JPS62288524A - Water contact display substance - Google Patents

Abstract

PURPOSE:To perform the display of a water contact state at any area simply and inexpensively without relying on manual work, by applying, fusing or adhering a hydrophilic substance to a base material, if necessary, along with a rubbery substance and a colorant. CONSTITUTION:A hydrophilic substance is applied, fused or adhered to a base material, if necessary, along with a synthetic resin, a rubbery substance, a plasticizer, a colorant and a surfactant to form a water contact display material. When said display material is contacted with water, the part contacted with water absorbs water to be wetted or swollen and, according to circumstances, further released, detached and collased to make it possible to confirm the area contacted with water. The hydrophilic substance is a water swellable polymer substance and, pref., block copolymer or graft copolymer having a bonding system of (hydrophobic segment)-(hydrophilic segment)-(hydrophobic segment) is used. When other substances are used along with the hydrophilic substance, especially, when the synthetic resin and the rubbery substance are used, the content of the hydrophilic substance is about 100-10wt%, pref., about 100-30wt%.

Description

[Detailed Description of the Invention] 3. Detailed Description of the Invention (Industrial Application Field) The present invention is directed to the location, location, water level, etc. of the invention that comes into contact with water by absorbing water and peeling, falling off, or collapsing. Or it relates to a water contact display that can recognize the fact that it has come into contact with water.

(Prior art) Conventionally, water contact indicators or water contact position indicators have been used to confirm the highest water level of rivers, lakes, groundwater, agricultural water, sewers, drainage ditches, etc., or in warehouses etc. in the event of a typhoon, etc. This was required for the purpose of understanding the damage caused by flooding of stored items and confirming contaminants caused by flooding.

However, this depends on the presence of an observer.

They required expensive measuring equipment and were often electrical, requiring a power source.

(Problems to be Solved by the Invention) Therefore, in order to be simple, inexpensive, and widely used, there has been a need for something that is unmanned and can be implemented anywhere.

In order to satisfy the above conditions, the present inventors conducted various research on display methods and found that when a substrate with a hydrophilic substance comes into contact with water, it absorbs water, swells, peels, etc. They discovered that this brings about changes and completed the present invention.

(Means for Solving the Problems) That is, the present invention involves applying, fusing, or A water-contacting product that is pasted and, when it comes into contact with water, the water-contacted part absorbs water, becomes moist or swells, and in some cases further peels off, falls off, or disintegrates, so that the position in contact with water can be recognized. It is a display object.

To explain the present invention in more detail, in the present invention, hydrophilic substances include organic substances and inorganic substances of low to high molecular weight that are water-soluble or water-swellable.

Specifically, low molecular weight hydrophilic organic substances include water-soluble polyhydric alcohols, such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, polyethylene glycol, polyglycerin, dipentaerythritol: Water-soluble surfactants, such as polyethylene glycol alkyl ether, polyethylene glycol alkylaryl ether, polyethylene glycol higher fatty acid ester, polyethylene glycol sorbitan, higher fatty acid ester, polyethylene glycol, polypropylene glycol-polyethylene glycol, polyethylene glycol higher aliphatic Nonionic surfactants such as amines, their sulfuric esters and phosphoric esters, higher fatty acids, alkyl sulfonic acids, alkylaryl sulfonic acids,
Anion activators such as alkyl sulfates, ammonium salts of alkyl phosphate acids, alkali metal salts, mono- or polyamine salts having 1 to 3 carbon atoms, alkanolamine salts, morpholine salts, higher aliphatic primary and secondary , cationic activators such as tertiary and quaternary amine salts, acetates, and the like.

Hydrophilic organic substances with medium to high molecular weight include water-soluble substances such as gum arabic, sodium alginate, polyvinyl alcohol, sodium polyacrylate, polyacrylamide, polyvinylpyrrolidone, polyethyleneimine, sodium polystyrene sulfonate, and polystyrene methylene trimethylamine hydrochloride. salts, carboxymethylcellulose soda salt, methylcellulose, hydroxyethylcellulose, chitosan lactate, etc.; and water-soluble polymer substances that are difficult to dissolve or have chemically or physically crosslinked parts, such as powders such as agar and gelatin; Starch-sodium polyacrylate grafted product, starch-polyacrylonitrile grafted product, cellulose-polyacrylic acid grafted product, vinyl alcohol-sodium acrylate copolymer, vinyl alcohol-sodium methacrylate copolymer, sodium polyacrylate, sodium salt of carboxymethyl cellulose , chemically crosslinked products and physical restraints of water-soluble polymers such as polyethylene oxide.

Among these, preferred is a polymer in which a hydrophobic polymer chain or copolymer 3n is bonded to a polymer or copolymer having a hydrophilic group in the form of a block copolymer or a graft copolymer.

A particularly suitable water-swellable hydrophilic polymer is (hydrophobic segment) - (hydrophilic segment) - (hydrophobic segment)
Typical examples include thioglycolic acid or maleic anhydride attached to the double bonds of a (polystyrene)-(polybutadiene)-(polystyrene) block copolymer, as shown in the Examples below. It is obtained by addition or addition polymerization of acid, acrylic acid, methacrylic acid, etc., and then neutralization with an alkali. In addition, hydrophilic polymers having this type of bonding and methods for producing the same are described in JP-A-54-135836, etc., disclosed by the present applicant. This type of water-swellable hydrophilic polymer hardly dissolves in water, but has an extremely high degree of water swelling and swelling power, and improves releasability.

In addition, various organic solvents such as toluene, xylene,
It can be dispersed in cyclohexane, methyl ethyl ketone, dioxane, methanol, etc., and the dispersion liquid can be quickly made into a uniform dispersion liquid with a solution-type adhesive.

Examples of inorganic substances that are water-soluble or water-swellable include bentonite and known water-soluble inorganic salts.

Furthermore, carboxylic acids such as succinic acid, adipic acid, phthalic acid, trimellitic acid, pyromellitic acid, maleic acid, fumaric acid, tartaric acid, and citric acid, or their partially neutralized products, carbonates such as sodium bicarbonate and sodium carbonate, iron, Also used is one in which metal powder such as zinc or tin is blended, and the solid acid dissolves in water and reacts with carbonate or metal powder, generating gas and increasing the volume.

Synthetic resins used in the present invention include single or copolymers of acrylic esters and methacrylic esters, ethylene-vinyl acetate copolymers, ethylene-vinyl acetate-vinyl alcohol copolymers, butyral resins,
Polyvinyl acetate, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, polyamide, polyester, polyurethane, alkyd resin, cellulose acetate, cellulose acetate butyrate, shellac, rosin ester, etc., and rubber-like substances include natural rubber. , recycled rubber, chlorinated rubber, cyclized rubber, styrene
Known rubbers include butadiene rubber, butadiene-nitrile rubber, isoprene rubber, chloroprene rubber, ethylene-propylene rubber, butyl rubber, acrylic rubber, urethane rubber, silicone rubber, among which copolymers include random copolymers, A -B type and ABA type block copolymers, etc. are all included.

Plasticizers include dibutyl phthalate, dioctyl phthalate, dioctyl adipate, dioctyl sebacate,
Conventionally known materials such as tricresyl phosphate and process oil may be used.

Further, the purpose of the present invention is to be able to recognize the water contact position, and in order to make it more obvious, it is preferable to use a coloring agent. Further, the color of the colorant is preferably a color that can be clearly distinguished from the color of the substrate, and colorants of all colors such as white, blue, green, brown, and black can be used.

As the coloring agent, known coloring agents such as water-soluble dyes, oil-soluble dyes, disperse dyes, organic pigments, and inorganic pigments can be used.

For example, dyes include azo dyes such as monoazo dyes, polyazo dyes, metal complex azo dyes, anthraquinone dyes, indigo/thioindigo dyes, phthalocyanine dyes, triphenylmethane dyes, xanthine dyes, dioxazine dyes, methine dyes, naphthalimide dyes, Perinone type etc. In addition, 41 pigments include phthalocyanine, azo, condensed azo,
Anthraquinone series, perinone/perylene series, indigo/
These include thioindigo type, isoindolinone type, azomethine azo type, dioxazine type, quinacridone type, aniline black type, triphenylmethane type, xanthine type, and carbon black.Inorganic pigment types include titanium oxide type, iron oxide type, These include iron hydroxide type, chromium oxide type, spinel type fired pigment, lead chromate type, vermilion chromate type, and navy blue type.

As surfactants, polyethylene glycol alkyl ether, polyethylene glycol alkyl allyl ether, polyethylene glycol higher fatty acid ester,
Nonionic surfactants such as sorbitan higher fatty acid ester, polyethylene glycol sorbitan higher fatty acid ester, polyethylene glycol-polybrobylene glycol-polyethylene glycol block copolymer, polyethylene glycol higher aliphatic amine, their sulfuric esters, phosphoric esters, higher fatty acids , ammonium salts of acids of alkyl sulfonic acids, alkylaryl sulfonic acids, alkyl sulfates, and alkyl phosphates;
Alkali metal salts, mono- or polyamine salts, alkanolamine salts.

Anion activators such as morpholine salts, higher aliphatic primary, secondary, tertiary and quaternary amines and cations such as their hydrochlorides, acetates, higher fatty acid salts such as stearic acid, oleic acid, etc. sexual activity such as ff1J.

The water contact display of the present invention is made by coating or pasting a hydrophilic substance on a base material together with other substances as necessary. The base material is selected depending on its intended use. The shapes are paper-like, thread-like, string-like, woven fabric-like, non-woven fabric-like, film-like, sheet-like, thin plate-like, thick plate-like, column-like, rod-like, vibrator-like, etc. It may be a part of it.

Plastic molded materials include vinyl chloride resin, styrene resin, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyethylene, polypropylene, nylon, polycarbonate, polyester, unsaturated polyester, acetal, acetyl cellulose, phenol resin, etc. Moldings, buildings, etc. made of wood, paper, 6, concrete, asphalt, etc., and fibers include cotton, rayon, acetate, vinylon, nylon, polyester, polyethylene, polypropylene, acrylic fiber, etc. .

A coating material containing a hydrophilic substance is prepared in the same manner as a method for preparing a conventionally known coating material or paint. However, the original purpose is to absorb water when in contact with water, cause swelling or swelling, and in some cases further peeling, JIIJ
Since it falls off and disintegrates, the physical strength of the coating film is not required as much as that of ordinary coating materials or paints. If the hydrophilic substance has no or low film-forming or adhesion ability, or if you want to control the performance after contact with water, it is recommended to use synthetic resins or rubber-like substances as described above. preferable. In the case of coating materials or paints, coating suitability such as viscosity adjustment is also improved. Is the hydrophilic substance obtained in advance as a coating material during synthesis?

Alternatively, hydrophilic substances are used together with media such as synthetic resins, rubbery substances, additives, and organic solvents in homogenizers, high-speed mixers, ball mills, mixing rolls, kneader-5 kneading extruders, etc. in the production of coating materials, paints, etc. Dissolve or disperse using known equipment. In the production of water-contact display materials, there are two types of media: solutions or dispersions using solvents, and solid types, and hydrophilic substances are also liquids.

There are solvent-dissolved types, solvent-dispersed liquid types, and powder-type types. There are also equiaxial methods such as coating and drying by evaporating the solvent, hot-melting, and pasting using adhesives. , the above devices are selected taking these into consideration.

When using other substances as the hydrophilic substance, especially when using synthetic resin or rubber-like material 11, the content of the hydrophilic substance is about 100 to 10%, preferably 1%.
It is about 00-30% of the market weight. These also vary depending on the required performance of the water-contacting display and the properties of the materials used, especially hydrophilic substances.

(Function/Effect) The Kuda water-contact display obtained by the present invention is made by attaching a hydrophilic substance to a base material together with a rubber-like substance, a coloring agent, etc. as necessary, and therefore it is easy to clean and inexpensive. The necessary amount of 11 can be supplied at any time, and when it comes into contact with water, irreversible conditions such as deformation due to swelling, peeling, and falling off occur, which can be confirmed at any time.

In addition, the material and shape of the base material can be selected arbitrarily.
It can be installed in any location or object, such as understanding the water depth and level of rivers, lakes, groundwater, agricultural water, sewers, drainage ditches, etc., and understanding the flood situation of warehouses, unmanned buildings, etc. It can be used effectively.

Next, the present invention will be specifically explained with reference to Examples. still,
In the text, parts or percentages are based on weight.

Example 1 Thioglycolic acid was added to 90% of the double bonds of a block copolymer (polystyrene component content 30%) having a bonding format of (polystyrene) = (polybutadiene) - (polystyrene), and the mixture was neutralized with caustic soda. Water swelling (
A hydrophilic polymer having a swelling degree of about 50 times) was prepared.

80 parts of the above hydrophilic polymer was mixed with toluene-cyclohexane-
400 parts of a mixture of dioxane dispersed in a mixed solvent, 100 parts of a toluene solution of butyl rubber (solid content 20%), and a blue oil-soluble dye (phthalocyanine solvent blue).
5 parts were stirred and mixed using a homogenizer to prepare a blue coating composition.

Separately, a screen was prepared so that 3 mm of coated area and 2 mm of uncoated area formed a vertical M pattern. The above-mentioned blue coating composition was screen-coated onto an acrylic plate having a length of 1 m, a width of 30 cm, and a thickness of 2II 1 m using the above-mentioned screen.

After preliminary drying at 50°C, it was dried at 130°C for 30 minutes.

The colored acrylic board was cut into thin rods with a width of 2 parts and a length of 1 m so that the pattern ran horizontally, and used as a water contact display. I set this in water. After about 20 minutes, the colored pattern under the water surface swelled and expanded laterally, and after another 10 to 20 minutes, it peeled off from the surface of the acrylic plate. When the water-contact display object was pulled up from the water, the part below the water surface fell off, and the pattern above the water surface remained, so the location of the water-contact part was clearly confirmed. In this way, water levels of rivers, lakes, agricultural water, etc. were measured. The water level of rainwater could also be checked in the same way.

Similarly, it was coated on a hard vinyl chloride plate and cut to be used as a water contact indicator. Further, it was applied to a polypropylene stick in a pattern of 5ffi11 every 5II11, and was similarly used as a water contact indicator.

Example 2 A water-swellable resin in the form of a polyethylene glycol (PEG)-tolylene diisocyanate (TDI)-polybutadiene (PB) bond (PEG/TDI/PB ratio is 82/15/3 by weight, swelling degree (approximately 13 times), 10 parts of acrylic rubber, and 5 parts of red azo pigment (C,1, Pigment Red 112), 60 parts of butyl acetate and butanol.
A red coating liquid was prepared by dissolving and dispersing the mixture in 300 parts of a mixed solvent of /40.

Using the same screen as used in Example 1, the length was 1 m.
, screen coating was carried out on a polyester film having a width of 30 cm. After preliminary drying at 50°C, it was dried at 130°C for 30 minutes.

Thereafter, the colored polyester film was cut into a thin ribbon shape with a width of 2CO+ and a length of 1 m so that the pattern ran in the horizontal direction, and a double-sided adhesive tape was attached to the back side to make a water contact display. This was attached to a plastic stick and set in water. After about 30 minutes, the colored pattern part under the water surface swells, and then
It was peeled off from the polyester film after about 0 minutes. When you pull up a water display object soaked in water, the part below the water surface falls off, and the pattern part above the water surface remains.
The location of the wetted parts was clearly identified.

In addition, the above-mentioned water contact indicators were pasted on grain bags stored in grain warehouses as a measure to identify contamination in the event of flooding or other flooding.

Water-swellable resin (swelling degree about 400 times) obtained by crosslinking a mixture of acrylic acid and sodium acrylate in place of the water-swellable resin (hydrophilic substance) of Examples 1 and 2. , polyvinyl alcohol (saponification degree 88%)
, gelatin powder, #grain powder, agar powder, polyethylene glycol-polybrobylene glycol-polyethylene glycol (80% polyethylene glycol), polyethylene glycol distearate, polyethylene glycol nonylphenyl ether, bentonite, and the same water contact display. I was able to make it.

Claims (3)

[Claims] (1) When a hydrophilic substance is coated, fused or pasted on a base material together with a synthetic resin, a rubbery substance, a plasticizer, a coloring agent, or a surfactant as necessary, and comes into contact with water, A water-contact display characterized in that a part absorbs water, becomes wet or swells, and in some cases further peels off, falls off, or collapses, so that the position in contact with water can be recognized. (2) The water contact indicator according to claim (1), wherein the hydrophilic substance is a water-swellable high-molecular weight substance. (3) Water contact according to claim (1), wherein the hydrophilic substance is a block copolymer or a graft copolymer having a bonding format of (hydrophobic segment) - (hydrophilic segment) (hydrophobic segment). display object.