the organic group is, for example,
Examples thereof include an alkyl group which may be substituted or not, a cycloalkyl group and an aryl group. When substituted, examples of the substituent include an alkyl group, an alkoxy group, an alkylthio group, and the like, and a group in which these substituents are combined (for example, an arylalkoxyalkyl group) or these substituents. A group in which an oxygen atom, a sulfur atom, a nitrogen atom or the like is bonded and combined (eg, an arylsulfonylaryl group) may be used as a substituent. The divalent or higher valent organic group means a divalent or higher valent group formed by removing one or more hydrogen atoms bonded to carbon atoms from the above-mentioned organic groups. Examples thereof include those derived from alkylene groups, (substituted) phenylene groups, polynuclear phenols such as bisphenols, and the relative positions of two or more free valences are arbitrary.
Particularly preferred are hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxydiphenyl, p, p'-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like.

Illustrating these phosphorus compounds, examples of the phosphoric acid ester include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate. , Trixylenyl phosphate, tris (isopropylphenyl) phosphate, tris (o-phenylphenyl) phosphate, tris (p-phenylphenyl) phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl (2- Ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, o-phenylphenyl dicresylphos Eto, dibutyl phosphate,
Monobutyl phosphate, di-2-ethylhexyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyloxyethyl acid phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate and These condensates and the like can be mentioned.

Examples of the phosphorous acid ester include trimethylphosphite, triethylphosphite, tributylphosphite, tri (2-ethylhexyl) phosphite, tributoxyethylphosphite, trioleylphosphite, triphenylphosphite, tricresylphosphite. Fight, trixylenylphosphite, tris (isopropylphenyl) phosphite, trisnonylphenylphosphite, tris (o-phenylphenyl) phosphite, tris (p-phenylphenyl) phosphite, trinaphthylphosphite, cresyldiphenyl Phosphite, xylenyl diphenyl phosphite, diphenyl (2-ethylhexyl) phosphite, di (isopropylphenyl) phenyl phosphite, o-phenylphenyl dicresi Phosphite, dibutyl phosphite, monobutyl phosphite, di-2-ethylhexyl phosphite, monoisodecyl phosphites and condensates thereof and the like.

Examples of phosphorus compounds other than those mentioned above include triphenylphosphine oxide, tricresylphosphine oxide, diphenyl methanephosphonate and diethyl phenylphosphonate.

These phosphorus compounds may be used alone or in combination of two or more. The blending amount of these phosphorus compounds is 100 parts by weight of the component (A),
A range of 1 to 30 parts by weight is preferable. If the amount is less than 1 part by weight, a sufficient flame retarding effect cannot be obtained, and if the amount is more than 30 parts by weight, the heat resistance of the obtained composition is remarkably reduced.
This may cause adverse effects such as an increase in volatile matter during molding.

The silicon-containing compound used in the present invention may be separate from the thermoplastic resin of the present invention or may be contained as a structural unit. Further, the silicon-containing compound may be either an organic silicon-containing compound or an inorganic silicon-containing compound, and if it is a compound containing silicon, a wide range of molecular weights, for example, several hundreds to several millions can be used. When blended separately with the thermoplastic resin, the form may be any of oil, varnish, gum, resin and the like.

The thermoplastic resin having a silicon-containing structure is not particularly limited, but silicone rubber-based graft polymer, silicone-modified polycarbonate-based resin, polyarylene silicon, methacryloxy group-modified silicone and vinyl-based resin Examples thereof include a combination, a copolymer of an amino-modified silicone and a maleic anhydride reaction product, and the like.

The compounding amount of these silicon-containing compounds is
0.05 as a silicon content per 100 parts by weight of component (A)
The range of 10 to 10 parts by weight is preferable. If the amount is less than 0.05 parts by weight, a sufficient flame retardant effect cannot be obtained, and if the amount is more than 10 parts by weight, the effect is not significantly increased, and further, the mechanical properties of the thermoplastic resin are deteriorated. Cause harmful effects.

The phenolic polymer used in the present invention is a polymer composed of phenol and / or a phenol derivative and other compound capable of forming a copolymer as required, and includes phenol resin and hydroxystyrene-based polymer. Coalescence, polyphenylene ether and the like.

The phenol resin is not particularly limited, but it can be obtained by reacting phenols with aldehydes and / or ketones under an acidic or alkaline catalyst by a known method. As phenols, phenol,
Cresol, xylenol, ethylphenol, propylphenol, butylphenol, amylphenol,
Nonylphenol, phenylphenol, phenoxyphenol, hydroquinone, resorcinol, catechol, dihydroxydiphenyl, bis (hydroxyphenyl) pentane, dihydroxydiphenylmethane, bis (hydroxyphenyl) butane, dihydroxydiphenylsulfone, dihydroxydiphenylketone, bis (hydroxyphenyl) propane, etc., And mixtures thereof.

The aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, glyoxal and the like. Further, examples of the ketones include acetone.

In the present invention, both a resol type resin and a novolac type phenolic resin can be used, but a novolac type phenolic resin is preferably used. It is also possible to use a novolac type phenol resin obtained by replacing a part or all of aldehyde and / or ketone with a diol compound and reacting with a phenol. Examples of preferable diol compounds include p-xylene-α, α′-diol and the like.

As the hydroxystyrene-based polymer, the following general formula (II),

Embedded image (In the formula, R1 to R4 represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group, a cyclohexyl group or an alkylphenyl group, m represents an integer of 1 to 5, and n represents 0 to 4
Represents the integer. And a polymer of a monomer represented by the formula (1). Further, not only a homopolymer of hydroxystyrene but also a copolymer of hydroxystyrene and another comonomer such as maleic anhydride, styrene, acrylonitrile, acrylic acid, methacrylic acid, acrylamide, acrylic acid ester, and methacrylic acid ester. Also includes.

The blending amount of these phenolic polymers is preferably in the range of 1 to 30 parts by weight per 100 parts by weight of the component (A). If the amount is less than 1 part by weight, a sufficient drip preventing effect cannot be obtained, and if the amount is more than 30 parts by weight, the resulting composition may have a significant decrease in impact resistance.

There is no particular limitation on the method of mixing the resin and the flame retardant, and any means for making them uniform can be adopted. For example, mixing, kneading, and the like using various mixing machines such as an extruder, a Henschel mixer, a Banbury mixer, a kneader, and a heating roll can be appropriately adopted.

In the present invention, if necessary, various fillers, additives and the like can be blended in an amount such that the effect is exhibited within the range of not impairing the flame retardancy. Examples thereof are fluororesin, glass fiber, asbestos, carbon fiber, aromatic polyamide fiber, potassium titanate whisker fiber, metal fiber, ceramics fiber, boron whisker fiber and other fibrous fillers, mica, silica, talc, clay, Fillers such as calcium carbonate, glass beads, glass balloons and glass flakes, mold release agents, lubricants, plasticizers, UV absorbers, light stabilizers, antioxidants, heat stabilizers, antiaging agents,
Examples include additives such as dyeing agents (face). Furthermore, an impact strength improver for improving the properties of the polymer blend,
A compatibilizing component and the like can also be added.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples. Examples 1 to 6 and Comparative Examples 1 to 4 According to the formulations shown in Table 1, after mixing with a Henschel mixer, a 30φ twin-screw extruder (PCM-30, manufactured by Ikegai Tekko KK).
Was melt-kneaded and extruded at 220 to 280 ° C., and pelletized by a pelletizer. A test piece is produced from the pellets thus obtained using an injection molding machine,
The flammability was evaluated. The results are shown in Table 1.

In the UL combustion test, a 127 mm × 12.7 mm × 1.6 mm combustion test piece was produced from the obtained pellets by injection molding, and subject 94 (UL-94) vertical of Underwriters Laboratory, Inc., USA was prepared. It measured according to a combustion test.

[0031]

[Table 1]

The raw materials in Table 1 are as follows. Thermoplastic resin (1): AS resin AS-W manufactured by Denki Kagaku Kogyo Co., Ltd. Thermoplastic resin (2): Modified maleimide resin MS-L2A manufactured by Denki Kagaku Kogyo Co., Ltd. ABS resin GR manufactured by Denki Kagaku Kogyo -G
T-14 Thermoplastic Resin (4): Mitsubishi Rayon Co., Ltd. Silicone / Acrylic Rubber Graft Copolymer Metabrene S-2001 Phosphorus Compound: Triphenyl Phosphate, Daihachi Chemical Industry Co., Ltd. Silicon-containing Compound: Toray Dow Silicone Resin Powder Trefill R-910

Phenol polymer (1): novolac type phenol resin MEH7800 manufactured by Meiwa Kasei Co., Ltd. Weight average molecular weight 1
000, the average structural formula is represented by the following formula (III).

Embedded image

Phenol polymer (2): Polyphenylene ether YPX-100L manufactured by Mitsubishi Gas Chemical Co., Ltd. Phenol polymer (3): p-vinylphenol polymer Marker Linker M manufactured by Maruzen Petrochemical Co., Ltd.

As for the silicon content, Examples 1 and 2 are examples of blending as a silicon-containing graft polymer, and Examples 3 to 4 are examples of blending separately from the thermoplastic resin. In any of the blending methods, a remarkable improvement in flame retardancy is observed as compared with the comparative example. Examples 5 to 6 are cases in which the type of polyphenol-based polymer used was changed, and in all cases, the flame retardant effect is large.

[0036]

As described above, the thermoplastic resin is a phosphorus compound,
By blending the silicon-containing compound and the phenolic polymer, the flame retardancy of the thermoplastic resin can be greatly improved. Further, the silicon-containing compound may be contained as a structural unit of the thermoplastic resin, and in the case of the raw material, excellent flame retardancy can be obtained with a small amount of the flame retardant compounded.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display area C08L 61:06)

Claims (2)

[Claims] 1. The following (A), (B), (C) and (D)
A flame-retardant resin composition containing each of the above components as essential components. (A) Thermoplastic resin (B) Phosphorus compound (C) Silicon-containing compound (D) Phenolic polymer 2. The composition according to claim 1, wherein the component (B) is 1 to 30 parts by weight, the component (C) is a silicon content in an amount of 0.05 to 10 parts by weight, and (D) per 100 parts by weight of the component (A). A flame-retardant resin composition obtained by mixing the components in a ratio of 1 to 30 parts by weight.