JPH10204381A - Aqueous film-forming dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aqueous film-forming dispersion that has excellent film- forming properties and can form a coating film having water resistance when applied to a substrate such as paper or cloth, by selecting a dispersion containing an organic solvent, in which a polymeric dispersoid comprising an activator and a thickner is dispersed. SOLUTION: This dispersion contains an organic solvent, in which a polymeric dispersoid having a mean particle diameter of 5-3,000μm and an average molecular weight of 1,000-500,000. The polymeric dispersoid should contain an activator and a thickener. The mixing ratio of the organic solvent to the thickener (polymer) should be 80:1 to 30:1 by weight, and the dispersion should contain 0.1-30wt.% activator and 0.01-20wt.% thickener. In a coating film formed from the dispersion, when the organic solvent is volatilized, the dispersoid remains in the film. It can function as the optimal means for applying to and allowing to remain on the dispersoid being a desired active component on the surface of a substrate. Therefore, it can find application to coating means for a detergent, a medicine, a coating material or the like.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an aqueous film-forming dispersion capable of adjusting the degree of water-solubility, particularly to a polymer-based dispersoid comprising an activator and a thickener (coating agent) [hereinafter simply referred to as "polymer". Referred to as an aqueous film-forming dispersion containing an organic solvent dispersed therein.

[0002]

2. Description of the Related Art Conventionally, as a dispersion applied to the surface of a substrate such as paper or cloth, for example, a coating liquid in which carboxymethyl cellulose (CMC) having a predetermined particle size is dispersed is used. [Japanese Patent Laid-Open No. 8-176994]
No.). In other words, according to this conventional technique, by focusing on the properties of CMC that imparts water retention and fluidity to a coating liquid, CMC having a predetermined particle size is blended in a specific ratio to improve water retention and dispersibility. It is intended to obtain a paper coating liquid having the following. However, the coating liquid using this CMC could not impart satisfactory film performance to paper, such as poor film-forming properties and a decrease in water retention over time. C
In addition to MC, coating solutions using polyacrylic acid or methacrylic acid have also been devised, but similar problems have been recognized in these coating solutions.

[0003] In view of the above, there is a strong demand for the development of a dispersion capable of forming a film having improved performance on the surface of a substrate such as paper or cloth.

[0004]

Means for Solving the Problems In view of the above problems, the present inventor has made intensive studies on improving the composition of a coating liquid in order to improve the film performance of the coating dispersion, and completed the present invention. It has been reached. That is, the gist of the present invention is an aqueous film-forming dispersion containing an organic solvent (diluent) in which a polymer comprising an activator and a thickener (coating agent) is dispersed.

[0005] With this configuration, according to the aqueous film-forming dispersion of the present invention, a film having excellent film-forming properties and water resistance, which has not been observed in conventional coating solutions, can be formed.

[0006] Further, in the film formed from the aqueous film-forming dispersion of the present invention, the activator (cleaning component) is retained and remains in the film after the organic solvent is volatilized. It will function and thus provide an optimal means for retaining the cleaning components on the desired substrate surface.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The aqueous film-forming dispersion of the present invention is a dispersion of a polymer in a dispersion medium containing an organic solvent as a main component. The mixing ratio of the organic solvent (diluent) and the polymer is as follows:
In order to obtain good miscibility and good film forming properties of the dispersion, organic solvent: polymer = 80: 1 to 30: 1, preferably 60: 1.
Adjust to a weight ratio of ~ 30: 1.

From the viewpoint of imparting good dispersibility to the final product dispersion, the polymer constituting the aqueous film-forming dispersion of the present invention is 5 μm to 3000 μm, preferably 400 μm to 400 μm.
A polymer having an average particle diameter of μm to 1000 μm and an average molecular weight of 1000 to 500,000, preferably 10,000 to 400,000 is used.

The organic solvent (diluent) constituting the aqueous film-forming dispersion of the present invention includes halogenated hydrocarbons,
Polyhydric alcohol derivatives, alcohols, ketones, aldehydes, hydrocarbons, cellosolves, mixed solvents of chlorides, mixed solutions of methanol / ethylene bromide, etc., specifically, methylene chloride, chloroform, glycol ethers (ethylene-based Glycol ethers and acetates, propylene glycol ethers and acetates), acetone, toluene, methyl cellosolves, ethyl cellosolves, butyl cellosolves, dimethylformamide, acetic acid, benzyl alcohol, ethylene chlorohydrin, pyridine, formic acid, aniline, etc. .

On the other hand, regarding the activator and the thickener (coating agent) constituting the dispersoid of the aqueous film-forming dispersion of the present invention, the activator may be an anionic surfactant, a nonionic surfactant or an amphoteric surfactant. Any of the surfactants can be applied, for example, linear alkyl benzene sulfonates,
Higher alcohol alkyl sulfates, alkyl ether sulfates, lauryl sulfoacetates, α-olefin sulfonates, lauroyl sarcosine salts, myristoyl sarcosine salts, pronic surfactants, polyethylene glycol, sucrose fatty acid esters, etc. There is.

As the thickener (coating agent), polymer polymers, thickening polysaccharides, gums, cellulose derivatives and the like are applicable. For example, crosslinked acrylic acid polymers, starches, dextrins , Sodium alginate, casein, gelatin, bentonite cod gum, guar gum, xanthan gum, roast gum, polyvinyl alcohol, methylcellulose, ethylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxycellulose and the like. These thickeners (coating agents) can be used alone,
Mixtures containing some of these simple substances can also be used,
In particular, the use of a cellulose derivative alone or a mixture containing a cellulose derivative is preferred because an aqueous film-forming dispersion having desired properties is easily obtained.

Next, the amounts of the above-mentioned activators and thickeners are selected in the following ranges with respect to the total amount of the dispersion. Activator: 0.1 to 30% by weight, preferably 3 to 9% by weight; Thickener: 0.01 to 20% by weight, preferably 0.5 to 4.0% by weight.

When the amount of the activator is less than 0.1% by weight, the detergency and the foaming function decrease, and when the amount of the activator exceeds 30% by weight, the generation of foam becomes remarkable and the adverse effect on the environment is reduced. Due to concerns, the above range was selected.
Similarly, when the amount of thickener is less than 0.01% by weight,
If the function and stability of the abrasion resistance of the dispersion are reduced, and if the amount of the thickener exceeds 20% by weight, the strength of the coated paper is increased and the coating is easily cracked. In addition, the range of the above-mentioned thickener was selected because the viscosity becomes excessively large and coating on the production line becomes difficult.

Further, in the dispersion of the present invention, a pigment, a water retention agent, a dispersant, an antifoaming agent, a preservative, a water resistance agent, a release agent may be used, if necessary, in consideration of the use of the final product. , Dyes, oils, resins, fragrances and antibacterial agents can be optionally added. Representative examples include titanium oxide, carbon black, disalloy yellows, phthalocyanine blue, and RE as pigments.
MAZOL TURQ BLUE; potassium polyphosphate as water retention agent;
Sodium benzoate, methyl parahydroxybenzoate, ethyl parahydroxybenzoate as preservatives: sodium polyacrylate, sodium polyphosphate as a dispersant; fluorine and silicon as water-resistant agents, release agents; isopropyl solvent, naphtha as oils Turpentine oil; and a urethane resin or the like as a resin may be further added and used.

For the purpose of suppressing the production cost, it is also possible to add calcium carbonate and borate as extenders.

[0016]

EXAMPLES The present invention will be specifically described below with reference to examples, but it should be understood that the present invention should not be construed as being limited based on the disclosure of these examples.

Examples 1 to 8: Preparation of aqueous film- forming dispersion [ Example 1 ] To 108 ml of ethyl alcohol, 11.42 g of sodium lauryl sulfoacetate and sodium sulfamate
0.02 g was added with stirring and dispersed. next,
To this dispersion was added 2.86 g of hydroxypropylcellulose, and the mixture was stirred at 1000 rpm for 30 to 50 minutes (Super Digital Stirrer: Iuchi Seieido Co., Ltd.).

In order to prevent the formation of a lump of hydroxypropylcellulose, particularly a semi-swelling lump, hydroxypropylcellulose (white powder) is added while passing the hydroxypropylcellulose through a sieve. (The same applies to the following Examples / Comparative Examples).

The details of the materials used in this embodiment are summarized in Table 1 below.

[0020]

[Table 1]

The properties of the dispersion obtained in this example were as follows.

Viscosity: 1000-3000 cps (B-type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 60 rpm) Non-volatile content: 14.3 W / W% Average particle size of polymer: 500-900 μm Average molecular weight of polymer : 110,000 to 150,000 Example 2 In 78.38 ml of ethyl alcohol, 9.00 g of sodium lauryl sulfoacetate and sodium sulfamate
0.01 g was added with stirring to disperse. Next, 1.00 g of hydroxypropyl cellulose was added to this dispersion.
Was added and the mixture was stirred at 1000 rpm for 30 to 50 minutes (Super Digital Stirrer: Iuchi Seieido Co., Ltd.) Next, 27.99 g of calcium carbonate was added to this dispersion and stirred to obtain a target dispersion.

The details of the materials used in the above-described embodiment are summarized in Table 2 below.

[0024]

[Table 2]

The properties of the dispersion obtained in this example were as follows.

Viscosity: 1800-3000 cps (B-type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 60 rpm) Non-volatile content: 38.0 W / W% Average particle size of polymer: 500-900 μm Average molecular weight of polymer [ Example 3 ] Propylene glycol tertiary butyl ether (59.63 ml) and hydroxypropyl cellulose (2.
20 g was added and the mixture was stirred at 1000 rpm for 30 to 50 minutes (Super Digital Stirrer: Iuchi Seieido Co., Ltd.). next,
6.00 g of sodium lauryl sulfoacetate and 24.80 g of calcium carbonate were added to the dispersion, and the mixture was stirred until it could be mixed uniformly. And finally, ethyl alcohol 18.96m
was added, and the mixture was similarly stirred until homogeneous mixing was achieved.
The details of the materials used in the above-described embodiment are summarized in Table 3 below.

[0027]

[Table 3]

The properties of the dispersion obtained in this example were as follows.

Viscosity: about 5000 cps (B-type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 60 rpm) Non-volatile content: 33.0 W / W% Average particle size of polymer: 500-900 μm Average molecular weight of polymer: [ Example 4 ] 2.2 g of hydroxypropylcellulose was added to 48.17 ml of propylene glycol tertiary butyl ether while sieving.
Stirred for ~ 30 minutes (Super Digital Stirrer: Iuchi Seieido Co., Ltd.). Then, 18.96 ml of ethyl alcohol was added, and the mixture was further stirred for 20 to 30 minutes. Next, 6.00 g of sodium lauryl sulfoacetate and 24.80 g of calcium carbonate were added to the dispersion, and the mixture was stirred until it could be mixed uniformly. And finally, isopropyl alcohol 12.74
ml was added, and the mixture was similarly stirred until it could be uniformly mixed to obtain a target dispersion. The details of the materials used in the above-described embodiment are summarized in Table 4 below.

[0030]

[Table 4]

The properties of the dispersion obtained in this example were as follows.

Viscosity: about 4000 cps (B type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 60 rpm) Non-volatile content: 33.0 W / W% Average particle diameter of polymer: 500 to 900 μm Average molecular weight of polymer: [ Example 5 ] Propylene glycol monomethyl ether acetate was added to 39.26 ml of hydroxypropyl cellulose.
2.20 g were added. Next, 11.47 ml of propylene glycol tertiary butyl ether was added to the dispersion, and the mixture was stirred at 1000 rpm for about 45 minutes (Super Digital Stirrer: Inei Seieido Co., Ltd.). Then, 12.01 ml of ethyl alcohol was added, followed by 9.00 g of sodium lauryl sulfoacetate and 21.80 g of calcium carbonate,
Stir until uniform mixing is achieved. Finally, 12.01 ml of ethyl alcohol was added, and the mixture was similarly stirred until it could be uniformly mixed to obtain a target dispersion.

The details of the materials used in this embodiment are summarized in Table 5 below.

[0034]

[Table 5]

The properties of the dispersion obtained in this example were as follows.

Viscosity: about 5000 cps (B type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 33.0 W / W% Average particle size of polymer: 500-900 μm Average molecular weight of polymer: Example 6 1.05 g of an alkyl methacrylate copolymer and then 17.00 g of sodium alkanesulfonate were added to 31.88 ml of distilled water. Then, 0.07 g of triethyl alcohol amine and then ethyl alcohol
63.21 ml was added, and the mixture was stirred until it could be uniformly mixed (Super Digital Stirrer: Inei Seiseido Co., Ltd.) to obtain the desired dispersion.

The details of the materials used in the above-described embodiment are summarized in Table 6 below.

[0038]

[Table 6]

The properties of the dispersion obtained in this example were as follows.

Viscosity: about 400 to 500 cps (B type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 18.12 W / W% Average particle diameter of polymer: 60 to 200 μm [ Example 7 ] To 113.61 ml of ethyl alcohol, 0.16 g of crosslinked sodium polyacrylate and then 1.80 g of hydroxypropylcellulose were added. And 8.00 g of sodium linear alkyl benzene sulfonate, then
Add 0.17g of sulfamic acid and stir until it can be mixed uniformly (Super Digital Stirrer: Iuchi Seieido Co., Ltd.)
Thus, the intended dispersion was obtained.

The details of the materials used in this embodiment described above are summarized in Table 7 below.

[0042]

[Table 7]

The properties of the dispersion obtained in this example were as follows.

Viscosity: about 1200 cps (B-type viscometer No. 3 rotor [BL format: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 10.13 W / W% Average particle size of hydroxypropyl cellulose: 500 to 9
00 μm Average molecular weight of hydroxypropyl cellulose: 55,000-
70000 Average particle size of sodium polyacrylate: 60 to 200 μm Example 8 To 37.84 ml of glycerin was added 1.00 g of hydroxypropylcellulose.

Next, ethyl alcohol 6 was added to the dispersion.
3.22 ml, then sodium lauryl sulfoacetate 6.00
g and 13.00 g of magnesium stearate were added, and the mixture was stirred until it could be uniformly mixed (Super Digital Stirrer: Inoui Seieido Co., Ltd.) to obtain a target dispersion.

Table 8 below summarizes the details of the materials used in this embodiment described above.

[0047]

[Table 8]

The properties of the dispersion obtained in this example were as follows.

Viscosity: about 3700-5000 cps (B-type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 20.0 W / W% Average particle size: 500-900 μm Average molecular weight: 110,000- 150000 Comparative Examples 1-3: Preparation of aqueous film- forming dispersion [ Comparative Example 1 ] 1.62 g of sodium carboxymethylcellulose was added to 26.64 ml of distilled water while sieving, and 1000
The mixture was stirred at rpm for 30 to 50 minutes (Super Digital Stirrer: Inoue Seieido Co., Ltd.) to obtain a first prepared solution.

On the other hand, 40.40 g of sodium lauryl sulfate was added to 37.93 ml of ethyl alcohol, and 1.08 ml of 3-methoxy-3-methyl-1-butanol and 0.18 g of citric acid were added.
Further, 0.16 g of sodium bicarbonate was further added to obtain a second preparation liquid.

Finally, the second prepared liquid was added to the first prepared liquid, and the mixture was stirred until it became uniform to obtain a dispersion.

The details of the materials used in this comparative example are summarized in Table 9 below.

[0053]

[Table 9]

In the dispersion obtained in this comparative example, the dispersion was completely separated on the second day after preparation, and uniform swelling was difficult. Also, no abrasion resistance was observed.

The properties of the dispersion obtained in this comparative example were as follows.

Viscosity: about 400 to 500 cps (B-type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 42.36 W / W% Average particle size of polymer: 180 to 1000 μm Average of polymer Molecular weight: 27000-33000 Comparative Example 2 1.00 g of hydroxypropylcellulose was added to 32.47 ml of glycerin while being sieved, and stirred at 1000 rpm (super digital stirrer: Iuchi Seieido Co., Ltd.) until it was uniformly dispersed. Then, add 25.28 ml of ethyl alcohol and use the same stirrer at 1000 rpm for 30 to 50.
Minutes. Next, 14.00 g of sodium sulfide, 5.00 g of sodium linear alkylbenzene sulfonate, and 25.28 ml of ethyl alcohol were added, and the mixture was stirred by the same stirrer until the mixture became uniform to obtain a dispersion.
Table 10 below summarizes the details of the materials used in this comparative example described above.

[0057]

[Table 10]

The dispersion obtained in this comparative example has a low viscosity (about
Although it was 200cps), there was a problem that stickiness remained.

The properties of the dispersion obtained in this comparative example were as follows.

Viscosity: about 200 cps (B type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 20.00 W / W% Average particle size of polymer: 500 to 900 μm Average molecular weight of polymer: 110,000 to 150,000 [ Comparative Example 3 ] To 47.41 ml of ethyl alcohol, 30.00 g of hydroxypropylcellulose was added.
Stirred for ~ 50 minutes (Super Digital Stirrer: Inei Seikeido Co., Ltd.). Next, 20.00 g of sodium linear alkyl benzene sulfonate was added, and the mixture was stirred by the same stirrer until it was uniformly dispersed. Finally, ethyl alcohol 1
5.8 ml was added and the mixture was stirred until it was uniformly dispersed to obtain a dispersion.

The details of the materials used in this comparative example are summarized in Table 11 below.

[0062]

[Table 11]

The dispersion obtained in this comparative example had a viscosity (20,0
00cps) was very high and could not be coated.

The properties of the dispersion obtained in this comparative example were as follows.

Viscosity: about 20000 ps (B-type viscometer No. 3 rotor [BL type: Tokyo Keiki Co., Ltd .; 6 rpm) Non-volatile content: 50.00 W / W% Average particle diameter of polymer: 500 to 900 μm Average molecular weight of polymer: 110,000 to 150,000 Example 9: Preparation of aqueous film- forming dispersion The properties of films formed by the dispersions obtained in Examples 1 to 8 and Comparative Examples 1 to 3 were examined.

That is, the dispersions obtained in the respective Examples and Comparative Examples were prepared using polyvinyl alcohol as a binder.
Apply to a 200 cm ² water disintegration paper (60 g / m ² ) with a basis weight of 20 g / m ² or more, apply friction while dipping the water disintegration paper in water,
The time required until the paper breaks was measured.

The results are summarized in Table 12 below. In the table, the case where the water disintegration paper was torn within 30 seconds was judged as “poor”, and the case where the water disintegration paper took more than 30 seconds was judged as “good”.

[0068]

[Table 12]

As is evident from the results shown in Table 12, a film having a suitable strength was formed by the dispersion of the present invention, and it was clear that the dispersion of the present invention contributed to the improvement of the strength of hydrolyzed paper. It became.

[0070]

According to the present invention, an aqueous film-forming dispersion which forms a film having excellent film-forming properties and water resistance, which was the intended purpose, has been realized.

Further, according to the aqueous film-forming dispersion of the present invention, the water solubility of the film and the water immersion time can be arbitrarily adjusted according to the adjustment of the film composition and / or the amount of the dispersion applied. Further, the film formed from the aqueous film-forming dispersion of the present invention, since the dispersoid is retained and retained in the film after the organic solvent is volatilized, the desired active ingredient on the substrate surface as a dispersoid It functions as an optimal means for coating and holding, and exhibits many excellent effects, such as being expected to be applied as an effective means for applying detergents, chemicals, and paints.

Claims (8)

[Claims] 1. An aqueous film-forming dispersion containing an organic solvent in which a polymer dispersoid is dispersed; wherein the polymer dispersoid contains an activator and a thickener, wherein the organic solvent and the thickener are Is a weight ratio of organic solvent: thickener = 80: 1 to 30: 1, and the aqueous film-forming dispersion contains 0.1 to 30% by weight of an active agent and 0.1 to 30% by weight.
An aqueous film-forming dispersion containing from 0.01 to 20% by weight of a thickener. 2. The method according to claim 1, wherein the organic solvent is a halogenated hydrocarbon,
The polyhydric alcohol derivative, alcohols, ketones, aldehydes, hydrocarbons, cellosolves, a mixed solvent of chlorides, a mixed solution of methanol / ethylene bromide and a mixture thereof.
2. The aqueous film-forming dispersion according to item 1. 3. The organic solvent includes methylene chloride, chloroform, glycol ethers (ethylene glycol ethers and acetates, propylene glycol ethers and acetates), acetone, toluene, methyl cellosolves, ethyl cellosolves, butyl cellosolves, The aqueous film-forming dispersion according to claim 2, which is dimethylformamide, acetic acid, benzyl alcohol, ethylene chlorohydrin, pyridine, formic acid or aniline. 4. The method according to claim 1, wherein the activator is an anionic surfactant,
4. A nonionic surfactant, an amphoteric surfactant and a mixture thereof selected from the group consisting of:
The aqueous film-forming dispersion according to any one of the above. 5. The activator may be a linear alkylbenzene sulfonate, a higher alcohol alkylsulfate, an alkyl ether sulfate, a lauryl sulfoacetate, an α-olefin sulfonate, a lauroyl sarcosine salt, a myristoyl sarcosine. The aqueous film-forming dispersion according to claim 4, which is a salt, a pronic surfactant, polyethylene glycol, or a sucrose fatty acid ester. 6. The aqueous solution according to claim 1, wherein the thickener is selected from the group consisting of polymer polymers, thickening polysaccharides, gums, cellulose derivatives and mixtures thereof. Membrane dispersion. 7. The thickening agent may be a crosslinked acrylic acid polymer, starch, dextrin, sodium alginate, casein, gelatin, bentonite cod gum, guar gum, xanthan gum, roast gum, polyvinyl alcohol, methyl celluloses, ethyl celluloses, The aqueous film-forming dispersion according to claim 6, which is hydroxypropylmethylcellulose, hydroxypropylethylcellulose or hydroxycellulose. 8. The aqueous film-forming dispersion liquid comprises a pigment, a water retention agent, a dispersant, an antifoaming agent, a preservative, a waterproofing agent, a mold release agent, a dye, an oil, a resin, a fragrance, an antibacterial agent, and the like. The aqueous film-forming dispersion according to any one of claims 1 to 7, further comprising a mixture.