JPH10338714A - New polyvinyl alcohol derivative - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyvinyl alcohol derivative giving an aqueous solution having high transparency, exhibiting excellent thickening effect by the addition of only a small amount of the compound, causing little viscosity variation by the presence of salt or the temperature change, having excellent dispersion stabilizing action and useful as a thickening agent, dispersing agent, etc., for building material, etc. SOLUTION: This new polyvinyl alcohol derivative has a structure obtained by optionally substituting a part or total of the H atoms of the OH groups of a PVA with a group of the formula (X)1 -(Y)m -H, substituting a part of the H atoms of the OH groups of a compound (A) obtained by the above process with a group of the formula Z-R and substituting a part or total of the H atoms of the OH groups remaining on a compound (B) obtained by the above process with a group of the formula (K)n -SO3 M. The compounds A and B may be crosslinked with a polyol polyglycidyl ether. In the above formulas, X and Y are each a 2-3C oxyalkylene; (l) and (m) are each 0-20; Z is CH2 CH(OH)CH2 O, CH2 CH(OH) or CO; R is a 6-40C alkyl, or alkenyl; K is a 1-5C alkylene which may have OH as a substituent; (n) is 0 or 1; M is H, an alkali metal, an alkaline earth metal, ammonium group or a substituted ammonium group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel polyvinyl alcohol derivative, and more particularly to a novel polyvinyl alcohol derivative which is excellent in transparency when used as an aqueous solution, exhibits excellent thickening at a low concentration, and exhibits a coexistence of a metal salt and a change in temperature. The present invention relates to a novel polyvinyl alcohol derivative which exhibits little change in aqueous solution viscosity and exhibits extremely good emulsion stability.

[0002]

2. Description of the Related Art Cosmetics, skin care products, hair cosmetics,
As one of the important components such as toiletry products, external medicines, water reducing agents for building materials, water-soluble paints, sizing agents, printing agents, paper processing sizing agents, various cellulose ethers are used as thickeners and gelling agents. Widely used as excipients, emulsion stabilizers and flocculants. Examples of such cellulose ethers include methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, water-soluble nonionic cellulose ethers such as ethylhydroxyethylcellulose, carboxymethylcellulose, cationized cellulose, and cationized hydroxyethylcellulose. Cellulose ethers and the like are commercially available and used.

[0003] Although these cellulose ethers are relatively superior in viscosity stability of an aqueous solution in the presence of an inorganic metal salt and an organic metal salt as compared with a polyacrylic acid thickener such as Carbopol, Low viscosity at the same aqueous solution concentration, especially when used as a thickener or emulsion stabilizer for cosmetics and toiletry products, it is necessary to use a large amount of cellulose ethers in order to fully exhibit the properties. Was. However, if cellulose ethers are blended in a large amount, stickiness, a problem on the touch surface such as film feeling occurs, and the change with temperature change is large,
There is a disadvantage that it is difficult to maintain a stable product form.

[0004]

As described above, these cellulose ethers and polyacrylic acid-based thickeners are ideal for use in cosmetics, toiletry products, building materials, textile / paper treatment agents, paints, and the like. Performance required as a thickener, that is, it dissolves easily and has an excellent thickening effect, and the coexistence of metal salts, surfactants, oils and other additives, and the effect on viscosity due to changes in temperature and pH. However, it did not fully satisfy all of the following factors: low change in viscosity over time, low stickiness, etc., excellent use feeling, and excellent microbial resistance.

Accordingly, an object of the present invention is to provide a thickener which sufficiently satisfies the above-mentioned properties.

[0006]

Under such circumstances, the present inventors have conducted intensive studies and as a result, obtained by introducing an alkyl group or an alkenyl group and a sulfonic acid group into polyvinyl alcohol or its alkylene oxide adduct. A novel polyvinyl alcohol derivative is excellent in water solubility, its aqueous solution shows a high viscosity at a low concentration, and an inorganic metal salt,
It is hardly affected by organic metal salts, surfactants, pH, temperature, etc., shows stable thickening, shows excellent emulsion stabilizing action, and furthermore, cosmetics, toiletry products, external medicines, building materials, paints, fibers, It has been found that when used in products such as paper processing agents, it has a good feeling of use, and the present invention has been completed.

That is, according to the present invention, a part or all of the hydrogen atoms of the hydroxyl group of polyvinyl alcohol has the following group (a):

-(X) _1- (Y) _m -H (a) wherein X and Y may be the same or different;
_{H 2 CH 2 O -, -} CH 2 CH (CH 3) O- or -CH (C
H ₃ ) CH ₂ O—, and 1 and m each represent a number of 0 to 20. ]

In the polyol compound [compound (A)] which may be substituted with a part of the hydroxyl group, a part of the hydrogen atom of the following group (b)

-ZR (b) wherein Z is -CH ₂ CH (OH) CH ₂ O-, -CH ₂ C
H (OH)-or -CO- is shown, and R represents a linear or branched alkyl or alkenyl group having 6 to 40 carbon atoms. ]

[Compound (B)] (wherein compound (A) or compound (B) may be cross-linked by polyol polyglycidyl ethers) and remains in compound (B). A part or all of the hydrogen atoms of the hydroxyl group is the following group (c)

-(K) _n -SO ₃ M (c) wherein K is 1 to 5 carbon atoms which may be substituted by a hydroxyl group.
N represents 0 or 1, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a substituted ammonium group. And a polyvinyl alcohol derivative.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The degree of condensation of the polyvinyl alcohol skeleton in the polyvinyl alcohol derivative of the present invention is not particularly limited, but is 20 to 100,000, particularly 100 to 1
0,000 is preferred. If the condensation degree is less than 20, good thickening cannot be obtained with a small amount, and if it exceeds 100,000, the solubility in water decreases.

In the compound (A), the group (a) is formed by adding ethylene oxide and / or propylene oxide to the polyvinyl alcohol.
This added mole number is 1 in the formula (a) for the purpose of increasing water solubility without lowering the viscosity stability against temperature change.
And m, from 0 to 0 per substituted hydroxyl group
It is necessary to be 40, and 0 to 20, particularly 0 to 10 is preferable.

The compound (A) or the compound (B) described below may be cross-linked by a polyol polyglycidyl ether. The cross-linking rate, that is, the ratio of cross-linked hydroxyl groups, depends on the viscosity and the solubility in water. In view of the above, 0.001 to 5%, particularly preferably 0.001 to 1% of the total hydroxyl groups of the compound before crosslinking is preferred.

The compound (B) is obtained by substituting a part of the hydrogen atom of the hydroxyl group of the compound (A) with the group (b). R in the group (b) is a linear or branched alkyl group or alkenyl group having 6 to 40 carbon atoms,
2, especially the range of 12-18 is preferred. Also, as Z,-
CH ₂ CH (OH) CH ₂ O— is particularly preferred.

The degree of substitution by the group (b) in the polyvinyl alcohol derivative of the present invention is preferably 0.0001 to 0.4, particularly preferably 0.001 to 0.2 per monohydroxyl group of the compound (A).

The group (c) is substituted for part or all of the hydrogen atoms of the remaining hydroxyl groups in the compound (B), and the remaining hydroxyl groups include those having a polyvinyl alcohol skeleton and those having a crosslink. And any of the groups (b). Examples of the group (c) include a sulfo group, a 2-sulfoethyl group, a 3-sulfo-2-hydroxypropyl group, and salts thereof, and a 2-sulfoethyl group, 3-sulfo-2
-Hydroxypropyl groups, their salts are preferred.

The degree of substitution by the group (c) in the polyvinyl alcohol derivative of the present invention is preferably from 0.001 to 0.6, particularly preferably from 0.01 to 0.5, per monohydroxyl group of the compound (A).

The polyvinyl alcohol derivative of the present invention comprises
For example, after partially hydrophobizing the hydrogen atom of the hydroxyl group of polyvinyl alcohol or its alkylene oxide adduct [uncrosslinked compound (A)] (introducing a hydrophobic substituent (b)) and performing necessary crosslinking, It can be produced by sulfonating all or a part of the remaining hydroxyl groups (introducing a sulfoalkyl group (c)).

The hydrophobizing reaction and the cross-linking reaction can be carried out by reacting the uncross-linked compound (A) with a hydrophobizing agent and a cross-linking agent in the presence of an alkali or an acid.

Examples of the hydrophobizing agent include α-epoxyalkanes (or alkenes), alkyl (or alkenyl) glycidyl ethers, and alkyl (or alkenyl) having an alkyl or alkenyl group corresponding to R in the group (b).
Esters and the like. These hydrophobizing agents can be used alone or in combination of two or more. In addition, the amount of the hydrophobizing agent used, the group (b) to the polyvinyl alcohol
Can be appropriately adjusted according to the introduction amount, but usually, compound (A)
Is preferably 0.0001 to 1.5 equivalents, particularly preferably 0.001 to 1.0 equivalent, to the number of hydroxyl groups.

Examples of the polyol polyglycidyl ether as a crosslinking agent include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, polyglycerin polyglycidyl ether, erythritol diglycidyl ether, erythritol triglycidyl ether. Examples include glycidyl ether, pentaerythritol diglycidyl ether, pentaerythritol triglycidyl ether, pentaerythritol tetraglycidyl ether, sorbitol diglycidyl ether, sorbitol triglycidyl ether, sorbitol tetraglycidyl ether, sorbitol pentaglycidyl ether, and sorbitol hexaglycidyl ether. Of these, ethylene glycol diglycidyl ether and polyethylene glycol diglycidyl ether are preferred for the purpose of imparting sufficient water solubility. These polyol polyglycidyl ethers,
They can be used alone or in combination of two or more. The amount used can be appropriately adjusted according to the desired degree of crosslinking, but is preferably 0.001 to 20 mol%, particularly preferably 0.001 to 5 mol%, based on all hydroxyl groups of the compound before crosslinking.

The alkali used when the hydrophobizing reaction and the cross-linking reaction are carried out in the presence of an alkali is not particularly restricted but includes hydroxides, carbonates, bicarbonates of alkali metals or alkaline earth metals. Among them, sodium hydroxide, potassium hydroxide, calcium hydroxide, magnesium hydroxide and the like are preferable. The amount of the alkali used is 0.01 to 10 times the amount of the hydrophobizing agent and the crosslinking agent used,
In particular, a molar amount of 0.1 to 0.5 gives good results and is preferred.

When the reaction is carried out in the presence of an alkali, the reaction temperature is preferably in the range of 0 to 200 ° C., particularly preferably in the range of 30 to 100 ° C. After completion of the reaction, the alkali is neutralized with an inorganic acid such as sulfuric acid, hydrochloric acid, phosphoric acid, or the like, or an organic acid such as acetic acid. When a haloalkanesulfonic acid salt such as hydroxypropanesulfonic acid salt is used, it can be directly subjected to a sulfonation reaction without neutralization.

When the hydrophobizing reaction and the cross-linking reaction are carried out in the presence of an acid, the acid is not particularly limited.
Mineral acids such as hydrochloric acid, boron trifluoride, aluminum chloride,
Any of Lewis acids such as zinc chloride, titanium tetrachloride, tin tetrachloride and the like can be used.However, boron trifluoride, zinc chloride, zinc chloride, etc. It is preferable to use a Lewis acid such as The amount of the acid to be used is preferably 0.01 to 1.0 mol times, particularly preferably 0.03 to 0.1 mol times with respect to the hydrophobizing agent and the cross-linking agent to be used.

When the reaction is carried out in the presence of an acid, the reaction temperature varies depending on the acid used, but is -78 to 150 ° C, particularly 0 to 120 ° C.
Is preferable. After the completion of the reaction, the acid is neutralized using an alkali. However, when chlorosulfonic acid, sulfur trioxide, sulfuric acid, or the like is used in the next sulfonation reaction, the acid is subjected to the sulfonation reaction without neutralization. You can also.

The hydrophobizing / crosslinking reaction can be carried out without solvent, but a solvent can be used as appropriate. When the alkali is used, examples of the solvent include water and lower alcohols such as isopropyl alcohol and tert-butyl alcohol.
A mixed solvent to which の 50% by weight of water is added can also be used. As a solvent when an acid is used, aromatic solvents such as benzene, toluene and xylene; halogen solvents such as methylene chloride, chloroform and carbon tetrachloride; hydrocarbon solvents such as hexane, cyclohexane and decane; diethyl ether; Ether solvents such as diisopropyl ether, tetrahydrofuran and 1,4-dioxane; and aprotic polar solvents such as dimethylformamide, dimethylsulfoxide and 1,3-dimethyl-2-imidazolidinone.

Next, the sulfonation reaction can be carried out by reacting the hydrophobized polyvinyl alcohol obtained by the above reaction with a sulfonating agent in the presence or absence of an alkali or an acid.

Examples of the sulfonating agent include vinyl sulfonic acid, halo C ₁ -C ₅ alkane sulfonic acid optionally substituted with a hydroxyl group, a salt thereof, and the like, which can be sulfonated with an alkali catalyst, chlorosulfonic acid, Any of those which can be sulfonated with or without an acid catalyst, such as sulfur oxide and sulfuric acid, can be used. Examples of the halo C ₁ -C ₅ alkanesulfonic acid which may be substituted with a hydroxyl group include 3-halo-2-hydroxypropanesulfonic acid,
Examples include halo-2- (hydroxymethyl) ethanesulfonic acid, 3-halopropanesulfonic acid, and 2-haloethanesulfonic acid, and examples of the substituted halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Particularly preferred sulfonating agents include vinyl sulfonate and 3-chloro-2-hydroxypropane sulfonate. These sulfonating agents can be used alone or in combination of two or more. The amount of the sulfonating agent can be appropriately adjusted according to the amount of the group (c) introduced into the polyvinyl alcohol,
Usually, it is 0.
A range of 001 to 5 equivalents is preferred.

As the alkali catalyst and the acid catalyst used in the sulfonation reaction, the same ones as described in the hydrophobization / crosslinking reaction can be exemplified. The amount of the alkali used is preferably 1.0 to 3.0 mole times, more preferably 1.05 to 1.5 mole times, based on the sulfonating agent used, and the amount of the acid used is 0 to 0.1 mole times the sulfonating agent used.
In particular, a molar amount of 0 to 0.05 is preferable.

When the reaction is carried out in the presence of an alkali, the reaction temperature is preferably from 0 to 150 ° C., particularly preferably from 30 to 100 ° C. When performing the reaction in the presence of an acid or in the absence of a catalyst, -78 to 150 ° C,
Particularly, the range of 0 to 100 ° C is preferable.

Although the sulfonation reaction can be carried out without a solvent, it can also be carried out using the same solvent as the hydrophobic / crosslinking reaction.

After the sulfonation reaction, the reaction is neutralized with an acid when an alkali is used, or with an alkali when an acid is used.
After separation by filtration and the like, washing and the like are performed as necessary, and then drying, the polyvinyl alcohol derivative of the present invention can be obtained as a purified product. You can also.

[0035]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto.

Example 1 A 500 ml separable flask was charged with polyvinyl alcohol (weight average molecular weight 31,000 to 50,000, manufactured by Aldrich).
100 g, 5 g of stearyl glycidyl ether, 5 g of caustic soda and 50 g of water were added and reacted at 80 ° C. for 5 hours. Thereafter, 200 g of water, 40 g of sodium 3-chloro-2-hydroxypropanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of caustic soda were added and reacted at 50 ° C. for 3 hours. After completion of the reaction, the obtained gel was neutralized with hydrochloric acid, precipitated by adding a large amount of isopropyl alcohol, further washed twice with an 85% isopropyl alcohol aqueous solution, decanted, and dried in a vacuum dryer. After drying at 8 ° C. for 8 hours, 95 g of a polyvinyl alcohol derivative (Product 1 of the present invention) was obtained.

The obtained polyvinyl alcohol derivative 3-
The degree of substitution of the stearyloxy-2-hydroxypropyl group was 0.018 based on the results of iodine stearylation with hydrogen iodide and the results of gas chromatographic determination thereof.
The degree of substitution of the 2-hydroxypropyl group was 0.19 as a result of colloid titration.

Example 2 In a 1000 ml separable flask, polyvinyl alcohol (weight average molecular weight: 31,000 to 50,000, manufactured by Aldrich)
100 g, stearyl glycidyl ether 2 g, ethylene glycol diglycidyl ether 0.5 g, caustic soda 5
g and 50 g of water, and reacted at 80 ° C. for 25 hours. Thereafter, 200 g of water, 160 g of a 25% aqueous solution of sodium vinyl sulfonate (manufactured by Aldrich) and 10 g of caustic soda were added and reacted at 50 ° C. for 6 hours. After completion of the reaction, the obtained gel was neutralized with hydrochloric acid, precipitated by adding a large amount of isopropyl alcohol, further washed four times with an 85% aqueous isopropyl alcohol solution, decanted, and dried in a vacuum dryer. Drying at 9 ° C. for 9 hours gave 93 g of a polyvinyl alcohol derivative (Product 2 of the present invention).

The obtained polyvinyl alcohol derivative 3-
The degree of substitution of the stearyloxy-2-hydroxypropyl group was 0.006 from the results of iodine stearylation with hydrogen iodide and the result of gas chromatography, and the degree of substitution of the sulfoethyl group was 0.18 from the results of colloid titration. .

Example 3 A 500 ml separable flask was charged with polyvinyl alcohol polyoxyethylene (weight average molecular weight 40,000-60,000).
120 g, 5 g of stearyl glycidyl ether, 5 g of caustic soda and 100 g of water were added and reacted at 80 ° C. for 8 hours. Thereafter, 200 g of water, 40 g of sodium 3-chloro-2-hydroxypropanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 g of caustic soda were added and reacted at 50 ° C. for 5 hours. After completion of the reaction, the obtained gel was neutralized with hydrochloric acid, precipitated by adding a large amount of isopropyl alcohol, further washed three times with an 85% isopropyl alcohol aqueous solution, decanted, and dried with a vacuum dryer. Drying at 8 ° C. for 8 hours gave 98 g of a polyvinyl alcohol derivative (Product 3 of the present invention).

The obtained polyvinyl alcohol derivative 3-
The degree of substitution of the stearyloxy-2-hydroxypropyl group was 0.011 based on the results of iodine stearylation with hydrogen iodide and the results of gas chromatography determination thereof, and the sulfo-
The degree of substitution of the 2-hydroxypropyl group was 0.20 from the result of colloid titration.

Example 4 A 1000 ml separable flask was charged with polyvinyl alcohol polyoxyethylene (weight average molecular weight 40,000-60,000).
120 g, stearyl glycidyl ether 5 g, ethylene glycol diglycidyl ether 1.0 g, caustic soda 5
g and 100 g of water, and reacted at 80 ° C. for 8 hours.
Thereafter, 200 g of water, 50 g of sodium 3-chloro-2-hydroxypropanesulfonate (manufactured by Tokyo Kasei) and caustic soda
15 g was added and the reaction was carried out at 50 ° C. for 5 hours. After completion of the reaction, the obtained gel was neutralized with hydrochloric acid, precipitated by adding a large amount of isopropyl alcohol, further washed three times with an 85% isopropyl alcohol aqueous solution, decanted, and dried with a vacuum dryer. After drying at 8 ° C. for 8 hours, 107 g of a polyvinyl alcohol derivative (Product 4 of the present invention) was obtained.

The obtained polyvinyl alcohol derivative 3-
The degree of substitution of the stearyloxy-2-hydroxypropyl group was 0.008 from the results of iodine stearylation with hydrogen iodide and the results of gas chromatographic determination thereof.
The degree of substitution of the 2-hydroxypropyl group was 0.27 from the result of colloid titration.

Comparative Example 1 A comparative product 1 was prepared using sodium polyacrylate (Carbopol 941, manufactured by Goodrich) as it was.

Test Example 1 Thickening test The products 1 to 4 of the present invention and the comparative product 1 were prepared by adding water and 0.3% by weight of NaCl
An aqueous solution was prepared by dissolving 0.5% by weight in each of the aqueous solutions. These viscosities were measured by a B-type viscometer (12 rpm, 1 minute). Table 1 shows the results.

[0046]

[Table 1]

Test Example 2 Emulsion Stability Test 20% by weight of isopropyl palmitate (ester oil) was added to a 0.2% by weight aqueous solution of the products 1 to 4 of the present invention and Comparative product 1, and a homogenizer (6,000 rpm, 1 minute) To prepare an emulsion. The stability when this emulsion was stored at 40 ° C. for one month was visually determined. Table 2 shows the results.

[0048]

[Table 2]

The novel polyvinyl alcohol derivative of the present invention has excellent thickening and emulsion stability, as evident from the viscosity increasing test (Test Example 1: Table 1) and the emulsion stability test (Test Example 2: Table 2). It exhibits excellent properties and does not impair the viscosity increase even in the presence of a salt, and is extremely excellent as a thickener and an emulsifier.

[0050]

The novel polyvinyl alcohol derivative of the present invention exhibits an excellent thickening / emulsifying effect even when added in a small amount, and gives an emulsion which exhibits little change in viscosity due to coexistence of salts and temperature and has extremely excellent stability. Therefore, the novel polyvinyl alcohol derivative of the present invention can be used as a thickener, a gelling agent, an emulsion stabilizer and the like for cosmetics, toiletry products, external medicines, building materials, water-soluble paints, sizing agents, printing agents, paper processing sizing agents and the like. Can be widely used.

Claims (5)

[Claims] 1. A part or all of the hydrogen atoms of hydroxyl groups of the polyvinyl alcohol of the following groups _{(a) - (X) l} - (Y) m -H (a) wherein, X and Y be the same or different -C
_{H 2 CH 2 O -, -} CH 2 CH (CH 3) O- or -CH (C
H ₃ ) CH ₂ O—, and 1 and m each represent a number of 0 to 20. ] Some of the hydroxyl groups the hydrogen atoms of the good polyol compound substituted [compound (A)], the in the next group (b) -Z-R (b ) [wherein, Z is -CH ₂ CH ( _{OH) CH 2 O -, -} CH 2 C
H (OH)-or -CO- is shown, and R represents a linear or branched alkyl or alkenyl group having 6 to 40 carbon atoms. [The compound (B)] (where the compound (A) or the compound (B) may be cross-linked by a polyol polyglycidyl ether) and the hydroxyl group remaining in the compound (B) A part or all of the hydrogen atoms represented by the following groups (c)-(K) _n -SO ₃ M (c) wherein K is 1 to 5 carbon atoms which may be substituted by a hydroxyl group.
N represents 0 or 1, and M represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, an ammonium group or a substituted ammonium group. And a polyvinyl alcohol derivative. 2. The compound (A) has a substitution degree per hydroxyl group of 0.001 to 0.4 for the substituent (b) and 0.001 for the substituent (c).
The polyvinyl alcohol derivative according to claim 1, which has a molecular weight of from 0.6 to 0.6. 3. The polyvinyl alcohol derivative according to claim 1, wherein the polyol polyglycidyl ether is ethylene glycol diglycidyl ether or polyethylene glycol diglycidyl ether. 4. R in the group (b) is an alkyl group or alkenyl group having 6 to 22 carbon atoms, and Z is —CH ₂ CH
(OH) a polyvinyl alcohol derivative according to any one of claims 1 to 3 CH ₂ O-in which. 5. The group (c) is a 2-sulfoethyl group, 3-sulfo-
5. A 2-hydroxypropyl group or a salt thereof.
The polyvinyl alcohol derivative according to any one of the above.