JPH0834893A - Aqueous emulsion composition of flame-retardant resin - Google Patents

Abstract

PURPOSE:To improve the effect of imparting flame retardancy to a fibrous or other substrate and improve the adhesion to the substrate. CONSTITUTION:An aqueous emulsion of a resin (A) having a content of vinylidene chloride units of 75wt.% or higher (preferably 75-93wt.%) is mixed with an aqueous emulsion of a resin (B) having a content of vinylidene chloride units of 30-65wt.% (preferably 40-65wt.%) in such a proportion that the amounts of the resins (A) and (B) are 25-80wt.% and 75-20wt.%, respectively. This mixture is compounded with 1-20 pts.wt. flame retardant per 100 pts.wt. the resins (A) and (B) to obtain the objective composition. Especially preferred examples of the flame retardant are antimony trioxide and antimony pentaoxide.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention is useful as a backing coating agent or binder for a flame-retardant resin aqueous emulsion composition, particularly a fiber interior material for vehicles, and for coating air-conditioning filters, paper, wallpaper, etc. The present invention relates to a flame-retardant resin aqueous emulsion composition that can also be used as an agent or the like.

[0002]

BACKGROUND OF THE INVENTION Aqueous resin emulsions are widely used as backing coating agents and binders for fiber interior materials for vehicles. In particular, the following flame-retardant resin aqueous emulsions are used for fiber interior materials for vehicles.

Vinyl chloride-based or vinylidene chloride-based resins such as vinyl chloride / vinylidene chloride copolymers, vinyl chloride / acrylic acid alkyl ester copolymers, vinylidene chloride / acrylic acid alkyl ester copolymers are flame retardant Aqueous emulsion of resin.

A resin water-based emulsion in which a flame retardant such as tetrabromobisphenol, antimony trioxide, trialkyl phosphate, hexabromocyclododecane, decabromodiphenyl oxide, and chlorinated phosphoric acid ester is added to the resin water-based emulsion.

In particular, in the case of a resin aqueous emulsion which is required to have high flame retardancy, a mixture of the above flame retardant resin aqueous emulsion with a flame retardant compounded in the above case has been used.

[0006]

In recent years, there has been a trend toward ever more lightweight fibrous interior materials for vehicles, from the viewpoints of weight reduction and cost reduction. If the coating amount is reduced, it is difficult to maintain sufficient flame retardancy with the conventional flame retardant resin aqueous emulsion, and if a large amount of flame retardant is added to maintain sufficient flame retardancy, the resin is There is a problem that the compatibility with the emulsion is deteriorated and various physical properties as a backing coating agent and a binder are deteriorated.

The present invention provides a flame-retardant resin aqueous emulsion in which the amount of the flame-retardant added is relatively small in order not to deteriorate the physical properties as a backing coating agent or binder, and moreover, it is possible to exert a high flame-retardant imparting effect. It is the one we are trying to provide.

[0008]

The flame-retardant resin aqueous emulsion composition of the present invention has a vinylidene chloride unit content of 7%.
An aqueous emulsion of 5% by weight or more of the resin (A) and an aqueous emulsion of the resin (B) having a vinylidene chloride unit content of 30 to 65% by weight are contained in a resin solid content of 2% by weight of the resin (A).
5 to 80% by weight and the resin (B) in an amount of 75 to 20% by weight, in the resin aqueous emulsion mixed solution,
A composition comprising a flame retardant in an amount of 1 to 20 parts by weight based on 100 parts by weight of the total resin solid content of the mixed liquid.

The flame-retardant resin aqueous emulsion composition of the present invention is a resin aqueous emulsion obtained by mixing the same resin (A) aqueous emulsion with 100 parts by weight of the resin solid content and the same amount of the same flame retardant. By comparison, or in the same aqueous emulsion of the same resin (B), the resin solid content of 10
Even when compared with a resin aqueous emulsion obtained by blending the same amount of the same flame retardant in 0 part by weight, the flame retardancy imparting effect is excellent. That is, in the present invention, an aqueous emulsion of the specific resin (A) and the specific resin (B)
The effect of imparting flame retardancy can be remarkably enhanced by mixing the above-mentioned aqueous emulsion with a certain ratio.

In the present invention, an aqueous emulsion of a resin (A) having a vinylidene chloride unit content of 75% by weight or more, or an aqueous emulsion of a resin (B) having a vinylidene chloride unit content of 30 to 65% by weight is prepared by simply using vinylidene chloride. A monomer containing a vinylidene chloride monomer whose content of the monomer is the same as the vinylidene chloride unit content of the target resin [vinylidene chloride unit content 100% by weight of resin (A)]
Is a monomer mixture of a vinylidene chloride monomer and another monomer copolymerizable therewith, except for producing an aqueous emulsion of be able to.

Other monomers copolymerizable with the vinylidene chloride monomer used in that case include, for example, acrylic acid ester (alkyl ester having 1 to 12 carbon atoms) and methacrylic acid ester (alkyl ester having 1 to 12 carbon atoms). Alkyl ester), acrylonitrile, vinyl chloride, vinyl acetate, ethylene, styrene, and the like, and mixtures of two or more thereof. Generally, acrylic acid ester, methacrylic acid ester, acrylonitrile, vinyl chloride and their 2 Mixtures of one or more are preferred. In addition to these monomers, as a functional group-containing monomer, a carboxyl group-containing monomer (eg acrylic acid, methacrylic acid, etc.), an amide group-containing monomer (eg acrylamide,
Methacrylamide, etc.), hydroxyl group-containing monomer (eg, hydroxyethyl acrylate, etc.), methylol group-containing monomer (eg, N-methylol acrylate, N-)
0.5 to 5% by weight of methylol methacrylamide etc.)
It is also possible to use a mixture of the monomers which is contained in a certain amount.

The resin (A) has a vinylidene chloride unit content of 75% by weight or more, preferably 75 to 93% by weight.
When the content is less than 75% by weight, the flame retardancy imparting effect of the obtained flame retardant resin aqueous emulsion composition is lowered. Further, when the content is too large, the flame retardancy-imparting effect remains unchanged, and the crystallinity of the resin increases, so that the binding effect when used as a backing coating agent or binder for fibrous interior materials. Tends to decrease.

The vinylidene chloride unit content of the resin (B) is 30 to 65% by weight, preferably 40 to 65% by weight.
If the amount is out of this range, the flame retardancy-providing effect of the obtained flame-retardant resin aqueous emulsion composition will decrease.

Further, the mixing ratio of the aqueous emulsion of the resin (A) and the aqueous emulsion of the resin (B) in the present invention is 25 to 80% by weight of the resin (A) based on the resin solid content.
The resin (B) is in a proportion of 75 to 20% by weight. If the ratio of the aqueous emulsion of the resin (A) is too small (that is, if the ratio of the aqueous emulsion of the resin (B) is too large), the flame retardancy-imparting effect is lowered and the resin (A) is reduced.
If the ratio of the aqueous emulsion is too large (that is, if the ratio of the resin (B) is too small), the flame retardancy-imparting effect is lowered. Therefore, the mixing ratio of both resin aqueous emulsions should be within the above range. is there.

Next, the mixing ratio of the resin emulsion mixed liquid and the flame retardant in the present invention is 1 to 20 parts by weight based on 100 parts by weight of the total resin solid content of the resin emulsion mixed liquid,
It is preferably 2 to 15 parts by weight. If the mixing ratio of the flame retardant is too small, the flame retardancy-providing effect of the resulting resin aqueous emulsion composition will decrease, and if the mixing ratio of the flame retardant is too large, the resulting resin aqueous emulsion composition will be backed by coating. When used as an agent or a binder, the binding effect is reduced.

As the flame retardant in the present invention, generally used chlorine flame retardants, bromine flame retardants, phosphorus flame retardants, inorganic flame retardants and the like can be used. Typical examples of the chlorine-based flame retardant include chlorinated paraffin, chlorinated polyethylene, and chlorinated alicyclic compounds. Examples of the brominated flame retardant include hexabromocyclododecane, decabromodiphenyl oxide, brominated polystyrene and the like. Examples of the phosphorus-based flame retardant include triphenyl phosphate and tris (trichloroethyl) phosphate. Further, examples of the inorganic flame retardant include antimony trioxide, antimony pentoxide, aluminum hydroxide, magnesium hydroxide and the like. Among these flame retardants, antimony trioxide and antimony pentoxide have particularly excellent flame retarding effects.

The method for mixing the resin aqueous emulsion mixed liquid and the flame retardant is not particularly limited. For example, when the flame retardant is a powder or a liquid, the flame retardant may be directly added to the resin emulsion mixture and mixed, or the resin emulsion mixture may be prepared by previously dispersing or emulsifying the flame retardant in water. You may add and mix.

In addition to the above-mentioned essential components, various additives such as a plasticizer, a thickener, an antifoaming agent, an antifreezing agent, a pigment, etc. may be added to the aqueous flame retardant resin emulsion of the present invention, if necessary. Sand, a filler, a wetting agent, a water repellent, a cross-linking agent, a pH adjuster and the like can be added.

[0019]

EXAMPLES The present invention will be described in detail below with reference to production examples of resin aqueous emulsions, examples and comparative examples. The "parts" and "%" described in these examples are based on weight.

Resin Aqueous Emulsion Production Example 1 A reaction vessel equipped with a temperature controller, a stirrer, a supply container, a thermometer and a nitrogen gas inlet tube was charged with the following mixture. Water 250 parts Sodium dodecylbenzene sulfonate 1 part Potassium persulfate 1.5 parts

Then, the inside of the reactor was purged with nitrogen gas and then depressurized, and the following mixture was continuously fed into the reactor at a constant rate for 4 hours by using a metering pump to keep polymerization at 60 ° C. for polymerization. . Vinylidene chloride 340 parts Ethyl acrylate 40 parts Butyl acrylate 20 parts Sodium dodecylbenzene sulfonate 4 parts Water 250 parts

After the completion of feeding the mixture, the polymerization was continued at 60 ° C. until the internal pressure of the reactor reached 0 Kg / cm ² G to obtain a resin aqueous emulsion having a resin solid content of 50%. .

The types of monomers and emulsifiers used in the emulsion polymerization of this Production Example and their amounts, and the vinylidene chloride unit content and chlorine content in the resin of the obtained resin aqueous emulsion were determined as follows. It is summarized in Table 1 below.

Resin Aqueous Emulsion Production Examples 2 to 6 The types of monomers and emulsifiers and their amounts used were changed as shown in Table 1 below, except that emulsion polymerization was carried out in the same manner as in Production Example 1. To produce respective resin aqueous emulsions. The content of vinylidene chloride unit and the chlorine content in the resin of the obtained resin aqueous emulsion were as shown in Table 1 below.

[0025]

[Table 1]

Example 1 75 parts of the resin aqueous emulsion obtained in the above resin aqueous emulsion production example 1 was mixed with 25 parts of the resin aqueous emulsion obtained in the resin aqueous emulsion production example 5, and then the mixed emulsion was added with hexa Bromocyclododecane powder 5 parts (10 parts for 100 parts total resin solids)
Part) was added and well stirred to obtain a flame retardant resin aqueous emulsion composition.

The composition of the obtained flame-retardant resin aqueous emulsion composition and the chlorine content in all the resins were as shown in Table 2 below.

Table 2 shows the results of the following flame retardant performance test and abrasion resistance test for the flame retardant resin aqueous emulsion composition.

Flame-retardant performance test: An aqueous resin emulsion (composition) was applied to a polypropylene needle-punched carpet having a basis weight of 250 g / m ² and a dry amount of 50 g / m 2.
^A sample is prepared by spray coating so as to be ² and drying at 120 ° C. for 20 minutes.

From this sample, width 100 mm, length 350 m
Take a test piece of m and sandwich it between the U-shaped clamps. With the U-shaped clamp kept horizontal, the Bunsen burner is placed so that the center of the tip of the Bunsen burner is located 20 mm below the center of the opening of the test piece. A Bunsen burner with an inner diameter of 10 mm was used, and the burner flame was 40 m.
Adjust to m. In this condition, apply 15 flames to the test piece.
The test piece is burned for 2 seconds, and the burning speed is measured and evaluated.

Abrasion resistance test: A sample was prepared in the same manner as in the test, and the diameter of the sample was 180 mm.
Then, a test piece having a circular hole of 6 mm in its center is prepared.

Next, the test piece was attached to a Taber type rotary rear presser (ASTM D-1175) and rotated for 5 minutes under the conditions of a wear wheel H-18, a rotation speed of 50 times / minute and a load of 500 g to wear it. The degree of wear is visually inspected and evaluated according to the following criteria. A: Almost no wear is observed B: Slight wear is observed X: A considerable amount of wear is observed

Examples 2 to 5 A flame retardant resin aqueous emulsion composition was prepared by changing the composition of the resin aqueous emulsion composition as shown in Table 2. The obtained resin aqueous emulsion composition was subjected to the same performance test as in Example 1 and the results are shown in Table 2.

Comparative Examples 1 to 6 A flame retardant resin aqueous emulsion composition was prepared by changing the composition of the resin aqueous emulsion composition as shown in Table 3. The obtained resin aqueous emulsion composition was subjected to the same performance test as in Example 1 and the results are shown in Table 3.

[0035]

[Table 2]

[0036]

[Table 3]

[0037]

The flame-retardant resin aqueous emulsion composition of the present invention has an excellent flame-retardant effect when applied to a fibrous base material and the like, and also has an excellent binding effect.

Continuation of front page (51) Int.Cl. ⁶ Identification code Office reference number FI Technical display location C09D 127/08 PFF C09J 127/08 JCP

Claims (3)

[Claims] 1. The content of vinylidene chloride units is 75% by weight.
The aqueous emulsion of the resin (A) and the aqueous emulsion of the resin (B) having a vinylidene chloride unit content of 30 to 65% by weight are contained in a resin solid content of 25 to 80.
Wt% and the resin (B) is mixed in a proportion of 75 to 20% by weight, and a flame retardant is added to the resin aqueous emulsion mixture in an amount of 1 to 20 relative to 100 parts by weight of the total resin solid content of the mixture.
A flame-retardant resin aqueous emulsion composition, which is blended in a ratio of parts by weight. 2. The flame retardant according to claim 1, wherein the resin (A) has a vinylidene chloride unit content of 75 to 93% by weight, and the resin (B) has a vinylidene chloride unit content of 40 to 65% by weight. Resin aqueous emulsion composition. 3. The flame retardant resin aqueous emulsion composition according to claim 1, wherein the flame retardant is antimony trioxide and / or antimony pentoxide.