JP2945551B2 - Flame retardant resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant resin composition, and more particularly, to a method which does not generate toxic gas or flame-droplets upon combustion.
The present invention relates to a highly safe flame-retardant resin composition.

[0002]

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

Therefore, in recent years, when many home appliances using flame-retardant resin have become widespread in ordinary households, a flame-retardant resin which is not only high in flame retardancy but high in safety and does not generate toxic gas is required. I was Under such circumstances, the pursuit of flame retardancy using non-halogen-based substances has been actively studied, and flame retardancy using silicone oil or silicone resin has recently attracted attention. This is because silicone oil and silicone resin are not only flame retardant themselves,
This is because it is a very low-toxic compound that does not generate toxic gas even during combustion.

[0004] Examples of the use of such properties of silicone include, for example, an example in which the surface of a metal hydroxide is surface-treated with a silane coupling agent to increase the heat resistance of a flame retardant, and a crosslinkable silicone oil. In addition to those which have achieved non-halogenation using a silicone resin called a so-called MQ resin, those which are used in combination with a phosphorus-based flame retardant have also been reported.

[0005]

However, these flame retardants also have a poor effect on styrene-based resins having a high melt viscosity, and have the drawback that, in particular, they cannot prevent flame-burning drippings during combustion. Was. Therefore, the present inventor
As a result of examining flame retardancy using various silicone compounds, CH ₂ = CHSiO _1.5 units or CH ₂ =
When a combination of an organopolysiloxane resin having a CH.CH ₃ SiO unit and a molecular weight in a certain range, a flame retardant, and, if necessary, a metal hydroxide, the generation of flame-burnt drippings is remarkably suppressed. This led to the completion of the present invention. Accordingly, an object of the present invention is to provide a flame-retardant resin composition which not only generates no toxic gas at the time of combustion but also significantly reduces the generation of flame-burning drippings.

[0006]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
Styrene-based thermoplastic resin: 100 parts by weight, CH ₂ =
CHSiO _1.5 units or CH ₂ ＣＨCH (CH ₃ ) Si
Hydroxy Motomata terminated while have a O units alkoxy
Organopolysiloxane resin having a molecular weight of 500 to 100,000 having 1 to 50 parts by weight: 1 to 50 parts by weight, at least one flame retardant selected from potassium pearl fluoroalkanesulfonate and a brominated flame retardant polycarbonate resin:
Achieved by a flame-retardant resin composition comprising 0.1 to 20 parts by weight and a metal hydroxide: 0 to 200 parts by weight.

The styrenic thermoplastic resin used in the present invention can be appropriately selected from known ones. In particular, polystyrene, high-strength polystyrene, butadiene / styrene copolymer, acrylonitrile / styrene copolymer, and acrylonitrile -Butadiene-styrene copolymers and the like are mentioned as suitable resins, and further, mixtures of these with other polyolefin-based resins and polycarbonate resins are also used. The organopolysiloxane resin as a component used in the present invention has a polymerizable vinyl group and has CH ₂ CHSiO _1.5 units or CH ₂ ＣＨCHＣＨCH ₃ SiO units,
Preferably, C ₆ H ₅ SiO _1.5 units and C ₆ H _5.
It contains CH ₃ SiO units or (C ₆ H ₅ ) ₂ Si units. In particular, phenyl vinyl polysiloxane resin has a high affinity with the above-mentioned thermoplastic resin, and is preferable in terms of molding workability.

Further, the components used in the present invention include:
CH ₂ ＣＨCHSiO _1.5 units or CH ₂ ＣＨCH ・ C
In addition to H ₃ SiO units, SiO ₂ units and (CH ₃ ) ₃
Organopolysiloxane resins which also contain _0.5 units of SiO can be used. This resin uses the conventional CH ₂
ＣＨCH (CH ₃ ) ₂ SiO is more advantageous in terms of economy and workability than organopolysiloxane composed of _0.5 units and SiO ₂ units.

The molecular weight of the organopolysiloxane resin as a component is from 500 to 100,000, preferably from 1,000
0 to 20,000. Specific examples of the above-mentioned organopolysiloxane resin include hydrolyzates of the following chlorosilanes or alkoxysilanes such as methoxysilane and ethoxysilane, and equilibrated products of cyclic siloxanes. Here, X is Cl, a methoxy group, an ethoxy group or the like, and n is an integer of 3 to 10.

CH ₂ ＣＨCHSiX ₃ and C ₆ H ₅ SiX ₃
Co-hydrolysate of CH ₂ ＣＨCHSIX ₃ and C ₆ H ₅ .C
H ₃ cohydrolyzate of SiX _2, CH ₂ = CHSiX ₃ and (C ₆ H _{5) 2} co-hydrolyzate of SiX _2, CH ₂ = CH
Co-hydrolysate of Si (CH ₃ ) X ₂ and C ₆ H ₅ SiX ₃ , (CH ₂ ＣＨCHSi (CH ₃ ) O) _n and C ₆ H ₅ S
An equilibrated product of iO _1.5 , CH ₂ ＣＨCHSiO _1.5 and [(C
₆ H ₅ ) ₂ SiO] _n equilibrium, CH ₂ ＣＨCHSiO
Equilibrium of _1.5 and (C ₆ H ₅ Si (CH ₃ ) O) _n , methyl silicate, (CH ₃ ) ₃ SiX and CH ₂ ＣＨCH
Co-hydrolyzate with SiX ₃ , methyl silicate, (CH
₃ ) Co-hydrolysates with ₃ SiX and CH ₂ ＣＨCHSi (CH ₃ ) X ₂ .

[0011] These end groups are silanol group, a methoxy group, an ethoxy group, an isopropoxy group, may be any of such isobutoxy group. These organopolysiloxanes used in the present invention are organopolysiloxanes that can be cured in the range of 100 ° C. to 300 ° C., and have the ability to start curing when the resin burns and prevent the resin from dripping by melting. It is. These organopolysiloxanes are liquids or solids at room temperature, and contain an appropriate amount of the above-mentioned alkoxy group or hydroxy group at the siloxane terminal so as to be cured at a high temperature.

For the above curing reaction, a catalyst may be added as necessary. These organopolysiloxanes are added in an amount of from 1 to 50 parts by weight, preferably from 5 to 10 parts by weight, based on 100 parts by weight of the thermoplastic resin. If the addition is less than 1 part by weight, the effect of preventing drip, which is a feature of the present invention, is insufficient. If the addition is more than 50 parts by weight, the strength of the resin is significantly impaired, and thus it is not suitable.

Examples of the flame retardant component used in the present invention include a sulfonic acid flame retardant and a brominated flame retardant polycarbonate resin. Is preferred. In addition, a flame retardant such as a flame retardant polycarbonate resin produced using brominated bisphenol A as a raw material is also suitable. In the present invention, in addition to these flame retardants, phosphate compounds such as triphenyl phosphate, tricresyl phosphate and cresyl diphenyl phosphate; and inorganic phosphorus flame retardants such as polyphosphate, red phosphorus, and ammonium polyphosphate. May be mixed.

The flame retardant is added in an amount of 0.1 to 20 parts by weight based on 100 parts by weight of the thermoplastic resin.
It is preferable to add 0 parts by weight. When the amount is less than 0.1 part by weight, the flame retardant effect is low. When the amount is more than 20 parts by weight, the resin strength is reduced and the appearance of the molded resin may be impaired. In the present invention, a metal hydroxide may be added as an inorganic flame retardant for the purpose of further improving flame retardancy.

The requirements for inorganic flame retardants include:
Metal hydroxides satisfy these requirements, being non-toxic, low in smoke emission, and not generating corrosive toxic gases on combustion. As the metal hydroxide used in the present invention, aluminum trihydrate and magnesium dihydrate are preferable, and although the flame retardancy is slightly lowered, calcium aluminate and the like are also used. If use is permitted, antimony trioxide can be used as appropriate.

Among these, magnesium dihydrate is most preferably used when the synthetic resin requires melt kneading at a high temperature. This is because, when aluminum trihydrate is used, foaming may occur in the molding resin because the release of water of crystallization starts at around 180 ° C. That is, the release of water of crystallization of magnesium dihydrate is 350 ° C., which is higher than the plasticization temperature of a commonly used general-purpose resin.

In addition, since metal hydroxides may absorb moisture in the air and impair the insulation of the resin, if water-resistant insulation is required, silane treatment or treatment with higher fatty acids is performed. However, in the present invention, since the curable polysiloxane is simultaneously kneaded with the resin, the above treatment is not particularly required. The metal hydroxide is added in an amount of 0 to 200 parts by weight based on 100 parts by weight of the thermoplastic resin. However, the addition of 200 parts by weight or more is not preferable because the resin strength is significantly deteriorated.

In the present invention, what should be noted when mixing the flame retardant into the resin is the temperature of the resin. Especially,
Since the curable polysiloxane has a wide curing temperature range from 150 to 300 ° C., it is necessary to use a different flame retardant for each curable polysiloxane. In addition, it is necessary to determine the kneading temperature according to the decomposition temperature of each flame retardant, and it is preferable to add the flame retardant first from the viewpoint of handling the resin at a temperature as low as possible. In this case, all the flame retardants may be mixed in advance into a paste and then added to the resin.

[0019]

The flame retardant resin composition of the present invention exhibits a small amount the amount of the flame retardant, on which does not generate toxic gases during combustion, vinyl group-containing polysiloxane radical polymerization to a gel structure during combustion Not only a hydroxyl group or an
Since it has a lucoxy group, it cures at a high temperature, so that dripping of the fired product is significantly reduced.

[0020]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Embodiment 1 Standard grade polystyrene 1
(C ₆ H ₅ SiO _1.5 ) _0.8 (CH ₂ =
CHSiO _1.5 ) _0.2 , end-terminated with silanol groups, softening point of 80 ° C. and average molecular weight of 2,000
10 parts by weight of an organopolysiloxane, 0.5 parts by weight of potassium perfluorobutanesulfonate (C ₄ F ₉ SO ₃ K), and 100 parts by weight of aluminum hydroxide,
After melt-kneading at 170 ° C., injection molding was performed at a nozzle temperature of 185 ° C.

This molded product was cut into a size of 127 × 12.7 × 3 mm, and its flame retardancy was judged by the following V rating of UL-94 (flammability test for classification of substances according to the notification of the underwriter laboratory (Bulletin)). did. V-0: The maximum burning time after removing the ignition flame is within 10 seconds, the average flaming combustion and / or non-flaming combustion must not exceed 5 seconds, and all test pieces Shall not drip particles that ignite absorbent cotton.

VI: The maximum burning time after removing the ignition flame is within 30 seconds, the average flaming combustion and / or flameless combustion must not exceed 25 seconds, and all The test piece shall not be dripped with particles that ignite absorbent cotton. V-II: The maximum burning time after removing the ignition flame is within 30 seconds, the average flaming combustion and / or non-flaming combustion must not exceed 25 seconds and at least one test Pieces may drip particles that ignite absorbent cotton. The results of the determination are as shown in Table 1.

Embodiment 2 FIG. The average composition formula is (Me ₃ SiO
_{0.5) 0.4 (CH 2 = CHSiO} 1.5) 0.1 (Si
O ₂ ) A test piece was prepared in exactly the same manner as in Example 1 except that an organopolysiloxane having an average molecular weight of 3,000, which was represented by _0.5 and whose terminal was blocked with a silanol group, was used to determine the flame retardancy. did. The results are as shown in Table 1.

Comparative Example 1. Standard grade polystyrene 1
Then, 0.5 parts by weight of potassium perfluorobutanesulfonate and 100 parts by weight of aluminum hydroxide were added to 00 parts by weight and melt-kneaded at 170 ° C.
Injection molding was performed at 5 ° C. A test piece was prepared from this molded article in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1.

Comparative Example 2 Standard grade polystyrene 1
100 parts by weight of aluminum hydroxide was added to 100 parts by weight of aluminum hydroxide, and the mixture was melt-kneaded at 170 ° C., and then pressed and molded at 185 ° C. A test piece was prepared from this molded article in exactly the same manner as in Example 1, and the flame retardancy was determined. The results are as shown in Table 1.

[0027]

[Table 1] ─────────────────────────────────── Sample judgment drip ──────── ─────────────────────────── Example 1 No V-0 Example 2 No V-0 Comparative Example 1 V-II Yes Comparative Example 2 With combustion ───────────────────────────────────

──────────────────────────────────────────────────の Continuing on the front page (51) Int.Cl. ⁶ Identification code FI (C08L 25/04 83:07 69:00) (72) Inventor Mitsuhiro Takada 1-chome, Hitomi, Matsuida-cho, Usui-gun, Gunma Prefecture 10 Shinetsu (72) Inventor Hiroshi Tsumura 2-13-1 Isobe, Annaka-shi, Gunma Prefecture Isobe Plant, Shin-Etsu Chemical Co., Ltd. (56) References JP-A 61-241344 ( JP, A) JP-A-50-78643 (JP, A) JP-A-63-297462 (JP, A) JP-A-3-199251 (JP, A) JP-A-59-500099 (JP, A) (58) ) Surveyed field (Int.Cl. ⁶ , DB name) C08L 25/00-25/18

Claims (5)

(57) [Claims] 1. Styrene thermoplastic resin: 100 parts by weight, CH ₂ 2CHSiO _1.5 units or CH ₂ ＣＨCH (C
H ₃₎ hydroxy terminated while have a SiO units Motomata
Is an organopolysiloxane resin having an alkoxy group and a molecular weight of 500 to 100,000: 1 to 50 parts by weight, at least one flame retardant selected from potassium pearl fluoroalkanesulfonate and a brominated flame retardant polycarbonate resin: 0 1 to 20 parts by weight, metal hydroxide: 0 to 200 parts by weight. 2. The method of claim 1, wherein the organopolysiloxane resin is CH ₂ ＝.
CHSiO _1.5 units or CH ₂ ＣＨCH ・ CH ₃ SiO
The flame-retardant resin composition according to claim 1, which has _1.5 units and _1.5 units of C ₆ H ₅ SiO. 3. The method of claim 1, wherein the organopolysiloxane resin is CH ₂ ＝.
CHSiO _1.5 units or CH ₂ ＣＨCH ・ CH ₃ SiO
The flame-retardant resin composition according to claim 1, comprising a unit and (C ₆ H ₅ ) ₂ SiO unit. 4. The method according to claim 1, wherein the organopolysiloxane resin is CH ₂ =
CHSiO _1.5 units or CH ₂ ＣＨCH ・ CH ₃ SiO
2. A unit having a unit and a C ₆ H ₅ .CH ₃ SiO unit.
3. The flame-retardant resin composition according to item 1. 5. The method according to claim 1, wherein the organopolysiloxane resin is CH ₂ =
CHSiO _1.5 units or CH ₂ ＣＨCH ・ CH ₃ SiO
The flame-retardant resin composition according to claim 1, which has a unit, a SiO ₂ unit and a (CH ₃ ) ₃ SiO _0.5 unit.