JPH0819198B2 - Polymer aqueous dispersion - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention is excellent in mechanical stability and dispersibility of a filler,
The present invention relates to a stable polymer aqueous dispersion which exhibits particularly excellent adhesion to hydrophobic fibers such as polypropylene, nylon and polyester.

[Prior art]

Conventionally, tufted carpet, upholstery cloth, automobile seats, pile fabrics such as artificial lawn, pile fixation to the fabric, lamination of secondary base fabric, generally for the purpose of imparting dimensional stability and elasticity, A composition in which an aqueous polymer dispersion such as SBR latex, natural rubber latex or synthetic resin emulsion is mixed with various additives such as an inorganic filler such as calcium carbonate and aluminum hydroxide and a thickener as necessary is backed. ing.

Recently, polypropylene split yarn woven fabrics have been widely used for tufted carpets as primary base fabrics (base fabrics into which piles are inserted) for artificial lawns. However, since this polypropylene fabric is non-polar and has almost no water absorption, the backing strength of the secondary base fabric (backing) is not sufficient when backing with a composition containing a conventional polymer aqueous dispersion as a component. In addition, the pile pull-out strength tends to be insufficient. On the other hand, in the manufacture of carpets and the like, there is a strong tendency to mix a large amount of inexpensive inorganic fillers as a component of the composition in order to reduce the production cost, and therefore the fillers have excellent dispersion and stability, and a large amount of fillers. There is a demand for a low-viscosity polymer aqueous dispersion that does not reduce the adhesive strength when blended with.

[Problems to be solved by the invention]

The present invention is intended to solve the following problems associated with conventional techniques.

(1) The conventional polymer aqueous dispersion does not have sufficient adhesive force to the polypropylene base fabric, and as a result, the fixing force (pulling strength) of the pile such as carpet is inferior in the peel strength of the secondary base fabric.

(2) The conventional polymer aqueous dispersions lack the ability to stably mix and disperse a large amount of inorganic fillers, and the blending of the fillers significantly reduces the adhesive strength.

(3) Conventional polymer aqueous dispersions lack mechanical stability.

[Means for solving problems]

The present inventors have conducted extensive studies to develop a polymer aqueous dispersion having excellent dispersibility of fillers, mechanical stability, compounding stability, and excellent adhesiveness to hydrophobic fiber fabrics. , A polymer aqueous dispersion obtained by radical polymerization of an ethylenically unsaturated monomer mixture that necessarily contains butadiene in an aqueous medium and a self-emulsifying epoxy resin at a specific ratio is used for the above purpose. They have found that they are satisfactory and have completed the present invention.

That is, the present invention comprises (1) an ethylenic monomer mixture of which at least 10% by weight is butadiene and (2) a self-emulsifying epoxy resin in an aqueous medium (1) :( 2) = 30-70: 70
A polymer aqueous dispersion characterized by being radically polymerized at a ratio of up to 30 (weight ratio).

In the present invention, butadiene, which is an essential component among the monomers emulsion-polymerized to obtain the aqueous polymer dispersion, is an internal plasticizer for the aqueous polymer dispersion and has good elasticity in the film and a filler such as calcium carbonate. The ratio is used at least 10% by weight with respect to the monomer mixture in order to impart compounding stability with, but if the ratio is less than 10% by weight with respect to the monomer mixture, the effect is not recognized. . More preferably, butadiene
20-80% by weight.

Other ethylenically unsaturated monomers copolymerizable with butadiene in the present invention include, for example, methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,
Butyl acrylate, butyl methacrylate, pentyl acrylate, pentyl methacrylate, hexyl acrylate,
Hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, octadecyl acrylate, octadecyl methacrylate, and other alkyl acrylates and methacrylic acid alkyl esters; styrene, α-methylstyrene, vinyl Ethylenically unsaturated aromatic monomers exemplified by toluene, chlorostyrene, 2,4-dibromostyrene and the like; unsaturated nitriles such as acrylonitrile and methacrylonitrile; acrylic acid, methacrylic acid, crotonic acid, maleic acid and Its anhydrides, fumaric acid, itaconic acid, and unsaturated dicarboxylic acid monoalkyl esters,
For example, ethylenically unsaturated carboxylic acids such as monomethyl maleate, monoethyl fumarate and mono-n-butyl itaconate; vinyl esters such as vinyl acetate and vinyl propionate; vinylidene halides such as vinylidene chloride and vinylidene bromide; acrylic acid. -2-hydroxyethyl,
2-hydroxypropyl acrylate, methacrylic acid-
Hydroxyalkyl ester of ethylenically unsaturated carboxylic acid such as 2-hydroxyethyl; glycidyl ester of ethylenically unsaturated carboxylic acid such as glycidyl acrylate, glycidyl methacrylate and acrylamide, methacrylamide, N-methylol acrylamide, N- Radical-polymerizable monomers such as methylol methacrylamide, N-butoxymethyl acrylamide, and diacetone acrylamide are mentioned.

These monomers together with butadiene internally plasticize the polymer aqueous dispersion, or impart hardness to the film,
To impart strength, mechanical stability of polymer aqueous dispersion,
It is appropriately used for the purpose of improving freeze stability and adhesive strength. The proportion of these monomers used is 0 to 90% by weight, preferably 20 to 80% by weight in the monomer mixture.

Further, the glass transition point (Tg) of the polymer aqueous dispersion is adjusted depending on the intended use by the combination of butadiene and other ethylenic monomer, and the range is -80 to + 100 ° C.

The self-emulsifying epoxy resin of the present invention is an epoxy resin in which a segment having a stable emulsifying power and / or dispersing power in water is introduced into the molecule, and such a resin is emulsified and / or emulsified in an aqueous medium without using an emulsifier. Alternatively, it can be dispersed.

For such a resin, a grafted epoxy resin obtained by polymerizing a monomer mixture containing a carboxylic acid monomer with a free radical generator such as benzoyl peroxide in the presence of the resin is already contained in an aqueous medium containing a base. Japanese Patent Application Laid-Open No. 53-1228, which describes that the epoxy resin and the carboxyl-functional polymer are reacted in the presence of a specific tertiary amine. JP-A-56-43362 discloses a self-emulsifying epoxy ester co-polymer capable of esterifying a carboxyl functional polymer with an epoxy resin in the presence of an amine esterification catalyst and self-emulsifying in water with a base. It is well known from the publications of Shokai 55-3481 and 55-3482, and as a commercial product, "Dick Fine GN-280" (Dainippon · The Chemical Industry Co., Ltd.) there is.

In the polymer dispersion of the present invention, the ratio of (1) an ethylenically unsaturated monomer mixture containing at least 10% by weight of butadiene to (2) a self-emulsifying epoxy resin is (1) in terms of solid content weight ratio. : (2) = 30 to 70:70 to 30 is preferable. If it is used in excess of the above range, the polymerization stability may deteriorate,
Alternatively, the strength is lowered and the compounding stability is lowered.

The method for producing the polymer aqueous dispersion of the present invention is a free radical generating catalyst such as an ethylenically unsaturated monomer mixture containing butadiene in the presence of a self-emulsifying epoxy resin in water, preferably without using an emulsifier. KPS (K ₂ S ₂ O ₃ ), APS
_{((CNH 4) 2 S 2} O 8), aqueous catalyst t- butyl hydroperoxide such as hydrogen peroxide solution, preferably by oily catalyst such as cumene hydroperoxide may be carried emulsion polymerization at 50 ° C. to 70 ° C. . Incidentally, since the present invention uses a self-emulsifying epoxy resin, an emulsifier is not particularly required, but other additives usually used in emulsion polymerization, such as a chain transfer agent, ethylenediaminetetraacetic acid for the purpose of stabilizing polymerization and buffering effect, Alternatively, it is acceptable to use an alkaline substance for pH adjustment as necessary. Furthermore, the copolymer aqueous dispersion after the completion of emulsion polymerization may be subjected to concentration and removal of unreacted monomers without any problem.

〔effect〕

The polymer aqueous dispersion of the present invention thus obtained has excellent mechanical stability as well as excellent dispersibility when a large amount of filler is compounded, and in a system that does not use an emulsifier, adhesiveness to hydrophobic fibers due to the emulsifier. Since it has excellent properties, it is suitable not only as a base resin for backing but also as a coating agent for adhesives, paper, fibers, plastics and the like.

Further, the polymer aqueous dispersion of the present invention has less skin surface phenomenon due to drying during storage, and what is surprising is that a carpet is prepared using a backing composition containing the polymer aqueous dispersion of the present invention. When manufactured, it prevents the occurrence of blisters (a phenomenon that causes boiling inside the adhesive when the adhesive dries and the adhesive partially blows out on the back surface of the carpet and significantly impairs the appearance) due to the emulsifier. It is an excellent thing that can be done.

In addition, the butadiene-based resin has extremely soft texture and elasticity, and also has the durability such as water resistance, solvent resistance, and abrasion resistance of the self-emulsifying epoxy resin that is a water-based polymer. Therefore, for example, fibers, surface and back surface processing of textile products, impregnating coating processing agents such as paper, coating materials, coating materials for building materials such as wall materials, surface coating agents such as synthetic leather or top layers, binders for foam processing materials, It can be used as various coating materials, adhesives, and various compound base resins.

〔Example〕

Next, the present invention will be described more specifically by way of examples.
In addition, "part" and "%" in each example shall be based on weight.

Example 1 120 ion-exchanged water in an autoclave replaced with nitrogen.
Parts, butadiene 60 parts, styrene 40 parts, self-emulsifying epoxy resin ["Dick Fine GN-280" manufactured by Dainippon Ink and Chemicals, Inc.) 50 parts, tertiary dodecyl mercaptan
Charge 0.2 parts and add 0.5 parts ammonium persulfate at a polymerization temperature of 60 ° C.
Then, the polymerization was started, and the reaction was allowed to proceed until the polymerization rate reached 98% or more based on the measurement method described in the lower column of Table 2. Next, the unreacted monomer was removed and concentrated by stripping to obtain a stable polymer aqueous dispersion (A) having a solid content of 50.3%, a pH of 8.3 and a viscosity of 155 cps. As a result of carrying out a stability test on this dispersion liquid (A), it was found that the aggregate was 0 and the stability was very excellent.

Next, using the above water dispersion (A), the composition shown in Table 1 was prepared to prepare an adhesive compound for carpet backing, and 1400 g (wet) per 1 m ² was applied to a carpet composed of an acrylic loop pile and a polypropylene primary base cloth. And apply jute as the secondary base cloth 14
A carpet was prepared by drying in a hot air dryer at 0 ° C for 10 minutes. Next, the carpet was cut into a width of 5 cm, and a peeling test of the secondary base cloth and a yarn removing test of the acrylic loop pile were performed. Moreover, the back surface of the carpet was observed and the blister was judged. The test results are shown in Table 2. From Table 2, the polymer aqueous dispersions of the examples of the present invention show good results.

Example 2 Solid content 50.0%, pH 8.1, was obtained in the same manner as in Example 1 except that 50 parts of the epoxy resin used in Example 1 was changed to 100 parts.
A polymer aqueous dispersion (B) having a viscosity of 115 cps was obtained. Thereafter, a stability test was conducted in the same manner as in Example 1 except that the polymer aqueous dispersion (B) thus obtained was replaced with the polymer aqueous dispersion (A), a carpet was prepared, and peel strength and yarn removal were conducted in the same manner. The strength was measured. The test results are shown in Table 2. From Table 2, it was confirmed that the polymer aqueous dispersion of the present invention showed good results.

Example 3 A polymer dispersion (C) having a solid content of 50.0, a pH of 8.4 and a viscosity of 90 cps was obtained in the same manner as in Example 1 except that 50 parts of the epoxy resin used in Example 1 was changed to 200 parts. Thereafter, the polymer aqueous dispersion (C) thus obtained is replaced with the polymer aqueous dispersion (A).
A stability test was performed in the same manner as in Example 1 except that the above was replaced with, and a peeling strength and a yarn removal strength were measured in the same manner. The test results are shown in Table 2. From Table 2, it was confirmed that the polymer aqueous dispersion of the present invention showed good results.

Comparative Example 1 Ion-exchanged water 120 in an autoclave replaced with nitrogen.
Parts, butadiene 60 parts, styrene 35 parts, acrylic acid 5 parts,
Sodium alkylbenzene sulfonate (NeoPerex F-
25 Kao Soap Co., Ltd.) 1.0 part, ethylenediaminetetraacetic acid 0.1 part, tertialidodecyl mercaptan 0.5 part were charged, and at a polymerization temperature of 60 ° C, 0.5 part of ammonium persulfate was added to start the polymerization until the polymerization rate became 98% or more. It was made to react. Next, the pH is adjusted with potassium hydroxide and unreacted monomers are removed and concentrated by stripping to obtain a solid content of 50.0% and a pH of 8.
4. A polymer aqueous dispersion (D) having a viscosity of 300 cps was obtained. Thereafter, a stability test was conducted in the same manner as in Example 1, a carpet was prepared, and the peeling strength and the yarn removal strength were measured in the same manner. The test results are shown in Table 2.

Comparative Example 2 Example 1 except that 60 parts of butadiene used in Example 1 was changed to 55 parts of butyl acrylate and 5 parts of butadiene.
A polymer aqueous dispersion (E) having a solid content of 50.0, a viscosity of 200 cps and a pH of 8.5 was obtained in the same manner as in. Thereafter, a stability test was conducted at the same end as in Example 1, a carpet was prepared, and the peeling strength and the yarn removal strength were measured in the same manner. The test results are shown in Table 2.

Comparative Example 3 The same polymerization as in Example 1 was attempted except that the epoxy resin used in Example 1 was changed from 50 parts to 10 parts, but a large amount of gel was generated during the polymerization, which was not practical.

Comparative Example 4 Solid content 50.0 and pH 8. in the same manner as in Example 1 except that the epoxy resin used in Example 1 was changed from 50 parts to 700 parts.
3. A polymer aqueous dispersion (F) having a viscosity of 20000 cps was obtained. Thereafter, a stability test was conducted in the same manner as in Example 1 except that the polymer aqueous dispersion (F) thus obtained was replaced with the polymer aqueous dispersion (A). However, this caused gelation during the stability test. The results are summarized in Table 2.

Comparative Example 5 A polymer water dispersion having a solid content of 50.1%, a viscosity of 245 cps, and a pH of 8.6 was carried out in the same manner as in Example 1 of the present application except that 75 parts of styrene and 25 parts of acrylonitrile were used as the ethylenically unsaturated monomer. Liquid G was obtained and evaluated in the same manner as in the present application. The results are shown in Table 3.

Comparative Example 6 The same operation as in Example 1 of the present application was conducted except that 87 parts of styrene and 13 parts of methacrylic acid were used as the ethylenically unsaturated monomer, and 10% by weight of a gel product was produced during the polymerization. The resulting dispersion is filtered and concentrated to a solid content of 49.1%, a viscosity of 640 cps,
A polymer aqueous dispersion H having a pH of 8.6 was obtained and evaluated in the same manner as in the present application.

Claims (1)

[Claims] 1. An (1) ethylenically unsaturated monomer mixture in which at least 10% by weight is butadiene and (2) a self-emulsifying epoxy resin in an aqueous medium, (1) :( 2) =
30-70: 70-30 (weight ratio), a polymer aqueous dispersion characterized by radical polymerization.