JPH08151402A - Water-based solution composition - Google Patents

Abstract

PURPOSE: To obtain a water-based solution composition improved in long-term stability of viscosity etc. by adding a stabilizer to a water-based solution prepared by mixing a nitric ester of carboxyalkyl cellulose with water, an organic solvent and a neutralizing agent. CONSTITUTION: This composition is prepared by adding 0.1-30wt.%, based on the nitric ester of carboxyalkyl cellulose, at least one stabilizer selected from among an epoxy compound, an organophosphorus compound, a phosphoric acid derivative, a pyrophosphate, a phenol compound, an oxy-acid, a dicarboxylic acid and a fatty acid to a water-based solution composition prepared by mixing a nitric ester of carboxyalkyl cellulose having 0.2 or above of eubstitution degree of nitration ester group per glucose anhydride unit and a 0.05 or above of the same degree of carboxyalkyl ether group with water, an organic solvent and a neutralizing agent.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The aqueous solution composition of the present invention is used for paints, plastic paints, leather paints, magnetic paints, printing inks, paper coatings, film processings, thermal papers, fiber processings, conductive pastes and the like. Regarding functional materials.

[0002]

2. Description of the Related Art Conventionally, cellulose esters such as nitrocellulose and cellulose acetate butyrate are paints, printing inks, paper coatings, film processings, thermal papers, fiber processings, and conductive pastes from the viewpoints of drying property and heat resistance. It is used as a material.

However, since a large amount of organic solvent is used for cellulose ester such as nitrocellulose or cellulose acetate butyrate as a coating material, air pollution due to volatilized solvent, deterioration of working environment, risk of fire, etc. There was a problem. In addition, the water-based cellulose acetate butyrate has a problem that it is physically unstable due to hydrolysis and viscosity increase during storage.

In order to solve these problems, nitric acid ester of carboxyalkyl cellulose (JP-A-5-39).
No. 301 and Japanese Patent Laid-Open No. 5-39302) have been proposed. Of these, Japanese Patent Laid-Open No. 5-39301 discloses that
By using a mixed solution of nitrate ester of carboxyalkyl cellulose, water and the minimum necessary organic solvent and neutralizing agent and using it as an aqueous material, it is possible to improve the drying property, heat resistance, etc., and reduce the organic solvent used. It is described that air pollution due to volatile solvents, working environment, fire risk, etc. can be improved. However, there is a practical problem that the mixed solution of the nitrate ester of carboxyalkyl cellulose, water, an organic solvent, and a neutralizing agent has a reduced viscosity during storage.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to a carboxyalkyl cellulose nitrate ester and water, an organic solvent,
It is an object of the present invention to provide an aqueous solution composition having improved stability with time such as viscosity of an aqueous solution obtained by mixing a neutralizing agent.

[0006]

In order to solve the above-mentioned problems, the present inventor has a degree of substitution of nitrate ester group of 0.2 or more and a degree of substitution of carboxyalkyl ether group of 0.05 or more per anhydrous glucose unit. In the aqueous solution obtained by mixing the nitrate ester of carboxyalkyl cellulose and water, an organic solvent, and a neutralizing agent, further as a stabilizer,
Distribution and storage by preparing an aqueous solution composition containing one or more of epoxy compounds, organic phosphorus compounds, phosphoric acid derivatives and pyrophosphates, phenolic compounds, oxy acids, dicarboxylic acids, fatty acids It was found that the viscosity was stable over a long period of time such as time, and the present invention was completed.

The nitric acid ester of carboxyalkyl cellulose used in the present invention is a known mixed acid for nitric esterification of carboxyalkyl celluloses such as carboxymethyl cellulose and carboxyethyl cellulose, for example, nitric acid esterification consisting of sulfuric acid / nitric acid and water. The treatment is carried out with a mixed acid, and the degree of substitution of the nitrate ester group contained in the nitrate ester of carboxyalkyl cellulose is 0.2 or more and the degree of substitution of the carboxyalkyl ether group is 0.05 or more. JP-A-5-39302 It refers to the aqueous cellulose derivative disclosed in the publication. When the nitrate ester group substitution degree is less than 0.2, the pigment dispersibility becomes insufficient, and when the carboxyalkyl ether group substitution degree is less than 0.05, the solubility in water becomes insufficient and the organic solvent used is A large amount is required.

Preferably, the degree of substitution of the nitrate ester group is
It is 0.5 or more and 2.5 or less, and the degree of carboxyalkyl ether group substitution is 0.3 or more and 2.0 or less. As the neutralizing agent used in the present invention, alkali metal hydroxides, alkali metal salts, alkaline earth metal hydroxides, alkaline earth metal salts, ammonia, ammonium salts, organic amines,
An organic amine salt or an aqueous solution of these can be used.

The carboxyl group contained in the nitrate of carboxylalkyl cellulose used in the present invention is neutralized by the above-mentioned neutralizing agent. Neutralized means that all or part of the hydrogen ions of the carboxyl group, preferably 50% or more, is a combination of one or more ions of alkali metal ions, ammonium ions or monobasic organic amines. It is said that the salt is replaced with.

The alkaline metal ions used for neutralizing the carboxyl groups contained in the nitrate of carboxyalkyl cellulose are, for example, lithium, sodium,
An ion of an element of Group 1 of the Periodic Table such as potassium and rubidium, and a monobasic organic amine means, for example, one amino group in a molecule such as ethylamine, propylamine, butylamine, triethylamine and diethylethanolamine. Means an ion of an organic compound containing. Other metal element ions and dibasic or more polybasic organic amine ions cause excessive interaction between molecules, resulting in insufficient solubility in water or a mixed solvent with an organic solvent. become.

As the organic solvent used in the present invention, alcohols, polyhydric alcohols, polyhydric alcohol derivatives, ketones, esters, ethers, carbonates and the like may be used alone or in combination of two or more. Different solvents can be used. Examples of alcohols include methanol, ethanol, n-propanol, n-butanol, n-pentanol, n-hexanol, n-heptanol, n-octanol, n-nonyl alcohol, n.
-Decanol, n-undecanol or isomers thereof, cyclopentanol, cyclohexanol and the like. Alcohols having 1 to 6 alkyl carbon atoms are preferable.

The polyhydric alcohols include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1, 2-cyclohexanediol, 1,7
-Heptanediol, 1,8-octanediol, 1,
Examples thereof include 9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol and the like.

Derivatives of polyhydric alcohol include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol isopropyl ether, ethylene glycol monobutyl ether, ethylene glycol isobutyl ether, propylene glycol monomethyl ether, propylene. Glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, cellosolve acetate, etc., or solvent pocket book (p. 479-p, 574) edited by Japan Society for Synthetic Organic Chemistry (September 2, 1990)
Polyhydric alcohols and their derivatives described on the 0th, published by Ohmsha Co., Ltd.

Examples of ketones include acetone, methyl ethyl ketone, methyl butyl ketone, methyl isobutyl ketone, diisopropyl ketone, cyclopentanone and cyclohexanone. Examples of the esters include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, amyl acetate, lactate ester, butyrate ester, dibutyl phthalate, dioctyl phthalate, and cyclic groups such as ε-caprolactone and ε-caprolactam. Examples include esters.

As the ethers, diethyl ether,
Examples include isopropyl ether, n-butyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane and the like. Examples of the carbonates include dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, ethylene carbonate and the like.

As the stabilizer used in the present invention, one or more kinds of epoxy compounds, organic phosphorus compounds, phosphoric acid derivatives and pyrophosphates, phenolic compounds, oxy acids, dicarboxylic acids, fatty acids and the like can be used. Can be used in combination. The epoxy-based compound is a compound having one or more epoxy groups in its chemical structure, and is a glycidyl ether-based epoxy resin, a cycloaliphatic epoxy resin, a glycidyl ester-based resin, a glycidyl amine-based resin, or a heterocyclic epoxy resin. Etc.

Examples of the glycidyl ether type epoxy resin include bisphenol A type epoxy resin and novolac type epoxy resin. Examples of the cycloaliphatic epoxy resin include 3.4 epoxycyclohexylmethylcarboxylate and 3.4 epoxy-6 methylcyclohexylmethylcarboxylate.

Examples of the glycidyl ester-based resin include phthalic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester. Examples of the glycidyl amine-based resin include diglycidyl aniline and triglycidyl-metaaminophenol. Examples of the heterocyclic epoxy resin include triglycidyl isocyanurate.

Examples of the phosphite ester as an organic phosphorus compound include triphenylphosphite, tris (nonylphenyl) phosphite, triethylphosphite,
Tris (2-ethylhexyl) phosphite, tridecylphosphite, tris (tridecyl) phosphite,
Diphenylmono (2-ethylhexyl) phosphite,
Diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, dilauryl hydrogen phosphite, diphenyl hydrogen phosphite,
Tetraphenyldipropylene glycol diphosphite, tris (tridecyl) phosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, tetra (tridecyl) -4-4'-isopropylidene diphenyldiphosphite, trilauryltrithiophosphite Fight, bis (tridecyl) pentaerythritol diphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, tristearyl phosphite, distearyl pentaerythritol diphosphite, Examples thereof include tris (2,4-di-t-butylphenyl) phosphite.

Examples of the phosphoric acid esters include triethyl phosphate, trimethyl phosphate, tributyl phosphate, ethyl diethylphosphonoacetate, ethyl acid phosphate, butyl acid phosphate,
Butylpyrophosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate,
Examples thereof include oleyl acid phosphate, tetracosyl acid phosphate, di (2-ethylhexyl) phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate and the like. Examples of the phosphoric acid derivative and pyrophosphoric acid include tetranalium pyrophosphate, disodium hydrogenphosphate and the like.

Examples of the phenol compound include 2.2'-methylenebis (4-methyl-6-t-butylphenol), tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl), n-octadecyl-3- (3,5-di). t-Butyl-4-hydroxyphenyl) propionate, triethyleneglycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], 2,6-di-t-butyl-4-methylphenol, trisnonylphenylphosphite, diphenylamine Examples of the oxy acid include glycolic acid, lactic acid, malic acid, tartaric acid, citric acid and the like.

As the dicarboxylic acid, oxalic acid, malonic acid,
Examples include succinic acid, glutaric acid, adipic acid, maleic acid and itaconic acid. Fatty acids include formic acid, acetic acid, propionic acid, butyric acid and the like. The amount of the stabilizer added in the present invention is 0.1% by weight or more and 30% by weight or less based on the nitrate of carboxyalkyl cellulose. If it is less than 0.1% by weight, the composition will undergo a large change with time, and if it exceeds 30% by weight, the drying property and heat resistance of the composition will not be exhibited.

In the aqueous solution composition of the present invention, another water-soluble resin can be included in the composition. The water-soluble resin is used for water-based paints, inks, water-based binders, etc., and includes maleic acid-styrene copolymer, maleic acid-acrylic acid ester-based copolymer, maleic acid-methacrylic acid ester-based copolymer, acrylic acid-styrene-based resin. Copolymer, acrylic acid-acrylic acid ester-based copolymer, acrylic acid-methacrylic acid ester-based copolymer, polyurethane resin, polyamide resin, shellac, casein, polyvinyl alcohol, or one of cellulose ethers such as hydroxyethyl cellulose, hydroxypropyl cellulose and carboxymethyl cellulose Alternatively, a combination of two or more kinds can be given as an example.

The aqueous solution composition of the present invention may contain a pigment and / or a dye depending on the purpose of use. As the pigment, titanium oxide, iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, wachchan red, color pigments such as quinacridone yellow, barium sulfate, calcium carbonate, extender pigments such as clay, magnetic iron oxide, barium titanate, One or a combination of two or more kinds of functional pigments such as gold and silver can be used. Known dyes such as methylene blue, malachite green, rhodamine, and alizarin can be used as the dye.

An example of the method for preparing the aqueous solution composition of the present invention will be described. The nitrate ester of carboxyalkyl cellulose is weighed in a closed container equipped with a stirrer, and water is added in a specified amount. Next, a specified amount of organic solvent is added and stirred to make the system uniform. Next, a neutralizing agent is added and stirred to be completely dissolved while heating, and a stabilizer is added in a predetermined amount to prepare an intended aqueous solution composition.

The aqueous solution composition of the present invention is a paint, a paint for plastics, a leather paint, a magnetic paint, a printing ink, a paper coating, a film processing, a thermal paper, a fiber processing,
And a coating material used for a conductive paste or the like and an additive thereof. Since it can be applied to the use required as an aqueous solution as described above, the use is not limited to the use shown above.

[0027]

The present invention will be described in more detail with reference to the following examples. The evaluation methods in the examples are as follows. <Viscosity measurement> The aqueous solution composition prepared by the above-mentioned preparation method was measured with a B-type viscometer (manufactured by Tokyo Keiki) at a temperature of 25 ° C.
The viscosity was measured at.

[0028]

Example 1 100 g of carboxymethyl cellulose (degree of carboxymethyl ether group substitution = 0.7) and 3 liters of a mixed acid consisting of sulfuric acid / nitric acid / water = 64.7 / 24.4 / 10.9% by weight were added to 5 liters. Put in reaction vessel, 5
The nitrification reaction is carried out with stirring at ℃ for 1 hour. The product was deoxidized with a centrifuge and immediately washed with a large amount of water to obtain 110 g of carboxymethyl cellulose nitrate.

The carboxymethyl cellulose nitrate obtained had a carboxyl group substitution degree of 0.7 and a nitrate ester group substitution degree of 1.8 as determined from the nitrogen content. 15 g of the obtained carboxymethyl cellulose nitrate ester, 56.1 g of ion-exchanged water, and n were used as the organic solvent.
-Butyl cellosolve (25.5 g) was placed in a separable flask and stirred. Next, 3.4 g of triethylamine was added as a neutralizing agent and completely neutralized and dissolved while heating at 80 ° C. with stirring, and a cycloaliphatic epoxy resin (trade name: Celoxide 2021P / as a stabilizer).
1 g of Daicel Industries Ltd.) was added to obtain an aqueous solution composition. The viscosity of the obtained composition is 200 mPa · se.
c, and the fluidity was good. The viscosity when left at 20 ° C. for 30 days remained at 160 mPa · sec, which was a slight change. In addition, no change in coloring was observed.

[0030]

Example 2 Example 1 was repeated except that the stabilizer was changed to 1 g of cycloaliphatic epoxy resin (trade name: Celoxide 2021P / manufactured by Daicel Industries Ltd.) and 0.2 g of lactic acid.
An aqueous solution composition similar to the above was obtained. The viscosity of the obtained composition was 200 mPa · sec, and the fluidity was good. Viscosity of 185 mPas when left at 20 ° C for 30 days
There was almost no change from ec, and the stability over time was good. In addition, no change in coloring was observed.

[0031]

Example 3 Stabilizers were used as phosphites (trade name:
An aqueous solution composition similar to that of Example 1 was obtained except that JP-333E / Johoku Chemical Industry Co., Ltd.) was changed to 1 g. The viscosity of the obtained composition was 200 mPa · sec, and the fluidity was good. The viscosity when left at 20 ° C. for 30 days remained at 150 mPa · sec, which was a slight change.

[0032]

Example 4 The same as Example 1 except that the stabilizer was changed to 1 g of a cycloaliphatic epoxy resin (trade name: Celoxide 2021P / manufactured by Daicel Industries Ltd.) and 0.2 g of maleic acid. An aqueous solution composition of The composition obtained had a viscosity of 210 mPa · sec and good fluidity. Viscosity of 185m when left at 20 ℃ for 30 days
There was almost no change from Pa · sec, and the temporal stability was good. In addition, no change in coloring was observed.

[0033]

Example 5 100 g of carboxymethyl cellulose (degree of carboxymethyl ether group substitution = 0.5) and 3 liters of mixed acid consisting of sulfuric acid / nitric acid / water = 62.6 / 25.0 / 12.4% by weight were added to 5 liters. Put in reaction vessel, 5
The nitrification reaction is carried out with stirring at ℃ for 1 hour. The product was deoxidized with a centrifuge and immediately washed with a large amount of water to obtain 120 g of carboxymethyl cellulose nitrate.

The obtained carboxymethyl cellulose nitrate had a carboxyl group substitution degree of 0.5 and a nitrate ester group substitution degree of 2.0 as determined from the nitrogen content.
Obtained carboxymethyl cellulose nitrate 15
g, ion-exchanged water 56.1 g, and n-butyl cellosolve 25.5 g as an organic solvent were put in a separable frus and stirred. Next, 3.4 g of triethylamine was added as a neutralizing agent and completely neutralized and dissolved by heating at 80 ° C. with stirring, and a cycloaliphatic epoxy resin (trade name: Celoxide 2021P / as a stabilizer). 1 g of Daicel Industries Ltd.) was added to obtain an aqueous solution composition. The viscosity of the obtained composition is 600 mPa · sec.
And the fluidity was good. The viscosity when left at 20 ° C. for 30 days showed almost no change to 550 mPa · sec, and the stability with time was good. In addition, no change in coloring was observed.

[0035]

Example 6 Example 5 was repeated except that the stabilizer was changed to 1 g of cycloaliphatic epoxy resin (trade name: Celoxide 2021P / manufactured by Daicel Industries Ltd.) and 0.2 g of lactic acid.
An aqueous solution composition similar to the above was obtained. The composition obtained had a viscosity of 700 mPa · sec and good fluidity. Viscosity of 670 mPas when left at 20 ° C for 30 days
There was almost no change from ec, and the stability over time was good. In addition, no change in coloring was observed.

[0036]

Example 7 100 g of carboxymethyl cellulose (degree of carboxymethyl ether group substitution = 0.7) and 3 liters of a mixed acid consisting of sulfuric acid / nitric acid / water = 58.8 / 20.2 / 21.0% by weight were added to 5 liters. Put in reaction vessel, 5
The nitrification reaction is carried out with stirring at ℃ for 1 hour. The product was deoxidized with a centrifuge and immediately washed with a large amount of water to obtain 100 g of carboxymethyl cellulose nitrate.

The carboxymethyl cellulose nitrate ester thus obtained had a carboxyl group substitution degree of 0.7 and a nitrate ester group substitution degree of 1.0 determined from the nitrogen content.
Obtained carboxymethyl cellulose nitrate 10
g, ion-exchanged water 68.8 g, and isopropyl alcohol 18 g as an organic solvent were placed in a separable flask and stirred. Next, 3.2 g of 28% ammonia water was added as a neutralizing agent and completely neutralized and dissolved by heating at 80 ° C. with stirring, and 0.5 g of citric acid was added as a stabilizer to obtain an aqueous solution. A solution composition was obtained. The viscosity of the obtained composition was 5700 mPa · sec, and the fluidity was good. Viscosity of 560 when left at 20 ℃ for 30 days
There was almost no change from 0 mPa · sec, and the stability over time was good. In addition, no change in coloring was observed.

[0038]

Comparative Example 1 Carboxymethyl cellulose nitrate was obtained in the same manner as in Example 5. 15 g of the obtained carboxymethyl cellulose nitrate ester and ion-exchanged water 56.
1 g and n-butyl cellosolve 25.5 as an organic solvent
and g were placed in a separable flask and stirred. Next, 3.4 g of triethylamine was added as a neutralizing agent, and the mixture was completely neutralized and dissolved while heating at 80 ° C. with stirring to obtain an aqueous solution composition. The viscosity of the obtained composition is
It was 600 mPa · sec, and the fluidity was good.
However, the viscosity when left at 20 ° C for 30 days is 350 mP.
The change with time was a large.

[0039]

The aqueous solution composition of the present invention comprises a paint, a plastic paint, a leather paint, a magnetic paint, a printing ink, a paper coating, a film processing, a thermal paper, a fiber processing,
Also, it can be used as a functional coating material such as a conductive paste. In this case, the water-based functional coating material has improved drying property, heat-resistant blocking property, etc., and the organic solvent can be significantly reduced, and air pollution by the volatile solvent,
Problems such as deterioration of working environment and fire risk are improved.

Further, the aqueous solution composition of the present invention itself and the coating composition containing the aqueous solution composition, such as a coating composition and a printing ink, are effective in long-term practical aging stability such as distribution and storage. Demonstrate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08K 5/524 C09D 101/32 PCT // C09D 5/24 PPT 11/08 PTJ

Claims (1)

[Claims] 1. A nitrate ester of carboxyalkyl cellulose having a degree of substitution with a nitrate ester group of 0.2 or more and a degree of substitution with a carboxyalkyl ether group of 0.05 or more per anhydrous glucose unit, water, an organic solvent, and neutralization. In the aqueous solution composition obtained by mixing the agents, one or more of an epoxy compound, an organic phosphorus compound, a phosphoric acid derivative and a pyrophosphate, a phenolic compound, an oxy acid, a dicarboxylic acid, a fatty acid, or a stabilizer is further added. An aqueous solution composition comprising two or more kinds.