JP2678461B2 - Flame-retardant resin aqueous composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention mainly relates to an aqueous flame-retardant resin composition for applying flame-retardant properties by applying processing to fibers, paper products, etc. And a chlorinated vinyl chloride-based resin powder and a specific amount of antimony trioxide are added to the resin aqueous dispersion of 1.

[Conventional technology and its problems]

In recent years, measures against fire have been extremely important. There is a great demand for flame-retardant interiors of various vehicles and houses, and various flame-retardant technologies for interior members such as automobiles have been proposed. Textile products used in automobile interiors, such as car seats, floor mats, door trims, and ceilings, have flame retardants added to the fibers, and special fibers made of flame-retardant polymers are used as the fibers themselves. A flame retardant material has been proposed. However, when the fiber itself contains a flame retardant, it is often impossible to obtain sufficient physical properties in terms of strength, feel, etc., and also when a special flame-retardant polymer is used as the fiber, the dyeing and hand feel However, it has not been put to practical use due to many problems and high cost.

Therefore, at present, a flame-retardant (co) polymer emulsion such as vinyl chloride type or vinylidene chloride type is used as a back coating agent used as a reinforcing agent for textiles, or the flame retardant (co) polymer is used. In many cases, a flame retardant is often added to an emulsion, an ordinary synthetic rubber-based, acrylic-based, (styrene) -acrylic (co) polymer emulsion, or a blend thereof with a flame retardant, and the mixture is applied.

Examples of such flame retardants include liquid or powdered phosphoric acid ester-based, halogenated phosphoric acid ester-based, halogen compound-based, guanidine-based, and triazine-based organic flame-retardants;
Inorganic flame retardants such as antimony-based, aluminum-based, and boron-based flame retardants; and the like are used alone or in combination.

However, the flame-retardant (co) polymer emulsion may have insufficient stability due to the generation of hydrochloric acid over time, or may be colored during coating, and sufficient flame retardancy can be obtained by itself. There are many problems such as not being. When the flame retardant is mixed with the (co) polymer emulsion, the liquid flame retardant generally acts like a plasticizer, softens the resin and impairs the texture, and in the long term, a fiber is used. This may cause problems such as transfer to products or volatilization to fog indoor window glass, and powdered flame retardants reduce the stability of the (co) polymer emulsion, so the blending amount There is a limit on its own, a small amount of flame retardant effect is not enough, and the texture often becomes extremely hard.

[Means for solving the problem]

The present inventors have conducted extensive studies to solve the problems of the above-mentioned conventional techniques, and as a result, a specific acrylic resin aqueous dispersion liquid, a chlorinated vinyl chloride resin powder and antimony trichloride in specific amounts, respectively. The present invention has been completed by discovering that the inclusion thereof can solve the above problems.

That is, the present invention, with respect to the total amount of ethylene-based monomer,
The total amount of monomers selected from alkyl ester-based monomers of acrylic acid, alkyl ester-based monomers of methacrylic acid and vinyl cyanide-based monomers is 50% by weight or more,
The rest are aromatic vinyl monomers, saturated fatty acid vinyl monomers, ethylene carboxylic acids, ethylene carboxylic acid amides, ethylene carboxylic acid amide methylol derivatives and derivatives, ethylene carboxylic acids and epoxies. Acrylic resin aqueous dispersion consisting of one or more acrylic (co) polymer emulsions obtained from monomers selected from esters with alcohols having a group and hydroxyalkyl esters of ethylene-based carboxylic acids Chlorinated vinyl chloride resin powder 5-100 with an average chlorine content of about 60-80% by weight with respect to 100 parts by weight of the solid content of the liquid
It is intended to supply an aqueous flame-retardant resin composition, characterized by containing 1 part by weight to 1 part by weight and 1 to 80 parts by weight of antimony trioxide.

 Hereinafter, the present invention will be described in more detail.

In the present invention, an acrylic resin aqueous dispersion comprising one or more acrylic (co) polymer emulsions means an ethylene monomer mainly containing an acrylic monomer as a surfactant and / or Alternatively, an acrylic (co) polymer obtained by emulsion polymerization in an aqueous medium in the presence or absence of a protective colloid, or by post-emulsifying an acrylic (co) polymer polymerized by a method other than emulsion polymerization The emulsion is a single substance or a blend of a plurality of these acrylic (co) polymer emulsions, and is not particularly limited, but usually emulsion polymerization is used for reasons such as ease of production and economy. The resulting acrylic (co) polymer emulsion is preferably a single substance or a blend of a plurality of acrylic (co) polymer emulsions.

Examples of the alkyl ester-based monomer of acrylic acid that can be used in the present invention include methyl acrylate, ethyl acrylate, n-butyl acrylate,
Isobutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, etc .; Examples of the alkyl ester-based monomer of methacrylic acid include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2 -Ethylhexyl methacrylate, stearyl methacrylate, etc .; Examples of vinyl cyanide-based monomers include acrylonitrile and methacrylonitrile;
Examples of the aromatic vinyl-based monomer include styrene and α
-Methylstyrene, vinyltoluene, ethylvinylbenzene, etc .; Examples of the saturated fatty acid vinyl monomer include:
Vinyl acetate, vinyl propionate, vinyl versatate, etc .; Examples of the ethylene-based carboxylic acid include, for example, acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, fumaric acid, etc. Anhydrides of ethylene-based carboxylic acids such as maleic acid, monoalkyl esters of ethylene-based dicarboxylic acids (monobutyl maleic acid, etc.), and ammonium salts or alkali metal salts thereof; examples of amides of ethylene-based carboxylic acids include , Acrylamide, methacrylamide, diacetone acrylamide, etc .; Examples of methylolated amides of ethylene-based carboxylic acids and their derivatives include N-methylol acrylamide and N
-Methylol methacrylamide, methylol-diacetone acrylamide, and etherification products of these methyl amides of ethylene-based carboxylic acids and alcohols having 1 to 8 carbon atoms (for example, N-isobutoxymethyl acrylamide); As the esters of ethylene-based carboxylic acid and alcohol having an epoxy group,
For example, glycidyl acrylate, glycidyl methacrylate, etc .; Examples of hydroxyalkyl esters of ethylene-based carboxylic acids include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2
-Hydroxyethyl methacrylate and the like;

The above-mentioned ethylene-based monomer is based on the total amount of the ethylene-based monomer forming the (co) polymer, the alkyl ester-based monomer of acrylic acid, the alkyl ester-based monomer of methacrylic acid, and cyanide. In the range in which the total amount of monomers selected from vinyl-based monomers is 50% by weight or more, the type and amount thereof are not particularly limited, such as fibrous products to be flame-retarded. It can be appropriately selected depending on the required substance.

The flame-retardant resin composition of the present invention, which uses an acrylic resin aqueous dispersion as the resin aqueous dispersion, can be particularly suitably used in the field of car seats and the like that require light resistance and weather resistance.

Here, the "total amount of ethylene-based monomers" refers to the total amount of ethylene-based monomers required to produce all (co) polymers present in the resulting acrylic resin aqueous dispersion. Among these, in the case of car seats, etc. that require a soft texture, the glass transition temperature measured by the DSC method is -4
It is particularly preferable to use an acrylic resin aqueous dispersion having a temperature of about 0 to -10 ° C.

In the present invention, the acrylic resin aqueous dispersion DSC
The method glass transition temperature (Tg) is a value measured and determined by the following.

About 10 mg of an acrylic resin aqueous dispersion sample is weighed in a cell and dried at 100 ° C. for 2 hours to be used as a measurement sample. Shimadzu DT-30 differential scanning calorimeter (Differential Sca
nning Calorimeter), the temperature rise rate from -80 ℃ to 20 ℃ /
Measure and determine at min. Nitrogen gas is used as the carrier gas at a flow rate of 20 c.c./min. For measurement.

The acrylic resin aqueous dispersion for maintaining the soft texture as described above comprises about 0.5 to about 5% by weight of the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer based on the total amount of the ethylene-based monomer. Preferably.

Examples of the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer include amides of ethylene-based carboxylic acid; methylolated ethylene-carboxylic acid amides and derivatives thereof; Examples thereof include esters of carboxylic acids and alcohols having an epoxy group; hydroxyalkyl esters of ethylene-based carboxylic acids; and the like. These monomers can be used alone or in combination of two or more kinds, Among these, it is preferable to use a methylol derivative of an ethylene-based carboxylic acid amide, and N-methylol (meth) acrylamide is used, from the viewpoints of polymerization reaction suitability, water resistance and solvent resistance of the resulting fiber product. Is particularly preferable.

When the amount of the heat-crosslinkable ethylene-based carboxylic acid derivative-based monomer is about 0.5% by weight or more, the resulting flame-retardant fiber product has excellent water resistance and solvent resistance, and about 5% by weight or less. Since there is no problem in terms of suitability for polymerization reaction, it is preferable to use the monomer in the range of about 0.5 to about 5% by weight.

Further, in the present invention, the stability of the obtained flame-retardant resin aqueous composition is that the above-mentioned ethylene-based carboxylic acid is further contained in an amount of about 0.5 to about 6% by weight based on the total amount of the ethylene-based monomer. In addition, it is particularly preferable from the viewpoint of excellent water resistance and solvent resistance when a heat-crosslinkable ethylene carboxylic acid derivative monomer is used. As such ethylene-based carboxylic acids, acrylic acid, methacrylic acid and / or itaconic acid are preferably used from the above effects and suitability for polymerization reaction.

Next, for example, in a field requiring a relatively hard texture such as a floor mat, an acrylic resin aqueous dispersion having a Tg of 10 ° C. or higher can be preferably used.

The acrylic resin aqueous dispersion of the present invention is usually obtained by emulsion-polymerizing an ethylene monomer appropriately selected from the above monomer group in an aqueous medium in the presence of a surfactant and / or a protective colloid. It is a single substance of the (co) polymer emulsion obtained by the above, or a blend of a plurality of these (co) polymer emulsions.

As the above-mentioned surfactant, as nonionic surfactants, for example, polyoxyethylene lauryl ether,
Polyoxyalkylene alkyl ethers such as polyoxyethylene stearyl ethers; polyoxyalkylene alkyl phenol ethers such as polyoxyethylene octylphenol ether, polyoxyethylene nonylphenol ethers; eg sorbitan monolaurate, sorbitan Monostearate,
Sorbitan fatty acid esters such as sorbitan trioleate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene sorbitan monolate; polyoxyalkylenes such as polyoxyethylene monolate and polyoxyethylene monostearate Fatty acid esters; for example, glycerin fatty acid esters such as oleic acid monoglyceride, stearic acid monoglyceride, etc .; for example, polyoxyethylene / polyoxypropylene / block copolymers; and the like can be exemplified, and as anionic surfactants, A fatty acid salt such as sodium oleate; an alkylaryl sulfonate such as sodium dodecylbenzenesulfonate; a sodium lauryl sulfate; Alkylsulfate ester salts; for example, sodium monooctyl sulfosuccinate, sodium dioctyl sulfosuccinate, sodium polyoxyethylene lauryl sulfosuccinate, and derivatives thereof; and, for example, polyoxyethylene lauryl ether sulfate sodium Examples of the cationic surfactants include lauryl amine acetate. Alkylamine salts such as; quaternary ammonium salts such as lauryltrimethylammonium chloride, alkylbenzyldimethylammonium chloride; If, polyoxyethylalkylamines; etc., and as amphoteric surfactants, for example, a alkyl betaines such as lauryl betaine. Further, those in which a part of hydrogen atoms of the alkyl group of these surfactants are replaced with fluorine can also be used. Furthermore, a so-called reactive surfactant having a radically polymerizable double bond in the molecular structure of the surfactant can also be used, and as such a reactive surfactant,
For example, reactive anionic surfactants such as sulfosuccinic acid alkylalkenyl ester salt type and alkenylsuccinic acid monoalkenyl ester salt type can be mentioned.

The amount of the surfactant used is usually about 0.1 to about 10% by weight, based on the total amount of the ethylene-based monomer, the reaction suitability of the emulsion polymerization, various stability of the resulting resin aqueous dispersion, and water resistance. Etc. About 0.5 to about 6% by weight is preferably used, and about 0.5 to about 4% by weight is particularly preferably used.

Examples of protective colloids that can be used in the present invention include, for example, polyvinyl alcohols such as partially saponified polyvinyl alcohol, fully saponified polyvinyl alcohol and modified polyvinyl alcohol; for example, hydroxyethyl cellulose, hydroxypropyl cellulose, carboxymethyl cellulose salt and the like. A cellulose derivative; and, for example,
Natural polysaccharides such as guar gum; and the like can be used, and these can be used alone or in combination of plural kinds. The amount used can be appropriately selected, and examples thereof include an amount of 0 to about 10% by weight based on the total amount of the ethylene-based monomer used.

The "in aqueous medium" in the present invention means in water or an aqueous solution of a water-soluble organic solvent, and such a water-soluble organic solvent is not particularly limited, and examples thereof include methyl alcohol, ethyl alcohol and isopropyl. Water-soluble alcohols such as alcohols; water-soluble ketones such as acetone; water-soluble ethers such as methyl cellosolve, cellosolve, butyl cellosolve, carbitol, butyl carbitol; It is possible to use it, and the amount used can be, for example, about 0 to about 50% by weight as the aqueous solution concentration of the water-soluble organic solvent. However, from the viewpoints of various stability of the resulting resin aqueous dispersion, as well as the water resistance and solvent resistance of the flame-retardant processed product, it is preferable to carry out the emulsion polymerization in water substantially free of these organic solvents. .

In addition, in the case of emulsion polymerization, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; organic compounds such as tert-butyl hydroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, etc. Peroxides;
A polymerization initiator such as hydrogen peroxide can be used. These can be used either in one kind or in a combination of plural kinds. The amount used can be appropriately selected, and is, for example, from about 0.05 to about 1% by weight, preferably from about 0.1 to about 0.7% by weight, and particularly about
The amount used may be exemplified by 0.1 to about 0.5% by weight.

In addition, a reducing agent can be used in combination during emulsion polymerization, if desired. Examples thereof include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and grape; reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. The amount used can be appropriately selected, and for example, the amount used can be exemplified as about 0.05 to about 1% with respect to the total amount of the ethylene-based monomer used.

The acrylic resin aqueous dispersion used in the present invention is preferably the thus obtained acrylic (co) polymer emulsion alone or a blend of a plurality of acrylic (co) polymer emulsions.

The solid content of the acrylic resin aqueous dispersion used in the present invention is not particularly limited, but it may be about from the viewpoint of productivity and ease of production.
It is preferably from 30 to about 65% by weight.

The flame-retardant resin aqueous composition of the present invention is obtained by adding chlorinated vinyl chloride resin powder and antimony trioxide to the acrylic resin aqueous dispersion as described above.

The vinyl chloride resin used in the production of the above chlorinated vinyl chloride resin may be a vinyl chloride homocopolymer or a vinyl chloride copolymer with another monomer copolymerizable with vinyl chloride. However, when a copolymer is used, the content of the other copolymerizable monomer is 15 parts by weight or less, preferably 6 parts by weight or less, based on 100 parts by weight of the vinyl chloride unit. Is good. Examples of the other copolymerizable monomer include the above-mentioned saturated fatty acid vinyl-based monomer, acrylic acid ester-based monomer, and methacrylic acid ester-based monomer, for example, maleic acid such as dibutyl maleate and diethyl maleate. Acid ester monomer, for example,
Fumaric acid ester-based monomers such as dibutyl fumarate and diethyl fumarate, for example, vinyl ether-based monomers such as vinyl methyl ether, vinyl butyl ether, and vinyl octyl ether, vinyl cyanide-based monomers described above, and olefin-based monomers. Examples thereof include monomers such as vinylidene chloride and vinyl bromide, and other vinylidene halides or vinyl halide monomers other than vinyl chloride.

The average chlorine content of the chlorinated vinyl chloride resin used in the present invention needs to be about 60 to 80% by weight from the viewpoint of excellent flame retardancy and good yellowing resistance of the resin layer. And preferably about 62-72% by weight.

The amount of the chlorinated vinyl chloride resin powder used is based on 100 parts by weight of the solid content of the acrylic resin aqueous dispersion containing one or more of the (co) polymers of the ethylene monomer. , 5 to 100 parts by weight is necessary.

If the amount used is less than 5 parts by weight, the flame retardancy may be insufficient, and if it exceeds 100 parts by weight, the appearance and / or strength of the resulting fiber product may be insufficient. May decrease, which is not preferable. The amount used is 10 to 90
It is preferably part by weight, more preferably 20 to 90 parts by weight.

Further, the particle size of the chlorinated vinyl chloride resin powder is not particularly limited, but from the viewpoint of flame retardancy and good appearance of the obtained fiber product, etc. It is preferred that 90 wt% or more have a particle size that passes through a Tyler 100 mesh screen, and more preferably about 90 wt% have a particle size that passes through a Tyler 200 mesh screen.

Further, the amount of antimony trioxide used is 1 to 80 parts by weight based on 100 parts by weight of the solid content of the resin aqueous dispersion. If the amount used is less than 1 part by weight, the flame retardancy may be insufficient, and if the amount exceeds 80 parts by weight, the flame retardancy may not be expected to be further improved. The appearance and / or strength of the resulting fiber product may be deteriorated, which is not preferable. The amount used is preferably 5 to 70 parts by weight.

The particle size of the antimony trioxide is not particularly limited, but from the viewpoint of flame retardancy and appearance of the resulting fiber product, etc., about 90% by weight or more of the amount of the antimony trioxide used is a Tyler 100 mesh screen. It is preferable to pass through.

Furthermore, the flame-retardant resin aqueous composition of the present invention, if desired, in a use range that does not prevent the excellent effects of the present invention,
Flame retardants other than the above can be used in combination. Examples of such flame retardants include organic compounds such as tricresyl phosphate, cresyl phenyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, phosphate ester-based flame retardants such as tributyl sulfonate; Halogen-containing phosphate flame retardants such as tolyl (β-chloroethyl) phosphate, tris (β-bromoethyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, tris (bromochloropropyl) phosphate; for example, chlorine Paraffin, brominated polyphenyl,
Inorganic compounds such as chlorinated polyphenyl, perchloropentane cyclodecane, tetrabromoethane, hexabromocyclododecane, 1,2,3-tribromopropane, tetrabromobisphenol A tetrabromophthalic anhydride and other halogen compounds; For example, borax,
Boron compounds such as zinc borate and barium metaborate; aluminum compounds such as miubanban and aluminum hydroxide; magnesium compounds such as magnesium hydroxide; zirconium compounds such as zirconium oxide; it can. The amount of these flame retardants used may be, for example, about 0 to 40 parts by weight with respect to 100 parts by weight of the solid content of the acrylic resin aqueous dispersion according to the present invention. Among these flame retardants, it is preferable to use magnesium hydroxide in combination, because the flame retardancy of the resulting fiber product can be further enhanced. When the magnesium hydroxide is used in combination, it is preferable to use 4 to 50 parts by weight based on 100 parts by weight of the solid content of the acrylic resin aqueous dispersion.

The flame-retardant resin aqueous composition of the present invention contains a cross-linking agent and a cross-linking catalyst in addition to the resin aqueous dispersion, the chlorinated vinyl chloride resin powder, the antimony trioxide and the above-mentioned flame retardant optionally used in combination. You can also do it. Examples of the cross-linking agent include urea-formaldehyde resin, melamine-
Aqueous solution or aqueous dispersion of amino resin such as formaldehyde resin; Resol or novolak phenol resin aqueous solution or water dispersion: various epoxy resin aqueous solution; aqueous dispersion of blocked epoxy isocyanate processing agent or water dispersion Liquid; and the like, and it is preferable to mix an aqueous solution or dispersion of an amino resin from the viewpoints of easy availability, crosslinking reaction effect, and the like. The cross-linking agent may be used in the range of 0 to about 400 parts by weight in terms of solid content based on 100 parts by weight of solid content of the acrylic resin aqueous dispersion.

Cross-linking catalysts are often used especially in the use of amino resins, for example, inorganic acids such as hydrochloric acid and sulfuric acid, and (anhydrous) phthalic acid, organic acids such as paratoluene sulfonic acid, and inorganic acids and organic acids. Ammonium salts, amine salts and the like can be mentioned, and the amount thereof is about 0.5 to about 5 parts by weight as an active ingredient with respect to 100 parts by weight of the solid content of the amino resin.
It can be appropriately used within a range of about 10 parts by weight.

Further, if desired, an aqueous solution or dispersion of a resin other than the above, such as a polyester resin and a polyurethane resin, can be blended within a use range that does not impair the excellent effects of the present invention.

Furthermore, organic or inorganic fillers such as titanium oxide, clay, talc, calcium carbonate, silica, asbestos, carbon black, and phthalocyanine blue, pigments, dyes, film-forming aids, plasticizers, anti-aging agents, and antiseptic agents. Agent,
There is no problem even if an ultraviolet absorber or the like is added.

The method for producing the flame-retardant resin aqueous composition of the present invention is not particularly limited, but for example, an acrylic resin aqueous dispersion comprising one or more of the acrylic (co) polymer emulsion according to the present invention. To the liquid, if necessary, water, a wetting agent and / or a dispersion liquid is added, and then the chlorinated vinyl chloride resin powder and antimony trioxide are added, and if necessary, the various additives described above, for example, chlorine. Flame retardants other than modified vinyl chloride resin powder and antimony trioxide; cross-linking agents, cross-linking catalysts; organic or inorganic fillers, pigments, dyes; film-forming aids; plasticizers; anti-aging agents; preservatives; UV absorbers. , Etc. and sufficiently stirred and mixed to obtain. Further, the above chlorinated vinyl chloride resin powder, antimony trioxide and various additives which are added as necessary are premixed with the above water, wetting agent and / or dispersant by stirring and kneading in a slurry state. Create things,
This may be mixed with the above acrylic resin aqueous dispersion. Examples of the above-mentioned wetting agent include sulfosuccinic acid ester salt-based anionic surfactants such as sodium dioctylsulfosuccinate; for example, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether,
Polyoxyethylene alkyl ether-based nonionic surfactants such as polyoxyethylene oleyl ether;
As the dispersant, for example, polycarboxylic acid sodium salt-based,
Polycarboxylic acid ammonium salt type, styrene / maleic anhydride copolymer salt type, condensed naphthalene sulfonate type,
Nonionic surfactant-based, polyphosphate-based, and the like, the amount of the wetting agent and dispersant used, as an active ingredient,
For each 100 parts by weight of the solid content of the resin aqueous dispersion
Amounts of about 0.1 to 4.0 parts by weight and 0.1 to 5.0 parts by weight can be exemplified. The above-mentioned "active ingredient" means water and / or water which may be contained in the wetting agent and the dispersant.
Or, it means after volatilizing volatile components such as alcohol. Commercially available wetting agents and dispersants with unclear contents of active ingredients are dried at 105 ° C for 3 hours according to JIS K6833. By doing, it can be obtained.

Thus obtained P of the flame-retardant resin aqueous composition of the present invention
H, viscosity and solid content are not particularly limited, but from the viewpoint of sedimentation stability of the composition and the like, generally,
PH4-10, preferably 7-10; viscosity (25 ° C, 20RPM,) 100
0 to 10000 cps, preferably 2000 to 7000 cps .; solid content 30 to
It is about 70% by weight, preferably about 35 to 60% by weight.

The flame-retardant resin aqueous composition of the present invention is applied to various products such as textile products by the various methods such as that, or by appropriately diluting it with water or the like and impregnating, spraying, coating or the like. be able to. Further, if necessary, the viscosity can be further increased to a desired viscosity with polyvinyl alcohol, a cellulose-based derivative, polyvinyl alcohol, a cellulose-based derivative, a polycarboxylic oxygen resin, a surfactant-based thickener, or the like.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. In addition, the preparation of the test sample and the test method used in the above examples are as follows.

(1) Preparation of sample A flame-retardant resin composition was added to each of cotton broad # 40 (approx. 120 g / m ² per unit area), polyester cloth (approx. 65 g / m ² per unit area), and polyamide (approx. 70 g / m ² per unit area). It was applied so as to have a solid content of 150 g / m ² , pre-dried at 100 ° C. for 1 minute and then dried at 140 ° C. for 10 minutes. This was cut into 30 cm × 15 cm, left for 24 hours in an atmosphere of 25 ° C. × 65% RH, and then subjected to various tests.

(2) Appearance of processed cloth The processed cloth using the cotton broad # 40 prototyped in (1) was examined for the degree of powder falling when lightly hand-rubbed.

◎ No powder falling ○ Little powder falling △ Powder falling × Powder falling violently unusable as a work cloth (3) Combustion test A combustion test was performed by the horizontal method according to MVSS-302.

The test was performed at 10 points, and the average burning rate was displayed. In addition, what was extinguished during the test was indicated by the burning distance until extinction. The results are shown in Table 1.

Example 1 330 g of water and 6 g of polyoxyethylene nonylphenyl ether were placed in a 2 round bottom flask equipped with a stirrer and dissolved by heating at 40 ° C. After replacing the inside of the flask with nitrogen, the temperature is raised to 70 ° C. While maintaining 70 ° C, a mixture of 286 g of ethyl acrylate, 286 g of butyl acrylate and 9 g of acrylic acid, water 26
Emulsion copolymerization was performed by continuously adding an aqueous solution prepared by dissolving 12 g of N-methyl acrylamide and 6 g of sodium dodecylbenzenesulfonate to 0 g, 60 g of an aqueous solution of 2% ammonium persulfate and 60 g of an aqueous solution of 2% sodium metabisulfite for 5 hours. did.
The obtained copolymer emulsion has a solid content of about 46% and PH2.
5. The emulsion was a milky white emulsion with a viscosity of 120 cps (25 ° C, 20RPM), and the Tg of the copolymer was about -38 ° C.

The above copolymer emulsion was used as an aqueous resin dispersion, and 100 parts by weight thereof were added with 15 parts by weight of a 5% aqueous solution of sodium dioctylsulfosuccinate (solid content of the aqueous resin dispersion).
About 1.6 parts by weight per 100 parts by weight), 23 parts by weight of chlorinated vinyl chloride resin powder with a chlorine content of about 68% that passes through a Tyler 100 mesh screen (50 parts by weight), antimony trioxide 6.
9 parts by weight (15 parts by weight: Chlorinated vinyl chloride resin powder 100
Add 30 parts by weight to 30 parts by weight), mix well, and then add water, alkali thickener, and ammonia water to mix, PH8.
7. A flame-retardant resin aqueous composition having a viscosity of 4200 cps. (25 ° C., 20 RPM) was obtained.

Using the obtained flame-retardant resin aqueous composition, the above (1)
Work cloths were prepared according to the test methods of (3) to examine the appearance, and a combustion test was performed. The obtained results are shown in Table 1 together with the monomer composition and Tg of the copolymer, the pH of the resin aqueous dispersion, the viscosity and the solid content, the composition of the flame retardant resin aqueous composition, the PH and the viscosity.

Examples 2 to 3 and Comparative Examples 1 and 2 Tests were conducted in the same manner as in Example 1 except that the compounding amount of the chlorinated vinyl chloride resin powder was changed. Example 1
The obtained results are shown in Table 1 as in the case of.

Examples 4 and 5 and Comparative Examples 3 and 4 Tests were conducted in the same manner as in Example 1 except that the compounding amount of antimony trioxide was changed. The results obtained are shown in Table 1 as in the case of Example 1.

Examples 6 to 8 Tests were performed in the same manner as in Example 1 except that magnesium hydroxide was added in a different amount. The results obtained are shown in Table 1 as in the case of Example 1.

Examples 9 and 10 An aqueous resin dispersion obtained in the same manner as in Example 1 except that the monomer composition of the copolymer was changed to a chlorinated vinyl chloride resin having a chlorine content and a particle size different from those in Example 1. The powder was blended in an amount different from that in Example 1, the amount of antimony trioxide was varied, and further, magnesium hydroxide was blended or not blended to obtain a flame-retardant resin aqueous composition. Using this, a test was conducted in the same manner as in Example 1. The obtained results are shown in Table 1 together with the monomer composition and Tg of the copolymer, the pH of the resin aqueous dispersion, the viscosity and the solid content, the composition of the flame retardant resin aqueous composition, the PH and the viscosity.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location // D06M 15/248 D06M 15/248

Claims (1)

(57) [Claims] 1. A monomer selected from alkyl ester monomers of acrylic acid, alkyl ester monomers of methacrylic acid, and vinyl cyanide monomer, based on the total amount of ethylene monomers. Is 50% by weight or more, and the remainder is aromatic vinyl monomers, saturated fatty acid vinyl monomers, ethylene carboxylic acids, ethylene carboxylic acid amides, ethylene carboxylic acid amide methylol. Acrylic (co) polymer emulsion obtained from a monomer selected from a compound and its derivative, an ester of an ethylene-based carboxylic acid and an alcohol having an epoxy group, and a hydroxyalkyl ester of an ethylene-based carboxylic acid. Alternatively, the average chlorine content is about 60 to 8 with respect to 100 parts by weight of the solid content of the acrylic resin aqueous dispersion composed of two or more kinds.
0 to 100 parts by weight of chlorinated vinyl chloride resin powder,
And an aqueous flame-retardant resin composition containing 1 to 80 parts by weight of antimony trioxide.