JPH10279905A - Aqueous film-forming composition and adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition improved in storage stability and water resistance, while maintaining its water-holding ability, dryability, viscosity, etc., by including an alkaline metal or ammonium salt of a specific carboxymethylcellulose. SOLUTION: This composition is obtained by compounding (A) a material resin component, (B) 0.1-20 wt.% of an alkaline metal or ammonium salt of a water-insoluble or water-swellable carboxymethylcellulose having a carboxymethylation degree of >=0.01 but <0.4 and a cellulose I type crystallization degree of >=60% but <88%, and as necessary, (C) a cross-linking component having hydroxyl group-reactive groups 0.1-5 equivalent times the total hydroxyl groups in nonvolatile components including the component A, (D) a surfactant for making the component A aqueous, (E) a basic substance for improving the dispersibility of the component A in water, etc., and as necessary, adding a drying-promoting component(s), film-forming auxiliary(ies), pigment(s), dye(s), viscosity regulator(s), antifoaming agent(s), antiseptic(s), plasticizer(s), various stabilizers, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a film-forming composition such as aqueous paints, inks and primers, and an aqueous adhesive composition, and more particularly to an aqueous solution containing a water-insoluble carboxymethyl cellulose alkali metal salt or ammonium salt. And film-forming compositions such as paints, correction fluids, inks and primers, and aqueous adhesive compositions.

[0002]

2. Description of the Related Art In recent years, attempts have been made to use aqueous materials in the fields of paints, adhesives and the like from the viewpoints of environmental problems, safety and the like. Conventionally, there have been many reports of using cellulose, pulp powder and its carboxymethyl derivative in aqueous film-forming compositions, adhesives and the like to impart characteristic physical properties.

[0003] Powders such as cellulose are widely used in the field of water-based paints and inks for the purpose of improving water retention, viscosity, drying property, etc. in addition to use as extenders.
For example, JP-A-4-236273, JP-A-5-1
JP-A-71094 is known. However, powders such as cellulose do not easily disperse in an aqueous medium, and thus have problems such as poor storage stability and poor dispersion in an adhesive layer or a coating film. Further, in order to improve the storage stability, it is necessary to use a dispersant such as a surfactant, and these dispersants remaining in the film during the formation of the film have caused problems such as a decrease in water resistance.

On the other hand, carboxymethylcellulose alkali metal salts or ammonium salts have long been used as water-soluble viscosity modifiers and are known. As an example of using carboxymethylcellulose alkali metal salt or ammonium salt for another characteristic purpose, for example, Japanese Patent Application Laid-Open No. Sho 62-124170 is known. This not only improved the fluidity by adjusting the viscosity, but also improved other properties such as cap-off properties.

[0005] However, the water resistance of a coating or an adhesive layer containing a water-soluble alkali metal salt or ammonium salt of carboxymethyl cellulose decreases. When a functional group that reacts with a hydroxyl group such as isocyanate is present in the raw material resin of the paint / adhesive, or when a cross-linking agent having these reactive functional groups is added, the hydroxyl group in the carboxymethyl cellulose alkali metal salt is removed. It is a well-known fact that although the water resistance is improved by cross-linking, the reactivity between the hydroxyl group of the glucose residue and the isocyanate is low, and the improvement of the water resistance only by this effect is limited. Therefore, the amount of the alkali metal salt or ammonium salt of carboxymethylcellulose into which a carboxymethyl group has been introduced to such an extent as to exhibit water solubility has been limited.

As reported in, for example, Japanese Patent Application Laid-Open No. 62-250083, a low-substituted sodium carboxymethylcellulose is exemplified as a water-insoluble cellulose derivative. According to the regulations, there has been no report that a characteristic aqueous film-forming composition or adhesive has been developed utilizing characteristics of sodium carboxymethylcellulose other than those derived from water-insoluble.

[0007]

As described above, conventional film-forming compositions such as water-based paints, inks, primers, etc., which contain powders such as cellulose, and water-based adhesives have a problem in stability during storage. Was. In addition, a dispersant or the like for improving storage stability causes a decrease in water resistance of the coating. On the other hand, when a conventional water-soluble carboxymethyl cellulose alkali metal salt or ammonium salt is contained, there is a problem in water resistance.

An object of the present invention is to solve the problems of storage stability and water resistance while maintaining properties such as water retention, viscosity and drying properties of powders such as cellulose.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, low-substituted carboxymethylcellulose alkali metal salts or ammonium salts having a specific degree of carboxymethyl etherification have been found to be composed of water-soluble cellulose fibers. Water-based paints, inks, adhesives, etc., containing this are required to retain water when containing powders such as cellulose due to the minimal chemical modification required for good dispersibility in cellulose. The present invention has been found to exhibit excellent dispersion stability, storage stability and water resistance while maintaining viscosity, fluidity and fluidity.

[0010] Further studies have shown that when the raw material resins such as aqueous paints, inks and adhesives have a functional group which reacts with a hydroxyl group, or when a crosslinkable component having such a functional group is further added to the system. Also found that the water resistance of the dried film or adhesive layer was further improved.

That is, the present invention relates to a water-insoluble or water-swellable carboxymethylcellulose alkali metal having a degree of carboxymethylation of 0.01 to less than 0.4 and a degree of crystallization of cellulose type I of 60% to less than 88%. A film-forming composition such as a water-based paint, ink, primer or the like containing a salt or an ammonium salt, and a water-based adhesive composition.

Further, the crosslinkable component, which further improves the water resistance of the coating or adhesive layer after drying, has a hydroxyl reactive group in an amount of 0.1 to 5 equivalents to all hydroxyl groups in the nonvolatile components. And a film-forming composition such as a water-based paint, ink, primer and the like, and a water-based adhesive composition.

Particularly, a film-forming composition such as an aqueous paint, ink, primer or the like containing 0.1 to 20% by weight of a water-insoluble carboxymethylcellulose alkali metal salt or ammonium salt, and an aqueous adhesive composition, This is preferable because the physical properties of the adhesive layer are further balanced.

In the present invention, the film-forming composition is
It refers to anything that provides industrial utility value by utilizing the film-forming properties, for example, paints, coating materials, sealers, primers, correction fluids, and the like.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

Cellulose and lignocellulose as raw materials of the alkali metal salt or ammonium salt of carboxymethylcellulose of the present invention are pulp, linter, wood flour, coconut husk powder, walnut husk powder, cotton or its crushed product, and cellulose in a copper ammonia solution. A natural or synthetic cellulose material containing cellulose, such as a fiber material (regenerated cellulose), which is dissolved in some solvent such as a morpholine derivative and spun again. Depending on the application, various kinds of disintegrated waste paper, waste paper deinked pulp and the like are used. These raw materials are appropriately selected depending on the intended use of the fine cellulose derivative.

In converting the raw materials into carboxymethyl ether, a known method for producing carboxymethyl cellulose is applied, and 0.01 as a whole per glucose unit.
It is prepared so as to have a degree of carboxymethyl etherification of at least 0.4 and less than 0.4, preferably from 0.03 to 0.38, more preferably from 0.05 to 0.35. If the degree of substitution is less than 0.01, the dispersion stability in water decreases, and the storage stability deteriorates. If the substitution degree is 0.4 or more, the water resistance of the dried film or adhesive layer is reduced. The substitution degree was measured by a known methanol nitrate method.

Even if the degree of substitution of the carboxymethyl ether group satisfies the above range, if the crystallinity of the cellulose I type is less than 60%, the cellulose is easily dissolved in water. , Sufficient water swelling property cannot be obtained, and in any case, the features of the present invention cannot be sufficiently exhibited. Furthermore, by having the above crystalline region, compared to the conventional water-soluble CMC,
There is an effect that light scattering is large in the formed film and the adhesive layer, and the concealing property of the base material is improved.In addition, since the CMC layer is formed around the particles as compared with the cellulose fine powder,
When a film is formed on transparent glass, it has a feature that the effect is large.

The amount of the carboxymethylcellulose alkali metal salt or ammonium salt to be added is 0.1 to 20% by weight, based on the weight of the aqueous coating composition, such as a paint, ink or primer, and the aqueous adhesive composition. Is from 0.5 to 15% by weight. If it is less than 0.1% by weight, desired water retention, viscosity and fluidity cannot be obtained. If the content is more than 20% by weight, the adhesion, solvent resistance and water resistance of the dried film or adhesive layer are reduced.

The average particle size of the carboxymethylcellulose alkali metal salt or ammonium salt is preferably as small as possible because the smoothness of the coating is improved. However, it is appropriately selected according to the purpose of use.

Further, by using carboxymethylcellulose alkali metal salt or ammonium salt by coloring, the coating can be colored, and the saturation when added to the paint can be improved.

Further, by using the alkali metal salt or ammonium salt of carboxymethylcellulose of the present invention, the concealing property with respect to the substrate is improved.

The crosslinkable component in the present invention has two or more hydroxyl-reactive groups in one molecule.

The hydroxyl group-reactive group in the present invention is a functional group capable of forming a chemical bond with a hydroxyl group by condensation or addition reaction. In particular,
Examples thereof include an epoxy group, an isocyanate group, an acid amide group, and an acid halide group. In addition, the above functional groups, such as blocked isocyanate groups and blocked amino groups, are masked with some kind of blocking agent, and include functional groups that exhibit reactivity due to factors such as heat and ultraviolet rays.

Specific examples of the crosslinking component include aqueous epoxy resins such as EPE041-T, EPE-0470, EPES0427 and EPEC-0.
435, EP-8100 (manufactured by Asahi Denka Kogyo Co., Ltd.), Aquatoto 510 (bisphenol A type, manufactured by Toto Kasei), Aquatoto 35201 (bisphenol A type, manufactured by Toto Kasei), and duranate X-1361 as an aqueous blocked isocyanate Duranate X-1119, Duranate X-1118
(Made by Asahi Kasei), coronate 2507 (hexamethylene diisocyanate type, made by Nippon Polyurethane), and an aqueous reactive urethane such as Elastron (made by Daiichi Kogyo Seiyaku).

The amount of the hydroxyl-reactive group is determined based on the total hydroxyl groups in the nonvolatile components of the aqueous film-forming composition or the adhesive composition.
It is prepared in an amount of 0.1 to 5 equivalents, preferably 0.2 to 3 equivalents. If the equivalent is less than 0.1 equivalent, the effect of improving water resistance is not seen.

The cross-linking agent may be added at any stage in the production process of the aqueous film-forming composition and the adhesive composition. However, the cross-linking reaction is likely to occur at the time when the film or the adhesive layer is formed after drying or baking. Since it is desirable, it is appropriately selected according to the type of the functional group used, the reactivity of the hydroxyl group of the reaction partner, the temperature at the time of production, and the like.

The raw resin component of the aqueous film-forming composition or the adhesive composition of the present invention includes a polyolefin resin, a modified polyolefin resin such as chlorinated or acid-modified, an acrylic resin, an epoxy resin, a urethane resin, an amino resin. A known resin such as a resin, an alkyd resin, and a silicone resin is used. Further, a modified product or a mixture of two or more of the above resins, such as melamine-modified alkyd and urethane-modified polyolefin, may be used.

The raw material resin and the carboxymethyl cellulose alkali metal salt or ammonium salt may be mixed and then made aqueous, or the raw material resin which has been made water-soluble by some method may be added to carboxymethyl cellulose alkali metal salt or ammonium salt. Salt may be added. When the carboxymethyl cellulose alkali metal salt or ammonium salt of the present invention is used, the viscosity does not easily increase.

In the aqueous resin process, a surfactant is appropriately used. As the surfactant used in the present invention, there is a non-reactive surfactant having no radical polymerizability and a reactive surfactant having radical polymerizability, and each may be used alone or in combination. Good.

Non-reactive surfactants include copolymers of ethylene oxide and propylene oxide, aliphatic alcohol polyalkylene oxide adducts (such as polyoxyethylene aliphatic alkyl ethers), and secondary alcohol polyalkylene oxide adducts (poly Oxyethylene 2
Grade alcohol ethers), alkyl amide polyalkylene oxide adducts, polyoxyalkylene alkyl phenyl ethers (polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl phenyl ether, etc.), polyoxyalkylene sterol ethers, polyoxyalkylene lanolin derivatives, alkyl phenols Alkylene oxide derivative of formalin condensate, polyoxyalkylene glycerin fatty acid ester (polyoxyethylene glycerin fatty acid ester, etc.), polyoxyalkylene sorbitol fatty acid ester (polyoxyethylene sorbitol fatty acid ester, etc.), polyoxyalkylene glycol fatty acid ester (polyoxyethylene Fatty acid esters, etc.), polyoxyalkylene fatty acid amides (polyoxyethylene Fatty acid amide, etc.), polyoxyalkylene alkylamines (polyoxyethylene alkylamine, ethylene oxide propylene oxide polymer adduct of alkyl alkanolamine, etc.), propylene glycol ester, sucrose ester, sorbitan alkyl ester, sorbitan fatty acid ester, polyglycerin Nonionic surfactants such as esters, fatty acid alkanolamides, fatty acid monoglycerides, and alkylamine oxides; alkyl sulfates, alkyl phenol sulfonates, sulfosuccinates, and the like, as well as carboxylate and phosphate salts. Surfactants that can be used, amphoteric surfactants such as alkyl betaines and alkyl imidazolines, and mixtures of two or more of these You can use.

Examples of the reactive surfactant include the following. As the reactive surfactant, those generally used as a reactive surfactant or a reactive emulsifier may be used, but those having an alkylphenyl group as a hydrophobic group and a polyoxyethylene group as a nonionic hydrophilic group are preferable. For example, alkyl propenyl phenol polyethylene oxide adducts, alkyl dipropenyl phenol polyethylene oxide adducts, and salts of sulfates thereof described in JP-A-4-53802 and JP-A-4-50204 are used. Among them, alkyl propenyl phenol ethylene oxide 20 mol adduct, 30 mol adduct thereof, 50 mol adduct thereof, and alkyl propenyl phenol ethylene oxide 10 mol adduct sulfate ammonium salt, 20 mol adduct sulfate ammonium salt Is preferred. Also, 1-alkylphenoxy-3- (2-propenyl) oxypropane-
A 2-ol polyethylene oxide adduct or a sulfate thereof is excellent in resin dispersing ability, and further preferably has high polymerizability due to having an α, β-unsaturated double bond.

These reactive surfactants can be reacted with a raw material resin by a known method in the presence of a radical reaction initiator to be immobilized on the resin.

The type and amount of the surfactant and the radical reaction initiator when the reactive surfactant is used can be appropriately changed according to the raw material resin or other additives such as alcohol. However, when the amount of the surfactant component is small, the emulsification efficiency in the aqueous process is reduced, the particle size is increased, the storage stability of the emulsion is reduced, and when the amount is large, the emulsion is formed using the aqueous resin composition. The water resistance of the coated film is significantly reduced.

In the present invention, a basic substance can be added as needed to improve the dispersibility of the raw material resin in water. Examples of the basic substance include sodium hydroxide, potassium hydroxide, ammonia, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, ethanolamine, propanolamine, diethanolamine, N- (β-aminoethyl) ethanolamine, N-methyldiethanolamine, N-methylethanolamine, dimethylamine, diethylamine, triethylamine, N, N-dimethylethanolamine,
N, N-diethylethanolamine, N, N-dibutylethanolamine, 2-dimethylamino-2-methyl-
Examples thereof include 1-propanol, 2-amino-2-methyl-1-propanol, and morpholine. The degree of hydrophilicity of the resin also varies depending on the type of base used, so it is necessary to select it appropriately depending on the conditions.

The amount of the basic substance to be used is 0.3 to 0.3 equivalent to the hydrophilic functional groups such as carboxyl group and sulfone group.
A range of 1.5 times is appropriate, preferably 0.5 to 1.5 times.
It is twice. In addition, in the addition of a basic substance, it is necessary to control the pH of the aqueous resin composition prepared in accordance with the stability of the compounded blocked isocyanate compound or the like to near neutrality.

Further, the aqueous resin composition of the present invention is used by adding a drying promoting component such as alcohol, if necessary, in order to increase the evaporation rate of water during drying. In addition, film forming aids, rust preventive pigments, coloring pigments, pigments such as extender pigments, dyes, thixotropic agents, viscosity modifiers, flow aids, surface conditioners, primary rust inhibitors, defoamers, preservatives, A required amount of various additives such as a fungicide, a plasticizer, various stabilizers for improving heat resistance and weather resistance, and an organic metal coordination compound is added and used.

Examples of the pigment include inorganic pigments such as carbon black, titanium oxide, chromium oxide, aluminum powder, zinc oxide, iron oxide mica, and navy blue, and coupling azo, condensed azo, anthraquinone, perylene, quinacridone, and the like. Organic pigments such as thioindigo, dioxazine and phthalocyanine are exemplified.

Examples of the inorganic filler include calcium carbonate, silica, talc, glass fiber, clay and the like.

Examples of the organic filler include a fluorine resin powder, a silicone resin powder, a polyamide resin powder, and a urethane resin powder.

Examples of the organic metal coordination compound include organic zirconium coordination compounds such as zirconium tetraacetylacetonate and diisopropoxy zirconium bisacetonate, and organic titanium coordination compounds such as titanium tetrakisacetylacetonate and diisopropoxytitanium bisacetylacetonate. And organic aluminum coordination compounds such as aluminum trisacetylacetonate and aluminum triisopropoxide.

These additives may be added before, during or after the production of the composition of the present invention.

Further, other aqueous resins such as aqueous acrylic resin, aqueous phenol resin, aqueous polybutadiene resin,
An aqueous resin such as an aqueous alkyd resin, an aqueous chlorinated rubber, an aqueous chlorinated polyolefin resin, and an aqueous silicone resin may be blended.

The aqueous film-forming composition and the adhesive composition thus obtained are extremely excellent in water retention, viscosity, drying properties, water resistance and storage stability. Further, by selecting a raw material resin or a cross-linking agent to be combined, the adhesion to various base materials can be improved.

[0045]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. Parts and% in Examples are parts by weight and% by weight, respectively.

The physical properties were measured by the following test methods.

1) DS measurement (methanol nitrate method) About 2.0 g of a sample was precisely weighed and placed in a 300 ml Erlenmeyer Erlenmeyer flask. 100 ml of methanol nitrate (a solution obtained by adding 100 ml of special grade concentrated nitric acid to 1 liter of anhydrous methanol) is added, and shaken for 3 hours to give sodium carboxymethylcellulose (N
a-CMC) was converted to carboxymethylcellulose (H-CMC). 1.5-2.0 g of the absolutely dried H-CMC was precisely weighed,
Placed in a 00 ml Erlenmeyer Erlenmeyer flask. H-CMC was wet with 15 ml of 80% methanol, 100 ml of 0.1N-NaOH was added, and the mixture was shaken at room temperature for 3 hours. Phenol as an indicator
Excess NaOH was back titrated with 0.1N H ₂ SO ₄ using phthalein. DS was calculated by the following equation.

[0048]

(Equation 1)

2) Measurement of Crystallinity The crystallinity of cellulose I was determined by measuring the X-ray diffraction of the sample. For the measurement of X-ray diffraction, an appropriate amount of a sample was placed on a glass cell, and an X-ray diffraction measuring device (RAD-2C system, manufactured by Rigaku Denki Co., Ltd.) was used. The calculation of the crystallinity of cellulose type I was performed by the method of Segal et al. (L. Segal, JJ Greenly e.
tal, Text. Res. J., 29, 786, 1959), and the 2θ of the diffractogram obtained from the X-ray diffraction measurement performed using the method of Kamide et al. (K. Kamide et al, Polymer J., 17, 909, 1985). = 4 ° ~
Using the diffraction intensity at 32 ° as a baseline, the diffraction intensity was calculated from the diffraction intensity of the 002 plane and the diffraction intensity of the amorphous portion at 2θ = 18.5 ° by the following equation. χc = (I002c−Ia) / I002c × 100 χc: Crystallinity (%) of cellulose type I I002c: 2θ = 22.6 °, diffraction intensity of 002 plane Ia: 2θ = 18.5 °, diffraction intensity of amorphous portion

[Trial Example-1] 100 parts of bleached sulfite pulp were mixed with 435 parts of isopropanol (IPA) and 65 parts of water.
The mixture was added to a mixture of 39.5 parts of NaOH and stirred at 45 ° C. for 0.5 hours. 50% monochloroacetic acid I in this slurry system
9.0 parts of a PA solution was added, and the mixture was heated to 70 ° C. and reacted for 1.5 hours. The obtained reaction product was sufficiently washed with acetic acid, further washed with water, and then neutralized with 20% aqueous ammonia. Subsequently, it was washed with 80% methanol, then replaced with methanol and dried to obtain carboxymethylcellulose ammonium salt having a DS of 0.06 and a crystallinity of cellulose type I of 72.7%. This product was pulverized dry using a pulperizer (manufactured by Hosokawa Micron). In addition, DS after grinding
Was not changed, and the total yield was 97.1%.

[Trial Production Example 2] 100 parts of linter pulp were mixed with 522 parts of isopropanol (IPA) and 78 parts of water.
NaOH was added to a mixture of 44.4 parts and stirred at 55 ° C. for 0.5 hour. 50% monochloroacetic acid I in this slurry system
45.0 parts of a PA solution was added, and the mixture was heated to 70 ° C. and reacted for 1.5 hours. The resulting reaction was washed with 80% methanol, then replaced with methanol and dried, and DS 0.3
0, a carboxymethylcellulose sodium salt having a degree of crystallinity of cellulose I of 65.5% was obtained. This product was wet-milled using a mass colloider (manufactured by Masuko Sangyo).
The DS after pulverization did not change, and the total yield was 9
It was 1.3%.

[Trial Production Example-3] 500 parts of maleic acid-modified chlorinated polypropylene (toluene solution having an average molecular weight of 60000, a grafted amount of maleic acid of 2.3%, a chlorine content of 24.5% and a solid content of 20%) was heated at 90 ° C. After adding 9.6 parts of morpholine, 15 parts of polyethylene oxide nonylphenyl ether (NS-212, manufactured by NOF Corporation) was added. After the toluene was distilled off under reduced pressure, water was gradually added while stirring at 100 ° C., and an aqueous modified polyolefin resin (solid content: 40%) was obtained by a phase inversion emulsification method.

[Trial Production Example-4] To 100 parts of a bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd., Aquatoto 510), 38 parts of Epicur 8799 (manufactured by Toto Kasei) were mixed, and water was added with stirring. An aqueous product having a solid content of 40% was obtained.

Example 1 100 parts of maleic acid-modified polyolefin (average molecular weight 30,000, grafted amount of maleic acid 5.0%) was heated to 90 ° C.
After adding 0 parts, 20 parts of polyethylene oxide polypropylene oxide block copolymer (Newpole PE-62, manufactured by Sanyo Chemical Industries) was added. In addition, a prototype example
10 parts of the carboxymethylcellulose ammonium salt obtained in 1 were added. After distilling off the toluene under reduced pressure, 10
Water was gradually added while stirring at 0 ° C., and an aqueous product (solid content: 40%) was obtained by a phase inversion emulsification method. The hydroxyl equivalent of the solid content was 274.

Example 2 Based on 100 parts of the aqueous modified polyolefin resin (solid content 40%) obtained in Prototype Example 3,
One part of the carboxymethylcellulose sodium salt obtained in Prototype Example 2 was added, and the mixture was sufficiently stirred to obtain an aqueous product. The hydroxyl equivalent of the solid content was 281.

[Example 3] The same operation was performed by replacing the aqueous modified polyolefin resin used in Example 2 with the aqueous epoxy resin obtained in Prototype Example 4, to obtain an aqueous product.
The equivalent ratio of the component having reactivity with the epoxy group including the epoxy group and the hydroxyl group was 0.84.

Example 4 An aqueous urethane resin (Superflex 90, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) prepared by adjusting the aqueous modified polyolefin resin used in Example 2 to a solid content of 40%.
The same operation was performed in place of 0) to obtain an aqueous product.

[Example-5] An aqueous melamine resin (water sol S69, manufactured by Dainippon Ink) having the aqueous modified polyolefin resin used in Example-2 adjusted to a solid content of 40%.
The same operation was performed in place of 5) to obtain an aqueous product.

[Example-6] To 100 parts of the aqueous compound obtained in Example-1, 30 parts of an aqueous blocked isocyanate (Duranate X-1118, manufactured by Asahi Kasei Corporation, solid content 30%) was added, and the mixture was stirred. An aqueous product was obtained. The equivalent ratio of hydroxyl group / isocyanate was 1.25.

[Comparative Example-1] The same operation was performed by replacing the carboxymethylcellulose ammonium salt used in Example-1 with powdered cellulose (KC Floc W-400G, manufactured by Nippon Paper) to obtain an aqueous product.

Comparative Example 2 The same operation was carried out except that the carboxymethylcellulose ammonium salt used in Example 1 was replaced with a water-soluble sodium carboxymethylcellulose sodium salt (manufactured by Nippon Paper, Sunrose F30LC, DS0.61). An aqueous product was obtained.

[Test Items] Examples-1 to 6, Comparative Example-1
2 was adjusted to a solid content of 20%, and the following test was performed. The results are shown in Table 1.

[Storage Stability Test] Each sample was collected in a 250-ml reagent bottle and allowed to stand in a constant temperature room at 40 ° C., and the degree of sedimentation of cellulose or a derivative and the degree of separation of an aqueous product were visually observed. The symbols in the table indicate that each of △, Δ, and × is stable for at least one month, stable for one week to one month, and unstable within one week.

[Water resistance test] Each sample was placed on a glass
6 using a coating rod and baking at 100 ° C. for 30 minutes in a blast drier to obtain a film thickness of 20 to 25 μm.
m. Each glass test plate was immersed in warm water at 40 ° C., and the degree of whitening, peeling, and blistering was observed. The symbols in the table indicate that each of ◎, △, Δ, and × is stable for 2 weeks or more, stable for 5 days or more, stable for 1 to 5 days, and has occurred abnormally within 1 day.

[Viscosity test] Each sample was spray-coated on a glass plate, and the degree of clogging and sagging were visually evaluated. The symbols in the table indicate good and bad, respectively.

[Water Retention Test] Three drops of each sample were placed on a high-quality paper (NPi Fine, basis weight: 64.0 g / m ² ), and the degree of stain on the paper was visually observed. The symbols in the table are
、, × indicate good and bad respectively.

[0067]

[Table-1]

[0068]

As described above, according to the present invention, an aqueous film-forming composition or a composition having good storage stability and water resistance while maintaining properties such as water retention, viscosity, and drying property of powder such as cellulose. An adhesive can be obtained.

Further, by using the water-insoluble or water-swellable carboxymethylcellulose alkali metal salt or ammonium salt of the present invention, the effect of further improving the dispersion stability in water and further improving the water resistance by adding a crosslinking component can be obtained. Things.

Claims (6)

[Claims] 1. A carboxymethylation degree of 0.01 to less than 0.4, and a cellulose type I crystallinity of 6
A film-forming composition comprising from 0% to less than 88% of a water-insoluble or water-swellable alkali metal salt or ammonium salt of carboxymethyl cellulose. 2. The film-forming composition according to claim 1, which comprises a crosslinkable component having a hydroxyl-reactive group in an amount of 0.1 to 5 equivalents to all hydroxyl groups in the nonvolatile components including the resin component. 3. An alkali metal salt or ammonium salt of water-insoluble or water-swellable carboxymethylcellulose is added to a water-soluble or water-swellable metal salt.
3. The film-forming composition according to claim 1, comprising 1 to 20% by weight. 4. The carboxymethylation degree is 0.01 or more and less than 0.4, and the crystallinity of cellulose type I is 6
An adhesive composition comprising 0% or more and less than 88% of a water-insoluble or water-swellable alkali metal salt or ammonium salt of carboxymethyl cellulose and a crosslinkable component. 5. The adhesive composition according to claim 4, further comprising a crosslinkable component having a hydroxyl reactive group in an amount of 0.1 to 5 equivalents to all hydroxyl groups in the nonvolatile components including the resin component. 6. A water-insoluble or water-swellable carboxymethylcellulose alkali metal salt or ammonium salt of 0.1 or less.
The adhesive composition according to claim 4, wherein the adhesive composition comprises about 20% by weight.