JPS6026863B2 - Thickening composition and method for producing the same - Google Patents

Description

[Detailed description of the invention] The present invention relates to glue compositions.

Conventionally, compositions containing vinyl acetate emulsion as a main ingredient have been used as glues for household use.

This is widely used because it has better dispersibility in water than other powdered glues, such as starch and polyvinyl alcohol, and has excellent finishing effects on colors and patterns. However, conventional liquid glue compositions based on vinyl acetate emulsion are non-ionic and have extremely weak adsorption to clothing, textiles, etc. Therefore, the amount of water used to dilute the liquid glue composition should be reduced to the minimum possible. It is used by diluting it with a small amount of water, for example, the same amount to three times the amount of the clothing to be starched. Although it is good that the liquid starch composition has good dispersibility in water, in actual use, it causes uneven adhesion of the glue and seriously impairs the finish and feel of the starched clothing.
As a result of intensive research to reduce this uneven adsorption of adhesives, the present inventors found that a cationic polymer compound obtained by emulsion polymerization of a vinyl monomer using a cationic polymer or a cationic activator can be used for fibers, It was discovered that it was a starch agent with extremely good adsorption properties for clothing, and it was developed as a starch agent in 1973-1431.
78, Samurai Gansho 52-6609 Hakama Isaki $-8053 disclosed in each specification. Thickening agents using these cationic polymer emulsions as the main ingredient have good adsorption properties to fibers and clothing, so unlike the adhesive compositions based on vinyl acetate emulsions, they cannot be used as a sizing agent when actually used. A large amount of water for diluting the composition can be used, and as a result, uneven adsorption of the adhesive is suppressed, resulting in an extremely good finish and texture. This glue composition containing a cationic polymer that has good adsorption properties for fibers and clothing has good adsorption properties, so even after washing, a portion of the glue composition remains without falling off from the clothing.

Therefore, when washing and sizing are repeated, the sizing agent gradually accumulates and remains on the fibers and clothing, making the texture hard and making it impossible to obtain the desired sizing texture. The present inventors aimed to improve such drawbacks.As a result of further intensive research, we unexpectedly found that a cationic activator, which is sometimes used when synthesizing a cationic polymer emulsion, was used after the synthesis of a cationic polymer emulsion. By using the added material as a sizing agent, the cationic polymer that is the sizing agent easily falls off when washed, and the sizing agent does not deteriorate even after repeated washing and sizing, and the present invention was developed. It was. The present invention provides such a cationic polymer emulsion paste composition with low accumulation and a method for producing the same, in which a vinyl monomer is emulsified using a cationic polymer and/or a cationic activator. A paste composition obtained by adding and mixing a B cationic activator to a cationic polymer emulsion obtained by polymerization, and a method for producing the same.

The cationic polymer emulsion used in the present invention is, for example, Samurai Iso-sho 51-143178
It is disclosed in the specifications of Japanese Patent Application No. 609-8053 and is obtained by emulsion polymerization of vinyl monomers using a cationic polymer and/or a cationic activator. Examples of the cationic polymer as a raw material for the cationic polymer emulsion used in the present invention include the following {i) to 8.

Aminoether of starch or cellulose or derivatives thereof represented by the following general formula '1' (wherein A:
Residues R of starch residues, cellulose residues or derivatives thereof
: alkylene group or hydroxyalkylene group R. , R2: are the same or different, and may contain a hydrogen atom, an alkyl, aryl or aralkyl group, or a nitrogen atom in the formula to form multiple rings.

(a: positive integer) {o} For example, cationic starch or cationic cellulose as shown in the following formula , R3: are the same or different, and may contain an alkyl group, an aryl group, an aralkyl group, or a nitrogen atom in the formula to form multiple rings.

×: Anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfuric acid, phosphoric acid, nitric acid, etc.) E: Positive integer} For example, the weight of vinyl cationic acid represented by the following formula (wherein, R4: hydrogen atom or methyl group, R5, R6, R7: the same or different hydrogen atom, alkyl group or substituted alkyl group having 1 to 4 carbon atoms, Y: oxygen atom or NH in an amide bond) Group, ×: Same as formula ■) Poly(N-methylvinylpyridinium salt) (in the formula, X:
(same as formula ■) Poly(N-vinyl-2,3-dimethylimidazolinium salt) (in the formula, ×: same as formula ■) Among those represented by the formula foot, preferred examples include the following formula {71 Poly(N-acrylamidopropyl-3-trimethylammonium salt) represented by the formula.

(In the formula, ×: Same as the formula ■) 0 A compound represented by the following formula ■ (In the formula, R, 2, R, 8: the same or different alkyl group or substituted alkyl group having 1 to 2 carbon atoms X: Same as formula '2') Among these, the most preferred are quaternary cationized starch represented by formula {21] or quaternary cationized cellulose, but these compounds are not specified.

The amount of the cationic polymer used in producing the cationic polymer emulsion is 0.00% relative to the cationic polymer of the vinyl monomer as the cationic nitrogen content in the cationic polymer of the vinyl monomer. 0.00 to 0.2% by weight. If it is less than 0.004% by weight, it is not sufficiently effective;
．． If the amount exceeds 1% by weight, the performance is good, but it causes coloring of the cationic polymer emulsion and is also economically disadvantageous.

For example, the cationic activator used in the production of the cationic polymer emulsion according to the present invention has the following formulas 00 to (1
There are things like those shown in 6).

◎Quaternary ammonium salt ◎Imidazolinium salt ◎Quaternary amide ammonium salt ◎Cationic polyamide (jetylene triamine or dipropylene triamine 1
About 1 to 2 moles of epichlorohydrin is added to a condensate with an acid value of 10 or less obtained by reacting about 2 moles of a fatty acid having 12 to 24 carbon atoms, and then a reaction mixture is formed in the presence of an alkaline agent. Cationic polyamide compound obtained by polymerizing and then neutralizing with acid).

In the above formula OQ~(16), R2,, R-side R powder and R27 are each an alkyl group having 11 to 22 carbon atoms or an 8-hydroxyalkyl group having 13 to 24 carbon atoms, and R23
, R2J and R25 are each an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms, a benzyl group, or -(
CH2CH20 n' days, and R28 has 12 to 12 carbon atoms.
24 aliphatic groups, n' is 1-3, m' is 2 or 3, and X is an anion.

The cationic surfactants used in the present invention are not necessarily limited to those mentioned above, and other cationic surfactants such as cationic surfactants derived from urea or biuret can also be used.

More preferable cationic activators are those with low solubility and have a total carbon number of 25-6q, preferably 30-6q.
50 is good. The amount of cationic activator used is from 0.1% to 3%, preferably from 0.2 to 1.5% by weight of the total emulsion system. The vinyl monomer used to obtain the cationic polymer emulsion according to the present invention is most preferably vinyl acetate; lower fatty acid vinyl esters such as vinyl butyrate and pinyl propionate; acrylic esters such as methyl acrylate, acrylic Ethyl acid, butyl acrylate; methacrylate esters, such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like.

Furthermore, monomers that can be polymerized with these monomers, such as styrene and ethylene, can also be used at the same time.
The amount of monomer used is preferably between 20 and 6% by weight, preferably between 25 and 5% by weight, based on the final emulsion.

When obtaining the cationic polymer emulsion according to the present invention, preferably a nonionic aqueous polymer such as polypinyl alcohol, modified starch, or cellulose derivative is used to ensure stable performance over a long period of time. Ru. As polyvinyl alcohol, polyvinyl acetate 70-1
00% saponified products and derivatives thereof, chemically modified starches such as hydroxyethylated starch and hydroxypyropyrolated starch, and cellulose derivatives such as hydroxyethyl cellulose and hydroxypropyl cellulose.

These nonionic water-soluble polymers have a viscosity of 1% aqueous solution of 3 to 500 centipoise, preferably 5 to 100 centipoise. The weight ratio of these nonionic waterport polymers and cationic polymers is preferably 3/2 to 3/0.
．． 01, more preferably 3/1 to 3/0.03.

In order to obtain the cationic polymer emulsion according to the present invention, a cationic polymer may be added if necessary. As a cationic monomer, for example, the following formula (1
Examples include those shown in 7) to (21).

{In formulas (17) to (21), R3. is a hydrogen atom or a methyl group, R32, R33, R34 are hydrogen atoms, carbon number 1-
A 5- to 6-membered compound ring may be formed together with 22 alkyl groups or a nitrogen atom. R' has 1 to 10 carbon atoms, preferably 2
~4 alkylene group, X is an anion. }If a cationic monomer is required, the amount added is 0.01 to 2% by weight, preferably 0.02 to 1% by weight of the total emulsion system.

The best polymerization initiator used to obtain the cationic polymer emulsion of the present invention is 2,2-azobis(2-amidinopropane), but other initiators include hydrogen peroxide, t-butyl hydroperoxide, and cumene. Hydroperoxide, t-butyl/gu oxide, methyl ethyl ketone/gu oxide, cyclohexanone peroxide, peracetic acid, perbenzoic acid, etc. can also be used.

The amount added is 0.01 to 5.0% relative to the vinyl monomer. It is preferable to use it in a range of % by weight. Reaction temperature is 40-120 pm
The polymerization time is preferably 50 to 90 o'clock, and the degree of spotting during polymerization is 3 to 9, preferably 4 to 8.

At this time, as a buffer, sodium carbonate, sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate,
0.05 to 2% by weight of inorganic salts such as monosodium phosphate, sodium chloride, and sodium sulfate, preferably 0.1
It is recommended to add up to 1% by weight. A cationic activator is further added to the cationic polymer emulsion thus obtained to obtain the composition of the present invention. Examples of the cationic activator to be added here include the above formulas (10) to (16).
). The cationic surfactants used in the present invention are not necessarily limited to those mentioned above, and other cationic surfactants such as cationic surfactants derived from urea or buret can also be used.

The content ratio of the cationic polymer emulsion and the cationic active agent to be added later is determined based on the effect and viscosity of the blended system. The solid content is 10 to 5% by weight, preferably 20 to 4% by weight, and the cationic active agent is 2 to 2% by weight, preferably 3 to 1% by weight.

If the cationic activator content is less than 2%, it will not be sufficiently effective.
If it exceeds 20%, there will be no further increase and it is not economically advantageous. The cationic activator used when synthesizing the cationic polymer emulsion and the cationic activator added after the emulsion synthesis may be the same.

However, when used in the synthesis of cationic polymer emulsions, cationic amorous agents cause a marked yellowing, which is considered to be due to thermal changes during synthesis, which is undesirable. The adhesive composition of the present invention contains additives for general polymer emulsions, such as plasticizers such as dibutyl phthalate, dioctyl phthalate, dibutyl adibate, dioctyl adibate, triacetin, etc., ethylene glycol, propylene glycol, Anti-freezing agents such as -L, other fragrances, bactericidal agents, preservatives, halo dyes, pigments, etc. may be optionally added.

Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 Two five-neck separable flasks equipped with a thermometer, a reflux condenser, and a nitrogen inlet tube were prepared, and the following synthesis and blending were carried out.

[Synthesis]

Polypynyl alcohol (completely saponified, degree of polymerization 1800) 6
．． Add 4 hours of ion-exchanged water and 90 hours of ion-exchanged water and dissolve by flooding.

After cooling to 4.0 cm, add 1.0 cm of poly(methacryloxyethyltrimethylammonium chloride) (1% aqueous solution with a viscosity of 200 centipoise at 20°C) and 0.03 cm of pinyl acetate monomer to completely dissolve. .

Furthermore, dimethyl distearyl ammonium chloride was added to flask A for 0.4 hours and to the other flask B for 10 hours.
Add evening. In addition, 100 ml of ion-exchanged water and 100 ml of carbonated soda
Add the solution and replace the air in the flask with nitrogen. Next, 80% of vinyl acetate monomer was added and 2,2-azopis (2
-amidinopropane) hydrochloride 0. Meyu ion exchange water 1
Add a solution of 0.0 ml and raise the temperature to 70 ml to start polymerization.
From 5 minutes after the start of polymerization, 72 units of vinyl acetate monomer are continuously added over a period of 2 hours. After the continuous addition was completed, the mixture was aged at 80° C. for 1 hour to complete the emulsion polymerization. [Blending] Water or water and dimethyl distearyl ammonium chloride are added and blended to the two types of cationic polyvinyl acetate emulsions obtained by the synthesis to obtain a paste composition.

The effects of the blended adhesive composition were investigated.

Gluing method: Wet a piece of cotton 6-sided flea broadcloth (20 x 15, about 4 pieces) with tap water and dehydrate it.

Then, dipped in 16 cc of a 0.2% by weight aqueous solution of the glue composition.
Thoroughly rub in town sand, dehydrate, air dry, and iron. Washing method: Wash the starched cloth with detergent (
Commercial product Kao Soap Co., Ltd., New Beads) o. 1
Wash with 5% by weight washing solution (20°C for each cycle), then wash with 5% washing solution.
Rinse, spin, air dry, and iron for minutes.

The cloth that has been glued and washed repeatedly is JISloo5-195.
The tension was measured by the cantilever method in accordance with No. 9.

According to the cantilever method JISloo5-1959, length 15 x chocolate 2.
Collect 5 test pieces of 5 arcs, and place the collected test pieces on a horizontal table with a smooth surface that has a slope of 45o at one end, aligning the short piece with the baseline of the scale.

Gently slide the test piece in the direction of the slope using an appropriate method, and when one end of the test piece touches the slope, read the position of the other end using a scale. Measure each of the five mystery pieces and find the average value.

The untreated cloth has a value of 4.2, and the higher this value, the harder it is. The measurement results are shown in Table 1, and the adhesive compositions of the present invention all had good adhesive properties.

Table 1 Example 2 Polyvinyl alcohol (completely saponified product, degree of polymerization 1800) was added for 6.4 hours and ion-exchanged water for 90 hours in a five-necked separate flask equipped with a thermometer, a rope strainer, a reflux condenser, and a nitrogen inlet tube. Add and heat to dissolve.

After cooling to 40 qo, 1.0 q of poly(methacryloxethyltrimethylammonium chloride) (1% aqueous solution with a viscosity of 200 centipoise at 20°C) and 0.03 q of the monomer were added until completely dissolved. Then, 0.4 tsp of dimethyl distearyl ammonium chloride is added.

Add a solution of 100 ml of sodium carbonate and 100 ml of ion-exchanged water, and replace the air in the flask with nitrogen. Next, 8 parts of vinyl acetate monomer were added, and a solution of 0.08 parts of 2, goazobis(2-amidinopropane) hydrochloride and 10 parts of ion-exchanged water was added, and the temperature was raised to 70 qo to initiate polymerization. From 5 minutes after the start of polymerization, 72 units of vinyl acetate monomer are continuously added over a period of 2 hours. After the continuous addition was completed, the mixture was aged at 80 oo for 1 hour to complete the emulsion polymerization. The resulting cationic polyvinyl acetate emulsion had a solid content of 44.5% by weight.
The following sizing composition was prepared, and the stiffness of the cloth was measured by repeating sizing and washing in the same manner as in Example 1. Thickening composition cationic polyvinyl acetate emulsion 45% by weight cationic activator 0-15 water
Total 100 The results are shown in Table 2, and all adhesives of the present invention had good adhesive removal.

Table 2 Example 3 Ion exchange with 4 parts of polypinyl alcohol (completely saponified, degree of polymerization 1800) was carried out in a 5-necked separable flask equipped with a thermometer, condenser, reflux condenser, nitrogen introduction device, and quantitative dropping device. Add 13 parts of water and dissolve at 80°C.

After cooling to 40do, trimethylaminohydroxypropylated starch (degree of cation substitution...average number of cation groups introduced per unit of hot water glycose...
...0.3 or more 1% aqueous solution viscosity 30 centipoise) 4.5
parts, polyoxyethylene (30) dodecyl ether 0.
Add 5 parts of sodium carbonate aqueous solution, 1 part of sodium carbonate, and 1 part of ion-exchanged water, and replace the air in the flask with nitrogen.

Next, 1 part of pinilmo/mer acetate was added, 0.1 part of 2,2'-azobis(2-amidinopropane) hydrochloride and 1 part of ion-exchanged water as a polymerization initiator were added, and the temperature was raised to 70° to start polymerization. did. Starting 10 minutes after the start of polymerization, 9 bases of vinyl acetate monomer were continuously added over a period of 100 minutes. After the continuous addition was completed, the mixture was aged at 80° C. for 1 hour to complete the emulsion polymerization reaction. The solid content of the cationic polymer emulsion thus obtained was 43%. Table 3 shows the results of preparing the following glue composition and measuring the hardness of the glue in the third washing process using the same method as in Example 1. The results show that the glue composition of the present invention exhibits excellent glue removal properties.

Thickening Composition Cationic Polyvinyl Acetate Emulsion 7% by Weight Cationic Activator 0 or 5 Dibutyl Adipate
3 Silicone (10,000 centistoke emulsion 35%) 2 Propylene glycol 3 Ethyl alcohol 5 Water 12 Table 3 Example 4 According to Example 1, using the same experimental equipment, polyvinyl alcohol (completely saponified, degree of polymerization 1600) 9 and 13 parts of ion-exchanged water were added to dissolve 8 parts.

After cooling to 40:00, cationic polymer (Table 4) 1.
Add a sodium carbonate aqueous solution of 0.5 parts of sodium carbonate and 5 parts of ion-exchanged water, and replace the air in the flask with nitrogen.

Next, 1 part of vinyl acetate monomer and a cationic monomer (Table 4) were added, and 0.1 part of 2,2'-azobis(2-aminopropane) salt and a polymerization initiator of 1 part of ion-exchanged water were added to make 70 qo. The temperature was raised to start polymerization. Polymerization start 10
After 10 minutes, 9 quarts of vinyl acetate monomer were added continuously over a period of 100 minutes. 80qo after continuous addition
The mixture was aged for 1 hour to complete the emulsion polymerization reaction. Table 4 shows the types of cationic polymer and cationic monomer and the properties of the produced emulsion.

Table 4 Thickening Composition Cationic Polyvinyl Acetate Emulsion 6% by Weight Lauryl Trimethylammonium Chloride
10 Diethylene glycol 4 Silicone (same as Example 3) 1 Dibutyl phthalate 3 Total photodye (Ciba-Geigy, Chinopal CBS) 0.01 Polyvinyl alcohol (degree of saponification 88%, polymerization part 500)
1 ethyl alcohol
3 Water 17.99 All of these adhesive compositions of the present invention had good adhesive removal properties when washed.

Claims (1)

[Claims] 1. (A) a cationic polymer emulsion obtained by emulsion polymerization of a vinyl monomer using a cationic polymer and/or a cationic activator; (B) a cationic activator; A glue composition containing. 2 Component (A) is 10 to 50% by weight as a cationic polymer solid content of vinyl monomer, and component (B) is 2 to 20% by weight.
% by weight of the adhesive composition according to claim 1. 3 The cationic nitrogen content of the cationic polymer of component (A) is 0.0 with respect to the cationic polymer of vinyl monomer.
04 to 0.2% by weight of the adhesive composition according to claim 1 or 2. 4 The cationic activator of component (A) is 0.2 to 1.5 with respect to the cationic polymer emulsion of vinyl monomer.
The adhesive composition according to claim 1 or 2, which is % by weight. 5. The paste composition according to claim 1, wherein the cationic polymer of component (A) is a cationic starch. 6. The adhesive composition according to claim 1, wherein the cationic polymer of component (A) is cationic cellulose. 7. The adhesive composition according to claim 1, wherein the cationic polymer of component (A) is a compound represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_4 is a hydrogen atom or a methyl group, R_5, R_6, R_7 are the same or different and are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a substituted alkyl group, Y is an oxygen atom or an NH group in an amide bond, X is an anion, and m is an integer from 1 to 10.)8 Component B is represented by the following formulas (10), (11), and (16).
The adhesive composition according to claim 1, which is selected from the group of compounds represented by: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_2_1 and R_2_2 each have 11 carbon atoms.
an alkyl group having 13 to 22 carbon atoms or β having 13 to 24 carbon atoms;
-hydroxyalkyl group, R_2_3, R_2_4, R_2_5 are each an alkyl group or hydroxyalkyl group having 1 to 3 carbon atoms,
benzyl group or -(CH_2CH_2O)-n'H, where n' is 1 to 3
number, R_2_8 is an aliphatic group having 12 to 24 carbon atoms,
m' is a number of 2 or 3, and X is an anion. )9 A sizing agent composition characterized in that a cationic activator is added and mixed with a polymer emulsion obtained by emulsion polymerization of a vinyl monomer using a cationic polymer and/or a cationic activator. How things are manufactured. 10 The amount of the cationic activator added in the composition is 2 to 20
10. The method for producing a sizing composition according to claim 9, which is % by weight.