JPS6031209B2 - aqueous dispersion - Google Patents

Description

[Detailed description of the invention] The present invention relates to an aqueous dispersion using mountain bark.

More specifically, it relates to a method in which a water-soluble polymer material is added to an aqueous dispersion of mountain bark containing a colorant, and the resulting aggregate is used as a coloring source for aqueous dispersed soot. Generally, when finishing a patterned wall by spraying, the paint components are co-dispersed with chip-like solids, or paint components of different colors are placed in microcapsules, co-dispersed, and the force of spraying is applied to the paint in the microcapsules. A method is used to create an irregular color pattern by causing the color to protrude. When co-dispersing chip-shaped solids, consideration must be given to using a quick-drying organic solvent paint to prevent the particles from falling off during spraying. Furthermore, in the microcapsule method, water-based paints are rarely used.

Water-repellent paints began to attract attention after the toxicity of organic solvents became a problem, but it was desired that colors could be applied without using special methods, and that the resulting walls would be nonflammable. Ta. On the other hand, in the case of wallpaper, fusuma paper, decorative paper, etc., patterns are usually applied by printing on the finished paper, or by gluing printed paper or plastic cloth together.

If paper with patterns can be made from the beginning, economical effects can be expected in terms of the process and the distribution route.
Furthermore, it is even more desirable from the standpoint of disaster prevention if the paper is a non-combustible paper that does not emit toxic gases. As a result of intensive studies on the above points, the present inventors found that the aggregate obtained by adding a water-bathable polymeric material to a mountain bark aqueous dispersion containing a colorant does not retain the colorant even when placed in an aqueous dispersion. It was discovered that the dispersed soot does not dissolve into the dispersed soot and become uniform in color, and that there are no side effects such as the water-soluble polymer material contained in the aggregates causing the aqueous dispersed soot to aggregate, and the present invention has been developed. I was able to complete it.

That is, the present invention is an aqueous dispersion obtained by adding a water-repellent polymeric material to an aqueous mountain bark dispersion containing a colorant, and dispersing the resulting aggregates in an aqueous dispersion soot.

The mountain bark used in the present invention is a general term for clay minerals having a large number of active hydroxyl groups on the surface.
a) sepiolite, hydrated magnesium alumina silicate
agnesiumalumin (on Mt. Msilica) attapalgite (Attap Mt.
go dai kite). It is commonly called mountain leather, mountain cork, mountain wood, etc. Meerschaum, which is famous for pipes, is also one of this type. The mountain skin used in the present invention can be used in any form, such as powdered raw stone that has been mined, dispersed in water or organic solvent, paste, or paper. However, dispersion in water or organic solvents (e.g. alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, amides such as dimethylacetamide and dimethylformamide, and chlorinated solvents such as methylene chloride and trichlene) is recommended. Preferably. Usually, an aqueous dispersion of mountain bark is used, and the concentration of mountain bark is about 0.001% to 5% by weight, preferably 5% or less. When making a water dispersion of mountain bark, the particle size of mountain bark is usually about 10
Skin A to 5 legs are used.

This aqueous dispersion, like other clays, can be obtained by simply placing mountain bark in water and mixing it with appropriate means.
If a polyhydric alcohol such as sugar is applied to mountain bark in advance, it can be easily dispersed in water. Dispersion can be accelerated by using hot water instead of water, or by adding alcohols such as methanol and ethanol, ketones such as acetone and methyl ethyl ketone, and esters such as ethyl acetate. You can stay there. For dispersion, any mixing method may be used, but a dispersion having a mountain bark concentration of about 1% or less can be pulverized and dispersed using, for example, a high-speed mixer. For highly concentrated liquids, for example, a three-roll method can be applied. For medium dispersions of 1-5%,
For example, a dispersion method such as a paper-making clay dispersion machine in which the rope azure and kneading are performed at the same time, or a speed line mill or agitator that allows the clay to pass through the space between two rotating whetstones is used.

The coloring agent contained in the mountain bark aqueous dispersion of the present invention includes:
All known dyes and pigments (organic pigments and inorganic pigments) can be used.

Synthetic dyes such as azo, anthraquinone, thioindigo, quinoline, and indanthrene, such as mokusaku, iron acid, alum, protein, potassium chromate, and wood ash, are used to dye madder, yam bark, and wood ash. 25 Lotus (Food Red No. 1 to 5, Food Red No. 101 to 106, Edible Dashi, Dashi, 1 - No. 2, food yellow No. 1-5, food green No. 1-3, food blue No. 1, 2, 101, food purple No. 1) and 3-carotene, salts of copper chlorophyllin with potassium or sodium, mandarin oranges Natural food pigments such as the yellow skin of the fruit, the yellow of curry, the brown of coffee, the pink of perilla, and the red produced by Monacus rubra, organic pigments of phthalocyanine, quinacridone, and benzidine types, oxides and hydroxides of various metals, Examples include inorganic pigments such as sulfides, sulfates, carbonates, and phosphates.

Specifically, the pigments include cadmium red, Bon Red 28, carmine red, toluidine red, fanar lake, pyrazolone red, lake red C, naphthol red, red red, thioindigo, mineral violet, quinacridone red, cadmium yellow, chrome yellow,
Molybdenum orange, benzidine yellow, Hansa yellow, zinc yellow, yellow ocher, alkaline azo complex, phthalocyanine green, chromium oxide, malachite green, guine green, chrome green, phthalocyanine blue, navy blue, ultramarine, indanslen blue −, metal powders such as cobite blue, dioxazine violet, titanium white, zinc white, antimony white, carbon black, iron black, zinc, aluminum, coin, copper, etc.
Examples include luster pigments such as mica powder, talc, natural mineral powders such as frogstone. 'Furthermore, pongee medicinal pigments such as blue yuzu, red yuzu, green sode, fume tsumugi, gray yuzu, hagi tsumugi, and irahosode may also be used.

It may also be a mixed raw material such as earth ash, straw ash, feldspar, mica, talc pigment, lime, etc. that melts into citron when heated to a high temperature. These colorants may be used alone or in combination. The coloring agent may be added at the same time as the mountain bark is dispersed in water, or may be added to a previously prepared mountain bark aqueous dispersion.

In particular, inorganic pigments may be synthesized in an aqueous mountain bark dispersion. Although any mixing means may be used, a method used when dispersing mountain bark in water is preferred. The colorant may be dissolved in the mountain bark aqueous dispersion, or may be in a dispersed state. The amount of coloring agent added to the mountain bark (dry mountain bark weight) varies depending on the degree of pulverization of the mountain bark, etc., but it is approximately 10 to 1/1000 of the mountain bark weight in the system.
It is 0.

In this way, an aqueous mountain bark dispersion containing a colorant is obtained. A water-repellent polymeric material is added to this mountain skin water dispersion to form an aggregate.

Examples of water-bathable polymer materials used in the present invention include anionic polymers (e.g., sodium polyacrylate, partially hydrolyzed salts of polyacrylamide (e.g., N
a, K,...) salts of maleic acid copolymers, etc.)
, cationic polymers (e.g., polyvinylpyridine hydrochloride, salts of vinylpyridine copolymers, partial hydrolysates of polyacrylamide, etc.), nonionic polymers (e.g.,
diallyldimethylammonium chloride polymer,
Thready polymer flocculants such as polyacrylamide, polyethylene oxide, polyvinyl alcohol, etc., or natural stringy polymers such as natto mucilage, 98 white, Tororo mallow, and okra fruit mucilage, water-soluble polymers, etc. I
J acid or its divalent or trivalent salts (e.g. salts with Group 2 or Group 3 ions such as MZ10, Ca20, Sr20, H20, Cd20, Z20, AI30, etc.) M〆10, Fe20,
Examples include salts with transition metal ions such as Fe30, Co20, C20, Ni20, etc.), CMC, etc.

In the case of stringy polymer flocculants and natural stringy polymers,
When made into a liquid by dissolving it in water or an organic solvent,
It only needs to be viscous steel enough to draw strings, and its molecular weight is about 50.
00 or more, preferably about 10,000 to 500×1 pi. In the case of water-soluble polyphosphoric acid or its salt, the lower limit of the molecular weight is about 350-500. Among these, particularly preferred are anionic polymers such as sodium acrylate, nonionic polymers such as polyethylene oxide, and black mallow.

The amount of water resistant polymer material added is approximately 0.0% of the dry weight of mountain bark.
0001% to 50%. The water-soluble polymer material may be in the form of a powder, or may be in the form of a solution prepared by dissolving it in the above-mentioned organic solvent. In this case, additives may be added to the solvent as necessary to make it easier to splinter. An example of this is to treat polyethylene oxide with an alcohol such as isopropanol in order to make it more easily soluble in water, and then to dissolve it in water. When a water-soluble polymeric material containing a coloring agent is added to an aqueous mountain skin dispersion, a colored aggregate is obtained at the top or bottom of the aqueous dispersion.

This may be used as is, but water may be removed by decantation or the like. If the aggregate concentration is too low to separate cleanly, it is preferable to add alcohol such as methanol or ethanol.

The agglomerates thus obtained are dispersed in an aqueous dispersion soot.

The aqueous dispersion used in the present invention includes, for example, water-based paints, water-based adhesives, water-based fiber treatment agents, pulp dispersions for Japanese paper containing mitsumata, kozo, gampi, etc., lead yuzu, alkaline pongee, and alkali monolime. Examples include dispersions of sode medicines such as yuzu, lime sode, feldspar yuzu, tanasu pongee, and mixtures thereof.

When using an aqueous dispersion as a paint for vertical walls or ceilings that require drip prevention, or as a nonflammable patterned paper, it is preferable to use an aqueous dispersion of mountain bark as an aqueous dispersion soot. Next, the aqueous dispersed soot and the aggregates are mixed and pounded.

For example, agitator, rotary Taiyo, upper and lower takahai, ultrasonic sanding means are available, but there are also homomixers and speed line mills that have the effect of grinding during rope sanding, and can be used for long periods of time or at high rotation speeds. It is not advisable to worship on a rope. Adjust the speed and duration of the rope as appropriate.
A wide-spread aqueous dispersion can be obtained by agitator-type crossing. In rotary dispersion, an aqueous dispersion with enhanced fibrous properties is obtained. It is also possible to simply mix the aqueous dispersion and the aggregate. The amount of aggregate added can be changed as appropriate depending on the pattern, but it is approximately 1/100 to 95% of the amount of the aqueous dispersion medium.
Weight percent is preferred. The aqueous dispersion thus obtained can also be made into a sheet by, for example, papermaking. Alternatively, it can be applied or sprayed onto a substrate to form a sheet on the surface. Furthermore, it is also possible to soak the substrate in an aqueous dispersion, absorb water, and cover the surface with a sheet. As for the spraying method, a very common spraying method is sufficient.

There is no need to develop a special spraying machine. When an aqueous dispersion of mountain bark is used as water-based dispersed soot, it is difficult to use on walls or ceilings due to the chicken-tropic properties of mountain bark in water and the fact that there is no difference in specific gravity between the water-based dispersed soot and aggregates. Even if you spray it, only the aggregates will not fall off. When making paper, any method may be used, such as a reduced-pressure oven filtration method as in general paper making, a natural oven filtration method such as Japanese paper-like flow-papering, and paper-making, or a method in which paper is made by absorbing water in a porous body. When paper is made using the aqueous dispersion of the present invention, (1) the furnace water resistance is improved and the wet strength is greater than when paper is made using only the mountain bark aqueous dispersion. (
b) In particular, when using an aqueous dispersion of mountain bark as an aqueous dispersion soot, completely non-combustible patterned paper can be made at once. (m) There is no hassle of printing. (W) Paper with no difference between the front and back can be made.
(V) This patterned paper can be further dyed, printed, drawn on, and used for calligraphy, etc., and can be used as wallpaper, fusuma paper, stickers for Sekibou utensils, interior decoration for subways, underground malls, etc. Widely used for decoration. When the aqueous dispersed soot is a pure medicine or its raw material, the mixed mountain bark melts at high temperatures and becomes a component of pongee medicine.

Furthermore, according to the present invention, the process of painting the surface of pottery or porcelain is omitted, and especially when pongee medicine containing mountain bark is used as an aqueous dispersion medium, sedimentation of the pongee medicine can be prevented, and the sheet By applying a wet pongee sheet on wet pottery or porcelain and drying it at the same time, the drying process that used to take place twice can be reduced to one time, and the bisque firing process can be omitted. There are advantages. Next, the present invention will be specifically explained with reference to Examples.

Example 1 Pengara 5 was added to 500' of 1% purified mountain bark aqueous dispersion.
If you add the group and mix it evenly with a household mixer, you will get a red mountain bark water dispersion.

Add 5% polyethylene oxide (molecular weight 250 x 1
Product name: Alcotox 100: Meisei Chemical Industry K.P. K.
If you add 1 part of the aqueous solution (manufactured by Akihabara Co., Ltd.) and throw it again, it will be colored red with Pengara and you will notice that it is a peeled ship. Since the upper straw becomes a transparent aqueous solution, red aggregates are formed when the top water is removed by decantation.

Separately, prepare 0.5% mountain bark water dispersion for 1 night, mix 2 to 3 w' of the above red aggregates with a net, mix, and mix with a high-speed mixer for about 3 minutes. An aqueous dispersion in which red fibrous aggregates are uniformly dispersed is obtained.

Of these, 500' was taken and kept in a bottle with a lid for 3 months, but no dispersion of the red pigment was observed, nor was any sedimentation of the aggregates themselves nor agglomeration of the mountain bark water dispersion. The remaining 500' is poured evenly onto a 30 skin x 30 skin plaster, allowed to absorb water, and then dried to produce white non-combustible paper with a red fiber pattern. This paper was left in the air for three months, but no bleeding or fading of the pigment into the white area was observed.

Example 2 Add phthalonanine green pigment 3 bait to 500ml of purified mountain skin aqueous dispersion of 21%, add 1 drop of household detergent, put in a household mixer, mix well, and use in Example 1. When polyethylene oxide is added to 2, a green colored aggregate is obtained.

The supernatant is completely transparent, and when the cloud-sized supernatant is discarded, a green aggregate is obtained. Prepare 1 volume of 0.5% mountain skin water dispersion, scoop out the aggregates obtained in Example 1, add the green aggregates 3, and mix with a high-speed mixer. After a certain amount of mixing, an aqueous dispersion containing floating red aggregates and green aggregates is obtained.

Take 500 of them and put them in a jar with a lid.
Although it was left for several months, no dispersion of the pigment occurred. Further, neither color mixing nor sedimentation of the aggregates occurred. the remaining 50
0 was applied uniformly onto a 100 mesh cloth of 30×30 size and then dried in a vacuum oven to obtain mountain paper with red and green fibrous aggregates randomly distributed.

Even after three months, there was no bleeding of pigment into the white fabric, and no signs of color mixing or discoloration of the aggregates were observed.

Example 3 1% purified mountain bark water dispersion 1.5 SoniFeS04.
On the 7th, add 20 to 1 female and stir thoroughly to dissolve the iron ions evenly.

Each 500 screams was divided into three parts, and two parts were used in Examples 4 and 5.

Add about 3 gd of Yellow Blood Salt K4 [Fe (CN) 6] and Chihito 20 to the remaining 500' of Fe20 ion-containing mountain bark water dispersion, and use it for home use until there are no lumps of Yellow Blood Salt. If you mix it with a mixer, you will get mountain skin with a blue colloidal powder. When polyethylene oxide 3' used in Example 1 is added to this, blue colored aggregates are subsequently deposited. The supernatant will be completely transparent, so remove it by decantation. When the three obtained blue aggregates are added to 50 cm of water and stirred in a household mixer for about 3 minutes, a fibrous, elongated aggregate with a length of 5 to 1 rib is formed.

This aggregate was added to a 0.5% purified mountain bark aqueous dispersion of 500ml, poured uniformly onto a 30 x 30 piece furnace cloth without damage, and dried in a vacuum oven to form a paper. Along this line, vellum paper with a blue cloud pattern was obtained.

When I stored about 50 mounds in a transparent bottle with a lid, the color did not bleed into the aqueous dispersion even after 3 months. Example 4 50% water was added to the mountain skin water dispersion containing iron ions used in Example 3.
When 0' and 2g of tannic acid are added and mixed, the mountain bark in the aqueous dispersion becomes jet black.

On the other hand, 2x titanium white was added to 500ml of 1% purified mountain bark aqueous dispersion, mixed with a household mixer until uniform, and then 2x of the polyethylene oxide aqueous solution of Example 1 was added. White fibrous flocculent aggregates settle out.

The upper part of the poison is transparent, so remove it by decantation.
About 3 to 5 pieces of this white aggregate is added to the above-mentioned black mountain skin aqueous dispersion and stirred in a high speed mixer for about 1 minute to obtain an aqueous dispersion with a white pattern on a black background. This dispersion 500
Even after storing the cry for half a year, the black dye did not enter the white aggregates, and the white pigment did not diffuse into the black background.

The remaining 500' was uniformly poured onto a 30 x 30 c urethane foam and dried by absorbing water to obtain vellum paper with a white fiber pattern on a black background. Example 5 Mountain bark aqueous dispersion containing iron ions obtained in Example 3 500
When I added tri-tannic acid to the '', it was dyed black.

After stirring thoroughly until the skin is uniformly black, 3M of the polyethylene oxide aqueous solution used in Example 1 is added to obtain a black aggregate. When this is filtered through gauze and the black mother liquor is discarded, a black aggregate is obtained. Add 2.5g of vermiculite from Fukushima prefecture expanded with hydrogen peroxide to 500ml of 0.5% purified mountain bark water dispersion,
If you mix it evenly with a household mixer, you will get a golden mountain bark water dispersion.

When the above-mentioned black aggregate 3' is added and gently stirred with a glass rod, a dispersion resembling black clouds floating in gold mud is obtained. Even when this dispersion was left for 100 days, the dye did not stain the mountain bark or vermiculite in the dispersion. After leaving it for 4 months, the solution was poured evenly onto a 30 x 30 furnace cloth.
After passing through a vacuum oven and drying, a non-combustible vermiculite/mountain bark paper with a pattern of golden black clouds floating on top was obtained. Example 6 Take an old newspaper chapter, add 500ml of water, and thoroughly loosen it with a household mixer.

To this, add 28 tannic acid and this FeS04 7 days 20
If you add it and worship it, you will get newsprint pulp dyed pitch black. Add 1 volume of 10% mountain bark aqueous dispersion to this and mix well to obtain a mixed dispersion of newspaper and mountain bark dyed jet black. When polyethylene oxide 2' used in Example 1 is added, black aggregates are changed. Add 2 polyethylene oxide aqueous solution to this newspaper dispersion.
Adding desks does not result in sufficient aggregates. Scoop this black aggregate with silk, add it to 500M of separately prepared 0.5% mountain bark water solution, and mix it with a high-speed mixer for about 2 minutes. You get a body. Even after standing for 3 months, the dye did not diffuse into the dispersion.

Example 7 When the aggregates were produced in Examples 5 and 6, 50% of the dyeing solution containing the polyethylene oxide used and excess iron tannate dye was left behind.

Approximately 50 M of the above dye solution is added to a 1% aqueous dispersion of purified mountain bark, and the dye is lightly framed with a crow's comb to obtain an aqueous dispersion in which the dye is partially coagulated.

Even after being left for three months, no diffusion of the dye was observed, and a stringy black pattern remained.

This dispersion was diluted twice and poured uniformly onto a 30x60 oven cloth, passed through a vacuum oven, and dried to obtain a black velvet paper with a cloud flow pattern. Example 8 Add 1.5 gr of yellow lead and 1.5 gr of red iron to 500 g of 1% mountain bark water dispersion and mix well with a household mixer to obtain a clear colored mountain bark water dispersion. .

When a 2M aqueous solution of 3% sodium polyacrylate (Aron A-20P manufactured by Toagosei Kagaku Kogyo K.K.) is added, a dark brown fibrous aggregate is obtained.

Remove the clear supernatant liquid by decantation. On the other hand, 1%
500ml of mountain bark water and 3g of brown sericite powder
If you add it and mix well, you will get a brown colored mountain bark water dispersion.

Add to this 3% cyanamide (Alflock, Sanyo Kasei K.
K. Addition of two volumes of aqueous solution (manufactured by ) produces brown aggregates. Remove the supernatant clear water by decantation. Add a drop of household detergent (family: Kao Soap KK alcohol-based) to 500ml of 1% mountain bark water dispersion, add 3g of Marin powder to this, and mix well with a household mixer. Obtains golden mountain bark water teaching liquid.

This was added to the polyethylene oxide aqueous solution 3 of Example 1.
When added, fibrous aggregates are obtained. In the 0.5% mountain bark aqueous dispersion, there were 5 maroon aggregates and 7 brown aggregates.
, add 10 golden aggregates on the table and mix with a high speed mixer for 2-3
When separated, an aqueous dispersion in which the three-colored fibrous aggregates are uniformly floating without mixing is obtained.

I stored it for 1 night in a bottle with a lid, but even after leaving it for 3 months, there was no sedimentation, floating, or reaction of the real powder.

Furthermore, no interdiffusion of dyes from each aggregate was observed. Furthermore, no adverse effects of the polymeric materials used for aggregation were observed. The remaining amount was uniformly poured onto a glass mat on a 60 x 90 oven cloth, and when it was over-dried in a vacuum oven, the glass mat and the mountain bark were stuck together to form paper.

Marin powder and pigments did not come loose or bleed from the colored patterned paper obtained. Example 9 Fukushima feldspar 65 bait, silica 23 with particle size of 100 mesh or less
Mochi, limestone 3, cobalt oxide 1.0 bait, red iron 8.
Add 400 parts of a 2% mountain bark water dispersion to No. 08, add 100 parts of water, and mix thoroughly with a household mixer.

This was molded into a plate shape of 5 skins x 5 skins x 1 arc using Shigaraki clay, then painted on a board bisque fired at 8000°C and heated to 1250oC.
When sintered, tiles with Kurobome style pongee medicine are created.
The above mixed aqueous dispersion becomes a raw material for Kuromome pongee medicine. When 100 pieces of this mixed aqueous dispersion are mixed with the aqueous solution 2 of polyethylene oxide used in Example 1 and stirred, the yuzu medicine raw material is mixed and aggregated with the bark, and an aggregate is obtained. . This supernatant liquid became transparent, so discard it by decantation. Separately, an appropriate amount of the above aggregate is added to the so-called ash medicine (ash yuzu) raw material, which is made by dispersing 80 pellets of grain powder of 100 mesh or less, 10 momme of punched ash, and 10 gr of straw ash into 500 bars.
When the mixture was mixed and dispersed, the Fuume Tsumugi raw material was co-dispersed with the Ashyu raw material without splintering even after being left for one month.

I made a board of 20 skins x 20 skins x 1 skin with a Shigaraki potter, and after drying, I sprayed it on an unglazed board and let it harden to 125,000, creating a tile with a black thread pattern in the transparent yuzu of the gray sleeve. did it. Example 10 An aqueous dispersion prepared by mixing 45 parts of Fukushima feldspar of 100 mesh or less, 45 scales of mortar, and 500 parts of a 2% mountain bark aqueous dispersion was made into a green Oribe-like yuzu medicine. It's baked.

Example 1 of 100 Oribe style yuzu mulberry raw materials containing this mountain skin
When 2M of the polyethylene oxide aqueous solution used in step 1 is added, the mixed raw materials coagulate and precipitate. This is referred to as Oribe Tsumugi raw material aggregate. Separately, add 7 pieces of Fukushima feldspar of 100 mesh or less, 10 pieces of Wara ash, and 10 grams of punch ash to 500 g of 2% mountain bark water dispersion.
When the ash pongee material is mixed well and coated on a clay plate to form a powder of 1250 qo), it becomes a transparent pongee with a whitish color.

Claims (1)

[Claims] 1. An aqueous dispersion obtained by adding a water-soluble polymer material to a mountain bark aqueous dispersion containing a colorant and dispersing the resulting aggregates in an aqueous dispersion medium.