JPS584875A - Size composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a size composition, and more particularly to a size composition that effectively adsorbs to various fabrics under conditions of a high bath ratio during sizing.

Starch has traditionally been used as a sizing agent, but various improvements have been made to make it easier to use.Currently, liquid sizing agents are used as starch agents, which can be easily diluted in cold water, making them easy to use and convenient to use. has been developed, and is used as a 10 to 15 weight aqueous solution of polyvinyl alcohol, ruboxymethyl cellulose, starch, polyvinyl alcohol, etc., mixed with antifoaming agents, antifungal agents, fluorescent whitening agents, fragrances, etc. .

However, these starch, polyvinyl alcohol, carboxymethyl cellulose, etc. have a glass transition temperature of 80.
A hard high-molecular compound (polymer) with a temperature of over 30°F (°C) and is inexpensive when used as a glue, but when used as a glue on clothing, it becomes too hard, gives a paper-like texture, and especially when it comes in contact with the skin. The inconvenience of skin irritation is often observed in the areas where the skin is exposed. In addition, it lacks a sense of thickness, making it unsuitable for use as a starch agent for high-grade clothing. Furthermore, aqueous solutions of these polymers have low concentrations but high viscosity, making them difficult to handle.

Polyvinyl acetate emulsion has been used to eliminate these drawbacks, but since polyvinyl acetate has poor adsorption to clothing, the emulsion is diluted with a small amount of water. A method of soaking it into clothing has been used, which has the disadvantage of causing non-uniform adhesive adhesion.

Various studies have been made to improve the drawbacks of these conventional glue bases, and recently, new glue compositions have been proposed in which the glue base retains a cationic charge. (For example, JP-A-55-
No. 70191, No. 53-94688, No. 52-510
．． 86, etc.) As a method for producing these cationically charged cationic polymer emulsions, a cationic surfactant, a cationic vinyl polymer, a cationic monomer, etc. are mixed in the presence of a nonionic water-soluble polymer. This is a method of imparting a cationic charge.

However, these cationic polymer emulsions have good adsorption properties (they can be used after being sufficiently diluted,
Adhesion of the glue to clothing is uniform and the problem of unevenness has been improved, but it is generally less stable than conventional anionic or nonionic emulsion polymers, and cationic polymers are not stable enough for practical use. The cationic glue composition using this cationic polymer emulsion is diluted and the cationic part is separated from the polymer particles during the processing process and the cationic property decreases. However, its performance is still not sufficient.

The present inventors have conducted extensive research to improve the drawbacks of such conventional cationic thickening compositions, and have found that cationic The present inventors have discovered that by using a cationic paste base obtained by coexisting a cationic polymer, the cationic property does not decrease even when diluted, but the adsorption to clothing increases.

The vinyl monomer used in the present invention is vinyl acetate,
Lower fatty acid vinyl esters such as vinyl butyrate and vinyl propionate, preferably vinyl acetate, are exemplified first, but furthermore, these lower fatty acid vinyl esters shown in the following (1) to (7), preferably copolymerized with vinyl acetate, are exemplified first. Possible monomers (in this case, lower fatty acid vinyl ester: copolymerizable monomers below = 80:20 to 100:0 (weight ratio))
Also used.

(1) Alkyl esters of acrylic acid, methacrylic acid, such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate; (2) Diesters of α, β ethylenically unsaturated dicarboxylic acids, such as dibutyl maleate. , diethyl maleate, and equivalent fumarate, itaconate, and ntraconate (3) styrene, ethylene (4) vinyl halides such as vinyl chloride (5) vinylidene halides such as vinylidene chloride (6) α, β ethylene Polymerizable unsaturated carboxylic acid amides and their N-aluminol derivatives, such as acrylamide and N-methylolamide (7) Lower fatty acid vinyl esters different from the lower fatty acid vinyl esters used previously. Preferably, these copolymerizable monomers include: Examples include alkyl esters of acrylic acid or methacrylic acid, and ethylene.

The unsaturated carboxylic acids used in the present invention include:
Acrylic acid, methacrylic acid, crotonic acid, maleic acid,
Fumaric acid, itaconic acid, a'conitic acid, sorbic acid,
Cinnamic acid, α-chlorosorbic acid, citraconic acid, p-
Examples include acids such as vinylbenzoic acid, as well as alkyl half esters, partial esters, or partial amides of unsaturated polycarboxylic acids such as itaconic acid, maleic acid, and fumaric acid.

Examples of alkyl half esters of unsaturated polycarboxylic acids include those having 1 to 6 carbon atoms, such as monomer itaconate, motsuputyl itaconate, monomethyl fumarate, motsuputyl fumarate, motsuputyl maleate, etc.
and lower alkyl half esters. Among these unsaturated carboxylic acids, preferred examples include acrylic acid,
Examples include methacrylic acid, crotonic acid, and maleic acid.

In the present invention, the cationic polymer that is present during the copolymerization of the vinyl monomer and the unsaturated carboxylic acid or added after the copolymerization is cationic cellulose or cationic starch (particularly water-soluble and whose cationic group is a quaternary ammonium cation). cationic vinyl polymers, ring-closing polymers of cationic diallyl compounds, and the like.

As the cationic starch or cationic cellulose, for example, those represented by the following formula (1) are preferable.

R.

3 (wherein, A: starch residue or cellulose residue R: alkylene group or hydroxyalkylene group RI +R2tR3: the same or different, an alkyl group, an aralyl group, an aralkyl group, or a nitrogen atom in the formula) may be included to form a heterocycle.

X: Anion (chlorine, bromine, °iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.) 1: Positive integer) Such cationic starch is, for example, glycidyltrimethylammonium added to starch under alkali, lJ conditions. It can be obtained by reacting chloride or 5-chloro-2-hydroxypropyltrimethylammonium chloride.

It can also be obtained by quaternizing dimethyl-aminoethylated starch. Furthermore, it can also be obtained by reacting starch with 4-chlorobutene trimethylammonium chloride. On the other hand, cationic cellulose can be obtained, for example, by subjecting hydroxyethyl cellulose to the above reaction.

The degree of cation substitution of cationic cellulose or cationic starch is 0.01 to 1, ie 0.0.
01-1, preferably 0.02-0.5 cationic groups are introduced.

A degree of substitution of 0.01 or less is not sufficient (although it may be 1 or more, it is preferably 1 or less from the viewpoint of reaction yield).

In addition, as the cationic vinyl polymer, the following formulas (2) to (
5) is exemplified.

+cH2-(1,+.

1 (wherein, R4: hydrogen atom or methyl group, R5+R6+"
? : Same or different, hydrogen atom, alkyl group or substituted alkyl group having 1 to 4 carbon atoms, Y: oxygen atom or NH group in amide bond, X: same as formula (1), m: integer from 1 to 10) "10 (In the formula, Ra, Ro + R + o: the same or different, a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, or a substituted alkyl group X: the same as formula (1)) (In the formula, X: formula C1) and The same) +CH,, -cH+n + poly(N-vinyl-2,6-dimethylimidazolinium chloride) The ring-closing polymer of the cationic diallyl compound is expressed by the following formula (
6) is exemplified.

(In the formula, R' and R' are the same or different and represent an alkyl group or substituted alkyl group having 1 to 2 carbon atoms, and X represents an anion.) s ~1ooo 6'pa (seven inch poise) (2
0°C), preferably 10 to 500 cps.

The relative content of these three components in zero-produced IJIK is such that when vinyl monomer is contained in an aqueous solution of 20 to 60% by weight, the cationic properties of this vinyl monomer polymer can be applied to clothing, etc. The polymer has a weight of 0.01 to 5 (preferably tL)
The unsaturated carboxylic acid copolymerized with the vinyl monomer for fixing this cationic polymer to the vinyl monomer polymer is the vinyl monomer 10
0.1 to 15 parts by weight (preferably 0.0 parts by weight)
2 to 5 parts by weight) is required. Although there is no problem in terms of performance even if the absolute content of unsaturated carboxylic acid increases, it is not economical because the amount of cationic polymer used increases. Furthermore, if the absolute content of unsaturated carboxylic acid is small, the fixation of the cationic polymer to the vinyl monomer and unsaturated carboxylic acid copolymer becomes weak, reducing the effect of the present invention.

When sizing is performed using the sizing composition of the present invention, the sizing effect similar to that obtained after ironing can be achieved by simply drying at room temperature. Furthermore, the size composition of the present invention is characterized by being solubilized or swollen under alkaline conditions during normal washing, and having great desizing properties.

In the present invention, it is necessary to coexist a cationic polymer when or after copolymerizing the vinyl monomer and the unsaturated carboxylic acid. During polymerization, the following components may be present in necessary amounts depending on the purpose.

The cationic monomer can be used as a modifier for adjusting the particle size distribution of the copolymerized compound. The cationic monomer is preferably a cationic monomer having one or more nitrogen atoms and one or more double bonds in the molecule, for example, the following formula (7
) to QO).

Formula (7) (In the formula, R1 represents a hydrogen atom or a methyl group, and "18
t RIG+ , "20 are the same or different and represent a hydrogen atom or an alkyl group having 1 to 22 carbon atoms, or a substituted alkyl group, X represents an anion, k represents an integer of 1 to 10, and Z represents an oxygen atom or represents an NH group in an amide bond.Also, R18? R19 and R2° may each contain N to form a ring.) Formula (8) (In the formula, "21 represents a hydrogen atom or a methyl group; .

"221 R231R24 are the same or different, and represent a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, a substituted alkyl group -
and X represents an anion. ) Formula (9) Among those mentioned above, what is more preferable than formula (10) is vinylbenzyltrimethylammonium chloride, acrylic ester or methacrylic ester of hydroquine alkyl trialkylammonium salt. The amount of the cationic monomer added is 0 to 2% by weight, preferably 0.02 to 12 to 1% by weight, based on the cationic paste base emulsion system.

Cationic surfactants can be used as emulsifiers. Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts,
Alkylquinolinium salt, alkyl ink, no linium salt, stearylamide methylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acylaminoethylpyridinium salt, alkoxymethylpyridinium salt, 1-methyl-1-acylaminoethyl-2 Examples include -alkylimidacillin, diacylaminopropyldimethylammonium salt, diacylaminoethyldimethylammonium salt, dialkyldi(polyoxineethylene)ammonium salt, dialkylmethylpolyoxyethyleneammonium salt, and the like.

Anionic surfactants can be used as emulsifiers. Examples of anionic surfactants include higher fatty alcohol sulfates prepared from sodium and potassium sulfate esters of C8 and I'8 alcohols such as lauryl alcohol, sodium and potassium salts of C3,8 fatty acids, and triethanolamine. ethanolamine salts such as triethanolamine oleate, triethanolamine stearate, funnel oil, sulfonic compounds such as sulfated lysylinate, sulfonated compounds such as sodium t-octylbenzene sulfonate, sodium t-octylphenol sulfonate. Examples include alkylaryl compounds.

A nonionic surfactant can be added as an emulsifier if necessary. Examples of nonionic surfactants are alkylphenoxypolyethoxyethanols with C7-18 alkyl groups and 9-60 or more ethylene oxide units, such as heptylphenoxypolyethoxyethanol, octylphenoxypolyethoxyethanol, methyl Octylphenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol,
dodecylphenoxypolyethoxyethanol, -ol, etc., or polyethquin ethanol derivatives of alkylphenols linked with methylene bonds, mercaptans such as nonyl, dodecyl, tetradecyl, and C6-1. Sulfur-containing centralizing agents condensed with alkylthiophenols and the required amount of ethylene oxide, ethylene oxide derivatives of long chain carboxylic acids such as lauric acid, myristic acid, palmitic acid, oleic acid, tall oil mixed acids, hydrophobic carbonization Etherified with a hydrogen chain. or an ethylene oxide derivative of an esterified polyhydroxy compound.The nonionic surfactant has an HLB of 12 to 19, preferably 15.
~18 are used.

Nonionic water-soluble polymers can be used in combination to obtain emulsions that are stable over long periods of time.

Examples of nonionic water-soluble polymers include polyvinyl alcohol, modified starch, and cellulose derivatives. The modified starch that can be used in the present invention is a water-soluble modified starch, and includes, for example, hydroxyethylated starch, hydroquinpropylated starch, and the like.

Further, polyvinyl alcohol 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 polyvinyl alcohol derivatives obtained by modifying these with, for example, aldehydes. The 5th aqueous solution viscosity is 50
Examples include those exhibiting 5 to 10,000 centipoise at °C. The nonionic cellulose derivative that can be used in the present invention is water-soluble hydroxyalkylated cellulose or alkyl cellulose, and the viscosity of a 5% aqueous solution thereof is 60.
It exhibits 5 to 10,000 centivoise at °C,
Tatoeba Hydroxyethylcellulose, Hydroxypropylcellulose, Methylcellulose (Methylation degree 10%)
) etc. The amount of these additives added is 0 to 10% by weight, preferably 1.0 to 4.0% by weight, based on the cationic polymer paste base emulsion system.

The polymerization initiator used in the copolymerization of the present invention is 2.2/-
Azobis(2-amidinopropane) is the best, but others include hydrogen peroxide, t-butylhydrobar oxide, cumenohydrono(-oxide, t-butyl peroxide, methyl ethyl ketone peroxide, cyclohexanone(-oxide, peracetic acid, Perbenzoic acid etc. can be used.

The amount added is 0.01 to 5.0 weight relative to the vinyl monomer.

It is best to use within a certain amount.

The reaction temperature is 40 to 120°C, preferably 50 to 90°C, and the polymerization temperature is 5 to 9, preferably 4 to 8.

At this time, sodium carbonate, sodium bicarbonate, sodium orthophosphate, sodium diphosphate,
Inorganic salts such as monosodium phosphate, sodium chloride, and sodium sulfate are preferably used in an amount of 0 to 2% by weight, preferably 0.1 to 1% by weight.

Therefore, it is desirable that the final emulsion of the cationic polymer paste base of the present invention has, for example, the following component contents.

Vinyl monomer 20 to 60% by weight, preferably 25
-50% by weight Cationic polymer 0.01-5% by weight, preferably 0.2-3% by weight Polymer monomer 0-2111G, preferably 0.0
2 to 1 weight - water-soluble non-ioic poly, - 0 to 10 weight - preferably 1
~4% by weight Inorganic salt 0~211Jl, preferably 0.1~1% by weight Water, etc. The remainder, that is, the preferred thickening composition of the present invention is obtained by emulsion polymerization with the composition as described above (however, cationic (The polymer may be added after the emulsion polymerization is completed), and it is convenient to add all the components at the same time and react, but it is more preferable to add vinyl monomers to a reaction vessel containing other than vinyl monomers. A method of gradually adding the body is preferred.

The emulsion polymerization method for obtaining the emulsion according to the present invention involves copolymerizing a vinyl monomer with a copolymerizable unsaturated carboxylic acid with or without a cationic polymer (in this case, emulsion This is a method of copolymerization (adding to the copolymerization system after the completion of copolymerization). The following method is further exemplified as a more preferable method. That is, in an aqueous polyvinyl alcohol solution, an aqueous nonionic modified starch solution, or an aqueous nonionic cellulose derivative solution, in the presence of a cationic starch, a cationic cellulose, a cationic vinyl polymer, or a ring-closing polymer of a cationic diallyl compound, a cationic interface is formed. Activator An anionic surfactant, a nonionic surfactant, a cationic monomer, or two or more of these are used to emulsify and co-emulsify a vinyl monomer other than the cationic monomer and an unsaturated carboxylic acid. This is a method of polymerization.

When synthesizing a copolymer, the use of a cationic monomer stabilizes the effect that the size of the polymer particles can be made arbitrary depending on the amount used or the structure of the cationic monomer used. Cationic polymers such as cationic monomer derivatives, cellulose, cationic vinyl polymers, or ring-closing polymers of cationic diallyl compounds act as protective colloids on polymer particles. In addition to the stabilizing effect, it adsorbs to polymer particles and has the effect of promoting adsorption of polymer particles to cloth, which tends to be negatively charged in water. In addition, in emulsion polymerization, cationic surfactants form micelles in water to solubilize vinyl monomers, provide a place for polymerization of vinyl monomers, and provide dispersion stability to the resulting polymer. It has the following effects.

Even if the emulsion used in the thickening composition of the present invention does not contain water-soluble nonionic polymers such as polyvinyl alcohol, nonionic modified starch, or nonionic cellulose derivatives, it is sufficient as a thickening agent. Although it is used as a composition, polyvinyl alcohol,
If non-ionic modified starch or non-ionic cellulose derivatives are used at the same time as cationic vinyl copolymer, the vinyl copolymer emulsion will become more stable and the physical properties imparted to the fabric, that is, the "tension" will be further improved. It has an improving effect.

If the "tightness" increases, for example, when ironing a Y-shirt or blouse with starch, it will give a crisp feel without wrinkles, and the long-lasting effect will become thicker. The parts that come into contact with the glue are softened by body heat, so the glued parts will not irritate or damage the skin, and the glue will be easily dissolved by sweat and will not stick to the skin. In this respect, when talking about pastes, adhesives and textile pastes are preferred to have strong adhesion, that is, to be hard as polymers, or to be extremely durable when washed with water. Unlike polymers that are easily washed off and used for prizes.

In addition to the cationic polymer paste base, the paste composition of the present invention may further contain additives for general polymer emulsions, such as dibutyl phthalate, dibutyl adipate, dibutyl adipate, triacetin, etc., as necessary. Antifreeze agents such as plasticizers ethylene glycol, fluoropylene gellicol, and ethanol, as well as other fragrances, fungicides, preservatives, fluorescent dyes, and pigments can be added.

When using the starch composition of the present invention, the method using a conventional starch composition is used, that is, the amount of water used to dilute the starch composition for clothing, the so-called bath ratio, is adjusted to about 1=1 to 1:4. However, for most effective use, the bath ratio should be 1:10 to 1:100, preferably 1:15 to 1:
It is better to set it to 40 and use it. Such an increase in bath ratio enables uniform gluing, and when used at home,
Applying a continuous strong agitation force like that of an electric washing machine, the sizing agent is made to flow by flowing the deicing solution, and while the sizing agent adsorbs well to thick fabrics, it has little adsorption to thin fabrics. produce an effect. Therefore, it has very good adsorption on thick fabrics such as sheets, while on the other hand, on clothes such as dress shirts and blacks, when applying glue to heavy areas of fabric such as body parts, the adsorption of the agent is very low. The amount of adsorption is small compared to the adsorption of the agent when pasting is applied to areas with double fabric or interlining, such as cufflinks.
The finishing effect is superior to conventional ones.

This finishing effect could not be achieved with conventional sizing agents that are nonionic or anionic.
Furthermore, it is superior to conventional cationic sizing agents that do not copolymerize unsaturated carboxylic acids, and its ability to increase the bath ratio and provide stirring power is completely different from conventional non-cationic sizing agents. I didn't have it. The stirring force when using the glue composition of the present invention may be such that continuous or intermittent stirring mechanical force is applied to the aqueous solution of the glue composition (e.g., when the glue composition of the present invention is used at home). The stirring force in this case is a pulsator.
It is convenient to use a washing machine with an agitator or tumbler set.

When starching using the starch composition of the present invention, the ratio of the starch composition to the weight of clothing is 0.2 to 6% by weight, preferably 0.2% to 6% by weight of the active content (solid content) of the starch composition relative to the weight of the clothing. 4~
It is 2% by weight.

- Hereinafter, specific examples of the present invention will be described in detail, but the present invention is not limited to these examples. Parts in the examples are parts by weight.

Example 1 Trimethylaminohydroxypropylated starch (nitrogen content 0.6%, 1% aqueous solution viscosity 40 Add 30 parts of vinyl acetate, 550 parts of ion-exchanged water, dissolve at 80°C, cool to 60°C, and add 20 parts of vinyl acetate, 2,2'
A polymerization initiator consisting of 0.5 parts of -azobis(2-amidinopronopronochloride) hydrochloride and 20 parts of ion-exchanged water was added, and the temperature was raised to 70°C to initiate polymerization.

Crotonic acid
A solution of 1 part of vinyl acetate and 1 part of vinyl acetate was added dropwise. After the addition was completed, the temperature was raised to 80°C to terminate the reaction.

Table 1 shows the results of measuring the effects of cationic polymer glue bases synthesized with various ratios of vinyl acetate monomer and crotonic acid. The gluing effect was measured by the following method.

(Sizing is a test) Using a machine turbotometer type cleaning test, put the sizing material synthesized as above in 500 ml of 1% sulfur-exchanged water at a solid content of 0.41 into a cleaning tank (1000 rnt internal volume). After dispersion, a 60# cotton cloth 201 was added and the mixture was stirred and glued for 5 minutes at a rotation speed of 100 revolutions/minute. After dehydration, it was air-dried and left in a constant temperature and humidity room at 25° C. and 965° relative humidity for a day and night, and then glued and tested for effectiveness.

Effect test for starching (1) Pure bending test method
The bending stiffness (9. To))
11 performances were decided.

(2) Sensory test method: 50% using a normal household washing machine! Add 209 active ingredients of the sizing base to tap water, disperse well, add 1 oooy cotton sheets, and stir for 6 minutes to glue. 6. In a dehydrator.
After dehydrating for 0 seconds, air dry. A pair of tactile tests were carried out by 10 people on the tension of the cloth treated with the above method (the control was carried out on cotton sheets treated with base number 1 without copolymerizing crotonic acid).41 for each group. We evaluated the performance of

+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) Test method for ease of starching
After iron pressing for 1 minute, each piece was cut into 51 pieces. Using a turbotometer type cleaning tester 1
00C1++/! For sizing, the cloth was washed for 10 minutes at a bath ratio of 1/200 and a rotational speed of 100 rpm using ion-exchanged water and a commercially available synthetic detergent (1), followed by washing, dehydration, and air drying. After that, it was further iron-pressed at 160°C for 1 minute, and then stored in a constant temperature and humidity room at 25°C and 65% relative humidity overnight.

The bending rigidity of the sample cloth is measured using a pure bending tester.

a - Bending rigidity after washing (after applying glue) - Bending stiffness after washing (after applying glue) - Bending stiffness before washing (after applying glue) - Bending rigidity before washing ( - □ 5 parts of polyvinyl alcohol (partially saponified product, degree of saponification 88%, degree of polymerization 500), 60 parts of trimethylaminohydroxyethylated starch (CI, 6%, viscosity of 1% aqueous solution 40 centipoise), and 500 parts of ion-exchanged water. In addition, 80°
After dissolving in C and cooling to 60°C, polyoxyethylene (20) 9 parts lauryl alcohol, 0.5 part sodium carbonate, 20 parts vinyl acetate, 2.2/-azobis(2-amidinopropane) hydrochloride 0.5 parts and 80 parts of ion-exchanged water were added, and the temperature was raised to 70°C to start polymerization. A solution of a mixture of various unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, or half esters of unsaturated polycarboxylic acids After the addition was completed, the temperature was raised to 80°C to terminate the reaction.

The sizing effect of the synthesized cationic polymer sizing base was measured in the same manner as in Example 1. The results are shown in Table 2.

Table 2 *Total of 20 parts added initially and y parts Various cationic polymers and vinyl monomers were used to synthesize cationic thickener bases and their performance was investigated.

[-Synthesis of cationic thickening base]

Using the same equipment as in Example 1, 7.5 parts of the cationic polymer shown in Table 3 and polyvinyl alcohol (degree of partial saponification 79) were added.
, degree of polymerization 1600) and 100 parts of ion-exchanged water were added, dissolved at 80°C, cooled to 60°C, and then
10 parts of vinyl monomer shown in Table 6, 1 part of crotonic acid,
Furthermore, if necessary, 2 parts of a nonionic surfactant or cationic surfactant or cationic monomer were added, and 0.1 part of sodium carbonate, 2,2'-azobis(2-amino dinocyclopropane) hydrochloride or cumene was added. 0.1 part of hydroperoxide and 20 parts of ion-exchanged water were added, and the temperature was raised to 70°C to start polymerization.

From 20 minutes after the start of polymerization, 90 parts of vinyl monomer was continuously added dropwise over a period of 300 minutes. After the dropwise addition was completed, the temperature was raised to 80°C to terminate the reaction.

Comparative Example 1 A cationic thickener base was synthesized with the same polymerization composition as in Example 6 but without using crotonic acid.

The bending rigidity of the pastes synthesized in Example 1 and Comparative Example 1 before iron pressing was measured in the same manner as in Example 1. 3rd result
Shown in the table.

Example 4 A paste composition was prepared using the cationic paste base synthesized in Example 3, and a tactile test was conducted using a conventional cationic paste composition and a paired comparison method.

The results are shown in Table 4.

Thickening composition> Emulsion 91 parts dibutyl phthalate 2 parts ethanol 6 parts propylene glycol 2 parts silicone emulsion 5 parts ion-exchanged water
1.5 parts (tested with glue) 20 using a regular household washing machine! 61 of the effective amount of various glue compositions were added to the tap water of 100 ml, and dispersed well. 5001 cotton sheets were added and the paste was stirred for 3 minutes. After dehydrating for 30 seconds in a dehydrator, air dry.

The performance of various sizing agents was evaluated by performing a tactile test on the tension of cloth treated with the above-mentioned method by pairwise comparison by 10 people.

+2 = Tension +1 = Slight tension 0: Same as control = 1: Slightly no tension -2: No tension The numbers in the table represent the number of people Example 5 Cool a stainless steel autoclave to below -50°C 35 parts of the cationic polymer of (a) or (b) below, 90 parts of a 10% solution of hydroquine ethyl cellulose, then 0.5 part of a 20% aqueous solution of hydrogen peroxide, 70 parts of ion-exchanged water, and then polyoxyethylene. (50) Add 1 part of dodecyl ether, 0.3 parts of sodium carbonate, and 6 parts of ion-exchanged water to an aqueous solution of 90 parts of vinyl acetate, 2 parts of crotonic acid, and 10 parts of ethylene, heat in a sealed container, and heat at 60'C. 2 hours,
The mixture was then heated at 80° C. for 1 hour to perform emulsion polymerization. A sheet sizing test was conducted in the same manner as in Example 4 using the obtained cationic sizing base, and all sheets showed good tension.

Patent applicant: Kao Soap Co., Ltd. Agent Kaoru Furutani

Claims (1)

[Scope of Claims] 1. A thickening composition containing a cationic thickening base obtained by copolymerizing a vinyl monomer and an unsaturated carboxylic acid or by allowing a cationic polymer to coexist after copolymerizing a vinyl monomer and an unsaturated carboxylic acid. thing. 2. The paste composition according to claim 1, wherein the vinyl monomer is a lower fatty acid vinyl ester. 3. The paste composition according to claim 1, wherein the vinyl monomer is a mixture of a lower fatty acid vinyl ester and a monomer copolymerizable therewith. 4 20 to 600 to 60 parts by weight of vinyl monomer 0.1 to 15 parts by weight of carboxylic acid per 100 parts by weight of vinyl monomer
The thickening composition according to any one of claims 1 to 5, which contains 0.01 to 5 parts by weight of cationic poly(i) and 0.5 parts by weight, wherein the cationic polymer is a cationic starch, cationic The glue composition according to any one of claims 1 to 4, which is selected from the group consisting of cationic vinyl polymers, cationic vinyl polymers, and ring-closing polymers of cationic diallyl compounds. ◇ 6 The cationic polymer has the formula (wherein M1: starch residue R dialkyresi group or hydroxyalkylene group RsAz"S' is the same or different, an alkyl group,
It may contain an aryl group, an aralkyl group, or a nitrogen atom in the formula to form a heterocycle. X: anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.); l: positive integer Thickening composition. 7 Cationic poly! - is the formula (in the formula, M, N, Reulose residue RX alkylene group or hydroxyalkylene group R, R,, R,: the same or different, B, alkyl group, aryl group, aralkyl group or in the formula It may contain 4 nitrogen atoms to form a heterocycle. !: Anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.) 1: Positive integer, ) Thickening composition 08 according to claim 5, which is cationic cellulose, wherein the cationic polymer is selected from the cationic vinyl polymer group represented by the following formula (2), (s) t (4) or (5) The paste composition according to claim 5, which is selected from the group consisting of: to (in the formula, R9: hydrogen atom or methyl group, R,, R,, R
7: Same or different] hydrogen atoms. Alkyl group or substituted alkyl group having 1 to 4 carbon atoms, Y: oxygen atom or MH group in amide bond, X2 formula (1)
m: an integer from 1 to 10) (wherein, a R5*'t: the same or different, hydrogen atom, alkyl group or substituted alkyl group having 1 to 2 carbon atoms; X; formula (1) ) 011, * In the formula, R' and R'ff are the same or different and represent an alkyl group or substituted alkyl group having 1 to 2 carbon atoms, and s
Represents the Xu anion. ) The paste composition according to claim 5, which is a ring-closing polymer of a cationic diallyl compound represented by: 10 Unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, aconitic acid, sorbic acid, cinnamic acid, α-chlorosorbic acid, citrate, and p-vinylbenzoic acid. The paste composition according to any one of claims 1 to 5, which is selected from the following reviews. 11. The thickening composition according to claim 10, wherein the unsaturated carboxylic acid is selected from the group consisting of acrylic acid, methacrylic acid, crotonic acid and maleic acid. 12. The glue composition according to any one of claims 1 to 5, wherein the unsaturated carboxylic acid is selected from the group consisting of alkyl half esters, partial esters, and partial molecules of unsaturated polycarboxylic acids. thing.