JPS648114B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fiber sizing agent used in general households. In particular, the present invention relates to improvements in non-accumulative cationic sizing agents. Conventionally, vinyl acetate resin emulsion-based starch has been widely used for starching clothes at home due to its good texture and ease of use, but recently it has been used for starching products with a high bath ratio, such as those in electric washing machines. It has been improved so that it can be glued even under certain conditions. That is, it is said that by imparting cationic properties to the surface of the vinyl acetate resin emulsion particles, adsorption to clothing fibers is increased and sufficient sizing can be achieved even in areas where the bath ratio is high. These improvements have reduced the labor involved in pasting the glue, which traditionally relied on manual processing, and made it possible to process uniformly.Furthermore, even after considerable dehydration after processing, there is little detachment of the glue. Therefore, it has become a place that also contributes to shortening the drying time of clothes. However, it has been pointed out that a drawback of such vinyl acetate resin-based chemical thickeners is that the thickener components tend to accumulate on clothing, regardless of whether cationic properties are imparted to the surface of the emulsion particles. That is, since the polyvinyl acetate component that adheres to clothing due to starching is water-insoluble, it cannot be removed sufficiently even by washing at home, and some percentage of the starch remains. However, when the concentration and frequency of gluing is high, the accumulation is remarkable. In order to improve these drawbacks, it has been proposed to copolymerize vinyl acetate monomer with an unsaturated carboxylic acid such as crotonic acid, and further impart cationic properties to the particle surface (Japanese Patent Application Laid-Open No. 1986-1999-1).
88414, 56-91075, 56-110709). In other words, the starch material obtained in this way can of course be processed in a washing machine, and when the starched clothing is washed, the carboxylic acid becomes a base by using the alkaline property of the detergent component, and the hydrophilicity is considerably increased.
It is said that the water-insoluble polyvinyl acetate periphery also falls off due to interfacial disturbance, and exhibits sufficient adhesive removal properties. Although this phenomenon has been confirmed by the present inventors, the previously proposed vinyl acetate-unsaturated carboxylic acid copolymer emulsion has one important defect that was not found in the vinyl acetate resin emulsion. It was discovered that there is. That is, in a sizing agent using a copolymer emulsion of vinyl acetate and a common unsaturated carboxylic acid such as crotonic acid, the protons of the carboxylic acid group introduced to make it non-accumulative inhibit the hydrolysis of the acetate ester group. The acid odor becomes stronger over time, perhaps due to the promotion, and this acid odor is difficult to compensate for by blending fragrances. Such acid odor is undesirable during sizing and washing, and greatly impairs its commercial value as a sizing agent for fibers whose period from manufacture to consumer use is not necessarily short. As a result of intensive research into non-accumulative technology using a copolymer of vinyl acetate monomer and unsaturated carboxylic acid, the present inventors discovered a copolymer that was satisfactory in terms of both non-accumulative properties and odor, and arrived at the present invention. It is something. That is, the present invention provides a fiber sizing agent containing a copolymer emulsion obtained by emulsion copolymerizing an unsaturated carboxylic acid represented by the following general formula with a vinyl acetate monomer in the presence of a cationic polymer. By using a special unsaturated carboxylic acid represented by the above general formula [], which was not used in the previously proposed vinyl acetate-unsaturated carboxylic acid copolymers, the drawbacks of the conventional ones were eliminated. It provides an excellent sizing agent. _CH2 =CH( _-CH2 ) _-oX ( _-CH2 ) _-nCOOH
[] (However, in the formula, n is 0 or 1, m is an integer from 1 to 6 (including straight chain and branched chain), and X is -CH ₂ -, -O-,

【formula】 【formula】

【formula】

Represents one of [Formula]. ) Specific examples of such unsaturated carboxylic acids include 3-allyloxypropionic acid (n=
1, m = 2, X: -O-), β-acryloxypropionic acid (n = 0, m = 2, X:

[Formula]), allyloxyacetic acid (n=1, m=1, X:-O
-), succinic acid allyl ester (n=1, m=2,
X:

[Formula]), undecylenic acid (n = 1, m = 6, X: -CH ₂ -), succinic acid allylamide (n = 1, m = 2, X:

[Formula]), and 3-allyloxypropionic acid and allyl succinate are preferred. The copolymerization ratio of the unsaturated carboxylic acid to the vinyl acetate monomer used in the present invention is particularly effective in the range of 99.5 to 88% by weight of the vinyl acetate monomer and 0.5 to 12% by weight of the unsaturated carboxylic acid. If the unsaturated carboxylic acid ratio is less than 0.5% by weight, the degreasing property during washing will be insufficient, and if it exceeds 12% by weight, a decrease in tension or the occurrence of an acetic acid odor may become noticeable in some cases. . A particularly preferred copolymerization ratio is 97.5 to 93.0% by weight of vinyl acetate monomer and 2.5 to 7.0% by weight of unsaturated carboxylic acid. Examples of cationic polymers that can be coexisting when producing the emulsion of the present invention include cationic cellulose, cationic starch, cationic vinyl polymers, and ring-closing polymers of cationic diallyl compounds. Particularly preferred are cationic cellulose and cationic starch. The degree of cation substitution of these cationic polymers is 0.01 to 1, preferably 0.02 to 0.5. Furthermore, the viscosity of the aqueous solution of these cationic polymers is 5 to 1% as a 1% aqueous solution.
1000 cps (20°C), preferably 10-500 cps. In the present invention, when the vinyl acetate monomer is taken as 100 parts by weight, the unsaturated carboxylic acid to be copolymerized with the vinyl acetate monomer is suitably contained in a range of 0.5 to 14 parts by weight (preferably 2.5 to 7.5 parts by weight). Yes, and the vinyl acetate monomer content in the emulsion is 20 to 60
% by weight (preferably 25-50% by weight), and the cationic polymer content is 0.01-5% by weight (preferably 0.2% by weight).
~3% by weight) is suitable. In order to improve the texture and make the copolymer emulsion of the present invention hydrophilic, a portion of the vinyl acetate monomer may be substituted with comonomers such as (meth)acrylic acid ester, ethylene, and hydroxyethyl methacrylate. It can be replaced with . When producing the copolymer emulsion of the present invention, cationic surfactants such as alkyltrimethylammonium salts and dialkyldimethylammonium salts, anionic surfactants such as higher fatty alcohol sulfates, sulfonated alkylaryl compounds, alkyl Nonionic surfactants such as polyethoxyethanol derivatives of phenol and ethylene oxide derivatives of long-chain carboxylic acids can be used as emulsifiers, if necessary. Furthermore, in order to obtain an emulsion that is stable over a long period of time, a nonionic water-soluble polymer may be used in conjunction with the copolymer emulsion of the present invention. Nonionic water-soluble polymers include PVA, modified starch,
Examples include cellulose derivatives. The modified starch that can be used in the present invention is a water-soluble modified starch. PVA that can be used in the present invention includes completely or incompletely saponified vinyl acetate homopolymers or copolymers of vinyl acetate and other monomers, or modified products of these with, for example, aldehydes.
Examples include PVA derivatives, and those exhibiting a 5% aqueous solution viscosity of 5 to 10,000 cps (30°C) are exemplified. The amount of these nonionic water-soluble polymers used is 0 to 10% by weight, preferably 1 to 4% by weight, based on the cationic copolymer emulsion of the present invention. Polymerization initiators used in the production of the copolymer emulsion of the present invention include ammonium persulfate, potassium persulfate, 2,2'-azobis(2-amidinopropane), hydrogen persulfate, t-butyl hydroperoxide, and cumene. Hydroperoxide, t-
Butyl peroxide, methyl ethyl ketone peroxide, peracetic acid, perbenzoic acid, etc. can be used, and the amount used is 0.01 to 5
It is best to use it within a range of % by weight. The reaction temperature is 40 to 120°C, preferably 50 to 90°C, and the pH during polymerization is 3 to 9, preferably 4 to 8. At this time, as a pH buffering agent, inorganic salts such as sodium carbonate, sodium bicarbonate, sodium orthophosphate, dibasic sodium phosphate, monobasic sodium phosphate, sodium chloride, and sodium sulfate, preferably 0 to 2% by weight, preferably 0. 1-1% by weight
Good to use. In order to increase the commercial value of the copolymer emulsion produced in this way, ethanol, ethylene glycol, propylene glycol, etc. are added as fragrances, fluorescent dyes, antifungal agents, or emulsion stabilizers under low temperature storage. Solvents and also plasticizers such as dibutyl phthalate, dioctyl phthalate, dibutyl adipate, dioctyl adipate, triacetin, etc. can be added to the copolymer emulsion. Next, the present invention will be specifically explained with reference to Examples. However, the present invention is not limited to these examples. In addition, in the examples, all parts and percentages are based on weight. Example 1 In a polymerization tank equipped with a reflux condenser, a thermometer, a stirrer, and a dropping funnel, 400 parts of water, 6 parts of polyvinyl alcohol (partially saponified product, degree of saponification 88%, degree of polymerization 500),
and cationized starch [(starch residue)-

[Formula] 35 parts of nitrogen content 0.6%, 1% aqueous solution viscosity (20℃) 40cp], dissolved at 90℃, cooled to 60℃ while stirring in a nitrogen atmosphere, )
A protective colloid solution was prepared by adding 10 parts of a nonionic surfactant (manufactured by a nonionic surfactant), 2 parts of soda carbonate, and 135 parts of water.
Next, 13 parts of vinyl acetate and 34 parts of a 3.0% aqueous solution of polymerization initiator (potassium persulfate) were added, and the temperature of the solution was raised from 60°C to 80°C.
The temperature was raised to ℃, and polymerization was started while stirring. 20 minutes after the start of polymerization, add potassium persulfate 2.6% aqueous solution 160
A mixture of 410 parts of vinyl acetate and 22 parts of 3-allyloxypropionic acid was added dropwise over 6 hours. After the dropwise addition was completed, the temperature was raised to 80°C to terminate the polymerization. The obtained emulsion was cooled to room temperature to obtain a copolymer emulsion having a solid content of 37.6% and a viscosity of 3770 cp. Example 2 13 parts of vinyl acetate and 34 parts of a 3.0% aqueous solution of a polymerization initiator (potassium persulfate) were added to a protective colloid solution prepared in the same manner as in Example 1, and the temperature of the solution was raised from 60°C to 80°C.
The temperature was raised to ℃, and polymerization was started while stirring. 20 minutes after the start of polymerization, add potassium persulfate 0.4% aqueous solution 160
A mixture of 409 parts of vinyl acetate and 23 parts of allyl succinate was added dropwise over 6 hours. After the dropwise addition was completed, the temperature was raised to 80°C to complete the polymerization. The obtained emulsion was cooled to a solid content of 38.5% at 30°C.
A copolymer emulsion with a viscosity of 760 cp was obtained. Example 3 13 parts of vinyl acetate and 34 parts of a 3.0% aqueous solution of a polymerization initiator (potassium persulfate) were added to a protective colloid solution prepared in the same manner as in Example 1, and the temperature of the solution was raised from 60°C.
The temperature was raised to 80°C, and polymerization was started while stirring.
0.4% aqueous solution of potassium persulfate from 20 minutes after the start of polymerization.
160 parts and 403 parts of vinyl acetate and 10-undecylenic acid
30 parts of the mixture was added dropwise over 6 hours. After the dropwise addition was completed, the temperature was raised to 80°C to terminate the polymerization. The resulting emulsion was cooled to room temperature and the solid content was reduced to 40.2
%, a copolymer emulsion with a viscosity of 2400 cp at 3°C was obtained. Example 4 13 parts of vinyl acetate and 34 parts of a 3.0% aqueous solution of a polymerization initiator (potassium persulfate) were added to a protective colloid solution prepared in the same manner as in Example 1, and the temperature of the solution was raised from 60°C.
The temperature was raised to 80°C, and polymerization was started while stirring.
2.6% potassium persulfate aqueous solution 20 minutes after the start of polymerization
A mixed solution of 160 parts of vinyl acetate and 410 parts of vinyl acetate and 23 parts of β-acryloxypropionic acid was added dropwise over 6 hours. After the dropwise addition was completed, the temperature was raised to 80°C to terminate the polymerization. The obtained emulsion was cooled to room temperature to obtain a copolymer emulsion having a solid content of 38.8% and a viscosity of 2810 cp at 30°C. Example 5 13 parts of vinyl acetate and 34 parts of a 3.0% aqueous solution of polymerization initiator (potassium persulfate) were added to a protective colloid solution prepared in the same manner as in Example 1, and the temperature of the solution was raised from 60°C to 80°C.
The temperature was raised to ℃, and polymerization was started while stirring. 20 minutes after the start of polymerization, add potassium persulfate 0.4% aqueous solution 160
A mixture of 413 parts of vinyl acetate and 20 parts of allyloxyacetic acid was added dropwise over 6 hours. After the dropwise addition was completed, the temperature was raised to 80°C to complete the polymerization. The obtained emulsion was cooled to obtain a copolymer emulsion having a solid content of 40.1% and a viscosity of 3820 cp at 30°C. Comparative Example 1 13 parts of vinyl acetate and 34 parts of a 3.0% aqueous solution of polymerization initiator (potassium persulfate) were added to a protective colloid solution prepared in the same manner as in Example 1, and the temperature of the solution was raised from 60°C.
The temperature was raised to 80°C, and polymerization was started while stirring.
0.4% aqueous solution of potassium persulfate from 20 minutes after the start of polymerization.
A mixture of 160 parts of vinyl acetate and 418 parts of vinyl acetate and 15 parts of crotonic acid was added dropwise over 6 hours. After the dripping is finished,
The temperature was raised to 80°C to terminate polymerization. The obtained emulsion was cooled to room temperature to obtain a copolymer emulsion having a solid content of 39.4% and a viscosity of 2330 cp at 30°C. Comparative Example 2 The same procedure was used as Comparative Example 1 except that crotonic acid was replaced with methacrylic acid, and the solid content was 39.7% and 30%.
A copolymer emulsion with a viscosity of 1280 cp at °C was obtained. The polymer compositions of the copolymer emulsions produced in Examples 1 to 5 and Comparative Examples 1 to 2 are listed in Table 1.

【table】

[Table] Using the copolymer emulsions prepared in Examples 1 to 5 and Comparative Examples 1 to 2 as a glue, the following methods were used to evaluate the glue sticking performance, glue removal property, and emulsion odor, especially after storage. The change in odor was tested. The results are shown in Table-2. (Gluing test) Using a tergotometer type cleaning tester, put 500 ml of ion-exchanged water and 0.4 g of solid content of the copolymer emulsion paste synthesized in the above example or comparative example into a cleaning tank (1000 ml internal volume). 60 after well dispersed
# Add 20g of cotton cloth and rotate at a rotation speed of 100 revolutions/minute 3
Stir for a minute to glue. Air dry after dehydration, 25℃, 65%
After leaving it in a constant temperature and humidity room with relative humidity for a day and night, it was subjected to a gluing effect test. (Gluing effect test) (1) Pure bending test method The cotton cloth glued by the above gluing test was
Cut into pieces of cm x 2.5 cm, make a set of 10 pieces, and use a pure bending tester (manufactured by Kato Iron Works).
In a constant temperature and humidity room at 25℃ and 65% relative humidity.
Bending rigidity (g·cm) was measured. (2) Sensory test method Add 20g of active ingredient to 30ml of tap water using a regular household washing machine, and disperse well.
Add 1000g cotton sheets and stir for 3 minutes to paste. After dehydrating for 30 seconds in a dehydrator, air dry. A pair of tactile tests were conducted by 10 people on the tension of the fabrics that had been starched using the above method (the standard was cotton sheets treated with the starch of Comparative Example 1, which was copolymerized with crotonic acid), and the performance of each starch was evaluated. . +2: There is tension +1: There is some tension 0: Same as the control -1: There is no tension -2: There is no tension, and the numbers in the table indicate the number of people who gave each evaluation. (3) Ease of adhesive removal test method In the adhesive test, air-dried cotton cloth was
It was iron pressed at 130°C for 1 minute, and then cut into pieces weighing 5 g each. Using a tergotometer-type cleaning tester, the starched cloth was washed for 10 minutes using 1000 ml of ion-exchanged water and a commercially available synthetic detergent (1 g) at a bath ratio of 1/200 and a rotational speed of 100 rpm. After that, wash with water, dehydrate, air dry, then iron press at 130℃ for 1 minute.
Store overnight in a constant temperature and humidity room at 25°C and 65% relative humidity. The bending rigidity of the test cloth is measured using a pure bending tester. a = Bending stiffness after washing (after gluing) - Bending stiffness after washing (before gluing) b = Bending stiffness before washing (after gluing) - Bending rigidity before washing (before gluing) Ease of glue removal (%) = b-a/b×100 (Odor evaluation) Put 30 c.c. of emulsion paste into a glass bottle at 50℃, seal it, and store it in a thermostat at 50℃ for 20 days, then open the lid and check the contents. The presence or absence of a sour odor or off-odor was determined.

【table】

Claims (1)

[Claims] 1 Vinyl acetate monomer and the general formula CH ₂ = CH (-CH ₂ )- _o X (-CH ₂ )- _n COOH [] (However, in the formula, n is 0 or 1, m is 1 An unsaturated carboxylic acid represented by an integer of ~ ₆ (including straight chain and branched chain), A fiber sizing agent comprising a copolymer emulsion obtained by emulsion polymerization of the following in the presence of a cationic polymer. 2 In the general formula [], n=1, m=2 and X
The fiber sizing agent according to claim 1, wherein is -O-. 3 In the general formula [], n=1, m=2 and X
The fiber sizing agent according to claim 1, wherein is [Formula]. 4. The fiber sizing agent according to claim 1, wherein the cationic polymer is cationic cellulose or cationic starch. 5. The fiber sizing agent according to claim 1, wherein the copolymerization ratio of the unsaturated carboxylic acid represented by the general formula [] to vinyl acetate is 0.5 to 12% by weight.