JPH10168319A - Flame-retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition by essentially including a siloxane- based copolymer having specific structural unit so as to afford high safety, low smoke when burned and slight deterioration of its physical properties. SOLUTION: This composition comprises (A) a siloxane-based copolymer of the formula [(a) is 1 or 2; (b) is 0 or 1; (l), (m) and (n) are each an integer of >=1; R<1> and R<2> are each H or a 1-20C hydrocarbon; R<3> and R<4> are each 1-20C divalent hydrocarbon or R<5> -X-R<6> (R<5> and R<6> are each a divalent aromatic hydrocarbon; X is a single bond, O, S, SO, etc.)] and (B) pref. 0.5-50wt.% of an organic polymer such as polyethylene terephthalate, polybutylene terephthalate or polycarbonate, and pref. furthermore, (C) 0.1-200 pts.wt., based on a total 100 pts.wt. of the components A and B, of a flame retradant and (D) 0.001-5 pts.wt., based on a total 100 pts.wt. of the components A and B, of an anti-dripping agent.

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 containing a siloxane-based copolymer, and more particularly, to high safety, low smoke emission during combustion, and reduced mechanical properties. The present invention relates to a flame-retardant resin composition having a low content.

[0002]

2. Description of the Related Art Organic polymers are useful industrial products used for plastics, films, fibers, adhesives, paints, extruded sheets, etc., and are generally lightweight, impact resistant, abrasion resistant, and electrically insulating. And excellent moldability. However, such organic polymers have drawbacks such as poor flame retardancy and generation of harmful gases during combustion.
Therefore, when such an organic polymer is used for applications requiring flame retardancy, it is general to make the flame retardant by adding a flame retardant represented by a halogen type. . However, such a halogen-based flame retardant not only poses a problem of safety of the flame retardant itself, but also has a problem that harmful gas is generated at the time of combustion and mechanical strength is reduced depending on an added amount. doing.

[0003] As other flame retardants, phosphorus-based flame retardants, metal hydroxides and metal oxides are known. But,
All of these have problems such as insufficient flame retardancy and a decrease in mechanical strength due to addition. As a means for improving the flame retardancy of organic polymers, siloxane compounds have attracted attention. The siloxane compound is characterized in that it has high safety and also has a high effect of improving flame retardancy.
However, in the conventionally proposed method of adding silicone oil or silicone resin, when the compatibility between the siloxane compound and the resin is low, a sufficient effect of improving the flame retardancy cannot be obtained or the siloxane compound is not applied to the surface. There is a problem of bleeding.

[0004] As means for solving such problems,
A technique relating to a siloxane-based copolymer is disclosed.
For example, JP-A-5-262975 discloses a flame-retardant polycarbonate-siloxane block copolymer. Further, JP-A-5-222173 and JP-A-7-2999 disclose a polyester (polyester carbonate) -siloxane block copolymer. However, these publications do not disclose a technique using a siloxane-based copolymer as a flame retardant. Furthermore, since these siloxane-based copolymers contain siloxane moieties in a block manner, the siloxane introduction rate is limited, the compatibility with organic polymers is poor, the mechanical properties are reduced due to phase separation, and the flame retardancy is improved. There is a problem that the effect is insufficient. Curry et al. Report a method for synthesizing a siloxane-based copolymer obtained from diol and bis (anilino) diphenylsilane (J. Appl. Polym. Sci., Vo.
l.9, pp.295 (1965)). Carraher, Jr. et al. Have reported a method for synthesizing a siloxane-based copolymer obtained from diol and dichlorodiorganosilane (J. Polym. Sci., Par.
tA-1, vol. 8, pp. 973 (1970)). In these methods, since the produced polymer is an alternating copolymer, the amount of siloxane to be introduced can be increased. Tokuhei 7-15
No. 053 discloses a flame-retardant blend of a siloxane copolymer of this type [poly (aryloxysiloxane)] and an aromatic polycarbonate. But,
In this method, there is a problem that the glass transition point of poly (aryloxysiloxane) is low, and when added in a large amount, the heat resistance of the organic polymer is reduced.

[0005]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned conventional problems, and it is an object of the present invention to provide high safety, low smoke emission during combustion, and low physical properties. An object of the present invention is to provide a flame-retardant resin composition with a small decrease.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, the above problems have been solved by using a siloxane copolymer having a specific structural unit as an essential component. They have found that they can be solved and completed the present invention.

That is, the present invention comprises a flame-retardant resin composition comprising the following components (A) and (B). (A) a siloxane-based copolymer represented by the following general formula (I):

[0008]

Embedded image

Wherein a is 1 or 2, b is 0 or 1.
It is. l, m, and n are each a positive integer of 1 or more. R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (provided that a part or all of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms), and R ^3. And R ⁴ each have 1 to 20 carbon atoms
Divalent hydrocarbon group (provided that part or all of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom.) Or -R ⁵ -X-R ⁶ in - a group represented by ( However, R ⁵ and R ⁶ represent a divalent aromatic hydrocarbon group,
The hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group. X is a single bond, -O-, -S-, -SO-,-
SO ₂ —, —CO—, a divalent hydrocarbon group having 1 to 20 carbon atoms. ). And (B) an organic polymer. The present invention also includes a flame-retardant resin composition comprising the above-mentioned flame-retardant resin composition and at least one of a component (C) a flame retardant and a component (D) an anti-dripping agent. .

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. In the present invention, a siloxane copolymer represented by the following general formula (I) is used as the component (A).

[0011]

Embedded image

Wherein a is 1 or 2, b is 0 or 1.
It is. l, m, and n are each a positive integer of 1 or more. R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (provided that a part or all of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms), and R ^3. And R ⁴ each have 1 to 20 carbon atoms
Divalent hydrocarbon group (provided that part or all of the hydrogen atoms of the hydrocarbon group may be substituted with a halogen atom.) Or -R ⁵ -X-R ⁶ in - a group represented by ( However, R ⁵ and R ⁶ represent a divalent aromatic hydrocarbon group,
The hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group. X is a single bond, -O-, -S-, -SO-,-
SO ₂ —, —CO—, a divalent hydrocarbon group having 1 to 20 carbon atoms. ). ].

R ¹ and R ² in the general formula (I)
Are each independently a hydrogen atom or a group having 1 to 20 carbon atoms.
(However, some or all of the hydrogen atoms in these hydrocarbon groups may be substituted with halogen atoms.), And even if the copolymer is a single group as a whole,
It may be composed of a plurality of groups. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, n-hexyl, phenyl, naphthyl, allyl, Examples include a vinyl group, a chloromethyl group, a 3,3,3-trifluoropropyl group, a perfluorobutyl group, a perfluorooctyl group, and the like. Of these, a methyl group and a phenyl group are preferred.

R ³ in the general formula (I) is a divalent hydrocarbon group having 1 to 20 carbon atoms (provided that some or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms). Or a group represented by —R ⁵ —X—R ⁶ — (where R ⁵ and R ⁶ each represent a divalent aromatic hydrocarbon group, and the hydrogen atom of the aromatic ring is a halogen atom, a carbon atom X may be substituted with a hydrogen group, an alkoxy group, or a phenoxy group, and X is a single bond, -O-, -S-, -SO
_{-, - SO 2 -, -} CO-, a divalent hydrocarbon group having 1 to 20 carbon atoms. ), And the copolymer may be a single group or a plurality of groups.

As a specific example, 2,2-bis (4-
Hydroxyphenyl) propane (alias: bisphenol A), bis (4-hydroxyphenyl) methane, 1,1
-Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (alias: bisphenol TM
C), bis (4-hydroxy-3,5-dimethylphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, 1,1-bis (4-hydroxyphenyl) cyclohexylmethane, 1,1- Bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 4,4′-dihydroxydiphenyl ether, bis (4-hydroxy-
3,5-dimethylphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-
3,5-dimethylphenyl) sulfone, 4,4′-dihydroxybenzophenone, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, tetrabromobisphenol A, tetrachlorobisphenol A,
Dihydroxydiphenyl, hydroquinone, resorcinol, dihydroxynaphthalene, dihydroxyanthracene, phenolphthalein, ferurescein, 2,
2'-dihydroxy-1,1-dinaphthylmethane, 4,
Aromatic diols such as 4'-dihydroxydinaphthyl,
Examples include groups derived from aliphatic diols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol, and alicyclic diols such as cyclohexane dimethanol. Of these, groups derived from bisphenol A and bisphenol TMC are preferred.

R ⁴ in the general formula (I) represents a divalent hydrocarbon group having 1 to 20 carbon atoms (provided that some or all of the hydrogen atoms in the hydrocarbon group are substituted with halogen atoms). Or a group represented by —R ⁵ —X—R ⁶ — (where R ⁵ and R ⁶ each represent a divalent aromatic hydrocarbon group, and the hydrogen atom of the aromatic ring is a halogen atom, a carbon atom X may be substituted with a hydrogen group, an alkoxy group, or a phenoxy group, and X is a single bond, -O-, -S-, -SO
_{-, - SO 2 -, -} CO-, a divalent hydrocarbon group having 1 to 20 carbon atoms. ), And the copolymer may be a single group or a plurality of groups.

Specific examples thereof include terephthalic acid, isophthalic acid, phthalic acid, diphenyl ether-4,4'-
Dicarboxylic acid, benzophenone-4,4-dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid,
Aromatic dicarboxylic acids such as 2,7-naphthalenedicarboxylic acid, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, and glutaric acid; 1,4-cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylic acid; ,
Alicyclics such as 2-cyclohexanedicarboxylic acid, 1,4-decahydronaphthalenedicarboxylic acid, 1,5-decahydronaphthalenedicarboxylic acid, 2,6-decahydronaphthalenedicarboxylic acid, and 2,7-decahydronaphthalenedicarboxylic acid And groups derived from dicarboxylic acids. Of these, groups derived from terephthalic acid and isophthalic acid are preferred.

In the general formula (I), a is 1 or 2, and b is 0 or 1. When a is greater than 2,
It becomes a block copolymer and the compatibility with the organic polymer decreases. Also, l, m, and n are each a positive integer of 1 or more. The upper limits of l, m, and n are not particularly limited, but each is preferably about 400 from the viewpoint of moldability of the composition.

The method for producing the siloxane copolymer of the present invention is not particularly limited, but a known polymerization method, for example,
It can be produced by melt polycondensation, solution polycondensation, or interfacial polycondensation. Among them, a method of reacting a polycarbonate, if necessary, a carboxylic acid diester and a siloxane compound, and a method of reacting a diol, a dicarbonate and, if necessary, a carboxylic acid diester and a siloxane compound are preferable. The siloxane-based copolymer of the present invention is contained in the resin composition in an appropriate amount as a flame retardant.
The content is not particularly limited, but is usually 0.5 to 50% by weight,
Preferably, the content is 1 to 30% by weight, more preferably 5 to 30% by weight. If it is less than 0.5% by weight, the effect of imparting flame retardancy is not sufficient, and if it exceeds 50% by weight, physical properties such as mechanical properties and heat resistance are greatly reduced. The weight average molecular weight of the siloxane copolymer of the present invention is preferably from 2000 to 2000.
It is 100,000, more preferably 2,000 to 10,000. When it is less than 2,000, the mechanical properties of the composition are greatly reduced, and when it exceeds 100,000, the moldability of the composition tends to be reduced.

As the organic polymer which is the component (B) of the present invention, known organic polymers can be used. Examples of such organic polymers include thermoplastic resins, thermosetting resins, and elastomers.For example, polybutadiene, polydienes such as polyisoprene, polyethylene, polypropylene, polyalkenes such as polyisobutylene, polyacrylic acid, polymethyl Poly (meth) acrylates such as methacrylate and polybutyl acrylate, (meth)
Copolymers of acrylic acid (ester) monomers, styrene monomers and acrylonitrile monomers, polyacrylamides such as polyacrylamide, polyvinyl ethers, polyvinyl alcohols, polyvinyl halides such as polyvinyl chloride, polyvinyl esters, polystyrene Polystyrenes such as polyoxymethylene, polyoxypropylene such as polyoxypropylene, polyamides such as nylon 6, nylon 6,6, polyimines, polyacetals, polyaramids, polycarbonates, polyethylene terephthalate, polybutylene terephthalate, and polyarylate. , Polyesters such as polyester-based liquid crystal polymers, polyurethanes, polyphenylene ether, polyphenylene sulfide, polysulfone, polyether The polar group was grafted with sulfonic acid, polyetherimide, polyamideimide, polyimide, polyetheretherketone, polysiloxane, ethylene-propylene copolymer, ethylene-propylene-diene monomer copolymer, maleic anhydride, glycidyl methacrylate, etc. Modified polyolefins, acrylic elastomers, acrylonitrile-butadiene-styrene copolymers, modified styrene-based thermoplastic elastomers with polar groups grafted with maleic anhydride, glycidyl methacrylate, etc., phenolic resins, epoxy resins, unsaturated polyester resins And the like. Among them, a thermoplastic resin is preferable in terms of compatibility with the siloxane copolymer.

Further, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyphenylene ether, acrylonitrile-butadiene-styrene copolymer, alloy of polycarbonate and acrylonitrile-butadiene-styrene copolymer, alloy of polycarbonate and polyethylene terephthalate, polyphenylene ether and Polystyrene alloys and the like are preferred.

The siloxane copolymer (A) of the present invention comprises:
The organic polymer (B) may be used alone or may be used for a blend of two or more kinds of the organic polymer (B). Further, a filler, a plasticizer, and the like may be added to these organic polymers as necessary.

In the present invention, other known flame retardants can be used as the component (C). Specific examples of the flame retardant include chlorine-based flame retardants such as chlorinated paraffin, chlorinated polyethylene, perchlorocyclopentadecane (trade name: dechlorane plus), tetrachlorophthalic anhydride, chlorendic acid, and chlorendic anhydride; Bromodiphenyl oxide, tetrabromobisphenol A (alias: TBA), tetrabromophthalate, tetrabromophthalate ester, tetrabromophthalate disodium, tribromophenol, dibromophenol, dibromomethcresol, poly (pentabromobenzyl polyacrylate), penta Bromophenol, bromophenoxyethanol, novolak-type brominated phenol, dibromocresyl glycidyl ether, brominated aromatic triazine, vinyl bromide, TBA-bis (2
-Hydroxyethyl ether), TBA-bis (2,3
-Dibromopropyl ether), TBA-bis (allyl ether), TBA epoxy oligomer, TBA carbonate oligomer, tribromophenyl allyl ether, tribromoneopentyl alcohol, bis (2
4,6-tribromophenoxy) ethane, polydibromophenylene ether, tetrabromocyclooctane, brominated polystyrene, ethylenebistetrabromophthalimide, ethylenebispentabromodiphenyl, hexabromocyclododecane, hexabromobenzene, octabromodiphenyl oxide, Brominated flame retardants such as dibromostyrene, tris (2,3-dibromopropyl) isocyanurate, tetrabromobisphenol S, and pentabromotoluene, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, trimethyl phosphate, triethyl phosphate, Cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bis (diphenyl) phosphate, 2-ethyl Phosphate ester flame retardants such as xyl phosphate, dimethyl methyl phosphate, triallyl phosphate, and aromatic phosphate, tris (chloroethyl) phosphate, trisdichloropropyl phosphate, tris-β-chloropropyl phosphate, chloroalkyl phosphate, tris (tris) Bromoneopentyl) phosphate, diethyl-N, N-bis (2-hydroxyethyl) aminomethylphosphate,
Halogen-containing phosphoric ester flame retardants such as tris (2,6-dimethylphenyl) phosphate, condensed phosphoric acid ester flame retardants such as aromatic condensed phosphoric acid esters and halogen-containing condensed phosphoric acid esters, ammonium polyphosphate, polyphosphoric acid Amides, polyphosphate-based flame retardants such as polychlorophosphonates, red phosphorus, aluminum hydroxide, antimony trioxide, antimony pentoxide, sodium antimonate,
Inorganic flame retardants such as magnesium hydroxide, zinc borate, zirconium compounds, molybdenum compounds and tin compounds, guanidine flame retardants, melamine flame retardants, metal sulfonic acid salts, metal carboxylic acid salts, metal perfluoroalkanesulfonic acid And metal salt-based flame retardants such as salts. These may be used alone or in combination of two or more. The content of the component (C) is usually between the components (A) and (B).
An appropriate amount is selected from 0.1 to 300 parts by weight, preferably 0.1 to 200 parts by weight based on 100 parts by weight of the total. If the amount is less than 0.1 part by weight, the effect of improving the flame retardancy will not be sufficiently exhibited, and if it exceeds 300 parts by weight, physical properties such as mechanical properties and heat resistance will decrease.

In the present invention, other known anti-dripping agents can be used as the component (D). Here, the anti-dripping agent is added for the purpose of preventing the organic polymer from melting and dropping during combustion,
Specifically, polytetrafluoroethylene is exemplified.
The content of the component (D) is usually 0.001 to 5 parts by weight, preferably 0.01 to 1 part by weight based on 100 parts by weight of the total of the components (A) and (B). If the amount is less than 0.001 part by weight, the effect of preventing dripping is not sufficiently exhibited, and if it exceeds 5 parts by weight, physical properties such as mechanical properties and heat resistance deteriorate.
The method for preparing the flame-retardant resin composition of the present invention is not particularly limited. For example, the flame-retardant resin composition is prepared by blending the above-mentioned components and melt-kneading with a twin-screw extruder or the like.

Various additives can be added to the flame-retardant resin composition of the present invention, if necessary. Examples of the additives include an antioxidant, an ultraviolet absorber, a lubricant, a plasticizer, a dye and a pigment. , A filler, a reinforcing material (for example, glass fiber or carbon fiber), or other auxiliaries, and these may be used alone or in combination of two or more. The amount added is appropriately determined according to the intended use. Also,
The timing of addition may be before, during, or after the polymerization. The flame-retardant resin composition of the present invention can be used for producing plastics, films, fibers, adhesives, paints, extruded sheets and the like.

The flame-retardant resin composition of the present invention makes use of excellent flame retardancy, moldability, mold release property and surface lubricity, and further has high heat resistance, toughness, hydrolysis resistance and mechanical properties. It is suitable for articles that require such. For example, it is particularly suitable for articles in the electric field, the lighting field, and the automobile field. Specifically, the copolymer of the present invention is a relay case,
It can be used for electric and electronic parts materials such as switches, connectors, covers, and housing materials, lighting parts materials such as lamp shades and lenses, and automotive parts such as headlight lenses, inner caps, and reflectors, but is of course limited to these. Not something.

The siloxane copolymer of the present invention has a siloxane structure at random and is excellent in compatibility with an organic polymer, and itself is excellent in flame retardancy and mechanical properties. Therefore, high flame retardancy can be realized while maintaining the mechanical properties and heat resistance of the organic polymer.
On the other hand, the block copolymer has a limitation in the siloxane introduction rate, and as described above, it is inevitable that the mechanical properties are reduced due to phase separation, so that the flame retardancy is not so much improved. Therefore, in terms of flame retardancy, the siloxane random copolymer of the present invention can be said to be superior to the block copolymer.

[0028]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by these, and can be appropriately modified and implemented within the scope of the invention. The properties of the polymer were measured according to the following method. (1) Silicon (Si) atom content of polymer After heating the polymer with sulfuric acid, adding sodium carbonate and calcium carbonate, and performing heat treatment in an electric furnace, IC
It was quantified by P (Inductively Coupled Plasma) emission spectroscopy. (2) Flame retardancy of polymer UL standard test After pelletizing the polymer, dried under reduced pressure at 120 ° C for 15 hours, a 1/8 inch thick test piece was prepared by injection molding and evaluated according to UL-94V standard. did. Measurement of Limiting Oxygen Index A polymer was pelletized, dried under reduced pressure at 120 ° C. for 15 hours, and a test piece was prepared by injection molding.
It was evaluated according to the SK7201 standard. (3) Smoke emission during polymer combustion The smoke emission during polymer combustion was visually evaluated. (4) Tensile properties of polymer (yield strength, elongation at break) Using an autograph AG-1000C manufactured by Shimadzu Corporation, A
According to STM D638, it was measured at a tensile speed of 10 mm / min.

Production Example 1 Synthesis of Siloxane Copolymer A1 1271 g (repeating unit 5) was placed in a 14-L reaction vessel equipped with a stirring blade, a nitrogen inlet, a cooling pipe, and a distilling outlet.
Mol) of dried polycarbonate (Panlite L-1250W manufactured by Teijin Chemicals Limited), 486 g (2.5 mol) of dimethyl terephthalate, 486 g (2.5 mol) of dimethyl isophthalate, 360 g (3.0 mol) )), 585 mg (1.7 mmol) of dibutyltin diacetate was charged, degassed with ultra-high purity nitrogen (60 Pa) -nitrogen purge was performed three times, and then heated under ultra-high purity nitrogen atmosphere. Started. After stirring at an internal temperature of 280 ° C. for 1 hour, the internal temperature was raised to 300 ° C., and distillation of by-produced dimethyl carbonate was started. Two hours later, the internal temperature was raised to 320 ° C, and stirring was continued for 2 hours under reduced pressure (26 Pa). Dissolve the obtained polymer in methylene chloride,
The polymer was purified by pouring into a large amount of hexane to reprecipitate the polymer. The obtained polymer was a polyester-siloxane copolymer, and had a silicon (Si) atom content of 3.5% by weight and a weight average molecular weight of 32,000.

Production Example 2: Synthesis of siloxane copolymer A2 1140 g (5.0 mol) of bisphenol A was used instead of polycarbonate, and 450 g of dimethyl carbonate was used instead of dimethyl terephthalate and dimethyl isophthalate. The procedure was carried out in the same manner as in Production Example 1 except for the above. The obtained polymer is a polycarbonate-siloxane copolymer and has a silicon (Si) atom content of 3.
8% by weight, and the weight average molecular weight was 38,000.

Example 1 The siloxane-based copolymer A1 obtained in Production Example 1 was prepared by using a commercially available polycarbonate resin (Panlite L manufactured by Teijin Chemicals Limited).
-1250) 30 parts by weight per 100 parts by weight,
The mixture was melt-kneaded with a twin-screw extruder (LABOTEX, manufactured by Nippon Steel Works) to obtain a pellet-shaped resin composition. Using this, a 1/8 inch test piece was prepared by injection molding, and the flame retardancy was evaluated. Table 1 shows the results. Table 2 shows the results of measuring the mechanical strength.

Example 2 A test piece was prepared in the same manner as in Example 1 except that the siloxane copolymer A2 obtained in Production Example 2 was used instead of the siloxane copolymer A1 obtained in Production Example 1. And the flame retardancy was evaluated. Table 1 shows the results.

Example 3 A test piece was prepared in the same manner as in Example 1 except that 10 parts by weight of an epoxy oligomer of TBA was further added as a flame retardant, and the flame retardancy was evaluated. Table 1 shows the results.

Example 4 A test piece was prepared in the same manner as in Example 1 except that 1 part by weight of polytetrafluoroethylene was further added as an anti-dripping agent. Table 1 shows the results.

Example 5 A test piece was prepared in the same manner as in Example 1 except that the amount of the siloxane-based copolymer A1 obtained in Production Example 1 was changed to 5 parts by weight, and a flame retardancy was evaluated. Table 1 shows the results.

Comparative Example 1 A test piece was prepared in the same manner as in Example 1 except that the siloxane-based copolymer A1 obtained in Production Example 1 was not used. Table 1 shows the results. Table 2 shows the results of measuring the mechanical strength.

Comparative Example 2 A test piece was prepared in the same manner as in Example 3 except that the siloxane copolymer A1 obtained in Production Example 1 was not used, and the flame retardancy was evaluated. Table 1 shows the results.

[0038]

[Table 1] A1: siloxane copolymer A1 B2: siloxane copolymer A2 PC: polycarbonate resin Panlite L-1250 C: epoxy oligomer of TBA D: polytetrafluoroethylene

[0039]

[Table 2]

Example 6 30 parts by weight of the siloxane copolymer A1 obtained in Production Example 1 was added to 100 parts by weight of a commercially available polyethylene terephthalate resin (Belpet EFG-7 manufactured by Kanebo Co., Ltd.). The mixture was melt-kneaded with a screw extruder (LABOTEX manufactured by Nippon Steel Works) to obtain a pellet-shaped resin composition. Using this, a 1/8 inch test piece was prepared by injection molding, and the flame retardancy was evaluated. Table 3 shows the results.

Comparative Example 3 A test piece was prepared in the same manner as in Example 5 except that the siloxane copolymer A1 obtained in Production Example 1 was not used, and a flame retardancy was evaluated. Table 3 shows the results.

[0042]

[Table 3] A1: Siloxane copolymer A1 PET: Polyethylene terephthalate resin Bellpet EFG-7

Example 7 30 parts by weight of the siloxane copolymer A1 obtained in Production Example 1 was added to 100 parts by weight of a commercially available polybutylene terephthalate resin (Duranex 2002 manufactured by Polyplastics Co., Ltd.). Twin screw extruder (LA made by Japan Steel Works, LA
BOTEX) to obtain a pellet-shaped resin composition. Using this, a 1/8 inch test piece was prepared by injection molding, and the flame retardancy was evaluated. Table 4 shows the results.

Comparative Example 4 A test piece was prepared in the same manner as in Example 5 except that the siloxane copolymer A1 obtained in Production Example 1 was not used, and a test piece was evaluated for flame retardancy. Table 4 shows the results.

[0045]

[Table 4] A1: siloxane copolymer A1 PBT: polybutylene terephthalate resin DURANEX 2002

Example 8 The siloxane copolymer A1 obtained in Production Example 1 was converted to a commercially available polycarbonate resin (Panlite L manufactured by Teijin Chemicals Limited).
-1250) 70 parts by weight, an acrylonitrile-butadiene-styrene copolymer (ABS1 manufactured by Nippon Synthetic Rubber Co., Ltd.)
2) 30 parts by weight were added to 30 parts by weight, and the mixture was melt-kneaded with a twin screw extruder (LABOTEX, manufactured by Nippon Steel Works) to obtain a pellet-shaped resin composition. Using this, a 1/8 inch test piece was prepared by injection molding, and the flame retardancy was evaluated. Table 5 shows the results.

Comparative Example 5 A test piece was prepared in the same manner as in Example 7 except that the siloxane copolymer A1 obtained in Production Example 1 was not used, and the flame retardancy was evaluated. Table 5 shows the results.

[0048]

[Table 5] A1: siloxane copolymer A1 PC: polycarbonate resin Panlite L-1250 ABS: ABS resin ABS12

Example 9 The siloxane copolymer A1 obtained in Production Example 1 was converted to a commercially available polycarbonate resin (Panlite L manufactured by Teijin Chemicals Limited).
-1250) and 30 parts by weight of polyethylene terephthalate resin (Kanbo Co., Ltd. Bellpet EFG-7) 30 parts by weight, and melt-kneaded with a twin screw extruder (LABOTEX, manufactured by Nippon Steel Works, Ltd.). Thus, a pellet-shaped resin composition was obtained. Using this, a 1/8 inch test piece was prepared by injection molding, and the flame retardancy was evaluated. Table 6 shows the results.

Comparative Example 6 A test piece was prepared in the same manner as in Example 8 except that the siloxane copolymer A1 obtained in Production Example 1 was not used, and a test piece was evaluated for flame retardancy. Table 6 shows the results.

[0051]

[Table 6] A1: siloxane copolymer A1 PC: polycarbonate resin Panlite L-1250 PET: polyethylene terephthalate resin Bellpet EFG-7

[0052]

As described above, the flame retardant resin composition of the present invention is particularly excellent in flame retardancy while maintaining excellent properties of the resin itself such as mechanical properties and heat resistance. Further, the flame-retardant resin composition of the present invention is particularly effective in suppressing smoke emission during combustion.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 27/18 C08L 27/18 55/02 55/02 67/02 67/02 69/00 69/00 71/12 71/12 // (C08L 83/10 67:02) (C08L 83/10 69:00) (C08L 83/10 71:12) (C08L 83/10 55:02) (C08L 83/10 69:00 55:02) (C08L 83/10 69:00 67:02) (C08L 83/10 71:02 25:06)

Claims (15)

[Claims] 1. A flame-retardant resin composition comprising the following components (A) and (B). (A) a siloxane-based copolymer represented by the following general formula (I): Wherein a is 1 or 2, and b is 0 or 1. l,
m and n are each a positive integer of 1 or more. R ¹ and R ² are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms (provided that a part or all of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms), and R ^3.
And R ⁴ are each a divalent hydrocarbon group having 1 to 20 carbon atoms (provided that some or all of the hydrogen atoms of the hydrocarbon group may be substituted with halogen atoms) or-.
A group represented by R ⁵ —X—R ⁶ — (provided that R ⁵ and R
⁶ represents a divalent aromatic hydrocarbon group, and a hydrogen atom of the aromatic ring may be substituted with a halogen atom, a hydrocarbon group, an alkoxy group, or a phenoxy group. Further, X represents a single bond, -O -, - S -, - SO -, - SO 2 -, - CO
-Represents a divalent hydrocarbon group having 1 to 20 carbon atoms. ). And (B) an organic polymer. 2. The content of the organic polymer of the component (B) is from 0 to 2.
The flame-retardant resin composition according to claim 1, wherein the content is 5 to 50% by weight. 3. The flame retardant resin composition according to claim 1, further comprising a component (C) a flame retardant. 4. The content of the flame retardant of component (C) is 0.1 to 3 based on 100 parts by weight of the total of components (A) and (B).
The flame-retardant resin composition according to claim 3, wherein the amount is 00 parts by weight. 5. The flame-retardant resin composition according to claim 1, further comprising a component (D) an anti-dripping agent. 6. The flame retardant according to claim 5, wherein the content of the anti-dripping agent of the component (D) is 0.001 to 5 parts by weight based on 100 parts by weight of the total of the components (A) and (B). Resin composition. 7. The flame-retardant resin composition according to claim 1, wherein the organic polymer as the component (B) is a thermoplastic resin. 8. The flame-retardant resin composition according to claim 7, wherein the organic polymer as the component (B) is polyethylene terephthalate. 9. The flame-retardant resin composition according to claim 7, wherein the organic polymer as the component (B) is polybutylene terephthalate. 10. The flame-retardant resin composition according to claim 7, wherein the organic polymer of the component (B) is a polycarbonate. 11. The flame-retardant resin composition according to claim 7, wherein the organic polymer as the component (B) is polyphenylene ether. 12. The flame-retardant resin composition according to claim 7, wherein the organic polymer as the component (B) is an acrylonitrile-butadiene-styrene copolymer. 13. The flame-retardant resin composition according to claim 7, wherein the organic polymer as the component (B) is an alloy of a polycarbonate and an acrylonitrile-butadiene-styrene copolymer. 14. The flame-retardant resin composition according to claim 7, wherein the organic polymer of the component (B) is an alloy of polycarbonate and polyethylene terephthalate. 15. The organic polymer as the component (B) is an alloy of polyphenylene ether and polystyrene.
The flame-retardant resin composition according to the above.