JPS5938985B2 - resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a resin composition that is liquid at room temperature, and more specifically, when applied to an article and then dried, it absorbs water and swells, but provides a dry product that does not dissolve in water. It is a resin composition that is liquid at room temperature, and has a wide range of uses such as improving the water absorption of synthetic resins and synthetic fibers, various water-stopping agents, preventing dew condensation on films, improving the temperature suitability of synthetic leather, and various water-retaining agents. The purpose of the present invention is to provide a novel water-swellable resin composition that is liquid at room temperature.

In the past, various water-swellable resins have been developed for improving the water absorption and hydrophilic properties of synthetic resins and synthetic fibers, as water-stopping materials for various joints, waterproof paints, soil water-retaining materials, etc. have a drawback that their water absorption capacity or water swelling degree is low, or that if these properties are improved, they tend to dissolve in water or leach into water, and are unable to maintain their shape. As a result of intensive research to solve the drawbacks of conventional water-swellable resins, the present inventor found that it has extremely high water absorption, absorbs a large amount of water and swells, and does not dissolve or leach out in water. We have developed a water-swellable resin that can maintain its shape, and when it is blended into a medium that is liquid at room temperature, including natural or synthetic resins, it can be easily applied to articles, and it can be applied to articles and then dried. The present invention was completed based on the finding that dried products still maintain strong water absorption and water swelling properties.

That is, the present invention comprises a block copolymer consisting of a water-swellable resin and a medium, in which the water-swellable resin has at least one bond type (hard segment, hydrophilic/curved segment → -+hard segment) in its structure; / or a graft copolymer, in which the hydrophilic segment has a large number of double bonds present in its main chain, from 40 to
It has a sulfonic acid salt added to 100% double bonds or a salt of an added mercaptocarboxylic acid residue (hereinafter simply referred to as a hydrophilic group), and the above-mentioned medium is a liquid material at room temperature containing a natural or synthetic resin. A water-swellable resin composition that is liquid at room temperature.

To explain the present invention in detail, the water-swellable resin used in the present invention and which mainly characterizes the present invention is disclosed in Japanese Patent Application Laid-open Nos. 54-47796, 54-83989, and 54-108895 by the applicant of the present application. It is described in detail in the book.
This water-swellable resin includes the basic structure as described above, and the hard segment in this structure is a polymer portion that easily forms a crystalline phase, such as polystyrene, poly-alpha-methylstyrene, polyethylene, etc. system, polypropylene system,
These are polymers such as polyacrylonitrile, polyurethane bonding, polyester containing aromatic rings, polyamide, and polyvinyl halide. This hard segment has a strong tendency to form a crystalline phase in the water-swellable/bending resin used in the present invention at a temperature below the softening point, and when a hydrophilic segment having a hydrophilic group absorbs water, or in water. It acts as a constraining phase that limits the tendency to dissolve.
A hydrophilic segment is a polymer in which sulfonic acid or mercaptocarboxylic acid is added to the double bonds in the polymer main chain, which has many double bonds, and these acid groups are used as salts. The rate of addition should be 40 to 100% of the number of double bonds in the polymer backbone. If the addition rate of these is less than 40%, the water swelling degree of the resin composition of the present invention will be insufficient and the object of the present invention will not be fully achieved. The backbone polymer structure of this hydrophilic segment includes a carbon chain, an ester bond chain, an amide bond chain, a urethane bond chain, etc., but a carbon chain is preferable from the viewpoint of water resistance, chemical resistance, etc. Since the hydrophilic group of the hydrophilic segment is ionic, it strongly absorbs water, embraces water, and has a strong tendency to dissolve in water. The constraining action of the hard segments prevents them from dissolving, and therefore, although the material as a whole absorbs water and swells significantly, it does not dissolve or leach out in water and retains its shape. The hydrophilic group possessed by such a hydrophilic segment is a salt of a sulfonic acid group or a mercaptocarboxylic acid residue added to a backbone polymer having a double bond, and these salts include:
Alkali metal salts, ammonium salts, trimethylamine,
These include lower amine salts such as triethylamine and morpholine, and alkanolamine salts such as monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, diethylethanolamine, and N-methyldiethanolamine. The method for producing the above-mentioned water-swellable resin is detailed in the specification of the prior patent application cited above, so it will not be explained in detail in this specification. A sulfonic acid group or a mercaptocarboxylic acid is added to a block copolymer and/or a graft copolymer having reactive groups (double bonds in the case of polybutadiene) in the segments sandwiched between the segments, and then neutralized with a base as described above. This method is used to make salt. As mentioned above, the water-swellable resin used in the present invention is composed of a combination of a hydrophobic hard segment and a hydrophilic segment, and the average molecular weight of both segments is about 1,000 or more, preferably about 3,000. As above, the composition ratio of both is 5 to 70% (by weight): hard segment: hydrophilic segment: 95 to 30%.

By changing this composition ratio, it is also possible to change the degree of water-swellability of the resulting water-swellable resin. Since the water-swellable resin developed by the present inventors as described above has many ionic groups, it is difficult to apply it to articles alone. to be used in a mixed manner.

Use in this manner greatly facilitates application to articles. In addition, a film etc. is formed by drying after application, but since the water-swellable resin used in the present invention has a strong affinity for water, the natural or synthetic resin surrounding the water-swellable resin is It is a surprising finding that the inherent performance of water-swellable resins can be demonstrated by overcoming the cohesive force. The medium used in the present invention is a medium that is liquid at room temperature and contains natural or synthetic resins, and these natural or synthetic resins are monomers, oligomers, or mixtures thereof that can form polymers or polymers. It's okay to be hot.

These resins include, for example, thermoplastic resins such as condensation polymers such as polyester, polyamide, and polycarbonate; polyadducts such as polyurethane; ethylene, propylene,
Butene, vinyl acetate, styrene, vinyl halide, vinylidene halide, acrylonitrile, acrylic acid,
Homopolymers, mixed polymers, block polymers or graft polymers of acrylic esters, methacrylic acid, methacrylic esters, butadiene, chloroprene, neoprene, and other addition-polymerizable monomers, natural rubber, butadiene rubber, styrene-butadiene rubber, butadiene Rubbers such as acrylonitrile rubber, chloroprene rubber, isoprene rubber, butyl rubber, polysulfide rubber, silicone rubber, fluoro rubber, urethane rubber, ethylene propylene rubber, chlorosulfonated polyethylene rubber, acrylic rubber; semi-synthetic materials such as acetyl cellulose There are resins, regenerated cellulose, and other resins known as binders for various paints and printing inks. Such natural or synthetic resins may be liquid or solid at room temperature, and may be dissolved or dispersed in water or an organic solvent. Although the water-swellable resin used in the present invention is ionic, it is insoluble in water and is also insoluble to sparingly soluble in organic solvents, so it is used mixed with the above-mentioned medium.

As a mixing method, methods used in conventional paint and printing ink technologies can be used as they are. Further, when blending the above-mentioned two, the water-swellable resin to be used may have a free ionic group or a salt type, but if the ionic group is free, it will ultimately be a salt type. Although the essential requirements constituting the resin composition of the present invention are as described above, various other additives may be optionally added depending on the purpose of use.

For example, plasticizers, various pigments, various fillers, ultraviolet absorbers, stabilizers, blowing agents, various inorganic salts, various alkaline agents, various acidic agents, and the like are used together in required amounts. The resin composition of the present invention is liquid at room temperature and can take the form of a paint, a coating material, a processing agent, a printing agent, etc., but the form of a paint is particularly useful. For example, if such a paint is applied to the joints, cracks, or joints of various structures and dries,
Not only will these gaps be filled, but if water tries to enter those areas after filling, the coating film that has been formed will expand further due to the water, completely preventing further water from entering. can be prevented. In particular, since the dried product obtained from the composition of the present invention repeatedly expands reversibly against ice, a long-term waterproof effect is expected. Also, various types of liquid compositions of the present invention may be used.・If used as an impregnating agent for products, it can improve the properties of various products. Furthermore, when applied to the surface of dew-condensing materials such as various plastic films, glass or metal plates, it exhibits an excellent dew-condensation prevention effect.
As exemplified above, the resin composition of the present invention has many uses, each of which exhibits excellent effects.

Next, the present invention will be specifically explained with reference to Examples. In addition,
Mid-sentence or? It is based on weight. Example 1
(Polystyrene H Polybutadiene H Polystyrene) (Polystyrene content 40%)Protscopolymer mainly has a telechelic type structure. Sulfuric acid and acetic anhydride 20 parts of a powder obtained by finely pulverizing the sodium salt of a water-swellable resin having a sulfonic acid group obtained by reacting acetylsulfonic acid prepared from % xylo-butanol (2:1
) 356 parts of mixed solvent solution and 2 parts of dioctyl phthalate
6.7 parts and uniformly and finely dispersed to obtain a paint-type water-swellable resin composition of the present invention.

This paint-type composition was applied onto release paper, and after air-drying overnight,
After preliminary drying at 70°C for 3 hours, it was dried at 100°C for 2 hours to obtain a water-swellable butyral resin film.

A small piece from the above film (20Ttm x 20mm x 0.3
A piece of 8 mm (10.154 g) was cut and immersed in distilled water to determine the degree of swelling, and the following results were obtained. This paint-type composition was applied thickly to the surfaces of joints of concrete segments so that the dry film thickness was 1 mm.

After drying, the segment having the water-swellable coating was left in contact with a sufficient amount of water, and the coating swelled to a thickness of about 2 mm. A container was created by joining the surface of the segment with the dry coating film thus obtained to another contoured segment, and when pressurized water (water head 5 m) was poured into the container and left, the segments bonded. The leakage of water gradually decreased and finally stopped completely. The water-swellable resin used in this example was produced by the method described in Example 6 of Japanese Unexamined Patent Publication No. 54-83989 by the applicant of the present invention.

Example 2 (Polystyrene H Polybutadiene H Polystyrene) (Polystyrene content 40%) A block copolymer mainly having a telechelic type structure was dissolved in citalohexane, and about 100 of the number of unsaturated double bonds in the polymer was dissolved in citalohexane. By adding thioglycolic acid to the number of double bonds, a mixed solvent of methanol, methyl ethyl ketone, and tertiary butanol of potassium tertiary butoxide (
3:8 21) solution to obtain a fine dispersion of a water-swellable resin having potassium bases of carboxyl groups with a solid content of 14%.

According to the formulation in the table below, a 15% styrene-butadiene synthetic rubber (bound styrene content is 23.5%) toluene solution was mixed with the fine dispersion of the above water-swellable resin to form a paint-type water-swellable resin composition. I got it.

This paint-type composition was applied onto release paper, and after air-drying overnight,
It was pre-dried at 70°C and then dried at 100°C for 2 hours to obtain a water-swellable styrene-butadiene synthetic rubber film. A small piece (8 CTfL x 20) was cut from the above film and immersed in distilled water to determine the degree of swelling, and the following results were obtained.

Separately, prepare a tricot cotton cloth on a release paper, impregnate it with a dispersion of a fiber treatment agent-type water-swellable resin composition with a ratio of water-swellable resin in the solid content of 20%, and after air drying, 6
It was pre-dried at 0°C and then dried at 80°C for 3 hours.

The weight ratio of cloth and resin in the dried resin-treated cloth was 1:1.
It was 5. When I cut a small piece of it and immersed it in distilled water, it expanded rapidly and completely covered the coarse grains of the tri-cut cloth. Looking at the swelling degree based on the weight, the water-swellable resin composition was found to have swelled approximately four times in water. The above-mentioned water-swellable resin-treated fabric can be incorporated into various joints and seams such as buildings, water piping, and awnings as a packing material and sealing material to easily prevent water leakage due to increase in density due to water absorption. , very useful.

Further, the paint-type water-swellable resin composition described above is also used in the same manner as in Example 1.

The water-swellable resin used in this example was obtained by using potassium tertiary butoxide as a neutralizing agent in place of sodium hydroxide in the method described in Example 1 of JP-A-54-47796 by the applicant. It was manufactured by

Example 3 Obtained by reacting polyurethane having an isocyanate group at the end consisting of 4,4'-diphenylmethane diisocyanate and ethylene glycol with polyethylene maleate having a hydroxyl group at the end (polyurethane H polyethylene maleate + polyurethane) Acidic sodium sulfite is added to approximately 70% of the number of unsaturated double bonds in a telechelic type and multiblock type copolymer (with a polyethylene maleate content of 60%). Add and dissolve 10 parts of the triethanolamine salt of the water-swellable resin having sulfonic acid groups obtained by adding and dissolving it in 90 parts of dimethylformamide, and add it to 20% dimethyl of synthetic leather base resin grade polyurethane using aliphatic polyester polyol. The mixture was uniformly stirred and mixed with 200 parts of formamide solution to obtain a coating agent type water-swellable resin composition.

This was applied to a fabric, and after drying, a urethane-based synthetic leather surface treatment agent was further applied to the surface to obtain synthetic leather with excellent sweat absorption.

The water-swellable resin used in this example was produced by the method described in Example 2 of JP-A-54-83989 by the applicant of the present application, except that the sodium salt was replaced with a triethanolamine salt.

Example 4 A block copolymer mainly having a telelock type structure (polystyrene H polyisoprene H polystyrene) (polystyrene content 40%) was dissolved in cyclohexane, and the unsaturated double bonds of the polymer were dissolved in it. Approximately 100% of the number
After adding thioglycolic acid to the number of double bonds, add toluene in an amount of 30% of cyclohexane, and neutralize with a mixed solvent solution of sodium hydroxide in methanol, methyl ethyl ketone, and dioxane (1:1:1). A fine dispersion of a water-swellable resin having a sodium salt of a carboxyl group with a solid content of 21.5% was obtained.

Separately, 7.5 parts of styrene-butadiene synthetic rubber (styrene bond amount 23.5%) and 7.5 parts of styrene-butadiene thermoplastic rubber (styrene bond amount 40%) were dissolved in 85 parts of toluene, and the solid content A 15% rubber solution was prepared. 15 parts of the fine dispersion of the water-swellable resin and 85 parts of the toluene solution of the rubber were uniformly stirred and mixed to obtain a paint-type water-swellable resin composition.

A synthetic rubber sheet containing a water-swellable resin obtained by coating this on a release paper and drying it exhibited a water swelling degree of 4 times in distilled water. This paint-type water-swellable resin composition was applied to an agricultural polyvinyl chloride film and dried to produce a film coated with the water-swellable resin composition with a coating thickness of 100 μm.

When we used this to create a hotbed to promote and protect the germination and growth of agricultural products, we were able to prevent the condensed water that would normally form on the inside of the film from adhering to it due to the difference in temperature between the inside and outside, thus preventing dew condensation. It also gave a dry feel even though it had absorbed moisture. Similarly, condensation could be prevented by applying it to the walls and ceiling materials of houses, especially the interior materials of bathrooms and the like.

In addition, instead of the toluene solution of the synthetic rubber mentioned above, a 15% methyl ethyl ketone-toluene (50:50) mixed solvent solution of carboxylated vinyl chloride vinyl acetate resin/dibutyl phthalate (80:20) was used, and a PVC stabilizer was used. When a paint-type water-swellable resin composition liquid was prepared by adding the above-mentioned water-swellable resin composition and applied to the above-mentioned films and interior materials, it showed the same dew-preventing effect and was useful.

The water-swellable resin used in this example was obtained by using a block copolymer in which the polybutadiene block is a polyisoprene block in the method described in Example 1 of JP-A-54-47796 by the present applicant. It was manufactured.

Claims (1)

[Claims] 1 A block copolymer and/or graft copolymer consisting of a water-swellable resin and a medium, where the water-swellable resin has at least one (hard segment, hydrophilic segment, hard segment) bond type in its structure, The hydrophilic segment has a sulfonate or a salt of a mercaptocarboxylic acid residue attached to 40 to 100% of the number of double bonds present in the main chain, A water-swellable resin composition that is liquid at room temperature, wherein the medium is a medium that is liquid at room temperature and contains a natural or synthetic resin.