JPH02196867A - Flame retardance-imparted resin aqueous emulsion - Google Patents

Abstract

PURPOSE:To provide the subject emulsion having excellent storage stability, forming coating films having flame retardant effects and useful for carpet backing materials, binders, structure outside coatings, etc., by emulsion- polymerizing an unsaturated monomer in the presence of a flame retardant in a specific ratio. CONSTITUTION:The objective emulsion is prepared by emulsion-polymerizing 1-10 pts.wt. of an unsaturated monomer (preferably n-butyl methacrylate) in the presence of 1 pt.wt. of a flame retardant (e.g. tetrabromobisphenol A; its particle size is preferably 0.01-15mum). The emulsion polymerization is preferably carried out in the presence of a protective colloid.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an aqueous resin emulsion imparted with flame retardancy useful for carpet backing materials and binders, exterior paints for buildings, and repair paints for wallpaper. be.

[Prior art]

Aqueous resin emulsions are used as carpet backing materials,
It is used in binder elastic paints and coating agents for needle bunch carpets.

In these applications, when the film obtained from the emulsion is required to have flammability (for example, coating agent for kitchen wallpaper,
(repair agents, automobile interior materials, etc.), as a method: - As an aqueous resin emulsion, flame-retardant materials such as vinyl chloride/vinylidene chloride copolymer, vinyl chloride/acrylic acid lower alkyl ester/acrylic acid copolymer, etc. A vinyl chloride resin aqueous emulsion is used.

■Resin aqueous emulsion contains tetrabromobisphenol, antemon trioxide, trifluorophosphate,
Contains flame retardants such as hexaprosocyclododecane, decabromodiphenyl oxide, and chlorinated phosphate esters.

method is implemented.

In the method (2) using an aqueous vinyl chloride resin emulsion, its application is limited in terms of adhesion to adherends and film forming temperature of the aqueous resin emulsion.

In the method (2) of post-adding the flame retardant to the aqueous resin emulsion, consideration must be given to the compatibility between the aqueous resin emulsion and the flame retardant, and the dispersibility of the flame retardant is poor.

[Problem to be solved by the invention]

The present invention provides an aqueous resin emulsion that has excellent storage stability and forms a flame-retardant film.

[Specific means to solve the problem]

The present invention provides an aqueous flame-retardant resin emulsion obtained by emulsion polymerization of an unsaturated monomer in a proportion of 1 part by weight or more and less than 1 part by weight in the presence of 1 part by weight of a flame retardant. .

Flame retardants The flame retardants used in the present invention include tetrabromobisphenol A1 antimony trioxide, trialkyl phosphate, hexabromocyclododecane, decabromodiphenyl oxide, hexabromobenzene, tJ [phosphoric acid ester, pentadibromodiphenyl ether, dibromo Ethylpenzole, polyvinyl chloride powder, aluminum hydroxide, magnesium hydroxide, etc. can be used.

These flame retardant particles have a particle size of 100 microns (μtn)
Hereinafter, those having a diameter of 0.01 to 15 microns are preferably used.

Unsaturated monomer The unsaturated monomer is n-propyl methacrylate (Tg
81C), styrene (100℃), acrylonitrile (
100℃), methyl methacrylate (105℃), methacrylic acid (130℃), itaconic acid (130℃), acrylamide (153℃), 2-ethylhexyl acrylate (Tg -8s℃), n-butyl acrylate ( -54℃
), ethyl acrylate (-22℃), impropyl acrylate (-5℃), 2-ethylhexyl methacrylate (
-5℃), n-propyl acrylate (8℃), fill butyl methacrylate (20℃), vinyl acetate (30℃)
, t-butyl acrylate (45°C), 2-methacrylate
Hydroxyethyl (55°C), ethyl methacrylate (6
5℃), inbutyl methacrylate (67℃), vinyl chloride (79℃), vinylidene chloride (-18℃), ethylene, etc. are used alone or in combination of two or more (the numbers in parentheses indicate the glass transition point of a homopolymer of monomers).

The type and amount of these monomers to be used are determined based on the glass transition point of the resulting resin, taking into account the single use of the resulting emulsion. For example, when using in room J (20℃), the glass transition point of the emulsion resin is 5℃.
〜+30'C. Forced drying (60~
200°C), the resulting aqueous emulsion resin may have a glass transition point of +40 to 180°C.

As a vinyl monomer component, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, etc.
Use of 1 to 3% by weight means that the adherend material (wood, concrete,
It is useful for increasing the adhesion of coatings to metals) and impregnated materials (carpets).

Preferred emulsions include (a) lower alkyl acrylate (alkyne group has 1 to 6 carbon atoms) ester 29
．． (b) 20-70% by weight of styrene, and (c) 0.5-3% by weight of unsaturated carboxylic acid, the emulsion polymerization solution comprising a carboxyl group based on the unsaturated carboxylic acid. (-COOK) is 1.4 x 10-3 ~ 1.8
An aqueous emulsion of a copolymer containing X 10-'' moles is preferred from the viewpoint of adhesion to adherends.

Emulsion polymerization Emulsion polymerization is a conventional method of emulsion polymerization of unsaturated (vinyl) monomers to obtain aqueous resin emulsions for use in paints and adhesives, except that a flame retardant is already present in the reacting aqueous system. is the same as

Aqueous resin emulsions are obtained by emulsion polymerization of vinyl monomers in the presence of flame retardants, protective colloids, potassium persulfate, and optionally surfactants.To impart moldability to carpets, Film forming temperature is 80-160℃
In order to impart elasticity to the carpet, the aqueous resin emulsion preferably has a milling temperature of 20° C. or lower.

As the heat-retaining colloid, water-soluble polymers such as hydroxymethylcetate/L-lose, human mixyethylcellulose, carboxyylcellulose, polyvinyl alcohol, polyvinylpyrrolidone, and xanthan gum are used. This protective colloid agent improves the dispersibility of the flame retardant particles in the emulsion and helps to encapsulate the flame retardant particles with the polymer of unsaturated monomer, thereby making the film obtained from the emulsion flame retardant. Prevent unevenness.

The flame retardant is used at a ratio of 10 parts by weight to 100 parts by weight or less, preferably 20 to 70 parts by weight, per 100 parts by weight of the unsaturated monomer to be emulsion polymerized. (If so, the proportion of the unsaturated monomer is 1 part by weight or more and less than 10 parts by weight). If the amount of flame retardant is too large, the polymerization stability of the unsaturated monomer during emulsion polymerization will be poor, and coarse blocked particles will be likely to be formed. The protective colloid agent is used in an amount of 2 to 20 parts by weight based on 100 parts by weight of the unsaturated monomer to be emulsion polymerized. If it is less than 2 parts by weight, the stability of the emulsion will be poor;
If too much is used, the water resistance of the resulting film will be impaired.

Optional ingredients for the emulsion include plasticizers, antifoaming agents, antisettling agents, flow regulators, antifreeze agents, lower alcohols, pigments, dyes, early strength Portland cement, Portland cement, sand,
Filler, wetting agent, water repellent, texture control agent, crosslinking agent, pHv
You may also mix a 4-blocking agent or the like.

A flame retardant may be further added later to the aqueous flame retardant resin emulsion obtained by carrying out the present invention, or an aqueous polyvinyl chloride emulsion or an aqueous polyvinylidene chloride emulsion may be blended.

Embodiments Hereinafter, the present invention will be explained in more detail with reference to Examples. Incidentally, parts and percentages in the examples are based on 9 weight unless the bamboo is inverted.

Example of emulsion production Example 1 Temperature controller, anchor stirrer, reflux condenser, supply container,
The following raw materials were charged into a reaction vessel equipped with a thermometer and a nitrogen introduction tube, and stirred at 60° C. for 1 hour to dissolve.

water 200
5 parts 35% aqueous solution of sodium salt of p-nonylphenol sulfuric acid half ester (anionic emulsifier) reacted with 20 moles of ethylene oxide 40 parts hydroxyethyl cellulose.

Next, after purging the inside of the reaction vessel with nitrogen gas, the following feed (1) 010% was added, and the mixture was heated to 90°C.

Supplies ■ Water 35
0 parts 35% aqueous solution of the above anionic emulsifier 4
Parts Styrene 224 parts 2-ethylhexyl acrylate 16ol Acrylic acid
8 parts acrylamide
8 parts hexabromocyclododecane to
ol.

Furthermore, after charging 10% of 2.5 parts of potassium persulfate dissolved in 85 parts of water (feed ■) into the container, the remaining feed! All and 40% of feed 1 are fed into the container over 3.5 hours, and after the feeding is finished, the temperature is kept at the same temperature for 2 hours to polymerize feed 1 and form a flame retardant-containing anionic resin aqueous emulsion (prepared). A membrane temperature of 20° C. and a solid content of 50% were obtained. Note that the pH was adjusted to 7.6 using ammonia water.

Example 2 Using decabromodiphenyl oxide as a flame retardant,
A flame retardant-containing resin aqueous emulsion was used in the same manner as in Example 1, except that the amount of unsaturated monomer used was as shown in Table IK.

Examples 3 to 4 A flame retardant-containing resin aqueous emulsion was obtained in the same manner as in Example 1, except that the amount of flame retardant used was 200 parts by weight and 300 parts by weight.

Example 5 Trialkyl-7 phosphate was used as the flame retardant, and the amount of unsaturated monomer used was as shown in Table 1.
A flame retardant-containing resin aqueous emulsion was obtained in the same manner as in Example 1.

Example 6 A flame retardant-containing resin aqueous emulsion was obtained in the same manner as in Example 2, except that polyvinyl alcohol 1 Gohsenol GH-17' (trade name of Nippon Gohsei Research Co., Ltd.) was used as the protective colloid agent.

Examples 7 to 8 A flame retardant-containing resin aqueous emulsion was obtained in the same manner as in Example 2, except that the amount of the protective colloid agent used was 15 parts or 15 parts.

Comparative Examples 1 to 3 Resin aqueous emulsions were obtained in the same manner as in Example 1 except that no flame retardant was used (Comparative Example 1).

Add 2.5 parts by weight of hexabromocyclododecane (Comparative Example 2) or 5 parts by weight to 200 parts by weight of this resin aqueous emulsion.
' M parts (Comparative Example 3) were temporarily added to obtain a flame retardant-containing resin aqueous emulsion.

The dispersibility of the flame retardant in these emulsions is shown in Table IK.

Application Example 1 The flame retardant-containing anionic resin emulsions of Examples 1 to 8 and Comparative Examples 1 to 3 were applied to a polyethylene terephthalate needle punch carpet with a basis weight of 11,300 f/ff/, and the solid content of the emulsion was 100 f/W? A needle-punch carpet (sample) with fibers fixed with resin was obtained by coating and impregnating the fibers and forcing drying at 80°C.

The combustion state and combustion rate of this product were investigated using the following method. The results are shown in Table 1.

[Dispersibility of flame retardant]

The aqueous resin emulsions obtained in Examples 1 to B and Comparative Examples 1 to 3 were stored in a room at 60° C. for one month, and their appearance was observed.

◎ Shows the same appearance as before storage, with no sediment or impurities.

○ Although there is some sediment #'i, there are no aggregates.

X There is a lot of sediment, and some particles are agglomerated.

〔Combustion quality〕

A test piece with a width of 100 m and a length of 350 cm was extracted from the sample,
Insert between the glyph-shaped clamps.

Hold the U-shaped clamp horizontally and place it so that the center of the tip of the Bunsen burner is 20 mm below the center of the opening of the test piece. A Bunsen burner with an inner diameter of 10 cm is used, and the flame of the burner is adjusted to 40 cm. A flame was applied to the test piece for 15 seconds, and the burning rate until the test piece burned 254 mm was determined.

In addition, when the flame extinguished before reaching the length of 254 square meters, it was defined as "self-extinguishing", and the length of the test piece was shown.

(See margins below) [Effects] A resin emulsion obtained by adding a flame retardant during emulsion polymerization exhibits superior flame retardancy than an aqueous resin emulsion in which a flame retardant is post-added.

Patent applicant Mitsubishi Yuka Verdate Co., Ltd. Agent
Patent attorney Masahisa Hase (and 1 other person)

Claims (1)

[Scope of Claims] 1) An aqueous flame-retardant resin emulsion obtained by emulsion polymerization of an unsaturated monomer in a proportion of 1 part by weight or more and less than 10 parts by weight in the presence of 1 part by weight of a flame retardant. 2) The aqueous flame retardant resin emulsion according to claim 1, wherein the emulsion polymerization is carried out in the presence of a protective colloid.