JPH0753879A - Flame retardant resin composition - Google Patents

Abstract

PURPOSE:To obtain the composition, containing a thermoplastic resin, a specific polymer and a flame retardant in respective specified proportions, excellent in drip-proof effects in combustion and balance among flame retardancy and light and impact resistances. CONSTITUTION:This flame retardant resin composition comprises (A) 100 pts.wt. thermoplastic resin (preferably polystyrene, polyethylene, etc.), (B) 0.05-1 pt.wt. polymer containing a compound unit expressed by the formula (R1 is H or an alkyl) as a constituent component (e.g. a phenol-formaldehyde novolak resin) and (C) 0.1-30 pts.wt. flame retardant (preferably bisphenol A polycresyl phosphate, etc.). Furthermore, the component (B) has preferably 85-140 deg.C softening point and other drip-proof agents such as polytetrafluoroethylene are preferably used in combination with the component (B) to provide effects thereof.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having excellent flame retardancy.

[0002]

2. Description of the Related Art With the strengthening of flame-retardant regulations, flame-retardant technology for resins has become an important technology in various fields, particularly in OA fields such as computers, word processors and copying machines, and televisions and game machines. It is becoming one of the indispensable characteristics in the field of general home electric appliances. Underwriter Laboratories (Underwriter Laboratories)
In order to rank the resin to a high flame retardancy level in the UL flammability test (UL94) under the regulations, it is important that the test piece does not drip in the process of the UL flammability test, and it is necessary to prevent the fire from spreading in an actual fire. In order to prevent dripping, it is an important issue to prevent resin dripping.

In response to these demands, a kind of thermoplastic resin represented by a polycarbonate resin is added with an anti-dripping agent for the purpose of preventing the resin from dripping during combustion. For example, the resin compositions described in JP-B-59-36657 and JP-A-60-13844 are polytetrafluoroethylene, JP-A-3-19095.
In the resin composition described in JP-A-8, a silicone resin is added for the purpose of preventing dripping, but these have inherently poor compatibility with the resin and have the drawback of lowering the mechanical properties and are economical. However, there is a disadvantage that it is disadvantageous.

As another method, US Pat. No. 4,632,946 describes a flame-retardant resin comprising a mixture of a thermoplastic resin, a phosphorus compound and a relatively large amount of a phenol novolac resin and a nitrogen-containing compound. Further, US Pat. No. 4,618,636 discloses a flame-retardant resin comprising a mixture of a rubber-reinforced aromatic vinyl resin, a halogen compound, a metal oxide and a phenol novolac resin.

However, since these flame-retardant resins cannot provide satisfactory light resistance and impact resistance, there is a problem in practical use as a housing material. Furthermore, JP-A-4
No. 45143 discloses a flame-retardant resin containing no halogen by combining a styrene resin with a phosphate compound and a thermosetting resin.
In this case as well, a large amount of thermosetting resin and phosphate compound are required to obtain the required flame retardancy, so that there is a problem that the balance between light resistance, impact resistance and heat resistance is poor.

[0006]

The problem to be solved by the present invention is to provide a flame-retardant resin which has an excellent effect of preventing dripping and which has an excellent balance of flame resistance, light resistance and impact resistance. Is to provide.

[0007]

Means for Solving the Problems As a result of intensive studies for solving the above problems, the present inventors have found that when a polymer represented by the following general formula (1) is added to a thermoplastic resin in a trace amount: Since the effect of preventing dripping during combustion is effectively exhibited and this property can be obtained by adding a small amount thereof, the balance of flame resistance, light resistance and impact resistance is particularly achieved without sacrificing other properties. The present invention has been completed by finding out that it becomes an excellent composition.

That is, the present invention relates to (A) thermoplastic resin 1
0.05 parts by weight of a polymer containing 00 parts by weight, and (B) a compound unit represented by the following general formula (1) as a constituent.
Parts by weight, and

[0009]

[Chemical 2] (R ₁ is a group selected from hydrogen or _one of alkyl groups) (C) Flame retardant A flame-retardant resin composition comprising 0.1 to 30 parts by weight is provided.

According to the present invention, addition of a small amount of the polymer represented by the above formula (1) has a sufficient anti-dripping effect, so that deterioration of mechanical strength and light resistance can be minimized. And the required flame retardancy is obtained.

The present invention will be described in detail below. The thermoplastic resin used in the present invention may be a homopolymer or a copolymer, and may be a rubber-reinforced type. Also, a blend of a plurality of resins may be used. Preferred thermoplastic resins are polystyrene, styrene-acrylonitrile copolymers, and polymers and copolymers of vinyl compounds, as represented by polymethylmethacrylate,
Polyphenylene ether, polyethylene, polypropylene, polyoxymethylene, polyamide, polyurethane,
It is also possible to use a combination of two or more of polyester, polycarbonate, those obtained by reinforcing these with a rubbery polymer, and an alloy of polystyrene and polyphenylene ether.

Here, as the vinyl compound, styrene,
Aromatic vinyl compounds such as α-methylstyrene and paramethylstyrene, alkyl (meth) acrylates such as methyl methacrylate, methyl acrylate, butyl acrylate and ethyl acrylate, (meth) acrylic acid such as acrylic acid and methacrylic acid, acrylonitrile,
Vinyl cyanide monomers such as methacrylonitrile, α, β-unsaturated carboxylic acids such as maleic anhydride, maleimide-based monomers such as N-phenylmaleimide, N-methylmaleimide, N-cyclohexylmaleimide, glycidyl methacrylate, etc. Examples of the glycidyl group-containing monomer include, but are preferably aromatic vinyl compounds, alkyl (meth) acrylates, vinyl cyanide monomers, maleimide-based monomers, more preferably styrene, acrylonitrile, N-phenylmaleimide and butyl acrylate. These vinyl compounds may be used alone or in combination of two or more.

As a preferable rubbery polymer, any one having a glass transition temperature of 0 ° C. or lower can be used.
Specifically, dibutadiene rubber such as polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, acrylic rubber such as polybutyl acrylate, polyisoprene, polychloroprene, ethylene-propylene rubber, ethylene-propylene- Block copolymers such as diene terpolymer rubber, styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, and hydrogenated products thereof can be used.

The polymer (B) used in the present invention is a polymer containing the compound unit represented by the general formula (1) as a constituent, and is generally synthesized by a condensation reaction of phenol and aldehyde. A typical example is a so-called phenol novolac resin.

Specifically, phenol formaldehyde novolac resin, cresol novolac resin, tert-butylphenol formaldehyde de novolac resin, paraoctylphenol formaldehyde novolac resin, cyanophenol formaldehyde novolac resin and their copolymers, and the formaldehyde part are acetaldehyde. It is also possible to use those substituted with an aldehyde having a large number of carbon atoms such as or n-propanol, but formaldehyde is preferable.

These novolac resins may be used either individually or in combination of two or more. The phenol novolac resin in the present invention is thermoplastic and has a softening point. The preferred softening point of the polymer (B) is 7
0 to 150 ° C, more preferable softening point is 85 to 140 ° C
Is.

The content of the polymer (B) is the same as that of the component (A).
When the amount is 00 parts by weight, it must be in the range of 0.05 to 1 part by weight. If the amount is less than 0.05 parts by weight, the effect of preventing dripping during combustion is insufficient and high flame retardancy cannot be obtained. If it exceeds 1 part by weight, the light resistance and impact resistance of the resin are deteriorated. Further, if it exceeds 5 parts by weight, the heat resistance is further deteriorated. Further, it is also effective to use other anti-dripping agents such as polytetrafluoroethylene, silicone resin, glass fiber, carbon fiber and the like.

(C) in the composition of the present invention is a so-called general flame retardant, and in addition to phosphorus compounds and halogen organic compounds, nitrogen-containing organic compounds such as melamine, magnesium hydroxide, aluminum hydroxide and the like. Inorganic compounds, arsenic oxide, antimony oxide, bismuth oxide. Further, metal oxides such as iron oxide, zinc oxide and tin oxide, fibers such as carbon fiber and glass fiber, expanded graphite, silica, silica-based glass melts and the like are used, but preferably phosphorus compounds or halogen-containing compounds. It is a combination of an organic compound and a halogen organic compound and antimony oxide.

Examples of the phosphorus-based flame retardant include trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, trihexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate,
Phosphoric acid esters such as tricresyl phosphate, trixylenyl phosphate, dimethylethyl phosphate, methyldibutyl phosphate, ethyldipropylphosphate, hydroxyphenyldiphenylphosphate and compounds modified with these various substituents, or red phosphorus, phosphine, Phosphorous acid, phosphorous acid, metaphosphoric acid,
Inorganic phosphorus compounds such as pyrophosphoric acid and anhydrous phosphoric acid, or general formula

[0020]

[Chemical 3] (In the formula, R ₁ , R ₂ and R ₃ represent the same or different hydrocarbon residues, R ₄ , R ₅ , R ₆ and R ₇ represent a hydrogen atom or a hydrocarbon residue, and R ₄ , R ₅ , R ₆ and R ₇ may be the same or different, and n represents the degree of polymerization.)
Examples of the condensed type phosphoric acid ester compound represented by the formula (2) are preferred. In the formula (2), R ₁ , R ₂ and R ₃ are all phenyl groups, and R ₄ , R ₅ , R ₆ and R ₇ Are phosphoric acid ester compounds in which all are hydrogen atoms. More preferred are the following general formulas R _{1 to} R ₄
Is a methyl group, bisphenol A polycresyl phosphate.

[0021]

[Chemical 4]

These phosphorus compounds are used alone or
A combination of two or more species can be used. The content of the phosphorus compound is determined according to the required level of flame retardancy, but the total amount of the resin composition is 0.1 to 100 parts by weight.
It must be 30 parts by weight. If it is less than 0.1 part by weight, the required flame retardant effect cannot be exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin is lowered. Preferably 0.5
To 20 parts by weight, and as a particularly preferable range,
This is the case where the phosphorus content is in the range of 0.5 to 15 parts by weight, and particularly 5 to 20 in the case of a phosphoric acid ester compound.
The range is parts by weight.

Examples of halogen-containing organic compounds include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, octabromodiphenyl oxide, tetrabromobisphenol A, tetrabromo. There are phthalimide, hexabromobutene, trichlorotetrabromophenyl-triphosphate, and hexabromocyclododecane, but a halogen-containing organic compound having the structure of the following general formula (4) is preferable.

[0024]

[Chemical 5] n = 0 or a natural number, X independently represents chlorine or bromine, i, j, k, and l are each an integer of 1 to 4, and R
And R'independently represent hydrogen, a methyl group, an epoxypropyl group of the following formula (5),

[0025]

[Chemical 6] Phenyl group or the following formula (6) (where m is 0,
1, 2, or 3).

[0026]

[Chemical 7] Particularly preferred are halogen compounds represented by the following general formula (7).

[0027]

[Chemical 8] n = 0 or a natural number, R and R ′ are both epoxypropyl groups of the following formula (5),

[0028]

[Chemical 9] Alternatively, it is a group of the following formula (8).

[0029]

[Chemical 10]

The content of the halogen-based compound is determined according to the required level of flame retardancy, but the total amount of the resin composition is 1
It is necessary to be 0.1 to 30 parts by weight with respect to 00 parts by weight. If it is less than 0.1 part by weight, the required flame retardant effect cannot be exhibited. If it exceeds 30 parts by weight, the mechanical strength of the resin is lowered. It is preferably in the range of 0.5 to 20 parts by weight, and particularly preferably in the range of 1 to 15 parts by weight.

For the purpose of modifying the resin, the resin composition of the present invention contains a conventional additive, that is, a lubricant, if necessary.
Antistatic agents, antioxidants, ultraviolet absorbers, colorants, titanium oxide, surface modifiers, dispersants, plasticizers, stabilizers and the like can be added. The method for producing the resin composition in the present invention is not particularly limited, and the resin composition can be produced by an ordinary method, for example, melt blending by extrusion kneading.

[0032]

The present invention will be described in detail with reference to the following examples. (Hereinafter, "part" means "part by weight"). (Thermoplastic resin A-1) Butadiene component 10% by weight Styrene component 66% by weight Acrylonitrile component 24% by weight ABS resin (acrylonitrile-butadiene-
Styrene resin).

(Thermoplastic resin A-2) HIPS resin (high-impact polystyrene resin) consisting of butadiene rubber component 10% by weight and styrene unit 90% by weight.

(Thermoplastic resin A-3) AAS resin (acrylonitrile-butyl acrylate-styrene resin) consisting of butyl acrylate rubber component 20% by weight acrylonitrile unit 24% by weight styrene unit 56% by weight.

(Thermoplastic resin A-4) A polycarbonate resin having a weight average molecular weight of 24,500.

(Polymer B) Phenol formaldehyde novolac resin B-1: Softening point 102 ° C. B-2: Softening point 108 ° C. B-3: Softening point 130 ° C.

(Flame Retardant C) (Phosphorus Compound) C-1: Triphenyl Phosphate C-2: Resorcin Polyphosphate In the formula (2) described herein, R _{1 to} R ₃ are all phenyl groups and R ₄ to A mixture of compounds of n = 1 and 2 wherein R ₇ is H. C-3: Bisphenol A Polycresyl Phosphate A compound in which all of R _{1 to} R ₄ in the formula (3) described herein are methyl groups.

(Halogen-Containing Organic Compound) C-4: A tribromphenol-terminated halogen-containing compound (softening point 100 ° C.) in which R and R ′ in the general formula (7) are both represented by the formula (8). C-5: A halogen-containing compound (softening point 102 ° C.) in which R and R ′ in the general formula (7) both have an epoxy group represented by the formula (5).

Examples 1-6, Comparative Examples 1-2 In addition to the composition (unit is parts by weight) of the resin prepared as described above in Table 1, all of Examples 1-6 and Comparative Examples 1-2. In the above, 5.2 parts of antimony trioxide, 0.4 part of a benzotriazole type ultraviolet absorber and 0.3 part of a hindered amine type light stabilizer were blended and kneaded with a twin-screw extruder in which a cylinder temperature was set to 220 ° C. After granulating, injection molding machine (cylinder temperature 220 ℃, mold temperature 45 ℃)
Was used to obtain a test piece for measuring physical properties. In addition, test pieces for combustion test and light resistance test were obtained using a compression molding machine at 195 ° C. The results of evaluation using the obtained test pieces are shown in Table 1.

Flame retardance: Measured based on the UL94 standard vertical combustion test (thickness 1/12 inch). V-0 or less x
And Regarding the presence / absence of dropped substances, "Yes" means that the resin drops during the test, and "No" means that there is no dropped substance.
It was determined. It should be noted that the one without dripping has a smaller spread of fire and is preferable in practical use. Light resistance: A color difference (ΔE) between before exposure and after exposure for 150 hours under conditions of 63 ° C. without rain was measured using a xenon weather meter. A smaller value indicates less discoloration, which is practically preferable. Izod impact value: ASTM D256, test piece thickness 1
/ 4 inch, with notch Unit kg ・ cm / cm

[0041]

[Table 1]

Examples 7 to 11 and Comparative Examples 3 to 4 The resins prepared as described above were blended in the composition shown in Table 2 (unit: parts by weight), and the twin-screw extruder was set to a cylinder temperature of 240 ° C. After kneading and granulating in (1), a test piece for measuring physical properties was obtained using an injection molding machine (cylinder temperature: 250 ° C., mold temperature: 65 ° C.). Moreover, the test piece for a combustion test and a light resistance test was obtained using the 220 degreeC compression molding machine. The results of evaluation using the obtained test pieces are shown in Table 2.

Flame retardance: Measured based on the UL94 vertical combustion test (thickness 1/12 inch). V-0 or less x
And Regarding the presence / absence of dropped substances, "Yes" means that the resin drops during the test, and "No" means that there is no dropped substance.
It was determined. It should be noted that the one without dripping has a smaller spread of fire and is preferable in practical use. Light resistance: A color difference (ΔE) between before exposure and after exposure for 150 hours under conditions of 63 ° C. without rain was measured using a xenon weather meter. A smaller value indicates less discoloration, which is practically preferable. Izod impact value: ASTM D256, test piece thickness 1
/ 8 inch, with notch Unit kg / cm / cm

[0044]

[Table 2]

As shown above, it is clear from the examples that the resin of the present invention has an excellent balance of flame retardancy, impact resistance and light resistance.

[0046]

The flame-retardant resin of the present invention has excellent flame retardancy,
It has excellent properties as a flame-retardant resin with a balance of light resistance and impact resistance.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 25/08 LEA 55/02 LLA 69/00 LPQ // (C08L 25/08 61:06) ( C08L 69/00 61:06)

Claims (2)

[Claims] 1. A polymer containing (A) 100 parts by weight of a thermoplastic resin, and (B) a polymer containing a compound unit represented by the following general formula (1) as a constituent, and: 1] (R ₁ is a group selected from _one of hydrogen and alkyl groups) (C) Flame retardant resin composition comprising 0.1 to 30 parts by weight of flame retardant. 2. The flame retardant resin composition according to claim 1, wherein the flame retardant comprises a phosphorus compound and / or a halogen-containing organic compound.