JPH01289865A - Flame retardant resin aqueous composition - Google Patents

Abstract

PURPOSE:To make it possible to form an aqueous flame-retarding resin composition which is suitable for imparting flame retardancy to fiber or paper products etc. by coating, by mixing a specified aqueous resin dispersion with a chlorinated vinyl chloride resin powder and antimony trioxide in a specified mixing ratio. CONSTITUTION:An aqueous resin dispersion comprising at least one emulsion of a copolymer of an ethylenically unsaturated monomer is mixed with 5-100pts. wt., per 100pts.wt. solid matter of the dispersion, chlorinated vinyl chloride resin powder and 1-80pts.wt. antimony trioxide. As the aqueous resin dispersion, a (co)polymer emulsion obtained by emulsion-polymerizing an ethylenically unsaturated monomer in the presence of a surfactant and/or a protective colloid in an aqueous medium, or a blend of a plurality of (co)polymer emulsions can be used, and, for example, the so-called acrylic resin aqueous dispersion can be suitably used.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a flame-retardant resin aqueous composition for imparting flame retardancy to UL, male, paper products, etc. by coating them. relates to a flame-retardant resin aqueous composition characterized in that it contains a chlorinated vinyl chloride type monofat powder and a specific amount of antimony trioxide in a specific resin aqueous dispersion.

[Conventional technology and its problems]

In recent years, measures against fire have become extremely important. There is also a strong demand for flame retardant interiors of various vehicles and houses.
In particular, various flame retardant techniques have been proposed for interior parts of automobiles and the like. To make fiber products used in automobile interiors, such as car seats, floor mats, door trims, and ceilings, flame retardant, fibers can be made flame-retardant by adding flame retardants to the vertebrae or making fibers from special flame-retardant polymers. Products that have flame retardant properties have been proposed. However, fibers that contain flame retardants themselves often do not have sufficient physical properties in terms of strength and texture, and even when fibers are made of special flame retardant polymers, dyeing and texture However, it has not been put into practical use due to many problems and high costs.

Therefore, currently, flame-retardant (co)i1 polymer emulsions such as vinyl chloride and vinylidene chloride are used as back coating agents used as reinforcing agents for textile products, or flame-retardant (co)polymers are used. Flame retardants are often blended into emulsions, common synthetic rubber-based, acrylic-based, styrene-acrylic-based (co)polymer emulsions, and blends thereof and applied to achieve flame retardancy.

Examples of such flame retardants include organic flame retardants such as liquid or powder phosphorus esters, halogenated phosphate esters, halogen compounds, guanidines, triazine, etc.; antimony-based, aluminum-based, and boron threads. Inorganic flame retardants such as, etc. are used alone or in combination as appropriate.

However, the above-mentioned flame-retardant (co)polymer emulsions may have insufficient stability due to the generation of dibasic acid over time, or may become colored during coating processing, and may not have sufficient flame retardancy on their own. There are problems such as in many cases not being possible. In addition, when the above-mentioned flame retardant is mixed with the above-mentioned (co)polymer emulsion, the liquid flame retardant generally acts like a plasticizer, softening the resin and impairing its texture, and over a long period of time. Powdered flame retardants may migrate to textile products or volatilize, causing problems such as fogging indoor window glass.Flame retardants in powder form reduce the stability of (co)polymer emulsions, so they should not be blended. There is a limit to the amount, the combustion effect is insufficient even in small amounts, and the texture is often extremely hard.

[Means for solving problems]

As a result of intensive research in order to solve the problems of the prior art as described above, the present inventors have identified a specific tM fat ice aqueous dispersion, chlorinated vinyl chloride resin powder, and antimony trioxide. The present invention was completed based on the discovery that all of the above-mentioned problems could be solved by containing the above amount.

That is, in the present invention, 5 to 5 parts of chlorinated vinyl chloride resin powder is added to 100 parts by weight of the solid content of an aqueous resin dispersion consisting of one or more types of (co)polymer emulsion of ethylene monomers. 100 parts by weight, and 1~ antimony trioxide
The object of the present invention is to provide an aqueous flame-retardant resin composition containing 80 parts by weight.

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

In the present invention, "aqueous resin dispersion consisting of one or more than 21 (co)polymer emulsions of ethylene monomers"
means emulsion polymerization of ethylene monomers in an aqueous medium in the presence or absence of surfactants and/or protective colloids, and post-emulsification of the (co)polymer polymerized by a method other than emulsion polymerization. Refers to a single (co)polymer emulsion obtained by or a blend of multiple (co)polymer emulsions, including but not limited to, ease of production, economic efficiency, etc. For these reasons, it is preferable to use a single (co)polymer emulsion or a blend of a plurality of (co)polymer emulsions usually obtained by emulsion polymerization.

Examples of the ethylene monomer that can be used in the present invention include methyl acrylate, ethyl acrylate,
n-butyl acrylate, isobutyl acrylate, 2
- Alkyl ester monomers of acrylic acid such as ethylhexyl acrylate, n-octyl acrylate, isononyl acrylate, lauryl acrylate, stearyl acrylate, etc., such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-
Alkyl ester monomers such as methacrylic powders such as ethylhexyl methacrylate and stearyl methacrylate; aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, ethylvinylbenzene, etc.; e.g. acetic acid Saturated fatty acid vinyl monomers such as vinyl, propionic vinyl, and vinyl versatate; Vinyl cyanide monomers such as acrylonitrile and methacrylonitrile; Olefinic monomers such as ethylene, propylene, butadiene, etc. Uma-tai: For example,
Ethylene carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, and fumaric acid, ethylene carboxylic acid anhydrides such as maleic anhydride, and monoalkyl esters of ethylene dicarboxylic acids (monobutisima 1). /inic acid, etc.), and ethylene carboxylic acids M such as ammonium or alkali metal salts thereof: For example, amides of ethylene carboxylic acids such as acrylamide, methacrylamide, diacetone acrylamide, etc.: For example, N-methylolacrylamide , N-methylolmethacrylamide, methylolated diacetone acrylamide, and etherified products of these monomers with alcohols having 1 to 8 carbon atoms (e.g., N-isobutoxymethylacrylamide), etc. Methylolated amides and derivatives thereof; esters of ethylene carboxylic acids and alcohols having epoxy groups, such as glycidyl acrylate, glycidyl methacrylate, etc.; such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-hydroxyethyl acrylate, Hydroxyalkyl esters of ethylene carboxylic acids such as Ghoul methacrylate; Esters of ethylene carboxylic acids and alcohols having an amine group, such as diethylaminoethyl methacrylate, diethylaminoethyl methacrylate, etc.; such as divinylbenzene, Monomers having two or more non-conjugated unsaturated groups such as diallyl phthalate, triallyl sialylate, diethylene glycol dimethacrylate and the like can be mentioned.

The type and amount of the above-mentioned ethylene monomer are not particularly limited, and can be appropriately selected depending on various required physical properties of the textile product to be subjected to flame separation processing. For example, in fields such as car sheets that require light resistance and weather resistance, the above-mentioned alkyl ester monomers of acrylic acid and alkyl ester monomers of methacrylic acid are added to the total amount of ethylene monomer. The total amount of monomers selected from cyanide vinyl monomers is 503i% or more, and the remainder is the above-mentioned aromatic vinyl monomers, saturated fatty acid vinyl monomers, and ethylene carboxylic acids. , amides of ethylene carboxylic acids, methylolated products of ethylene carboxylic acid amides and derivatives thereof, esters of ethylene carboxylic acids and alcohols having an epoxy group, hydroxyalkyl esters of hyethylene carboxylic acids, etc. A so-called aqueous acrylic resin dispersion obtained from monomers is preferably used.

Here, "the total amount of ethylene monomers" refers to the total amount of ethylene monomers required to produce all (co)polymers present in the resulting aqueous resin dispersion.

Among these, in the case of products that require a soft feel such as car sheets, it is particularly preferable to use an aqueous acrylic resin dispersion having a glass transition temperature of about -40 to -10°C as measured by the DSC method.

In the present invention, the DSC method glass transition temperature (Tg) of the aqueous resin dispersion is a value measured and determined as follows.

Weigh out approximately 10 cm of resin emulsion sample into a cell, and
A sample dried at ℃ for 2 hours is used as a measurement sample.

Shimadzu Farms DT-30 differential scanning calorimeter (Diffe)
Rental Scanning Calorime
ter) at a heating rate of 20°C/m from -80°C.
Measure and determine in. In addition, the measurements are carried out using nitrogen gas as the carrier gas at a flow rate of 20 c, c-/m1n-.

The aqueous acrylic resin dispersion that is intended to maintain the above-mentioned soft texture contains about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to about 0.5 to by of thermally crosslinkable ethylene carboxylic acid derivative monomers to the total amount of ethylene monomer to the above-mentioned soft texture. Preferably, it comprises 5 parts by weight.

Among the above-mentioned monomers, examples of the thermally crosslinkable ethylene carboxylic acid derivative monomers include ethylene carboxylic acid amides; methylolated products of ethylene carboxylic acid amides and their conductors: ethylene Examples include esters of carboxylic acids and alcohols having epoxy groups; hydroxyalkyl esters of ethylene carboxylic acids; these monomers can be used alone or in combination of two or more. Among these, it is preferable to use methylolated products of ethylene carboxylic acid amide from the viewpoint of suitability for polymerization reaction and excellent water resistance and solvent resistance of the resulting textile products, and N-methylol (meth)
Particular preference is given to using acrylamide.

Since there is no problem in terms of polymerization reaction suitability, the monomer has a concentration of about 0.
It is preferred to use a range of 5 to about 5 fqb.

In addition, in the present invention, the above-mentioned ethylene-based carbon] 31 is further added from about 0.5 to
Containing about 6% by weight improves the stability of the obtained aqueous flame-retardant resin composition, as well as the water resistance, solvent resistance, etc., especially when a thermally crosslinkable ethylene carboxylic acid derivative is used as a single-cap body. More preferable from the point of view of excellence. As such ethylene carboxylic acids, it is preferable to use acrylic acid, methacrylic acid and/or itaconic acid in view of the above-mentioned effects and polymerization reaction suitability.

Next, for example, in fields that require a relatively hard texture such as floor mats, an aqueous acrylic resin dispersion with a Tg of 10°C or higher: The vinyl monomer is 50% by weight or more, and the remainder is the alkyl ester monomer of acrylic acid or methacrylic acid, vinyl cyanide monomer, ethylene carboxylic acid, or amide of ethylene carboxylic acid. monomers selected from the following, methylolated products of ethylene carboxylic acid amides and derivatives thereof, esters of ethylene carboxylic acids and alcohols having an epoxy group, hydroxyalkyl esters of ethylene carboxylic acids, etc.
Styrene/acrylic resin or styrene resin aqueous dispersion obtained by polymerization: The saturated fatty acid vinyl monomer accounts for 70% or more of the ethylene monomer, and the remainder The above-mentioned alkyl ester monomers of acrylic acid or methacrylic acid, alkyl ester monomers of methacrylic acid, vinyl cyanide monomers, ethylene carboxylic acids, amides of ethylene carboxylic acids,
by polymerizing monomers selected from methylolated products of ethylene carboxylic acid amides and derivatives thereof, esters of ethylene carboxylic acids and alcohols having an epoxy group, hydroxyalkyl esters of ethylene carboxylic acids, etc. The obtained vinyl acetate acrylic resin or vinyl acetate resin aqueous dispersion; etc. can be preferably used,
Among them, when post-molding is performed after flame retardant treatment, such as for automobile floor mats, from the viewpoint of penetration of moldability, styrene/acrylic resin or styrene resin, among others, is used.
The aromatic vinyl monomer is 60% by weight or more, and the remainder is an alkyl ester-based it form of acrylic acid or methacrylic acid, a vinyl cyanide monomer, ethylene-based carboxylic acids, and amides of ethylene-based carboxylic acids. Particularly preferred are styrene/acrylic resins or styrene resins obtained from monomers selected from the following.

The aqueous resin dispersion of the present invention is usually obtained by emulsion polymerization of 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. (co)polymer emulsion, or a blend of (co)polymer emulsions having these numbers of υ.

Examples of the above-mentioned surfactants include nonionic surfactants such as polyoxyalkylene alkyl phenol such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, etc. Polyoxyalkylene alkylphenol ethers such as ethers, polyoxyethylene nonylphenol ethers; for example, sorbitan monolaurate, sorbitan monostearate,
sorbitan fatty acid esters such as polyoxyethylene fulvitan monolaurate; polyoxyalkylene sorbitan fatty acid esters such as polyoxyethylene monolaurate, polyoxyethylene monostearate, etc. Polyoxyalkylene fatty acid esters such as: for example, glycerin fatty acid esters such as oleic acid monoglyceride, stearic acid monoglyceride, etc.: for example, polyoxyethylene-containing polyoxypropylene φ block copolymer; Examples of the agents include fatty acid salts such as oleic soda; alkylaryl sulfonates such as sodium dodecylbenzenesulfonate; and lauryl sulfonate, for example.

Alkyl sulfosuccinate salts such as monooctyl sodium sulfosuccinate, dioctyl sodium sulfosuccinate, polyoxyethyl nonlauryl sulfosuccinate, and derivatives thereof: For example, polyoxyethylene lauryl ether sulfate Examples of cationic surfactants include polyoxyalkylene alkyl ether sulfur ester salts such as soda; polyoxyalkylene alkylaryl ether sulfur ester salts such as polyoxyethylene nonylphenol ether sodium sulfate; Alkylamine salts such as laurylamine acetate;
For example, lauryltrimethylammonium chloride,
Examples of the amphoteric surfactants include quaternary ammonium salts such as alkylbenzyldimethylammonium chloride, such as polyoxyethylalkylamine, and amphoteric surfactants, such as alkylbetaines such as laurylbetaine. Furthermore, surfactants in which some of the hydrogen atoms in the alkyl groups of these surfactants are replaced with fluorine can also be used. Furthermore, so-called reactive surfactants having a radically polymerizable double bond in the molecular structure of the surfactant can also be used. Examples of such reactive surfactants include:
Sulfoconophosphate alkyl alkenyl ester [ffi
, reactive anionic surfactants such as alkenyl succinic acid monoalkenyl ester salt type.

The amount of surfactant used is usually 0.1 to about 101! based on the total amount of ethylene monomers. [t% used,
From the viewpoint of reaction suitability for emulsion polymerization, various stability of the obtained aqueous resin dispersion, water resistance, etc., it is preferable to use about 0.5 to about 6% by weight, and preferably about 0.5 to about 4% by weight. Particularly preferred.

Examples of protective colloids that can be used in the present invention include polyvinyl alcohols such as partially saponified polyvinyl alcohol, completely saponified polyvinyl alcohol, and modified polyvinyl alcohol; Cellulose derivatives such as methylcellulose salts; and, for example,
Examples include natural polysaccharides such as guar gum, and these can be used alone or in combination of multiple types. The amount used can be selected as appropriate, and for example, the amount used can be 0 to about 10% by weight based on the total amount of the ethylene monomer used.

In the present invention, "in an aqueous medium" means in water or in an aqueous solution of a water-soluble organic solvent, and such water-soluble organic solvents are not particularly limited, and include, for example, methyl alcohol, ethyl alcohol, isopropyl Water-soluble alcohols such as alcohol; For example, water-soluble ketones such as acetone: For example, methyl cellosolve, cellosolve,
Water-soluble ethers such as butyl cellosolve, calpitol, butyl carpitol, etc. can be used alone or in combination, and the amount used is about 0 to about 50% by weight as the concentration of the water-soluble organic solvent in the aqueous solution. can be exemplified. However, from the viewpoint of the various stability of the resulting aqueous resin dispersion, as well as the water resistance and solvent resistance of the combustible processed product, it is preferable to carry out the emulsion polymerization in water that does not substantially contain these organic solvents. .

Furthermore, in emulsion polymerization, persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate, etc.; organic compounds such as tertiary butyl hanedroperoxide, cumene hydroperoxide, paramenthane hydroperoxide, Polymerization initiators such as peroxides; hydrogen peroxide can be used.

These can also be used either singly or in combination. The amount used can be selected as appropriate, for example, about 0.05 to about 1
The amount used may be more preferably about 0.1 to about 0.7% by weight, particularly about 0.1 to about 0.5% by weight.

Further, during emulsion polymerization, a reducing agent may be used in combination, if desired. Examples include reducing organic compounds such as ascorbic acid, tartaric acid, citric acid, and glucose; reducing inorganic compounds such as sodium thiosulfate, sodium sulfite, sodium bisulfite, and sodium metabisulfite. The amount used can be selected as appropriate, and for example, the amount used can be about 0.05 to about 1 tsun based on the total amount of the ethylene monomer used.

The aqueous resin dispersion used in the present invention was thus obtained (
A single co)polymer emulsion or a blend of multiple (co)polymer emulsions is preferred.

The solid content of the aqueous resin dispersion used in the present invention is not particularly limited, but is preferably about 30 to about 65% by weight in terms of productivity and ease of manufacture.

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

The vinyl chloride resin used in the production of the above-mentioned chlorinated vinyl chloride resin may be a vinyl chloride homopolymer, or a vinyl chloride copolymer with vinyl chloride and other polymers copolymerizable with vinyl chloride. However, when using a copolymer, the content of other copolymerizable heptamers is 15 parts by weight or less, preferably 6 parts by weight, per 100 parts by weight of vinyl chloride units. It is ↓ that it is below the department. Examples of other copolymerizable monomers include the above-mentioned saturated fatty acid vinyl monomers, acrylic ester monomers, and methacrylic ester monomers, such as dibutyl maleate and diethyl maleate. 71 twin acid ester monomers, such as dibutyl fumarate, diethyl tuma l/-1-, and other fumaric acid ester monomers; vinyl ether monomers, such as vinyl methyl ether, vinyl methyl ether, and vinyl octyl ether; Examples include vinylidene halides or vinyl halide monomers other than vinyl chloride such as vinyl chloride, vinyl bromide, etc. I can do it.

The average chlorine content of the above-mentioned chlorinated vinyl chloride-based plum fat is generally about 57 to about 85 wt. It is preferably about 80 weight f/, particularly about 62 to about 72 weight f/.

The amount of the chlorinated vinyl chloride resin powder used is based on 100 parts by weight of the solid content of the resin aqueous dispersion consisting of one or more types of (co)M combination of the ethylene monomers.
It is necessary that the amount is 5 to 100 parts by weight.

If the amount used is too small (less than 5 parts by weight), flame retardancy may be insufficient, and if it is too much (more than 100 parts by weight), the appearance and/or strength of the resulting textile products etc. This is not preferable as it may cause a decrease in The usage amount is 10~
It is preferably 90 parts by weight, and more preferably 20 to 90 parts by weight.

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 textile products, the particle size of the chlorinated vinyl chloride resin powder is approximately It is preferred that at least 90 weight widths have a particle size that passes through a Tyler 100 mesh sieve, and more preferably about 90 weight widths or more have a particle size that allows them to pass through a Tyler 200 mesh sieve.

Further, the amount of antimony dioxide used is 1 to 80 parts by weight based on 100 parts by weight of solid content of the aqueous resin dispersion. If the amount used is too small (less than 1 part by weight), the flame retardancy may be insufficient, and even if it is excessive (more than 80 parts by weight), further improvement in flame retardance may not be expected. In addition, the appearance and/or strength of the obtained textile products may deteriorate, which is undesirable. 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 good appearance of the resulting textile products, etc., it is preferable that at least about 90 portions of the antimony trioxide used pass through a Tyler 100 mesh sieve.

Furthermore, the aqueous flame retardant resin composition of the present invention may contain flame retardants other than those mentioned above, if desired, within the range of use that does not interfere with the excellent effects of the present invention. Examples of such flame retardants include organic compounds such as phosphoric acid ester flame retardants such as tricresyl phosphate, cresyl phenyl phosphate, triphenyl phosphate, diphenyl octyl phosphate, and tributyl phosphate; (β-chloroethyl) phosphate, tris(β-bromoethyl) phosphate, tris(
Halogen-containing phosphoric acid ester flame retardants such as dichloropropyl) phosphate, ) IJs(dibromoglovir) phosphate, tris(bromochloropropyl) phosphate, etc.: For example, chlorinated paraffin, brominated polyphenyl, chlorinated polyphenyl, Perchloropenta cyclodecane,
Tetrabromoethane, hexabromocyclototicane, 1
゜2. Halogenated compounds such as 3-tribromopropane, tetrabromobisphenol A1, tetrabromohetatalic anhydride, etc., and inorganic compounds include, for example, borax,
Examples include boron compounds such as zinc borate and barium metaborate; for example, aluminum compounds such as alum and aluminum hydroxide; magnesium compounds such as magnesium hydroxide; and zirconium compounds such as zirconium oxide. can. The amount of these flame retardants to be used can be, for example, 0 to 40 parts by weight based on 100 parts by weight of the solid content of the resin dispersion according to the present invention. Among these flame retardants, the combined use of magnesium hydroxide can improve the flame retardancy of the resulting textile products.
/i! This is preferable because it can be increased. When magnesium hydroxide is used in combination, it is preferably used in an amount of 4 to 50 parts by weight based on 100 parts by weight of the solid content of the resin dispersion.

The flame retardant resin aqueous composition of the present invention contains a crosslinking agent and a crosslinking catalyst in addition to the above resin aqueous dispersion, chlorinated vinyl chloride resin powder, antimony trioxide, and the above flame retardant used in combination if desired. You can also. As the crosslinking agent,
For example, aqueous solutions or dispersions of amine resins such as urea-formaldehyde resins and melamine-formaldehyde resins; aqueous solutions or dispersions of nyresol-based or novolac-based phenolic resins; aqueous solutions or dispersions of various epoxy resins; blocked incyanates; Examples include aqueous solutions or dispersions of crosslinking agents; from the viewpoint of ease of availability, crosslinking reaction effects, etc., blending of aqueous solutions or dispersions of amine resins is preferred. The blending amount of the crosslinking agent is O to about 4 parts by weight based on 100 parts by weight of the solid content of the aqueous resin dispersion.
It can be used in a range of 0.00 parts by weight.

Crosslinking catalysts are often used especially when using amino resins, for example, inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as (anhydrous) phthalic acid and p-toluenesulfonic acid, and the combination of these inorganic and organic acids. Ammonium salts, amine salts, etc. can be mentioned, and the amount used is about 0.5 parts as an active ingredient per 100 parts by weight of the solid content of the amino resin.
It can be used as appropriate in the range of 10 to about 10 parts.

Furthermore, if desired, an aqueous solution or dispersion of a resin other than the above, such as a polyester resin or a polyurethane resin, may be blended within a usage range that does not impede the excellent effects of the present invention.

Furthermore, organic or inorganic fillers such as titanium oxide, clay, Merck, carbonate, calcium, silica, asbestos, carbon black, and phthalocyanine blue, pigments, dyes, film-forming aids, plasticizers, anti-aging agents, Preservative,
There is no problem in adding ultraviolet absorbers, etc.

The method for producing the aqueous flame-retardant resin composition of the present invention is not particularly limited, but for example, one or more of the (co)polymer emulsions of ethylene monomers according to the present invention may be used. Water, a wetting agent, and/or a dispersion liquid are added to the resin aqueous dispersion as necessary, and then the chlorinated vinyl chloride resin powder and antimony trioxide are added, and the various additives described above are added as necessary. For example, flame retardants other than chlorinated vinyl chloride resin powder and antimony trioxide: crosslinking agents, crosslinking catalysts: organic or inorganic fillers, pigments, dyes:
It can be obtained by adding a film-forming aid, a plasticizer, an anti-aging agent, a preservative, an ultraviolet absorber, etc., and thoroughly stirring and mixing the mixture. In addition, the above-mentioned P-vinyl chloride resin powder,
Antimony dioxide and various additives added as necessary are stirred and mixed in advance using the above water, wetting agent and/or dispersant to create a slurry-like kneaded product, and this is mixed with the above resin. It may also be mixed with an aqueous dispersion. The above-mentioned wetting agents include, for example, sulfosuccinate salt-based anionic surfactants such as dioctyl sulfoconophosphate sodium salt; for example, polyoxyethylene nonyl ether, polyoxyethylene lauryl ether, polyoxyethylene oleyl ether Polyoxyethylene alkyl ether type nonionic surfactants such as: Examples of dispersants include polycarboxylic acid sodium salt type, polycarboxylic acid ammonium salt type, styrene/maleic anhydride copolymer salt type, and condensed naphthalene sulfone. Examples include acid salt-based surfactants, nonionic surfactant-based surfactants, and surfactant-based wetting agents and dispersants. 0.1 for each
-4.0 parts by weight and 0.1 to 5.0 parts by weight can be exemplified. Furthermore, the above “active ingredients” are:
Wetting agents and dispersants refer to products after volatile components such as water and/or alcohol that may be contained in them have been volatilized, and the content of active ingredients in commercially available wetting agents and dispersants. If the value is unclear, it can be determined by drying them at 105° C. for 3 hours according to JIS K6833.

PH of the aqueous gambling resin composition of the present invention obtained by smelting
, viscosity, and solid content are not particularly limited, but from the viewpoint of sedimentation stability of the composition, generally P
H4-10, Preferably, 7-10: If
c25℃, 2(lR)%)
1000 to 10000 cps, preferably 2000 to 7000 eps = solid content 30 to 70% by weight, preferably about 35 to 60% by weight.

The aqueous flame-retardant resin composition of the present invention is S as it is, but is
It can be appropriately diluted with water or the like and applied to various products such as textile products by various methods such as impregnation, l'JtW, and coating. Sweet, if necessary, polyvinyl alcohol, cellulose derivatives, polycarboxylic acid resin,
The viscosity can be further increased to a desired level using a surfactant-based thickener or the like.

〔Example〕

Hereinafter, the present invention will be explained in more detail by giving examples as well as specific drawing examples. In addition, in the above-mentioned example, the preparation of the test sample and the test method used are as follows.

(1) Preparation of samples A flame-retardant resin composition was applied in solid form to cotton broadcloth #40 (fabric weight 1209. arm), polyester cloth (fabric weight 65 f//f?), and polyamide (fabric weight approximately 70 f/2 arm). 1502 in minutes. Apply it so that it forms a monument, dry it at 100°C for 1 molecule, and then dry it at 140°C for 10 minutes. This is 30cr
It was cut into a size of 11 x 15 m, left for 24 hours in an atmosphere of 25° C. x 65% L1, and then subjected to various tests.

(2) Appearance of processed fabric The degree of powder falling off was examined when the processed fabric using the #40 cotton broadcloth prototyped in (1) was lightly inserted by hand.

◎No powder falling ○Little powder falling △Powder falling × Severe powder falling, unusable as processed cloth (3) Combustion test A combustion test was conducted by the horizontal method in accordance with M%'SS-302.

The test was conducted at 10 points and expressed as an average burning rate.

In addition, if the flame was extinguished during the test, the burning distance until the flame extinguished was expressed. The results are shown in Table 1.

Example 1 Water 33o9 and polyoxyethylene nonylphenyl ether 69 were placed in a round bottom flask equipped with a stirrer 2, 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 the temperature at 70°C, a mixture of ethyl acrylate 286f, butyl acrylate 28fif and acrylic acid 92, an aqueous solution prepared by dissolving 12 V of N-methylolacrylamide and 62 sodium dodecylbenzenesulfonate in 260 ml of water was filtered for two stages. Aqueous sodium monium sulfate solution 602.2 Sodium metabisulfite aqueous solution 609 was added continuously over 5 hours to ensure emulsion copolymerization. The resulting copolymer emulsion had a solid content of approximately 46%, a PI (2,5, and a viscosity of 1).
It was a milky white emulsion at 20 cps (25°C, 2011 (Phi)), and the Tg of the copolymer was about -38°C.

The above copolymer emulsion was used as an aqueous resin dispersion, and 1 part by weight of 5% sodium dioctyl sulfosuccinate was added to 100 parts by weight of the copolymer emulsion as an aqueous resin dispersion. 1.6 parts by weight), 23 parts by weight (50 parts by weight) of chlorinated vinyl chloride resin powder with a chlorine content of 68 qb passing through a Tyler 100 mesh sieve, 6.9 parts by weight (15 parts by weight) antimony trioxide Department:
Add 30 parts by weight to 100 parts by weight of chlorinated vinyl chloride resin powder, mix well, and add water, an alkaline thickener,
Add and mix ammonia water, pH 8.7, viscosity 4200
cps, (25° C., 20 RPM, ) a flame retardant resin aqueous composition was obtained.

Using the obtained flame-retardant resin aqueous composition, the above (11-
Create a processed cloth according to the test method in (3), examine its appearance,
A combustion test was conducted. The obtained results are shown in Table 1 together with the monomer composition and Tg of the copolymer, the PH, viscosity, and solid content of the aqueous resin dispersion, and the blending composition, PH, and viscosity of the aqueous flame-retardant resin composition.

Examples 2 to 3 and Comparative Examples 1.2 Tests were conducted in the same manner as in Example 1, except that the amount of chlorinated vinyl chloride resin powder was changed. As in Example 1, the results obtained are shown in Table 1.

Example 4.5 and Comparative Example 3.4 Tests were conducted in the same manner as in Example 1 except that the amount of antimony trioxide was changed. As in Example 1, the results obtained are shown in Table 1.

Examples 6 to 8 Tests were conducted in the same manner as in Example 1, except that magnesium hydroxide was further added in a different amount.

As in Example 1, the results obtained are shown in Table 1.

Example 9.10 A chlorinated vinyl chloride resin having a different chlorine content and particle size from Example 1 was added to the resin aqueous dispersion obtained in the same manner as in Example 1 except that the monomer composition of the copolymer was changed. A flame-retardant resin aqueous composition was obtained by blending different amounts of powder from those in Example 1, varying the amount of antimony trioxide, and blending with or without magnesium hydroxide. Using this, a test was conducted in the same manner as in Example 1. The obtained results are calculated based on the monomer composition and Tg of the copolymer, and the PH1 of the aqueous resin dispersion.
The viscosity and solid content are shown in Table 1 together with the blending composition, pH and viscosity of the flame retardant resin aqueous composition.

Claims (1)

[Claims] (1) Solid content of an aqueous resin dispersion consisting of one or more types of (co)polymer emulsion of ethylene monomers: 1
00 parts by weight, chlorinated vinyl chloride resin powder 5~
100 parts by weight, and 1 to 80 parts by weight of antimony trioxide.