JP2854380B2 - Flame-retardant resin aqueous emulsion and method for producing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Object of the Invention (Industrial Application Field) The present invention relates to a carpet backing material, paper, nonwoven fabric,
The present invention relates to a flame-retardant resin-based aqueous emulsion useful as a binder for woven fabrics and curtains, an exterior paint for buildings, a repair paint for wallpapers, and the like.

(Prior Art) Aqueous resin emulsions are used as backing materials for carpets, binders for needle punched carpets, elastic paints, various coating agents, and the like.

In these resin aqueous emulsions, when the film is required to be flame-retardant (for example, a coating material for a kitchen wallpaper or a repair agent, or an interior material of an automobile, etc.), the following are conventionally used. Resin aqueous emulsions have been used.

Vinyl chloride-vinylidene chloride copolymer, vinyl chloride-acrylic acid lower alkyl ester / acrylic acid copolymer, vinylidene chloride-alkyl acrylate copolymer, etc. Vinylidene resin aqueous emulsion.

Tetrabromobisphenol, antimony trioxide,
Aqueous resin emulsion containing flame retardant such as trialkyl phosphate, hexabromocyclodecane, decabromodiphenyl oxide, chlorinated phosphate, etc.

However, flame-retardant resin emulsions have limited applications in terms of adhesion to adherends, film forming properties, flame retardancy-weather resistance, and hot yellowing, and are aqueous resin emulsions containing flame retardants. However, there is a problem in compatibility between the resin emulsion and the flame retardant, and when the compatibility is poor, the flame retardant is separated, so that a large amount of the flame retardant is required.

Japanese Patent Application Laid-Open No. 22366/1990 according to the inventors of the present invention discloses that an unsaturated monomer is mixed with 1 part by weight of a flame retardant in an amount of 10 to 200 parts by weight and emulsion-polymerized. Aqueous flame-retardant resin emulsions are described, but the flame retardancy was not yet sufficient.

(Problem of the Invention) A first object of the present invention is to provide a flame-retardant resin aqueous emulsion which is excellent in storage stability and gives a film having more excellent self-digestibility. A second object of the present invention is to provide a flame-retardant resin aqueous emulsion capable of providing a film having excellent flame retardancy.

(B) Configuration of the Invention (Means for Solving the Problems) The first aspect of the present invention is to provide a vinyl monomer 40 having a halogen group.
~ 80% by weight and 60 ~ 20 unsaturated monomers copolymerizable therewith
% By weight of a halogen-containing monomer constituent unit of an aqueous halogen-based copolymer aqueous emulsion obtained by emulsion polymerization of 100% by weight with a flame-retardant synergist at a temperature of 100 ° C.
An object of the present invention is to provide a flame-retardant resin aqueous emulsion containing an organic compound having a decomposition half-life longer than a time and capable of forming a free radical in a ratio of 0.1 to 5 parts by weight.

The second aspect of the present invention is a vinyl monomer 40 having a halogen group.
~ 80% by weight and 60 ~ 20 unsaturated monomers copolymerizable therewith
% By weight and 100 parts by weight of the monomer mixture are combined with a halogen-containing vinyl compound having a half-life of decomposition longer than 2 hours at a temperature of 100 ° C. as a flame-retardant synergistic effect to form a free radical. An object of the present invention is to provide a method for producing a flame retardancy-imparting resin aqueous emulsion, characterized in that a copolymer emulsion is obtained by emulsion polymerization in the presence of 0.1 to 5% by weight of a monomer.

The aqueous flame-retardant-imparting resin emulsion of the present invention contains a halogen-based copolymer resin as a binder component and a halogen group of a flame-retardant component, and a flame-retardant synergist. For example, it is remarkably excellent in its ability to impart flame retardancy by being applied or impregnated to, for example, carpets, wallpaper, various flammable buildings, and the like.

Furthermore, compared with a halogen-based copolymer aqueous emulsion in which a flame-retardant synergist is not used in combination, the Cl group or Br in the copolymer is used for the purpose of improving the weather resistance of the obtained film.
Even if the group content is reduced, a film having the same flame retardancy as that of the related art can be provided, so that the weather resistance can be improved.

Examples of the vinyl monomer having a halogen group that gives the aqueous resin emulsion of the present invention include vinyl chloride, vinylidene chloride, vinyl bromide, vinylidene bromide, mono- or dichlorostyrene, bromostyrene, and chloroprene.
Considering copolymers with other vinyl monomers, vinyl chloride, vinylidene chloride and chlorostyrene are preferred.

The vinyl monomer having a halogen group is used in an amount of 40 to 80% by weight of the vinyl monomer. If it is less than 40% by weight, the flame retardancy of the film is not sufficient. If it exceeds 80% by weight, the weather resistance of the film tends to deteriorate.

Examples of the vinyl monomer copolymerizable with the halogen group-containing monomer include vinyl acetate, acrylonitrile, methyl acrylate, ethyl acrylate, n-propyl acrylate, iso-propyl acrylate, ethylene,
N-butyl acrylate, iso-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and their lower alkyl methacrylate equivalents are mainly used. If necessary, acrylic acid, itaconic acid, acrylic Monomers having a functional group such as 2-hydroxyethyl acid, 2-hydroxyethyl methacrylate, acrylamide, and methylolacrylamide may be used at a ratio of 10% by weight or less.

The type and copolymerization ratio of these unsaturated monomers are appropriately selected in consideration of the intended use of the obtained resin emulsion, the glass transition point of the obtained resin, and the like. For example, when used at room temperature (20 ° C.), the resin is selected so that the glass transition point of the resin of the emulsion is −65 ° C. to + 30 ° C. When the resin is used after being forcedly dried (60 to 160 ° C.), the resin is selected so that the glass transition point of the resin of the obtained emulsion is 30 to 100 ° C.

Flame retardant synergist in the present invention, i.e. temperature 100
Organic compounds having a decomposition half life of more than 2 hours at 0 ° C. and capable of forming free radicals include, for example, dibenzylbenzene, benzyltriol, 1-phenyl-1,3,3
Hydrocarbons such as trimethylindane and biscumyl, and organic peroxides such as di-t-butyl peroxide, dicumyl peroxide, and ci-t-aluminum peroxide.

These flame-retardant synergists may be dissolved in the unsaturated monomer to be emulsion-polymerized and added to the emulsion polymer, or may be directly dissolved in the emulsion polymerization system or dissolved in an organic solvent such as toluene. And may be added later to the aqueous resin emulsion obtained by emulsion polymerization. From the viewpoint of dispersibility, it is preferable that a flame retardant synergist is present in the emulsion during emulsion polymerization.

The flame retardant synergist is contained in an amount of 0.1 to 5 parts by weight based on 100 parts by weight of the vinyl monomer having a halogen group. If the proportion is too small, the flame-retardant synergistic effect cannot be sufficiently obtained, and if it is too large, the effect corresponding thereto cannot be improved, and if added to the emulsion polymerization system, the polymerization stability is impaired. It is.

Emulsion polymerization for producing the second aqueous flame retardant resin emulsion of the present invention is carried out in the presence of a flame retardant synergist, except that this type of emulsion is used for conventional paints and adhesives. And emulsion polymerization for producing a resin aqueous emulsion (emulsion liquid). That is, the emulsion polymerization is carried out by mixing a mixture of a vinyl monomer having a halogen group and an unsaturated monomer copolymerizable therewith with a flame-retardant synergist, sodium dodecylbenzenesulfonate or p-nonylphenol sulfate. The emulsion polymerization is carried out in an aqueous medium in the presence of a surfactant such as a half ester and an initiator such as potassium persulfate.

If the flame-retardant synergist is not present during the emulsion polymerization, the synergist is added to the aqueous resin emulsion after the emulsion polymerization by dissolving the same in an organic solvent.

Various additives such as a visualizer, an antifoaming agent, an anti-settling agent, a flow controlling agent, an anti-freezing agent, a lower alcohol, a pigment, a dye, Strong Portland cement, Portland cement, sand, fillers, wetting agents, water repellents, hand controlling agents, cross-linking agents, pH controlling agents and the like can be blended.

(Examples, etc.) Hereinafter, examples and comparative examples will be described in more detail.
“Parts” and “%” described in these examples are all based on weight.

Example 1 A reactor equipped with a temperature controller, a stirrer, a supply vessel, a thermometer, and a nitrogen gas inlet tube was charged with 250 parts of water, 1 part of sodium dodecylbenzenesulfonate, 16 parts of potassium persulfate, and the inside was filled with nitrogen gas. Replace, then depressurize,
After nitrogen gas was further introduced, the pressure was reduced again.

Then, while maintaining the temperature inside the reaction vessel at 60 ° C. and stirring, the reaction vessel was purged with nitrogen gas from the supply vessel, and then vinylidene chloride 250 parts methyl acrylate 150 parts butyl acrylate 100 parts dicumyl par A mixture consisting of 5 parts of oxide, 250 parts of water, and 10 parts of sodium dodecylbenzenesulfonate was continuously supplied over 6 hours using a metering pump.

After the completion of the supply of the predetermined amount of the mixture, the internal pressure of the reaction vessel becomes 0 kg /
The polymerization was continued at 50 ° C. until cm ² G was reached to produce a resin aqueous emulsion having a solid content of 50%.

Table 1 shows the types and amounts of unsaturated monomers, flame retardant synergists, and emulsifiers used in the emulsion polymerization described in Example 1.

Examples 2 to 4 Various methods were performed using the same method as described in Example 1 except that the types and amounts of unsaturated monomers, flame retardant synergists, and emulsifiers were changed as shown in Table 1. An aqueous resin emulsion was prepared.

Comparative Examples 1 to 3 Various aqueous resin emulsions were produced using the same method as that described in Example 1 except that no flame retardant synergist was used.

Examples 5 to 6 To 1,000 parts of the aqueous resin emulsion obtained in Comparative Example 1, a solution prepared by dissolving 5.0 parts of a flame retardant synergist biscumyl or dicumyl peroxide in 30 parts of toluene was added. , A flame retardant resin-based aqueous emulsion was produced.

For each of the resin emulsions obtained in Examples 1 to 6 and Comparative Examples 1 to 3, the following flame retardancy test,
An evaluation test for yellowing resistance of the resulting film was performed.

The flame retardancy test method resin aqueous emulsion, a polypropylene needle-punched carpet having a basis weight 300 g / m ^2, coating such that the solid content of the emulsion is 60 g / m ^2, impregnated, by forced drying at 80 ° C. Resin To obtain a needle punch carpet (sample) in which the fibers were fixed.

About the obtained sample, the combustion state and the burning speed were examined by the following methods.

That is, a test piece having a width of 100 mm and a length of 350 mm is taken from a sample and sandwiched between U-shaped clamps. The U-shaped clamp was placed horizontally, and the center of the tip of the Bunsen burner was placed 20 mm below the center of the opening of the test piece. The Bunsen burner uses an inner diameter of 10 mm, and the flame of the burner is 40 mm
It was adjusted to be. A flame was applied to the test piece for 15 seconds to burn the test piece, and the flame retardancy was evaluated according to the following criteria.

Complete combustion: When burned to 254 mm Self-extinguishing: When the flame was extinguished before reaching the length of 254 mm, it was evaluated as “self-extinguishing” and the burning length (mm) of the test piece was indicated.

Evaluation of yellowing resistance of film (acceleration test) A resin aqueous emulsion was applied on a glass plate so that the thickness of the dried film became 100 µm, and dried at 60 ° C for 5 hours. This was irradiated with ultraviolet light at 20 ° C. for 1 week with an ultraviolet irradiation lamp, and the degree of yellowing of the film was visually determined.

◎: no yellowing ○: slight yellowing △: fairly yellowing ×: brown (2) Effect of the Invention The flame-retardant resin-based aqueous emulsion of the present invention has an extremely large flame-retardant effect and simultaneously has yellowing resistance (weather resistance).
Excellent.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI D21H 21/34 D21H 5/00 E (58) Field surveyed (Int.Cl. ⁶ , DB name) C09K 21/14 C08F 214/08 C08L 27 / 00 D06M 15/244 D21H 21/34 WPI / L (QUESTEL)

Claims (2)

(57) [Claims] (1) 40 to 80% by weight of a vinyl monomer having a halogen group and 60 to 20% by weight of an unsaturated monomer copolymerizable therewith.
Has a half-life of decomposition longer than 2 hours at 100 ° C as a flame-retardant synergist for 100 parts by weight of halogen-containing monomer constituent units of an aqueous emulsion of a halogen-based copolymer obtained by emulsion polymerization of A flame-retardant resin aqueous emulsion containing an organic compound capable of forming free radicals in a proportion of 0.1 to 5 parts by weight. 2. A vinyl monomer having a halogen group of 40 to 80% by weight and an unsaturated monomer copolymerizable therewith with 60 to 20% by weight.
100 parts by weight of a monomer mixture with a vinyl monomer having a decomposition half life of more than 2 hours at a temperature of 100 ° C. as a flame-retardant synergist and a halogen-containing organic compound capable of forming a free radical A method for producing an aqueous emulsion of a flame-retardant resin, comprising obtaining a copolymer emulsion by emulsion polymerization in the presence of 0.1 to 5% by weight of the above.