JP2003064229A - Flame retarder for thermoplastic resin and flame- retardant thermoplastic resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame retarder for a thermoplastic resin of which the flame retardance can be improved without impairing physical properties that the thermoplastic resin has inherently and a flame-retardant thermoplastic resin. SOLUTION: This flame retarder for a thermoplastic resin is composed of a metal salt of a sulfonic acid of a styrene-based polymer and the content of a metal sulfate is 5 mass % or below. The flame-retardant thermoplastic resin contains the above flame retarder. A desirable flame retarder for a polycarbonate resin is a metal salt of a sulfonic acid of a styrene-based polymer of which 15-45 mol % of the total monomer units is an aromatic monomer unit having a sulfonic acid group on the aromatic skeleton and the content of a metal sulfate is 5 mass % or below.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant imparting agent for a thermoplastic resin and a flame retardant thermoplastic resin, which can improve the flame retardancy without deteriorating the physical properties inherent in the thermoplastic resin, In particular, the present invention relates to a flame retardant imparting agent for a thermoplastic resin and a flame retardant thermoplastic resin, which are suitable for a polycarbonate resin.

[0002]

2. Description of the Related Art Generally, a polycarbonate resin, which is a thermoplastic resin, has excellent transparency and moldability as well as excellent impact resistance.
It is used in various fields including OA equipment parts. In the fields of these electric / electronic parts, products, and OA equipment parts, high flame retardancy and impact resistance are required.

Conventionally, as a method of making a polycarbonate resin flame-retardant, it has been known to add a flame-retardant such as a halogen compound, a phosphorus compound or an inorganic compound. Has been achieved.

However, in recent years, the demand for safety against fire has been highlighted, and along with the development of more advanced flame retardant technology, there is a strong demand for technological development without environmental problems or deterioration of physical properties.

On the other hand, there is known a composition in which an aromatic vinyl resin having an aromatic ring substituted with a sulfonic acid group such as polystyrene sulfonate is added. For example, a method for producing a stabilizing resin of sodium polystyrene sulfonate and polyvinyl chloride (JP-A-7-268028) and a method for producing a stabilizing resin of sodium polystyrene sulfonate and polyolefin (JP-A-6-3312883, 1-8090). (Patent Publication No. JP-A-2-6928), a thermosensitive printing paper containing an alkanolamine salt of polystyrene sulfonic acid (JP-A-2-136285), and a thermosensitive recording material comprising an acrylic emulsion containing a polystyrene sulfonate (JP-A-2-6928).
3), a polystyrene sulfonate, and a thermosetting resin containing polystyrene containing a methylol group (JP-A-1-
294729), a heat-sensitive recording material containing polystyrene sulfonate (Japanese Patent Application Laid-Open No. 6-3312883, 1-
8090), an organic semiconductor material containing polystyrene sulfonate (JP-A-6-3215722), and an antistatic polyester film containing sodium polystyrene sulfonate (JP-A-6-14152).
5), microcapsules for pressure-sensitive copy paper containing polystyrene sulfonate (German Patent 32328).
No. 11,3037309), a heat-resistant resin composed of polystyrene / polyphenylene oxide alloy [Proc
eedings of the 6th Sony Research Forum p.552 (199
6)], compatibility of polymer system in which sulfonate is introduced into polystyrene / polyphenylene oxide [Polyme
r, Vol. 33, No. 6, 1210 (1992)] and the like are known, but these are basically different from the present invention in the technical idea (configuration, etc.).

On the other hand, Japanese Examined Patent Publication (Kokoku) No. 57-43100 discloses the addition of sodium polystyrene sulfonate to impart flame retardancy to a polycarbonate resin, and Japanese Patent Laid-Open No. 11-172063. Discloses that polystyrene sulfonate is used as a flame retardant for thermoplastic resins. However, the polystyrene sulfonate used in each of these publications has a problem in that it does not exhibit sufficient flame retardancy without impairing the physical properties of the resin.

[0007]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art and is intended to solve the problems.
An object of the present invention is to provide a flame-retardant imparting agent for a thermoplastic resin and a flame-retardant thermoplastic resin, which can improve the flame retardancy without deteriorating the original physical properties of the thermoplastic resin.

[0008]

Means for Solving the Problems As a result of intensive studies on the above-mentioned problems of the prior art, the present inventors have found that styrene having a metal sulfate content within a specific range as a flame retardant additive for thermoplastic resins. It was found that the sulfonic acid metal salt of the base polymer has excellent flame retardancy, and succeeded in obtaining the flame retardancy-imparting agent for the thermoplastic resin and the flame retardant thermoplastic resin, and completed the present invention. It came to do. That is, the present invention resides in the following (1) to (4). (1) Made of sulfonic acid metal salt of styrenic polymer,
Further, the flame retardancy-imparting agent for a thermoplastic resin, wherein the content of the metal sulfate is 5% by mass or less. (2) A flame-retardant thermoplastic resin comprising the flame-retardant imparting agent described in (1) above. (3) The aromatic monomer unit having a sulfonic acid group in the aromatic skeleton is composed of 15 to 45 mol% of a sulfonic acid metal salt of a styrene-based polymer with respect to all monomer units, and the content of the metal sulfate salt is 5 A flame-retardant imparting agent for polycarbonate resin, which is characterized by being at most mass%. (4) A flame-retardant polycarbonate resin containing the flame-retardant imparting agent described in (3) above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below. The flame retardancy-imparting agent for a thermoplastic resin of the present invention (hereinafter referred to as "flame retardancy-imparting agent of the present invention") is composed of a sulfonic acid metal salt of a styrene-based polymer and has a metal sulfate content of 5 It is characterized by being less than or equal to mass% (hereinafter, simply referred to as "%"), and the flame-retardant thermoplastic resin of the present invention contains the flame-retardant imparting agent having the above-mentioned constitution. To do.

In the flame retardant-imparting agent of the present invention, the essential monomer unit constituting the styrene polymer has a styrene skeleton, and examples thereof include styrene and α-.
Methyl styrene and the like can be mentioned, and these can be used alone or in combination. In the present invention, the sulfonic acid metal salt of the styrene-based polymer of the present invention can be obtained by polymerizing these monomers, sulfonation by a conventional method, and neutralization with a basic metal substance. As the basic metal substance that can be used, for example, lithium hydroxide,
Examples thereof include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides, metal hydroxides such as aluminum and zinc, and preferably alkali metal hydroxides from the viewpoint of ease of production. Things are desirable.

In the present invention, the styrenic polymer may be obtained by copolymerizing styrene, or α-methylstyrene with another monomer unit, in addition to polystyrene and poly-α-methylstyrene. Examples of such other monomer units include aromatic hydrocarbon monomers such as vinyltoluene and vinylnaphthalene, conjugated dienes such as butadiene, isoprene, pentadiene and cyclopentadiene, and olefins such as butene and isobutylene. These other monomers may be used alone or in combination of two or more.

In the present invention, the polymer obtained by polymerizing these monomers is sulfonated with sulfuric anhydride, sulfuric acid, fuming sulfuric acid, a complex of sulfuric anhydride and a Lewis base, or the like to give a styrene polymer. The compound can be obtained. The polymerization method may be radical polymerization, anionic polymerization or cationic polymerization, but a production method of sulfonation of a polymer by cationic polymerization described in JP-A-3-52902 by the same applicant as the present application is particularly preferable. Applied. The sulfonic acid metal salt of the styrene-based polymer of the present invention can also be obtained by polymerizing styrene sulfonic acid or its metal salt, or α-methyl sulfonic acid or its metal salt, or by copolymerizing these with other monomer units. It can be manufactured.
Examples of the other monomer units include styrene and α
-Aromatic hydrocarbon monomers such as methylstyrene, vinyltoluene, vinylnaphthalene, vinyltoluenesulfonic acid or its salts, aromatic sulfonic acid monomers such as vinylnaphthalenesulfonic acid or its salts, butadiene, isoprene, pentadiene, cyclopentadiene, etc. Conjugated dienes, butadiene, isoprene, pentadiene, sulfonated salts of conjugated dienes such as cyclopentadiene or salts thereof, ethylene, propylene, butene, olefins such as isobutylene, acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, Itaconic acid, citraconic acid or monovalent metal salts of these acids, divalent metal salts, ammonium salts, organic amine salts, and these acids and alcohols,
Examples thereof include esters with a hydroxyl group-containing compound such as polyethylene glycol and isethionic acid. These other monomers may be used alone or in combination of two or more. In the case of this production method, preferably, a polymer of styrene sulfonic acid or a metal salt thereof, or a copolymer of styrene sulfonic acid or a metal salt thereof and the above-mentioned other monomer, wherein styrene sulfonic acid or a metal salt thereof is used. 10 salt
It is desirable that the content is from mol% to 99 mol%.

Next, when the sulfonic acid metal salt of the obtained styrenic polymer is itself soluble in water,
The metal sulfate is crystallized by cooling in the state of an aqueous solution (or a water-containing solvent solution), and the metal sulfate is removed by purification such as precipitation or filtration for purification. At this time, the aqueous solution concentration of the sulfonic acid metal salt of the styrene-based polymer is 5 to 40%, preferably 30 to 35%, and the cooling temperature of 15 ° C or higher is 10 ° C to -10 ° C, preferably, 5 ℃ ~
Cool to minus 5 ° C. The cooling rate at that time is 15
It is preferable that the temperature from 0 ° C. to 0 ° C. is 5 hours or more (3 ° C./hr or less), and the temperature is 0 ° C. or less and held for 1 hour or more. In this case, seed crystals may be added as a crystallization accelerator. A commercially available metal sulfate (Na salt, K salt, etc.) is used as the seed crystal, but it is not particularly limited. The obtained purified product may be post-treated with an ion exchange resin or the like, if necessary. Further, in the case of a sulfonic acid metal salt of a styrene-based polymer, which has a low total sulfonic acid group introduction rate to the styrene unit and is poorly water-soluble, it can be purified by removing the metal sulfate salt by liquid-liquid extraction with water. it can.

The content of residual metal sulfate in the purified flame retardant-imparting agent of the present invention is required to be 5% or less, preferably 0.01 to 5%, more preferably
It is desirable to set it to 0.01 to 3%. If the content of the metal sulfate exceeds 5%, the effect of the present invention cannot be achieved. Particularly, in the case of polycarbonate resin,
The resin in which the flame retardant-imparting agent according to the present invention is kneaded has a large yellowing color, and cannot be put to practical use. In the present invention, the content of the metal sulfate is set to 5% or less (0 to 5%), but in order to purify it to less than 0.01%, a great deal of labor is required and it is economical. 0.0 from the point that
It is desirable to be 1 to 5%.

The weight average molecular weight of the polymer of the present invention is 400 to 500,000, preferably 1,000.
It is desirable to set it to ˜200,000. If the weight average molecular weight is less than 400, the effect of imparting flame retardancy to the polymer obtained is insufficient and the resin kneading property is poor.
On the other hand, when the weight average molecular weight exceeds 500,000, the physical properties of the thermoplastic resin to which the chemical is added are not satisfied,
It is inferior in resin kneadability. Further, the polymer of the present invention
From the viewpoint of further improving the present invention, the sulfonic acid group introduction rate of the aromatic monomer unit having a sulfonic acid group in the aromatic skeleton is preferably 10 to 110 mol% with respect to all the monomer units, and more preferably, It is desirable to set it to 15 to 100 mol%.

In particular, a polycarbonate resin is used as the thermoplastic resin, and in the styrene-based polymer, the styrene-based polymer is a styrene-based polymer having 15 to 45 mol% of aromatic monomer units having a sulfonic acid group in the aromatic skeleton with respect to all the monomer units. In the case of a flame-retardant polycarbonate resin using an acid metal salt as a flame-retardant imparting agent, there is no further yellowing, and it is possible to sufficiently maintain the inherent transparency of the polycarbonate. It becomes possible to exert flammability.

The amount of the sulfonic acid metal salt of the styrenic polymer of the present invention added is 100 parts by mass of the thermoplastic resin.
0.01 to 3 parts by mass is preferable, and particularly preferably 0.
02-2 parts by mass. If the addition amount is less than 0.01 parts by mass, it is difficult to obtain sufficient flame retardancy, and if it exceeds 3 parts by mass, the physical properties of the resin are likely to deteriorate.

The thermoplastic resin applicable in the present invention includes, for example, polycarbonate type, polyphenylene ether type, polystyrene type, poly (meth) acrylate type, polyester type, polyolefin type, polyvinyl chloride type, polyamide type, polyphenylene sulfide type. Etc. Polycarbonates, polyesters, and polyphenylene ethers are preferable, and polycarbonates are particularly preferable.

The flame retardant-imparting agent for thermoplastic resin of the present invention thus constituted is composed of a sulfonic acid metal salt of a styrenic polymer and has a metal sulfate content of 5% or less, preferably, The content is 0.01 to 5%, and the flame retardancy-imparting agent makes it possible to further improve the flame retardancy without impairing the original physical properties of the thermoplastic resin.

The flame-retardant thermoplastic resin of the present invention may contain an anti-dripping agent in order to suppress dripping, in addition to the flame-retardant imparting agent having the above constitution. As the anti-dripping agent that can be used, for example,
Examples thereof include silicone compounds and fibril-forming fluoropolymers. The fibril-forming fluoropolymer is preferably one that forms a fibrillar structure in a thermoplastic resin, such as polytetrafluoroethylene,
Tetrafluoroethylene-based copolymers (eg, tetrafluoroethylene / hexafluoropropylene copolymer), partially fluorinated polymers as described in US Pat. No. 4,379,910, and polycarbonates produced from fluorinated diphenols. Etc. Examples of the silicone compound include silicone oil, (poly) organosiloxanes such as dimethylsiloxane, phenylmethylsiloxane, polydimethylsiloxane obtained by polymerizing these, polyphenylmethylsiloxane, and a copolymer. It is also possible to mix and use these. Further, these compounds may be either liquid or powder. The amount of these anti-dripping agents added is 10
0.01 to 5 parts by mass is preferable with respect to 0 parts by mass, and particularly preferably 0.02 to 3 parts by mass. If the amount of the anti-dripping agent added is less than 0.01 part by mass, the effect of preventing dripping during combustion may be poor,
Further, if it exceeds 5 parts by mass, granulation becomes difficult, which may hinder production.

The flame-retardant thermoplastic resin of the present invention includes
If necessary, for example, various additives including an inorganic filler, other synthetic resins, elastomers, etc. may be blended within a range that does not impair the effects of the present invention. The inorganic filler that can be used is one that is blended for the purpose of improving or increasing the mechanical strength and durability of the resin composition, for example, glass fiber, glass beads,
Glass flakes, carbon black, calcium sulfate,
Calcium carbonate, calcium silicate, titanium oxide, alumina, silica, asbestos, talc, clay, mica,
Examples include quartz powder. Examples of the various additives include, for example, hindered phenol-based, phosphite-based, phosphate-based, amine-based antioxidants, benzotriazole-based, benzophenone-based ultraviolet absorbers, hindered amine-based light Stabilizers, aliphatic carboxylic acid ester-based, paraffin-based, internal lubricants such as silicone oil and polyethylene wax, commonly used flame retardants,
Examples include flame retardant aids, release agents, antistatic agents, colorants and the like. Examples of other synthetic resins include polyester (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide, polyethylene, polypropylene, polystyrene, acrylonitrile styrene (A
Examples thereof include S) resin, acrylonitrile butadiene styrene (ABS) resin, and polymethylmethacrylate. Furthermore, examples of the elastomer include isobutylene-isoprene rubber, styrene-butadiene rubber, ethylene-propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core-shell elastomer MB.
S, MAS, etc. are mentioned.

The flame-retardant thermoplastic resin of the present invention comprises a styrene metal salt of a styrene-based polymer (flame-retardant imparting agent) containing 0.01 to 5% of the above-mentioned metal sulfate, and a thermoplastic resin. It can be prepared by mixing a resin and various additive components used as necessary and kneading. It is also possible to mix the flame retardancy-imparting agent of the present invention and various additives into a thermoplastic resin at a high concentration to prepare a masterbatch, and dilute and use the masterbatch. For the above blending and kneading,
A commonly used method, for example, a ribbon blender,
It can be carried out by a method using a Henschel mixer, a Banbury mixer, a drum tumbler, a single screw extruder, a twin screw extruder, a cokneader, a multi-screw extruder, or the like. In particular, in the case of a flame-retardant polycarbonate resin using a polycarbonate resin as the thermoplastic resin, there is no yellowing, and the transparency originally possessed by the polycarbonate is sufficiently maintained, and it has excellent flame retardancy. Become. The flame-retardant thermoplastic resin of the present invention thus obtained has excellent flame retardancy without deteriorating the physical properties of the thermoplastic resin, and various known molding methods, for example, injection molding , Blow molding, extrusion molding,
By applying compression molding, calender molding, rotational molding, etc., it can be used to manufacture various molded products including molded products in the field of home appliances.

[0023]

EXAMPLES Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

[Production Examples 1 to 7 and Comparative Production Examples 1 to 4] Flame-retardant properties for thermoplastic resins which fall within the scope of the present invention (production examples) or outside the scope of the present invention (comparative production examples) by the following method An agent (polymer) was produced. The weight average molecular weight of the polymer (1) and the sulfonic acid group introduction ratio to the styrene unit (2) were measured by the following methods.

(1) Method for measuring weight average molecular weight of polymer Standard sodium polystyrene sulfonate was used as a standard substance, and TSK-G3 manufactured by Tosoh Corporation as a separation column.
000SW and G4000SW (7.5mm ID x 30c
m) was used and the ultraviolet ray detector (measuring wavelength 238 nm) was used to determine by the GPC method. (2) Method of measuring sulfonic acid group introduction rate to styrene unit Calculate sulfonic acid group introduction rate per aromatic ring unit from the ratio of carbon atom and sulfur atom measured by elemental analyzer (EA-1108 type manufactured by Carlo Erba Co.) (When the water-soluble polymer contained a sulfate, its amount was quantified by ion chromatography, and its sulfur atom amount was subtracted from the sulfur atom amount obtained by an elemental analyzer).

(Production Example 1) Polystyrene having a weight average molecular weight of 5,000 (Example 1 of JP-A-3-52902)
100 parts by mass of the described polymer) is dissolved in 400 parts by mass of 1,2-dichloroethane, and 1.0 part of acetophenone is further added.
A mass solution was added to prepare a raw material solution. This raw material solution was continuously supplied to a sulfonation reactor equipped with a turbine-type stirrer together with SO ₃ , which is a sulfonating agent, to carry out a sulfonation reaction at 45 ° C. In this case, feed rate, feed solution 24 g / min, SO ₃ 3.61 g / min, molar ratio of SO ₃ to styrene units in the polystyrene 1.07, also the reactor as a capacity 400ml jacketed used. The obtained sulfonated product was neutralized with a 10% aqueous potassium hydroxide solution, and the separated and concentrated 34% aqueous potassium polystyrenesulfonate solution was cooled to crystallize and remove potassium sulfate for purification. In that case, it cooled from 15 degreeC to 0 degreeC over 7 hours (2.1 degreeC / hr), and hold | maintained at 0 degreeC for 2 hours, and crystallized. Further drying, a powder of potassium polystyrene sulfonate was obtained. The obtained potassium polystyrene sulfonate (polymer A) had a weight average molecular weight of 10,000, a sulfonic acid group introduction ratio to the styrene unit of 98 mol%, and a residual potassium sulfate content of 1.8%.

(Production Example 2) 1,2-dichloroethane 54
A solution in which 180 parts by mass of benzoic acid was dissolved in 0 parts by mass was cooled in an ice bath, and 65 parts by mass of sulfuric anhydride was added dropwise to this to prepare a benzoic acid-sulfuric acid anhydride complex. This complex solution was added to polystyrene having a weight average molecular weight of 5,000 (JP-A-3-52).
240 parts by mass of the polymer described in Example 1 of Japanese Patent No. 902) was added dropwise to a solution dissolved in 1000 parts by mass of 1,2-dichloroethane to cause a reaction. The reaction solution was stirred for 1 hour while cooling with an ice bath, and the temperature was further raised to 60 ° C. and stirred for 1 hour to complete the reaction. The reaction solution was extracted with water, the aqueous phase was washed with ether several times, neutralized with an aqueous potassium hydroxide solution, and then cooled in the same manner as in Production Example 1 to crystallize and remove potassium sulfate for purification. did. Further drying, a powder of potassium polystyrene sulfonate was obtained. The weight average molecular weight of the obtained polystyrene sulfonate (polymer B) was 5,500, the sulfonic acid group introduction ratio to the styrene unit was 30 mol%, and the residual potassium sulfate content was 1.0.
%Met.

(Production Example 3) To 100 parts by mass of 1,2-dichloroethane (containing 5.1 times mol of water with respect to tin tetrachloride), 0.15 parts by mass of anhydrous tin tetrachloride was added. The mixture was stirred under reflux. To this, add 100 parts by weight of styrene to 5 parts.
It dripped over time. After completion of the dropping, stirring was carried out for 3 hours under reflux. The polystyrene obtained had a weight average molecular weight of 5,000. In the obtained polystyrene solution,
Further, 200 parts by mass of 1,2-dichloroethane was added to prepare a raw material solution. This raw material solution was continuously supplied to a sulfonation reactor equipped with a turbine-type stirrer together with SO ₃ , which is a sulfonating agent, to carry out a sulfonation reaction at 45 ° C. In this case, the feed rate is 24 g / min of the raw material solution, SO
₃ 4.05 g / min, the molar ratio of SO _{3 to} styrene unit in polystyrene was 1.15, and the reactor used had a jacket and a capacity of 400 ml. The obtained sulfonated product was neutralized with a 10% aqueous sodium hydroxide solution, and then separated and concentrated. The mixture was cooled in the same manner as in Production Example 1, and sodium sulfate was crystallized and removed by filtration for purification. Further, it was dried to obtain a powder of sodium polystyrene sulfonate.
The weight average molecular weight of the obtained sodium polystyrene sulfonate (Polymer C) was 13,700, the sulfonic acid group introduction ratio to the styrene unit was 105 mol%, and the residual sodium sulfate content was 3.5%.

(Production Example 4) 1,2-dichloroethane 20
A solution in which 25.4 parts by mass of 1,4-dioxane was dissolved in 0 parts by mass was cooled in an ice bath, and 46 parts by mass of anhydrous sulfuric acid was added dropwise to this to prepare a dioxane-anhydrous sulfuric acid complex. This complex solution was converted into polystyrene having a weight average molecular weight of 9,400 (polymer described in Example 8 of JP-A-3-52902).
240 parts by mass was added to a solution dissolved in 1000 parts by mass of 1,2-dichloroethane and reacted. The reaction solution was stirred for 1 hour while cooling in an ice bath, and the temperature was further raised to 60 ° C.
After stirring and stirring for 1 hour, a small amount of water was added to quench. An aqueous sodium hydroxide solution was added to the obtained reaction solution, the mixture was neutralized with stirring with a homogenizer, and then separated into an aqueous phase and a solvent phase (1,2-dichloroethane phase) by centrifugation, and water was added to the solvent phase. In addition, the extraction operation was performed twice. Then, the solvent phase was dried to obtain a powder of sodium polystyrene sulfonate. The weight average molecular weight of the obtained sodium polystyrene sulfonate (Polymer D) was 1100.
0, the sulfonic acid group introduction rate to the styrene unit was 20 mol%, and the residual sodium sulfate content was 0.03%.

(Production Example 5) 1,2-dichloroethane 10
2 parts by mass of benzoyl peroxide was added to 0 parts by mass, and 100 parts by mass of styrene monomer was added with stirring under reflux to obtain 10 parts by mass.
The mixture was stirred under reflux for an hour. The weight average molecular weight of the obtained polystyrene was 37,000. Moreover, 1,4-dioxane 84.
The solution in which 7 parts by mass was dissolved was cooled in an ice bath, and 76.9 parts by mass of sulfuric anhydride was added dropwise to prepare a dioxane-anhydrous sulfuric acid complex. This complex solution was added to the obtained polystyrene 1
00 parts by mass was added to a solution prepared by dissolving 400 parts by mass of 1,2-dichloroethane with stirring. The mixture was stirred for 1 hour while cooling with an ice bath, the temperature was further raised to 60 ° C., and the mixture was stirred for 1 hour. Water was added to the reaction solution for extraction, neutralization with an aqueous solution of sodium hydroxide, followed by cooling in the same manner as in Production Example 1 for crystallization, filtration and removal of sodium sulfate for purification. Further drying, a powder of sodium polystyrene sulfonate was obtained.
The obtained sodium polystyrene sulfonate (polymer
E) had a weight average molecular weight of 74,000, a sulfonic acid group introduction ratio to the styrene unit of 82 mol%, and a residual sodium sulfate content of 3.1%.

(Production Example 6) 100 parts by mass of sodium styrenesulfonate was dissolved in 400 parts by mass of purified water, and after nitrogen substitution, 1.6 parts by mass of potassium persulfate and 3.0 parts by mass of ammonium persulfate were added. Polymerization was carried out by stirring at 50 ° C. for 6 hours. The obtained aqueous solution of sodium polystyrene sulfonate was used as an ion exchange resin (Amberlite MB1;
(Manufactured by Organo). Then, it was neutralized with sodium hydroxide and further dried to obtain sodium polystyrenesulfonate powder. The weight average molecular weight of the obtained sodium polystyrene sulfonate (Polymer-F) was 50,0.
00, the introduction ratio of sulfonic acid group per styrene unit is 10
0 mol% and residual sodium sulfate content were 0.02%.

(Production Example 7) Weight average molecular weight of 5,000
Polystyrene (described in Example 1 of Published Patent H3-52902)
100 parts by mass of 1,2-dichloroethane
Dissolves in 400 parts by mass and further 1.0 acetophenone
A raw material solution was prepared by adding parts by weight. This raw material solution is
Sulfonating agent in a sulfonation reactor with a bottle-type stirrer
Is SO ₃Continuously supplied with
A phonation reaction was performed. In this case, the feed rate is
24 g / min, SO₃3.61 g / min in polystyrene
SO for styrene units₃Has a molar ratio of 0.98 or
Also, the reactor should have a jacket and a capacity of 400 ml.
used. The sulfonated product obtained was added to 500 parts by mass of water.
After stirring for 1 hour, the mixture is allowed to stand to separate 1,2-dichloroethane.
Released. The resulting polystyrene sulfonic acid aqueous solution was
On-exchange resin (Organo's Amberlite IRA96
Desulfate using SB) and neutralize with aqueous potassium hydroxide solution
Then, concentrate and dry it to obtain polystyrene sulfonate.
Obtained a powder of lithium. Obtained polystyrene sulfonic acid
The weight average molecular weight of potassium (polymer-G) is 10,000.
0, the introduction rate of sulfonic acid group per styrene unit is 95
%, And the residual potassium sulfate content was 0.01%.

(Comparative Production Example 1) Weight average molecular weight 5,000
100 parts by mass of polystyrene (polymer described in Example 1 of JP-A-3-52902) of No. 0 was dissolved in 400 parts by mass of 1,2-dichloroethane, and 1.0 part by mass of acetophenone was further added to prepare a raw material solution. did. This raw material solution was continuously supplied to a sulfonation reactor equipped with a turbine-type stirrer together with SO ₃ , which is a sulfonating agent, at 45 ° C.
The sulfonation reaction was carried out. In this case, feed rate, feed solution 24 g / min, SO ₃ 3.61 g / min, molar ratio of SO ₃ to styrene units in the polystyrene 1.0
7. The reactor used had a jacket and a capacity of 400 ml. The obtained sulfonated product was neutralized with a 10% aqueous potassium hydroxide solution, separated, concentrated, and further dried to obtain a potassium polystyrenesulfonate powder. The obtained potassium polystyrene sulfonate (polymer H) had a weight average molecular weight of 10,000, a sulfonic acid group introduction ratio to the styrene unit of 98 mol%, and a residual potassium sulfate content of 7.2%.

(Comparative Production Example 2) A solution prepared by dissolving 180 parts by mass of benzoic acid in 540 parts by mass of 1,2-dichloroethane was cooled in an ice bath, and 65 parts by mass of sulfuric acid anhydride was added dropwise thereto to add benzoic acid-sulfuric acid anhydride. The complex was prepared. This complex solution was added to polystyrene having a weight average molecular weight of 5,000 (JP-A-3-5
240 parts by mass of the polymer described in Example 1 of 2902 gazette) was added dropwise to a solution dissolved in 1000 parts by mass of 1,2-dichloroethane to cause a reaction. The reaction solution was stirred for 1 hour while cooling in an ice bath, and the temperature was further raised to 60 ° C.
The reaction was completed by stirring for a period of time. This reaction solution is extracted with water,
The aqueous phase was washed several times with ether, neutralized with an aqueous potassium hydroxide solution, and then dried to obtain a powder of potassium polystyrene sulfonate. The weight average molecular weight of the obtained potassium polystyrene sulfonate (Polymer I) was 5,50.
0, the sulfonic acid group introduction rate to the styrene unit was 30 mol%, and the residual potassium sulfate content was 5.4%.

(Comparative Production Example 3) 1,2-dichloroethane (containing 5.1 times mol of water relative to tin tetrachloride) 10
After 0.15 parts by mass of anhydrous tin tetrachloride was added to 0 parts by mass, the mixture was stirred under reflux. To this, 100 parts by mass of styrene was added dropwise over 5 hours. After completion of the dropping, stirring was carried out for 3 hours under reflux. The polystyrene obtained had a weight average molecular weight of 5,000. 200 parts by mass of 1,2-dichloroethane was further added to the obtained polystyrene solution to prepare a raw material solution. This raw material solution was added to a sulfonation reactor equipped with a turbine-type stirrer, SO
_It was continuously supplied together with ₃ , and the sulfonation reaction was carried out at 45 ° C. In this case, the feed rate is 24 g / min of the raw material solution,
SO ₃ 4.05 g / min, the molar ratio of SO _{3 to} styrene units in polystyrene was 1.15, and the reactor used had a jacket and a capacity of 400 ml. The obtained sulfonated product was neutralized with a 10% aqueous sodium hydroxide solution, separated and concentrated, and further dried to obtain a powder of sodium polystyrene sulfonate. The weight average molecular weight of the obtained sodium polystyrene sulfonate (Polymer J) was 13,700, the sulfonic acid group introduction ratio to the styrene unit was 105 mol%, and the residual sodium sulfate content was 10.
It was 5%.

Comparative Production Example 4 2 parts by mass of benzoyl peroxide was added to 100 parts by mass of 1,2-dichloroethane, and 100 parts by mass of styrene monomer was added with stirring under reflux.
The mixture was stirred under reflux for 10 hours. The weight average molecular weight of the obtained polystyrene was 37,000. Also, 1,2
-1,4-dioxane 8 in 400 parts by weight of dichloroethane
The solution in which 4.7 parts by mass was dissolved was cooled in an ice bath, and 76.9 parts by mass of sulfuric acid anhydride was added dropwise to prepare a dioxane-anhydrous sulfuric acid complex. This complex solution was added to a solution prepared by dissolving 100 parts by mass of the obtained polystyrene in 400 parts by mass of 1,2-dichloroethane while stirring. Stir for 1 hour while cooling in an ice bath, then raise the temperature to 60 ° C and
Stir for hours. Water was added to this reaction solution for extraction, neutralization with an aqueous sodium hydroxide solution, and drying to obtain sodium polystyrene sulfonate powder. The obtained sodium polystyrene sulfonate (Polymer-K) had a weight average molecular weight of 74,000, a sulfonic acid group introduction ratio to the styrene unit of 82 mol%, and a residual sodium sulfate content of 13.0%.
Met.

[Examples 1 to 9 and Comparative Examples 1 to 6] Sulfonic acid metal salts of styrene-based polymers obtained in the above Production Examples 1 to 7 and Comparative Production Examples 1 to 4 [Polymers A to K (Polymer G) A) and a commercially available polycarbonate resin with an anti-dripping agent shown below; Iupilon S300
0 (manufactured by Mitsubishi Engineer Plastics Co., Ltd.) was blended with the amounts shown in Tables 2 and 3 below and supplied to an extruder at 300 ° C.
Was kneaded and pelletized. The resulting pellets are 120
After drying at ℃ for 4 hours, molding temperature 300 using injection molding machine
Injection molding was performed at ℃ to obtain a test piece having a predetermined shape. In addition, a commercially available polycarbonate resin; Iupilon S3000 (manufactured by Mitsubishi Engineer Plastics Co., Ltd.) and potassium polystyrene sulfonate (polymer G) obtained in Production Example 7,
The dripping agent shown below was blended in an amount 10 times the amount shown in Table 2 below, and the mixture was fed to an extruder at 300 ° C.
Was kneaded and pelletized to prepare a master batch of Polymer G and a dripping agent. After drying 100 parts by mass of the obtained masterbatch pellets at 120 ° C. for 4 hours, a commercially available polycarbonate resin (Iupilon S3000) 9
Mixing 100 parts by mass and using an injection molding machine, molding temperature 3
Injection molding was performed at 00 ° C to obtain a test piece having a predetermined shape. Using these test pieces, flame retardancy, appearance, heat resistance and light resistance were evaluated by the following methods. The results are shown in Tables 2 and 3 below.

[Used (* 1-shown in Tables 2 and 3 below)
* 6) Anti-dripping agent] (* 1): fibril-forming fluoropolymer (polytetrafluoroethylene, "Teflon (registered trademark) 6-J" manufactured by Mitsui DuPont Fluorochemical Co., Ltd.) (* 2) : Silicone compound (methylphenyl-based liquid silicone oligomer, "X-40" manufactured by Shin-Etsu Chemical Co., Ltd.
-9243 ") (* 3): Silicone compound (methylphenyl liquid silicone oligomer," X-40 manufactured by Shin-Etsu Chemical Co., Ltd. "
-9244 ") (* 4): Methylphenyl-based solid silicone resin (" X-40-9805 "manufactured by Shin-Etsu Chemical Co., Ltd.) (* 5): Epoxy group-containing silicone powder (manufactured by Toray Dow Corning Silicone Co., Ltd.) "DC4-705
1 ") (* 6): Polyether-modified silicone (GE Toshiba Silicone" TSF4452 ")

[Flame Retardancy Test Method] Using an injection molding machine,
Test pieces (125 × 13 × 1.6 mm and 125 × 13 × 3.2 mm) for flame retardancy evaluation were molded, and 5 pieces of each of the test pieces were placed in a thermostatic chamber at a temperature of 23 ° C. and a humidity of 50%. After being left for a period of time, flame retardancy was evaluated according to UL94 test (flammability test of plastic material for parts of equipment) defined by Underwriter Laboratories. The afterflame time test was performed twice each. The UL94 is a method for evaluating the flame retardancy from the afterflame time and the drip property after the flame of a burner is indirectly flamed for 10 seconds on a test piece of a predetermined size held vertically, and V shown in Table 1 below. -0, V-
It is divided into 1 and V-2 classes.

[0040]

[Table 1]

[Evaluation Method of Appearance] Test piece (75 mm × 7
The appearance of a 5 mm × 3.2 mm resin plate) was visually evaluated according to the following evaluation criteria. Evaluation criteria: ◎: good transparency, colorless ◯: slightly cloudy, colorless Δ: slightly cloudy, slightly yellow x: cloudy, yellow or yellow with good transparency

[Heat Resistance Evaluation Method] Test piece (75 mm ×
The degree of turbidity of the resin plate after storing (75 mm × 3.2 mm resin plate) at 140 ° C. for 500 hours was visually compared with that before storage and evaluated according to the following evaluation criteria. Evaluation criteria: ◯: No change △: Some deterioration can be seen ×: Only deterioration

[Evaluation Method of Light Resistance] Test piece (75 mm ×
30 x xenon lamp on 75 mm x 3.2 mm resin plate)
The degree of change in yellowing after 0 hour irradiation was visually compared with that before irradiation and evaluated according to the following evaluation criteria. Evaluation criteria: ◯: No change △: Slightly yellowed ×: Yellowed

[0044]

[Table 2]

[0045]

[Table 3]

As is clear from the results of Tables 2 and 3, the thermoplastic resins (polycarbonate resins) of Examples 1 to 9 using the flame retardancy-imparting agent for thermoplastic resin within the scope of the present invention are the same as those of the present invention. Compared with the thermoplastic resin (polycarbonate resin) of Comparative Examples 1 to 6 using the flame retardancy-imparting agent for thermoplastic resin out of the range, the flame retardancy, appearance, heat resistance and light resistance are excellent. It has been found.

Examples 10 to 12 and Comparative Example 7 The sulfonic acid metal salt of the styrene-based polymer obtained in the above Production Examples 1 to 3 and Comparative Production Example 1 was used as a commercially available polycarbonate resin; Iupilon S3000 (Mitsubishi Engineering Plastics). (Manufactured by the same company) was blended in the amounts shown in Table 4 below, supplied to an extruder, kneaded at 300 ° C., and pelletized. The obtained pellets were dried at 120 ° C. for 4 hours and then injection molded at a molding temperature of 300 ° C. using an injection molding machine to obtain a test piece having a predetermined shape. These test pieces were evaluated for flame retardancy, appearance, heat resistance and light resistance. The following limiting oxygen index was used for the test method of flame retardancy. The other test methods are the same as above. The results are shown in Table 4 below.

(Measuring Method of Limiting Oxygen Index) JIS K
7201-2: 1999 compliant (Test condition: 126 mm
It was measured using a test piece of × 13 mm × 3 mm). The limiting oxygen index is a value indicating the minimum oxygen concentration necessary for maintaining combustion of the test material under the above-mentioned test conditions, in volume% in air. The larger this value, the higher the flame retardancy of the material.

[0049]

[Table 4]

As is clear from the results in Table 4 above, the thermoplastic resins (polycarbonate resins) of Examples 10 to 12 using the flame retardancy-imparting agent for thermoplastic resins within the scope of the present invention.
Is excellent in flame retardancy, appearance, heat resistance and light resistance as compared with the thermoplastic resin (polycarbonate resin) of Comparative Example 7 using a flame retardant for a thermoplastic resin which falls outside the scope of the present invention. It turned out to be

[0051]

According to the invention described in claim 1, it is possible to provide a good flame retardancy without deteriorating the original physical properties of the thermoplastic resin and, at the same time, to improve the kneadability with the resin. A flammability imparting agent is provided. According to the invention of claim 2, good flame retardancy is provided without deteriorating the original physical properties of the thermoplastic resin, and at the same time, deterioration of the resin containing the flame retardant-imparting agent such as yellowing occurs. A flame-retardant thermoplastic resin that does not exist is provided. According to the invention described in claims 3 and 4, good flame retardancy is provided without impairing the physical properties inherent to the polycarbonate resin, and at the same time, the kneadability with the resin is improved, and the inherent transparency of the polycarbonate resin is maintained. Provided are a flame retardant for a polycarbonate resin and a flame-retardant polycarbonate resin which are sufficiently maintained and have excellent flame retardancy.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Minako Kanamaru             1-3-7 Honjo, Sumida-ku, Tokyo Rio             Within the corporation (72) Inventor Yoichiro Kono             1-3-7 Honjo, Sumida-ku, Tokyo Rio             Within the corporation F term (reference) 4J002 BB00X BC01W BC02X BC03W                       BC05W BC08W BC09W BD00X                       BG03X CF00X CG00X CH07X                       CL00X CN01X FD13W

Claims (4)

[Claims] 1. A flame retardant imparting agent for a thermoplastic resin, comprising a sulfonic acid metal salt of a styrene polymer and having a metal sulfate content of 5% by mass or less. 2. A flame-retardant thermoplastic resin comprising the flame-retardant imparting agent according to claim 1. 3. A sulfonic acid metal salt of a styrenic polymer in which the aromatic monomer unit having a sulfonic acid group in the aromatic skeleton is 15 to 45 mol% with respect to all the monomer units, and the content of the metal sulfate salt. Is 5% by mass or less, and a flame retardancy-imparting agent for a polycarbonate resin. 4. A flame-retardant polycarbonate resin comprising the flame-retardant imparting agent according to claim 3.