JPH01321981A - Thickening composition - Google Patents

Abstract

PURPOSE:To obtain a liquid seizing agent composition for home use having tension and good touch by copolymerizing two or more kinds of monomers of an ester of acrylic acid or methacrylic acid and styrene monomer, etc., with a specific cationic monomer. CONSTITUTION:Two or more kinds of monomers selected from an ester of acrylic acid or methacrylic acid and 1-20C aliphatic alcohol and styrene monomer and a cationic monomer shown by formula I (R1 is H or methyl; R2 to R4 are H, 1-4C alkyl, etc.; Y is O or NH group in amide bond; X<-> is monovalent anion; m is 1-10), formula II (R5 to R7 are H or 1-2C alkyl; X<-> is as shown above) or formula III (R8 is 8-22C hydrocarbon; R9 and R10 are 1-3C alkyl; R11 is H or methyl; X is as shown above) are subjected to emulsion polymerization to give a liquid sizing agent composition for home use containing an aqueous resin dispersion, having <=0.5mum particle diameter of aqueous resin, 0-60 deg.C glass transition temperature and <=50 deg.C lowest film-forming temperature.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is directed to a thickening composition, and more particularly, to a thickening composition that has excellent adsorption to fibers at high bath ratios, does not give a stiff feeling to clothing, and has a good texture. This invention relates to a glue composition that can impart tension.

[Prior art and problems to be solved by the invention] Clothing finishing agents used at home include fabric softeners, starch agents, antistatic agents, and water and oil repellents, all of which improve the functionality or texture of textile products. It is used to hold and recover.

At present, the functions and effects of these finishing agents have become established in daily life, and it seems that the treatment of clothing with finishing agents has become part of washing habits. This is simply because the above-mentioned finishing agents are designed so that anyone can easily use them at home.

By the way, among these finishing agents, glue is used for boat fishing in order to maintain the shape of clothing and give it a nice finish.

Starch has traditionally been used as a thickening agent, but various improvements have been made to make it easier to use.Currently, liquid starch is used as a stable thickening agent that is easy to dilute in cold water and is easy and convenient to use. has been developed, and a 10 to 15% by weight aqueous solution of carboxymethyl cellulose, starch, polyvinyl alcohol, etc., mixed with an antifoaming agent, an antifungal agent, a fluorescent whitening agent, a fragrance, etc., is used.

However, these starch, polyvinyl alcohol, carboxymethyl cellulose, etc. have a glass transition temperature of 80.
It is a hard high-molecular compound (polymer) with a temperature of ℃ or above, and is inexpensive as a glue, but when used as a glue on clothing, it becomes too hard and gives a paper-like texture, especially in areas that come into contact with the skin. The inconvenience of causing skin irritation is often seen. In addition, the thickness does not vary, making it unsuitable for use as a starch agent for high-grade clothing.

Furthermore, as clothing is worn and washed repeatedly, it generally loses its elasticity, and its original shape gradually loses its original shape.

Starch additives are used to add elasticity and firmness to garments that have lost their elasticity, and to adjust the shape of the garments, but the drawback is that the texture of the garments treated as described above deteriorates.

Furthermore, aqueous solutions of these polymers have the disadvantage of being difficult to handle due to their high viscosity even at low concentrations, as well as their poor adsorption to fibers, making them difficult to process using high bath ratios, i.e., in household washing machines. cannot be processed.

Polyvinyl acetate emulsions have been used to eliminate these drawbacks, but even polyvinyl acetate emulsions cannot sufficiently overcome the above drawbacks.

[Means to solve the problem]

As a result of intensive research in order to improve the drawback of such conventional glue compositions, such as poor texture, the present inventors found that esters of acrylic acid or methacrylic acid and aliphatic saturated alcohols, styrene monomers and cationic monomers It has been discovered that a latex obtained by copolymerizing and having a small average particle diameter of 0.5- or less can make clothes feel good on the skin, and the adsorption to fibers at a high bath ratio is also significantly improved. Reached.

That is, the present invention relates to the following general formula (1) having a polymerizable unsaturated bond and two or more monomers selected from acrylic acid or methacrylic acid, an ester of an aliphatic saturated alcohol having 1 to 20 carbon atoms, and a styrene monomer. - An aqueous resin dispersion obtained by copolymerizing one or more cationic monomers selected from the cationic monomers represented by (7) in the presence of an emulsifying and dispersing agent, the average particle size of the aqueous resin is 0.5-
Provided is a household liquid glue composition comprising as an essential component an aqueous resin dispersion having the following properties and a glass transition temperature of 0°C to 60°C and a minimum film forming temperature of 50°C or less. .

(In the formula, R1: hydrogen atom or methyl group R21 R3, R4: same or different hydrogen atom, alkyl group having 1 to 4 carbon atoms or substituted alkyl group Y: oxygen atom or NH group in amide bond XCI, chlorine, Monovalent anions such as bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc. m: an integer of 1 to 10) (wherein, R51R & 1R?: the same or different, hydrogen atom, carbon number 1 to 2 alkyl group or substituted alkyl group 1 to 3 alkyl groups 1111:
Hydrogen atom or methyl group Xe: same as formula (1)) + 1 11 Ro. OHO (In the formula, R81R91R101RIll
3)) C113・MCI (In the formula, XO: (same as 11) CO3-CI ■ The aqueous resin dispersed in the aqueous resin dispersion constituting the thickening composition of the present invention has an average particle size of 0.5. trm or less, preferably 0.2- or less, and particles with a particle size of 0.5- or less account for 50% or more of the total weight of the dispersed resin, preferably 6
5% or more is preferably used. When the particle size of the latex exceeds 0.5 μm, the threads are bound to each other to a large extent, causing unevenness on the fiber surface, which tends to deteriorate the texture. The particle size of the polymer in this specification is determined by a light scattering method, and is measured using a Coulter Model N4 (submicron particle analyzer) manufactured by Coulter Electronics.

The glass transition temperature of the dispersed aqueous resin of the present invention is 0°C to 60°C.
However, preferably 0°C to 50°C is suitable. Tg is 0
If it is less than ℃, the tension of the cloth will be insufficient, making it unsuitable as a glue. Further, if the temperature exceeds 60° C., problems such as whitening occur with colored cloth. The glass transition temperature of the polymer used in this specification was that described in "Polymer Data Handbook Basic Edition" Polymer Data or rPolymer 1landbookJ. The Tg of a copolymer of two or more types of monomers is determined according to the following formula. For example, in the case of a copolymer of monomers A, B and C, Tg of the copolymer (Tg) A (Tg)
B(Tg).

(Tg)A, (Tg)++, (Tg). : A,
Tg of each homopolymer of B and C W, , W, , Wc: composition ratio of each of A, B, and C in the copolymer, and minimum film forming temperature (MFT) of the dispersion aqueous resin of the present invention
is required to be below 50°C, preferably below 35°C. This is because the ability of the dispersed aqueous resin to form a film on the fiber surface is closely related to its performance as a sizing agent. In this specification, the minimum film forming temperature refers to the temperature measured as follows. That is, the film forming temperature manufactured by Nippon Rigaku Kogyo ■ (
MPT) test equipment, a sample solution adjusted to 10% solid content was spread on a stainless steel plate with a temperature gradient to a film thickness of 0.2N, then dried, and the minimum value at which a uniform film was formed was obtained. The temperature was observed and measured with the naked eye (Reference J
, Applied PolymerScience I
V, 10.81-85 (1960)).

If the MFT is high, the condition of the resin during drying will be poor, and the adhesiveness required as a sizing agent will not be sufficiently developed, resulting in a significant decrease in tension performance. In such cases, the physical properties of the film can be improved by adding plasticizers to the resin used for boat fishing, but if the MFT specific to the dispersion water-based resin exceeds 50°C, the addition of these plasticizers will However, it becomes difficult to improve the physical properties of the film and exhibit its tensile performance.

Further monomers used include acrylic acid or methacrylic acid and aliphatic saturated alcohol (C+-Czo).
The most suitable monomers are esters and styrene-based monomers, and it is necessary to copolymerize two or more of these monomers. The purpose of this is to copolymerize these monomers to adjust the glass transition temperature of the polymer to 0°C to 60°C, which is suitable for use as a glue.
At the same time, it is believed that the physical properties of these copolymers are deeply involved in the finish feeling that is pleasant to the touch.

Further, in the present invention, it is necessary to copolymerize a specific cationic monomer into the polymer. This improves the adsorption of the emulsion and at the same time makes the adsorption state uniform on the fiber surface, giving a finished feel that is pleasant to the touch.

When clothing is treated with the starch composition of the present invention, it has a significantly better texture than conventional starches, and can be finished with a nice touch.

These effects are due to the fact that the emulsion latex particles are fine particles, so that the latex can uniformly adhere to the fibers without uniformly agglomerating.

In other words, with conventional emulsion-type glues, latex particles form clusters on the fiber surface, or preferentially adhere to the gaps or depressions between filaments, resulting in extremely poor adhesion. It was uniform. Such non-uniform adhesion is effective because it can efficiently restrict the movement of fiber filaments and threads to each other if the purpose is simply to create tension, but on the other hand, it can cause unnecessary damage to the surface of the fibers. Due to the unevenness formed, it felt stiff to the touch, which led to a poor texture.

On the other hand, when the particle size of the latex is made smaller, the latex particles uniformly cover the surface of the fibers and simultaneously adsorb to the contact points of the fiber filaments, resulting in unevenness on the surface of the fibers, unlike traditional glues. The effect is that there is no rough feeling when touched.

Acrylic acid or methacrylic acid used in the present invention and 0
Esters with aliphatic saturated alcohols of 1 to C2° include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, nonyl acrylate, Examples include nonyl methacrylate.

Preferred cationic monomers are the formulas (1) and (
2) and (3), particularly preferred are acrylic or methacrylic esters of trialkylammonium salts, vinylbenzyltrimethylammonium chloride, and those represented by the following formula (8).

C) 13 Ctlz = Cl1-CHz-0-CHz-CH-C
) Iz -N-Re
Preferably 0.05 to 6% by weight is used.

In order to produce the copolymerized aqueous resin dispersion of the present invention, it is generally synthesized by emulsion polymerization in an aqueous emulsifier dispersant solution, using an initiator if necessary, and adding monomers dropwise.
- A method may also be used in which solution polymerization is first performed in a polar solvent such as a lower alcohol or ketone, and then the solvent is replaced with water. In the case of emulsion polymerization, the order of dropping the monomers does not matter.

The emulsifier used in the present invention is selected from the following nonionic, anionic, and cationic surfactants.

Examples of cationic surfactants include alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylethylammonium salts, alkyldimethylbenzylammonium salts, alkylpyridinium salts, alkylquinolinium salts, alkylisoquinolinium salts, stearyl Amidomethylpyridinium salt, acylaminoethylmethyldiethylammonium salt, acylaminoethylpyridinium salt, alkoxymethylpyridinium salt, 1-methyl-1-acylaminoethyl-2-alkylimidacillin, diacylaminopropyldimethylammonium salt, diacyl Examples include aminoethylenemethylammonium salt, dialkyldi(polyoxyethylene)ammonium salt, and dialkylmethylpolyoxyethyleneammonium salt.

Examples of anionic surfactants include higher fatty alcohol sulfates prepared from sodium and potassium salts of sulfate esters of 08 to CIO alcohols such as lauryl alcohol, and sodium, potassium, and triethanolamines of fatty acids of C to CI3. ethanolamine salts such as triethanolamine oleate, triethanolamine stearate, funnel oil, sulfonic compounds such as sulfated wasylic acid, sulfonated alkylaryls such as sodium t-octylbenzene sulfonate, sodium t-octylphenol sulfonate. Examples include compounds.

Examples of nonionic surfactants are alkylphenoxypolyethoxyethanols with 07-Cl11 alkyl groups and 9-30 or more ethylene oxide units, such as heptylphenoxypolyethoxyethanol, octylphenoxypolyethoxyethanol, methyloctyl Phenoxypolyethoxyethanol, nonylphenoxypolyethoxyethanol, dodecylphenoxypolyethoxyethanol, etc., or polyethoxyethanol derivatives of alkylphenols linked with methylene bonds, mercaptans such as nonyl, dodecyl, tetradecyl, etc.
- Emulsifiers containing sulfur by condensation of CI3 alkylthiophenol with 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 It is an ethylene oxide derivative of an etherified or esterified polyhydroxy compound with a hydrocarbon chain. Nonionic surfactants have an HLB of 12
-19, preferably 15-18 are suitably used.

In addition to the cationic polymer, the thickening composition of the present invention further includes additives for general polymer emulsions, if necessary.
For example, antifreeze agents such as ethylene glycol, propylene glycol, and ethanol, other fragrances, disinfectants, preservatives, fluorescent dyes, pigments, thickeners, antifoaming agents, and the like can be added.

Further, plasticizers such as dibutyl phthalate, dibutyl adipate, dioctyl adipate, triacetin, etc. can be added within a range that does not impede the physical properties of the film of the aqueous resin composition of the present invention.

〔Example〕

The present invention will be described below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 300 parts by weight of ion-exchanged water, X parts by weight of Emulgen 150 (manufactured by Kao ■), 2. After adding 0.1 part by weight of 2'-azobis(2-amidinopropane) hydrochloride, the temperature was raised to 70°C, and then 7 parts by weight of methyl methacrylate, 2 parts by weight of butyl acrylate, and ethyl methacrylate were added. A mixture of 10 parts by weight of trimethylammonium chloride (manufactured by Nitto Kagaku ■) was added dropwise over 300 minutes to carry out polymerization. After the dropwise addition was completed, the mixture was left at 70° C. for 240 minutes to ripen, and then used as a sample.

The average particle diameter of the latex of the 16 types of samples obtained was measured using the Coulter Counter N4, and the latex was evaluated as a glue by the following method.

The test results are shown in Table 1.

(1) Pure bending test method Using a turbotometer-type cleaning tester, put 500 ml of ion-exchanged water and 0.4 g of the paste synthesized as above in a cleaning tank (1000 - internal volume) in solid content. After thoroughly dispersing the mixture, add 20g of 60# cotton cloth and stir for 3 minutes at a rotation speed of 100 rpm. After dehydration, air dry at 25℃.
After leaving it for a day and night in a constant temperature and constant temperature room at 65% relative humidity, the adhesive was subjected to an effectiveness test.

The above-mentioned gluing was carried out using a 2cm x 2.
Cut the pieces into 5 cm pieces, make a set of 10 pieces, and test the bending rigidity (g-cm) using a pure bending tester (manufactured by Kato Iron Works) in a thermostatic room at 25°C and 565% relative humidity. It was measured.

(2) Evaluation of Tightness Using a normal household washing machine, add 20g of the active ingredient of the sizing base to 30A tap water, disperse well, add 1000g of cotton sheets, and stir and glue for 3 minutes. 30 in a dehydrator
After dehydrating for a few seconds, air dry. The performance of each base material was evaluated by performing a tactile test on the tension of the cloth treated with the above-mentioned method by a pair of comparisons conducted by 10 people.

+2: Stretchy +1 = Slightly taut 0: Same as control -1: Slightly not taut - 2: Not taut (3) Texture evaluation The cotton sheets treated in the same manner as in (2) were evaluated as follows. Performance was evaluated using evaluation criteria.

+2: Good texture +1 = Slightly smooth texture 0: Same as control -1: Slightly poor texture - 2 = Poor texture Example 2 Using the same apparatus as in Example 1, 300 parts by weight of ion-exchanged water, Emulgen 935 (manufactured by Kao ■) 4.0 parts by weight, 2
, 2′-azobis(2-amidinopropane) hydrochloride 0.
After adding 1 part by weight, the temperature was raised to 70°C without stirring, and the monomers (A) and (B) shown in Table 2 and ethyl methacrylate and methyl ammonium chloride were added at 3.0° C.
Parts by weight of the mixture were added dropwise over 300 minutes to carry out polymerization. After completion of dropping, the mixture was left to stand at 70° C. for 240 minutes to ripen, and then used as a sample. Table 2 shows the evaluation results of the obtained samples.

Example 3 Using an apparatus similar to Example 1, 300 parts by weight of ion-exchanged water, 3.0 parts by weight of Emulgen 150 (manufactured by Kao ■), 2
．． 2”-azobis(2-amidinopropane) hydrochloride 0.
After adding 1 part by weight, the temperature was raised to 70°C, and a mixture of 45 parts by weight of ethyl methacrylate, 50 parts by weight of 2-ethylhexyl acrylate, and cationic monomer X part by weight was added dropwise over 300 minutes to perform polymerization. .

After completion of the dropwise addition, the mixture was left at 70° C. for 240 minutes to ripen, and then used as a sample. Table 3 shows the evaluation results of the obtained samples.

Claims (1)

[Scope of Claims] 1 A compound having the following general formula ( An aqueous resin dispersion obtained by copolymerizing one or more monomers selected from the cationic monomers represented by 1) to (7) in the presence of an emulsifying and dispersing agent, the average particle size of the aqueous resin is 0.5 μm or less,
A household liquid paste composition comprising as an essential component an aqueous resin dispersion having a glass transition temperature of 0°C to 60°C and a minimum film forming temperature of 50°C or less. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (1) (In the formula, R_1: hydrogen atom or methyl group R_2, R_3, R_4: same or different, hydrogen atom, alkyl group having 1 to 4 carbon atoms, or substituted alkyl group) Y: Oxygen atom or NH group in an amide bond : Same or different, hydrogen atom, alkyl group or substituted alkyl group having 1 to 2 carbon atoms :C8-22 which may have a substituent
Hydrocarbon group R_9, R_1_0: Alkyl group with 1 to 3 carbon atoms R_1_1: Hydrogen atom or methyl group , R_8, R_9, R_1_0, R_1_1, X
^■: Same as formula (3)) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(5) (In the formula, R_8, R_9, R_1_0, R_1_1, X
^■: Same as formula (3)) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(6) (In the formula, X^■: Same as formula (1)) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(7 )