JP2000086851A - Composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide aqueous compositions which are excellent in storage stability of its solution and give coated films being high in water resistance. SOLUTION: Aqueous compositions comprise (A) a carboxyalkyl cellulose nitrate ester and (B) a vinyl alcohol based polymer containing at least one monomer unit selected from the group consisting of a >=6C fatty acid vinyl ester, an α-olefin and >=4C vinyl ether and an amine or an ammonium salt in the molecule.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous composition such as a paint, a printing ink, a paper processing agent, a film processing agent, a leather coating, a fiber processing agent and the like.

[0002]

2. Description of the Related Art Conventionally, cellulose esters such as nitrocellulose and cellulose acetate butyrate have been used as functional materials such as paints, plastic paints, printing inks, paper processing agents, and fiber processing agents in view of drying and heat resistance. It's being used. However, cellulose esters such as nitrocellulose and cellulose acetate butyrate may use a large amount of an organic solvent, which may cause air pollution and deterioration of the working environment due to the volatile solvent. Also,
Aqueous cellulose acetate butyrate has the problem that it is physically unstable, for example, it undergoes hydrolysis due to aging during storage and thickens. In order to solve these problems, nitric acid esters of carboxyalkyl cellulose have been proposed (JP-A-5-39301,
JP-A-5-39302).

[0003] However, although the viscosity stability and the like are improved, there is a problem that the water resistance of a film formed after drying is low because the film is inherently aqueous.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide an aqueous composition which is excellent in storage stability of a solution and in which the resulting film has high water resistance.

[0005]

Means for Solving the Problems The inventors of the present invention have made intensive studies on the above-mentioned objects and found that carboxyalkyl cellulose nitrate (A), fatty acid vinyl ester having 6 or more carbon atoms, α-olefin And an aqueous composition comprising a vinyl alcohol-based polymer (B) containing at least one monomer unit selected from the group consisting of vinyl ethers having 4 or more carbon atoms and containing an amine or ammonium salt in the molecule. Found to be suitable for the initial purpose.

The carboxyalkyl cellulose nitrate (A) constituting the composition of the present invention is obtained by introducing a nitrate ester group by treating carboxyalkyl celluloses such as carboxymethyl cellulose and carboxyethyl cellulose with a mixed acid of sulfuric acid and nitric acid. It is an aqueous cellulose derivative.

The degree of substitution of the nitrate ester group is 0.2 or more per anhydroglucose unit. If the nitrate ester group substitution degree is less than 0.2, the pigment dispersion stability becomes insufficient.

The degree of substitution of the carboxyalkyl ether group is
A unit having an amount of 0.05 or more per anhydroglucose unit is used. The degree of carboxyalkyl ether group substitution is 0.
If it is less than 05, the solubility in water becomes insufficient.

The composition of the present invention contains at least one monomer unit selected from the group consisting of a fatty acid vinyl ester having 6 or more carbon atoms, an α-olefin and a vinyl ether having 4 or more carbon atoms, and The vinyl alcohol-based polymer (B) containing an amine or ammonium salt in the molecule (hereinafter sometimes abbreviated as PVA) can be obtained by various methods. For example, the following method can be mentioned. (1) At least one monomer selected from the group consisting of fatty acid vinyl esters having 6 or more carbon atoms, α-olefin and vinyl ether having 4 or more carbon atoms, and an ethylenically unsaturated monomer having an amine or ammonium salt And a method in which a vinyl ester monomer such as vinyl acetate is copolymerized and then saponified by a known method. (2) at least one monomer selected from the group consisting of a fatty acid vinyl ester having 6 or more carbon atoms, an α-olefin and a vinyl ether having 4 or more carbon atoms, and an ethylenically unsaturated monomer having an epoxy group such as allyl glycidyl ether; A method in which a mercaptan having an amine or an ammonium salt is added to a side chain epoxy group of a copolymer comprising a saturated monomer and a vinyl ester-based monomer such as vinyl acetate, using NaOH or the like as a catalyst, followed by saponification. . (3) It can react with a hydroxyl group of a vinyl alcohol polymer having at least one monomer unit selected from the group consisting of a fatty acid vinyl ester having 6 or more carbon atoms, an α-olefin and a vinyl ether having 4 or more carbon atoms. A method in which a compound having a functional group in a molecule and having an amine or ammonium salt is reacted with a vinyl alcohol-based polymer. (4) A vinyl alcohol polymer having at least one monomer unit selected from the group consisting of a fatty acid vinyl ester having 6 or more carbon atoms, an α-olefin and a vinyl ether having 4 or more carbon atoms, and having a mercapto group. A method in which an ethylenically unsaturated monomer having an amine or ammonium salt is polymerized in the presence of coalescence. In this method, a polyvinyl alcohol-based block polymer is obtained. The PVA used in the present invention includes the above-mentioned synthesis methods. Although not limited to these synthesis methods,
Generally, the above method (1) is suitably used.

In the above method (1) and the like, as the fatty acid vinyl ester monomer used for copolymerization with vinyl acetate, for example, vinyl pivalate, vinyl laurate, vinyl stearate and the like can be mentioned. Carboxyl groups such as 1,1,3,3-tetramethylbutyric acid vinyl ester, 2,2,4,4-tetramethylvaleric acid vinyl ester or saturated branched fatty acid vinyl ester having an average of 10 carbon atoms are tertiary or quaternary; Preferred are branched fatty acid vinyl esters present at the α-position to the lower carbon atom.

In the above method (1) and the like, α-olefin monomers used for copolymerization with vinyl acetate include ethylene, propylene, 1-hexene, 1-octene, 1-decene and 1-dodecene. , Linear α-olefins such as 1-tetradecene and branched α-olefins such as isobutylene, 2-methyl-1-butene and 3,3,4,4-tetramethyl-1-pentene. Used.

In the above method (1) and the like, the vinyl ether having 4 or more carbon atoms used in the copolymerization with vinyl acetate includes ethyl vinyl ether, n-propyl vinyl ether, i-propyl vinyl ether, n-butyl vinyl ether, -Butyl vinyl ether, decyl vinyl ether and the like are used.

In the above method (1) and the like, the ethylenically unsaturated monomer having an ammonium salt used in copolymerization with vinyl acetate includes (meth) acrylamidopropyltrimethylammonium chloride, (meth)
Ethylene unsaturated monomer having a known ammonium salt such as acryloyloxyethylammonium chloride, allyltrimethylammonium chloride, 3-butenyltrimethylammonium chloride, diallyldimethylammonium chloride, and dimethylaminopropyl
Examples include known ethylenically unsaturated monomers having an amine such as (meth) acrylamide, allyldimethylamine, and 3-butenyldimethylaminediallylmethylamine. Further, in the above method (3), the compound has a functional group capable of reacting with a hydroxyl group of the vinyl alcohol polymer in the molecule,
Examples of the compound having an amine or an ammonium salt include an epoxy compound such as glycidyltrimethylammonium chloride.

The PVA constituting the composition of the present invention contains at least one monomer unit selected from the group consisting of fatty acid vinyl esters having 6 or more carbon atoms, α-olefins and vinyl ethers having 4 or more carbon atoms. Although it is a vinyl alcohol polymer containing an amine or ammonium salt in the molecule, it may have any other functional group as long as the effects of the present invention are not impaired. Examples of the monomer unit that provides such a functional group include acrylonitrile, methacrylonitrile, acrylic acid, methacrylic acid, (anhydrous) fumaric acid, (anhydride) maleic acid, (anhydride) itaconic acid, allylsulfonic acid, and methallyl. Sulfonic acid, vinylsulfonic acid, acrylamide-2-methylpropanesulfonic acid, methacrylamide-2-methylpropanesulfonic acid, sulfopropyl acrylate, sulfopropyl methacrylate and their alkali salts, acrylamide, methacrylamide, N-vinylpyrrolidone , Vinyl chloride, vinyl bromide, vinyl fluoride, vinylidene chloride, vinylidene fluoride, tetrafluoroethylene and the like. Further, those having a functional group at the terminal obtained by polymerizing a vinyl ester monomer such as vinyl acetate in the presence of a thiol compound such as thiolacetic acid or mercaptopropionic acid may be used.

The composition of the present invention comprises (B) at least one monomer unit selected from the group consisting of fatty acid vinyl esters having 6 or more carbon atoms, α-olefins and vinyl ethers having 4 or more carbon atoms. The content of the fatty acid vinyl ester, α-olefin and vinyl ether in the vinyl alcohol-based polymer containing an amine or ammonium salt in the molecule is not particularly limited and may be appropriately selected depending on various situations. Usually, 0.1 to 50 mol%, preferably 0.5 to 45 mol% as a monomer unit,
It is more preferably from 1.0 to 35 mol%, particularly preferably from 3 to 15 mol%. If the amount of the monomer unit is less than 0.1 mol%, the effect may not be sufficiently exhibited, and if it exceeds 50 mol%, the characteristics as a vinyl alcohol polymer may not be sufficiently exhibited. The content of the amine or ammonium salt is not particularly limited and may be appropriately selected depending on various circumstances. Generally, the content of the amine or ammonium salt is 0.1 to 30 mol%, preferably 0.1 to 30 mol%, as a monomer unit containing the functional group. It is 0.3 to 25 mol%, more preferably 0.5 to 10 mol%. If the amount of the functional group is less than 0.1 mol%, the effect of introducing the functional group may not be sufficiently exhibited, while if it exceeds 30 mol%, the inherent properties of polyvinyl alcohol may not be sufficiently exhibited. The degree of polymerization of PVA constituting the composition of the present invention varies depending on the purpose of use, and cannot be unambiguously determined.
The viscosity of a 4% aqueous solution of PVA is preferably 2 mPa · S or more, more preferably 5 mPa · S or more, and 10 mPa · S.
The above is more preferred. The saponification degree of the PVA used in the present invention is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, further preferably 80 mol% or more, and particularly preferably 90 mol% or more.

In the composition of the present invention, the composition ratio may be appropriately selected depending on the composition of the functional groups of (A) and (B), but (A) / (B) is usually 100% based on the solid content. /0.1 to 100/100, preferably 100/1 to 100/9.
0. If the proportion of (B) is less than 0.1,
When the compounding effect of (B) does not appear, and when it is more than 100, the storage stability of the composition decreases.

In the aqueous composition of the present invention, if necessary,
Various cationic polymers such as polyvinyl alcohol, cationized cellulose, diallyl quaternary ammonium salt polymer, diallyl quaternary ammonium salt / acrylamide copolymer, various starches such as starch, modified starch, oxidized starch, cationized starch, sodium alginate , Maleic anhydride-isobutene copolymer, maleic anhydride-styrene copolymer, maleic anhydride-methyl vinyl ether copolymer, and other water-soluble polymer compounds, urea-formalin resin, urea-melamine-formalin resin, phenol- Formalin resin, etc., methanol, ethanol, n-propanol, isopropanol, n-butanol, n-pentanol, n-hexanol, n-octanol, n-nonyl alcohol, n-decanol, n-undecanol or isomers thereof Alcohols such as cyclohexanol, 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,
Polyhydric alcohols such as 9-nonanediol, 1,10-decanediol, glycerin, pentaerythritol, diethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene Glycol monobutyl ether, ethylene glycol monoisobutyl ether, propylene glycol monomethyl ether,
Polyhydric alcohol derivatives such as propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether;
Further, esters such as methyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, citric acid,
Organic acids such as tartaric acid, malic acid, lactic acid, and glycolic acid can also be used as appropriate as long as the performance is not impaired. Further, the aqueous composition of the present invention includes a conventionally known plasticizer such as dibutyl phthalate, a solvent such as toluene, a preservative, a fungicide, an antifoaming agent, clay, kaolin, talc, calcium carbonate, wood powder and the like. Various additives such as a filler, an extender such as flour, and a pigment such as titanium oxide can be appropriately added as necessary.

The composition of the present invention is characterized in that there is little decrease in storage stability and that it has high film water resistance. Therefore, the use of the composition of the present invention, wood, plywood, paper, plastic, fiber, inorganic and other adhesives and treatment agents, various paints, printing inks, molded products such as films and sheets, cement additives and the like It is preferably used.

[0019]

The present invention will be described more specifically below with reference to examples and comparative examples. In Examples and Comparative Examples,
“Parts” and “%” are based on weight unless otherwise specified.

Preparation of nitric acid ester of carboxymethylcellulose: Carbomethoxycellulose (Selogen 5A,
According to a known method, the degree of carboxymethyl ether group substitution and the degree of nitrate ester group substitution per anhydrous glucose unit were 0.7 and 0.7, respectively, using Daiichi Kogyo Seiyaku Co., Ltd., carboxymethyl ether group substitution degree = 0.7). 1.9
(Polymer a) was synthesized.

Preparation of nitric acid solution of carbomethoxycellulose (solution A): 100 g of polymer a, 842.8 g of ion-exchanged water and 200 g of isopropyl alcohol were placed in a closed mixer and stirred. Further, 51.4 g of 10% aqueous ammonia was added as a neutralizing agent. The solution was completely dissolved with heating to obtain a solution having a solid content of 10%.

Preparation of carbomethoxycellulose nitrate solution (solution B): 100 g of polymer a, 863.9 g of ion-exchanged water, and 200 g of isopropyl alcohol were placed in a closed mixer and stirred. Further, 30.3 g of triethylamine was added as a neutralizing agent. The solution was completely dissolved with heating to obtain a solution having a solid content of 10%.

Production of vinyl alcohol-based polymer: According to a known method, PVAs of Polymers 1 to 9 shown in Table 1 were respectively synthesized, dissolved in ion-exchanged water at 90 ° C., and a 10% aqueous solid solution (solution) 1-9) were obtained.

[0024]

[Table 1]

Example 1 Solution A and solution 1 were mixed at a weight ratio of 1: 1 to prepare a mixed solution, and the water resistance and viscosity stability were evaluated by the following evaluation methods. (1) Water resistance test The obtained mixed solution was cast on a Teflon sheet at room temperature,
A 100 μm thick film was obtained. The obtained film was immersed in distilled water at 20 ° C. for 24 hours, the dissolution rate and the degree of swelling were determined from the following formula, and the performance was evaluated according to the following evaluation criteria
The results are shown in Table 2 by symbols. [Formula used for evaluation] Elution rate (%) = {(W1-W2) / (W1)} × 100 Swelling degree (times) = W3 / W2 W1: Weight before immersion W2: Dry weight of film after immersion W3: Weight before immersion of the film before drying [Evaluation criteria] Elution rate 未 満: Less than 15% ○: 15% or more and less than 20% △: 20% or more and less than 30% ×: 30% or more Swelling degree ：: 1.5 times Less than Δ: 1.5 times or more and less than 2.0 times ×: 2.0 times or more (2) Viscosity stability test The obtained mixed solution was sealed in a closed container and left at 40 ° C. for one month. Using a BH type viscometer, the viscosity before and after standing was 40
The thickening ratio was determined from the following equation, and the performance was evaluated according to the following evaluation criteria. The results are shown in Table 2 by symbols. [Formula used for evaluation] Thickening ratio (times) = η2 / η1 η1: Viscosity immediately after solution preparation η2: Viscosity after leaving at 40 ° C. for one month [Evaluation criteria] ○: Less than 1.2 times △: 1.2 Times or more and less than 2.0 ×: 2.0 times or more

Examples 2 to 9 Evaluations were made in the same manner as in Example 1. Table 2 shows conditions and results
Shown in

[0027]

[Table 2]

Comparative Examples 1 to 4 According to a known method, the PV of Comparative Polymers 1 to 4 shown in Table 1 was
A was synthesized respectively, and each was dissolved in ion-exchanged water at 90 ° C. to obtain 10% aqueous solid solution (Comparative Solutions 1 to 4). Evaluation was performed in the same manner as in Example 1. Table 2 shows the conditions and results.

[0029]

EFFECT OF THE INVENTION The composition of the present invention is characterized in that it has little deterioration in storage stability and has high film water resistance. Therefore, the composition of the present invention can be used for wood, plywood, paper,
Adhesives and processing agents for plastics, fibers, inorganic substances, etc., printing inks, various paints, molded products such as films and sheets,
It can be used as a cement additive or the like.

Claims (1)

[Claims] 1. A carboxyalkyl cellulose nitrate (A) and at least one monomer unit selected from the group consisting of fatty acid vinyl esters having 6 or more carbon atoms, α-olefins and vinyl ethers having 4 or more carbon atoms. An aqueous composition comprising a vinyl alcohol polymer (B) containing an amine or ammonium salt in the molecule.