JPH0222366A - Aqueous emulsion of flame-retardant resin - Google Patents

Abstract

PURPOSE:To obtain the subject emulsion having excellent flame retardance and useful as a backing material for carpet, a binder, an exterior coating for building and a mending paint for wall paper by emulsion-polymerizing a specific amount of an unsaturated monomer in the presence of a flame-retardant. CONSTITUTION:The objective emulsion is produced by the emulsion- polymerization of 10-200 pts.wt. of an unsaturated monomer [e.g., n-propyl methacrylate, etc., preferably combined with 0.1-3wt.% of (meth)acrylic acid, etc. ] in the presence of 1 pt.wt. of a flame-retardant (e.g., tetrabromobisphenol A, antimony trioxide or trialkyl phosphate).

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,
Needlepan Aca-bet's binder is used for elastic paints, coating agents, etc.

In these applications, when flame retardancy is required for the film obtained from the emulsion (for example, coating agents for kitchen wallpaper,
(repair agents, automobile interior materials, etc.), and the method includes: - As a resin aqueous 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, antimony trioxide, trialkyl phosphate,
Contains flame retardants such as hexaphumocyclododecane, decabromodiphenyl oxide, and chlorinated phosphate esters.

method is implemented.

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

In the method of (2) in which the flame retardant is post-added to the resin aqueous emulsion, consideration must be given to the compatibility between the resin aqueous emulsion and the flame retardant. It becomes necessary.

[Problem that the invention attempts to solve]

The present invention provides an aqueous resin emulsion that has excellent storage stability and forms a film with a sufficient flame retardant effect using a small amount of flame retardant.

[Specific means to solve the problem]

The present invention provides an aqueous flame retardant resin emulsion obtained by emulsion polymerization of 10 to 200 parts by weight of K and an unsaturated monomer in the presence of 1 part by weight of a flame retardant.

Flame retardants used in the present invention include tetrabromobisphenol A1 antimony trioxide, trialkyl phosphate, hexabromocyclododecane, decabromodiphenyl oxide, hexabromobenzene, tetrabromoethane, tris(2゜3-dibromopropylene in Cyanurate), chlorinated phosphate ester, pentadibromodiphenyl ether, cyfuromoethylbenzole, polyvinyl chloride powder, polyvinylidene chloride powder, aluminum hydroxide, magnesium hydroxide, etc. can be used.

Flame retardants can be dissolved directly in water systems or in unsaturated monomers.
Alternatively, it can be dissolved in a solvent such as xylene, toluene, or mineral spirits and added to an aqueous system.

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

Aqueous resin emulsions are obtained by emulsion polymerization of vinyl monomers in the presence of flame retardants, anionic surfactants such as dodecylbenzenesulfonate, p-nonylphenol sulfuric acid half ester, and calcium persulfate. , in order to impart moldability to the carpet, the film forming temperature must be 80°C.
In order to impart elasticity to the carpet, the aqueous resin emulsion having a temperature of 160°C to 160°C preferably has a film forming temperature of 20°C or lower.

As a vinyl monomer, n-propyl methacrylate (Tg
81°C), styrene (100°C), ac+7o nitrile (100°C), methyl methacrylate (105°C), methacrylic acid (130°C), itaconic acid (130°C), acrylic acid (153°C), acrylic acid 2-ethylhexyl (Tg-85℃), n11-butyl acrylate (-5
4°C), ethyl acrylate (-22°C), inglovir acrylate (-5°C), 2-ethylhexyl methacrylate (-5°C), n-propyl acrylate (8°C), n-butyl methacrylate (20°C) ℃), vinyl acetate (30℃)
, t-butyl acrylate (45°C), 2-methacrylate
Hydroxyethyl (55°C), ethyl methacrylate (6
5°C), inbutyl methacrylate (67°C), vinyl chloride (79°C), vinylidene chloride (-18°C), ethylene, etc. are used alone or in combination of two or more (numbers in parentheses indicate these vinyl glass transition point of a homopolymer of monomers).

The type and amount of these monomers to be used are determined by considering the usage temperature of the resulting emulsion and using the glass transition point of the resulting resin as a guide. For example, when used at room temperature (20°C), the glass transition point of the emulsion resin is 165°C.
Select ゛ so that the temperature is ~+30℃. Forced drying (60
~2.00'C), the glass transition point of the resulting aqueous emulsion resin may be +40 to 180°C.

As a vinyl monomer component, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, etc.
1 to 3 weights in the city center is 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 (alkyl group has 1 to 6 carbon atoms) ester/l-
29.5-79.5% by weight, 03) Styrene 20-7
An emulsion polymerization solution of 0% by weight and 0.5 to 3% by weight of unsaturated carboxylic acid (C), in which the carboxyl group (-COOH) based on the unsaturated carboxylic acid is 1.4 x 10-3 to 1.
An aqueous emulsion of the copolymer containing the copolymer in a proportion of 8×10 mol is preferable from the viewpoint of adhesion to the adherend.

Emulsions include plasticizers, antifoaming agents, antisettling agents, flow regulators, antifreeze agents, lower alcohols, pigments, dyes, early strength Portland cement, Portland cement, sand,
Fillers, wetting agents, water repellents, texture control agents, crosslinking agents, pH control agents, and the like may be added.

The flame retardant is used in an amount of 0.5 to 10 parts by weight, preferably 2 to 7 parts by weight, per 100 parts by weight of the unsaturated monomer to be emulsion polymerized (if the flame retardant is 1 part by weight, The proportion of saturated monomers is 10 to 200 parts). If the amount of flame retardant is small, no improvement in flame retardancy can be expected. On the other hand, if the amount is too large, the polymerization stability of the unsaturated monomer during emulsion polymerization is poor, and blocked coarse particles are likely to be formed. Note that when vinyl chloride or vinylidene chloride is used as the unsaturated monomer, the amount of flame retardant used can be reduced (0.5 to 2 parts by weight).

The flame retardant-imparting resin aqueous emulsion of the present invention may further be blended with a polyvinyl chloride aqueous emulsion or a polyvinylidene chloride aqueous emulsion to which a flame retardant is added later.

Embodiments Hereinafter, the present invention will be explained in more detail with reference to Examples. Note that parts and percentages in the examples are based on a 9-fold standard unless otherwise specified.

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 inlet tube.

water 200
Part 35% aqueous solution of the sodium salt of the ester of p-nonylphenol in sulfuric acid (anionic emulsifier) reacted with 20 moles of ethylene oxide 5 parts 20% solution of p-nonylphenol (nonionic emulsifier) reacted with 25 moles of ethylene oxide 20 Department.

Next, after purging the inside of the reaction vessel with nitrogen gas, 10% of the following feed I was added, and the mixture was heated to 90°C.

Supply I Water 200
Parts 35% aqueous solution of the above anionic emulsifier 25 parts Sderene 224 parts 2-ethylhexyl acrylate 160 parts acrylic acid
8 parts acrylamide
8 parts Hexabromofukulododecane 10
Department.

Furthermore, after dissolving 2.5 parts of potassium persulfate in 85 parts of water and charging 10% of the nine (feeds ■) into the container, all of the remaining nine feeds (■) and 40% of the feed ■ was fed into the container over a period of 3.5 hours, and after the feeding was completed, it was kept at the same temperature for 2 hours to polymerize the feed (2) to form a flame retardant-containing anionic resin aqueous emulsion (film forming temperature ZOC, solid content 50 %) was obtained. In addition, it was prepared using ammonia water to pH-7.6.

Example 2 Using decabromodiphenyl oxide as a flame retardant,
In addition, 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 3 The amount of flame retardant used was 20 parts by weight. Otherwise, a flame retardant-containing resin aqueous emulsion was obtained in the same manner as in Example 1.

Example 4 Trialkylphosphinitra was used as a 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.

Comparative Examples 1-2 Aqueous resin emulsions were obtained in the same manner as in Example 1, except that no flame retardant was used.

Add 2.5 parts by weight of hexabromocyclododecane to 200 parts by weight of this resin aqueous emulsion (Comparative Example 1) or 5 parts by weight.
Part by weight (Comparative Example 2) was subsequently added to obtain a flame retardant-containing resin aqueous emulsion.

Table 1 shows the dispersibility of the flame retardant in these emulsions.

Application Example 1 The flame retardant-containing anionic resin emulsions of Examples 1 to 4 and Comparative Examples 1 to 2 were applied to a needle-punch carpet made of polyethylene terephthalate with a basis weight of 300 f/-, and the solid content of the emulsion was 100? A needle bump carpet (sample) in which the fibers were fixed with resin was obtained by coating and impregnating the fibers with a resin.

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 4 and Comparative Examples 1 to 2 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.

O Although there is some sediment, there are no aggregates.

× 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 m was taken from the sample.
Insert between U-shaped clamps.

Hold the U-shaped clamp horizontally and place the Bunsen burner so that the center of its tip is 20 mm below the center of the opening of the test piece.The Bunsen burner used has an inner diameter of 10 m, and the flames of the burner were set in a 40 mm order. Adjust to A flame was applied to the test piece for 15 seconds, and the burning rate until the test piece burned 254 m 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.

(The following is a blank space) Example 5 A flame retardant-containing resin aqueous emulsion was obtained in the same manner as in Example 2, except that the quantitative ratio of the unsaturated monomers was changed as shown in Table 2.

Comparative Example 3 A resin aqueous emulsion was obtained in the same manner as in Example 5, except that no flame retardant was used.

Comparative Example 4 22.5 parts of hexabromocyclododeca was post-added to 200 parts by weight of the aqueous resin emulsion of Comparative Example 3 to obtain an aqueous resin emulsion.

Application Example 2 The flame retardant-containing resin aqueous emulsions obtained in Example 5 and Comparative Example 4, and the resin aqueous emulsion of Comparative Example 3 were mixed with cement, sand, etc. in the formulation shown in Table 2, and JIS A-
A sheet-like test piece was prepared by the method shown in the waterproof type described in No. 6910.

The combustion state and combustion rate of this product were investigated using the method shown in Application Example 1, and a tensile test was conducted at room temperature using the method of JISA-6910.

〔effect〕

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 Verdissier Co., Ltd. Agent
Patent attorney Masahisa Hase (and 1 other person)

Claims (1)

[Claims] 1), 10 parts of unsaturated monomer in the presence of 1 part by weight of flame retardant
Aqueous emulsion of flame retardant resin obtained by emulsion polymerization in a proportion of ~200 parts by weight.