JPS60155776A - Cationic non-accumulation type washing size - 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] [Technical field of invention] The present invention relates to cationic non-accumulative laundry starches.

More specifically, it relates to a laundry paste that is designed to be electrically attracted to the fabric to be glued in a glue bath, thereby sizing the fabric, and to elute the adsorbed main ingredients along with dirt during washing.

When pasting fabrics with starch paste, which has traditionally been used as laundry starch, or non-ionic laundry starch such as polyvinyl acetate emulsion, the fabric is dipped in a starch bath, squeezed, and the required amount is applied to the fabric. It was necessary to increase the concentration of the paste bath so that the main ingredients remained, and the paste that was squeezed out and not included in the fabric was wasted.

Recently, attention has been focused on the fact that textiles become negatively charged in water, and a cationic laundry glue has been developed that electrophoresizes and is adsorbed in water.

With cationic laundry starch, if the necessary amount for the fabric to be glued is present in the bath, no matter how thick the bath concentration is, that is, no matter how much water there is, almost all of the starch will be applied to the fabric. Because it is adsorbed to the laundry, there is no need to dehydrate it when sizing the laundry. Just add the required amount of Oyashiro to the water after rinsing, and the sizing can be done evenly. Moreover, there is almost no loss to waste water. This has the advantage of being completely eliminated.

However, this kind of cationic laundry glue also has a drawback; it is extremely electrically adsorbed, so if the fabric becomes dirty, the glue will not come off even after washing, and the dirt will gradually accumulate. A problem arose.

The present inventors proposed an alkali-soluble cationic polyvinyl acetate emulsion, which is a copolymerization of crotonic acid and vinyl acetate, in order to prevent the aforementioned drawbacks (Japanese Patent Publication No. 5
7-29485).

When fabrics pasted with this emulsion are washed with a heavy-duty detergent, the detergent's alkali makes the paste water-soluble, making it extremely easy to remove the adhesive.

However, as stated in the same publication, vinyl acetate and unsaturated carboxylic acids are difficult to emulsion polymerize, and a small amount of p-tonic acid can be practically copolymerized, so we were able to propose this. Unsaturated carboxylic acids other than crotonic acid are emulsion copolymerized with vinyl acetate. Tonic acid has the problem of being difficult to emulsion copolymerize with acrylic monomers.
The challenge was to solve this problem.

As a result of subsequent research, the present inventors discovered that by using a chain transfer agent during polymerization, vinyl acetate can be copolymerized with acrylic acid, methacrylic acid, itaconic acid, maleic acid, etc., which had previously been difficult to copolymerize. The present invention was completed by discovering that acidic acid, acrylic esters, methacrylic esters, etc., that is, unsaturated carboxylic acids and vinyl monomers, can be easily copolymerized to form a stable emulsion.

That is, the present invention comprises A (1) a chain transfer agent, (2) a water-soluble cationic polymer, and (3) optionally a water-soluble colloid, B (1) a vinyl monomer, and (2) an inorganic monomer. This is a cationic non-accumulative laundry starch whose main ingredient is a copolymer emulsion obtained by emulsion polymerization of saturated carboxylic acid.

Chain transfer agents used in the present invention include hydrocarbons such as benzene, toluene, and cyclohexane, halogen-based agents such as carbon tetrachloride, bromotrichloromethane, alcohol-based agents such as ethanol and isopropanol, phenol, and 6-methylphenol. Phenols, carbonyls such as acetaldehyde and butionaldehyde, esters such as ethyl acetate and methyl glycolate, nitrogen compounds such as triethylamine and nidotetramethane, ethers such as butyl ether and benzyl methyl ether, n - Examples include sulfur compound-based agents such as butyl mercaptan and diethyl dithioglycolate, and acid-based agents such as acetic anhydride and benzoic acid.
For coloring and hygiene reasons, alcohol-based (ethanol, isobutetrapanol) and carbonyl-based (acetaldehyde,
(e.g., tetrapionaldehyde) are suitable.

Water-soluble cationic polyester used in the present invention! - includes cationic starch, cationic cellulose, cationic polyvinyl alcohol and other cationic polymer electrolytes.

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

3 (wherein, A: starch residue or cellulose residue, Ro: alkylene or hydroxyalkylene group, R).

R2, R3: are the same or different, and may form a heterocycle by including an alkyl group, allyl group, aralkyl group, or a nitrogen atom in the formula, X←): anion (chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.), no positive integers. ] To make such a cationic starch, for example, glycidyltrimethylammonium chloride or 6-chloro-2-starch is added to the starch under alkaline conditions.
Human hydroxypropyltrimethylammonium chloride may also be reacted. Further, dimethylaminoethylated starch may be quaternized.

Furthermore, it can also be obtained by reacting starch with 4-tetraruputent trimethylammonium chloride.

Cationic cellulose can be obtained, for example, by subjecting hydroxyethyl cellulose to the above reaction.

The degree of substitution of cationic groups in cationic starch or cationic heptadylose is 0.01 to 1 per mole of anhydroglucose group.
Moles, preferably 0.02 to 0.5 moles are suitable.

If it is less than 0.01 mol, the effect of the present invention is not sufficient, and if it is more than 1 mol, it is not suitable from the viewpoint of reaction rate.

The cationic polyvinyl alcohol is preferably one cationized with a quaternary ammonium group. Methods for introducing quaternary ammonium groups into polyvinyl alcohol include reacting polyvinyl alcohol with a quaternary ammonium salt containing a glycidyl group, or etherifying polyvinyl alcohol with shrimp flurhydrin and then aminating it. There is.

The degree of cationic group substitution of cationic polyvinyl alcohol is 0.0 per mole of hydroxyl group of polyvinyl alcohol.
It is preferably 1 mol or more.

Examples of other cationic polymer electrolytes include those of the following formula.

4 ■ [In the formula, R4; hydrogen atom or methyl group, R5, R6, R
rt: Same or different 1. Hydrogen atom, carbon number 1-4
alkyl group or substituted alkyl group, Y: oxygen atom or NH group in amyl bond, X←): anion (chlorine, bromine,
anion such as iodine, sulfuric acid, sulfonic acid, methyl sulfate, phosphoric acid, nitric acid, etc.), m: an integer of 1 to 10] In formula C, R8, R8, R. : Same or different, hydrogen atom, alkyl group having 1 to 2 carbon atoms, or substituted alkyl group (→ alkyl group, chloride (in the formula, Q represents an allyl group) H3 Quaternary polyethyleneimine salt ditertiary amine Shibalai F#iJ compound (in the formula,
xly is 1 or more, R represents an alkyl group) 1. Condensate of 6-di-4-pyridylpropane and dino-1lide alkane (-0H2-OH) 1 Light trimethylammonium chloride] sulfonium chloride) The water-soluble polymeric protective compound used in the present invention includes:
Polyvinyl alcohol or its derivatives having a degree of saponification of 70 mol or more and a degree of polymerization of 500 to 600 degrees, and nonionic cellulose derivatives such as hydroxyethyl cellulose, hydroxyprevyl cellulose, and methyl cellulose are suitable.

Vinyl monomers used in the present invention include vinyl acetate, vinyl propionate, vinyl esters of lower fatty acids such as vinyl esters of saturated fatty acids branched at the α position, alkyl acrylates, alkyl methacrylates, α, Diesters of β-ethylenically unsaturated dicarmenic acids, styrene, ethylene, vinyl chloride, acrylamide,
Examples include monomers such as N-methylolacrylamide and cationic monomers such as N-vinyl-N-(3'-dimethylaminopropyl)-7damide and trimethylaminoyl acrylate acrylate. .

Examples of the unsaturated carboxylic acid used in the present invention include acrylic acid, methacrylic acid, ricitonic acid, maleic acid, itaconic acid, and monoesters of unsaturated dicarboxylic acids such as itaconic acid and maleic acid.

The usage ratio of vinyl monomer and unsaturated carboxylic acid is 10
0 heavy lid part: The range of 0.1 to 60 heavy lid part is preferable.

In the present invention, when emulsion copolymerizing a vinyl monomer and an unsaturated carboxylic acid, a nonionic surfactant or a cationic surfactant may be used in combination, if necessary.

Examples of nonionic surfactants that can be used in combination include polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxyethylene alkyl ester, sorbitan alkyl ester, polyoxyethylene sorbitan alkyl ester, and polyoxyethylene topolyoxyptetrapyrene. Particularly useful nonionic surfactants are polyoxyethylene alkylphenol ethers such as polyoxyethylene octylphenol ether and polyoxyethylene nonylphenol ether.

In addition, examples of cationic surfactants include quaternary ammonium salts, alkyl amine salts, alkyl biridium halides, alkyl bicorylum hydrides, benzalkonium succilides, akylamidomethylpyridium chlorides, and alkyloxy Methylpyridium chloride, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and particularly useful nacationic surfactants include lauryltrimethylammonium chloride,
Quaternary ammonium salts such as stearyltrimethylammonium chloride.

In order to produce the cationic non-accumulative laundry starch of the present invention, vinyl monomers and unsaturated carboxylic acids are subjected to emulsion polymerization using a conventional emulsion polymerization method in the presence of the aforementioned chain transfer agent and water-soluble cationic polymer. good.

The amount of the chain transfer agent to be used is preferably 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of vinyl monomer and unsaturated carmenic acid.

The amount of the water-soluble thione pirimer used is 0.5 parts by weight or more based on 100 parts by weight of the vinyl monomer and unsaturated carboxylic acid when used alone, and 0.5 parts by weight when used in combination with a surfactant.
1 part by weight or more is preferred.

Typical emulsion polymerization methods include a monomer dropping emulsion polymerization method, an emulsifying monomer dropping emulsion polymerization method, a batch charging emulsion polymerization method, a split charging emulsion polymerization method, a seed emulsion polymerization method, and the like.

The polymerization initiator used during emulsion polymerization is not particularly limited, but the stability of the emulsion using an azo polymerization initiator or a redox polymerization initiator is unlikely to be impaired.

This emulsion can be used alone as a cationic non-accumulative laundry glue, but if necessary, it may be added with plasticizers such as dibutyl adipate, dioctyl adipate, triacetin, etc., ethylene glycol, brypylene glycol, etc.
Antifreeze agents such as ethanol, other coloring agents, bactericidal agents, preservatives, fluorescent dyes, linting agents, fragrances, and the like can be added.

According to the present invention, the emulsion copolymerization of acrylic acid, methacrylic acid, itaconic acid, etc., with vinyl acetate, and the emulsion copolymerization of acrylic acid ester, methacrylic acid ester, etc. with p-tonic acid, which had been considered difficult in the past, have become stable. can be done,
The resulting emulsion is also extremely stable, making it possible to provide laundry paste of excellent quality.

Next, the present invention will be explained with reference to Examples, Comparative Examples, and Test Examples.

Example 1 A polymerization reactor equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel was ion-exchanged with polyvinyl alcohol 69 having a 200014% aqueous solution with a viscosity of about 30 mPa5 and a saponification degree of 86.5-89 mol%. 110 g of water was added and the internal temperature was raised to 100°0 to dissolve. This is about 40
After cooling to °O, ethanol 109 was added and then etherified with a quaternary amine to form a cationic starch (degree of cationic group substitution 0.1, nitrogen content approximately 0.8% by weight).
6 g of sodium carbonate and an aqueous sodium carbonate solution prepared by dissolving 0.5 g of sodium carbonate in 5 g of ion-exchanged water were added, and while the air in the reaction vessel was replaced with nitrogen gas, the internal temperature was raised to 68 to 70 O0.

Separately, 2 g of crotonic acid is mixed and dissolved in vinyl acetate 989, and this mixed monomer 109 is placed in a reaction container.
Polymerization was initiated by adding 6 g of an aqueous solution prepared by dissolving persulfate power IJ 0.69 in 12 g of ion-exchanged water. Polymerization start 6
After 0 minutes, the remaining 90 g of the mixed monomer and the remaining 99 g of the potassium persulfate aqueous solution were added dropwise over 4 hours to carry out a polymerization reaction.
% cationic emulsion was obtained. pH during polymerization reaction
was kept at 4-5.

Examples 2 to 8 Using the same method as in Example 1, using a chain transfer agent, a water-soluble cationic polymer, a vinyl monomer, and an unsaturated carboxylic acid having the composition shown in Table 1, and using or not using a polymeric protective colloid. A stable cationic non-accumulative emulsion was obtained by carrying out a polymerization reaction.

Comparative Examples 1 to 4 When a polymerization reaction was carried out using the components of the composition shown in Table 1 in the same manner as in Example 1, none of them agglomerated or agglomerated during the reaction.
A stable emulsion could not be obtained due to precipitation and formation of lumps.

Comparative Examples 5 to 6 A polymerization reaction was carried out in the same manner as in Example 1 using the components shown in Table 1 to obtain emulsions for comparison.

Test Examples 1 to 10 Using the emulsions obtained in Examples 1 to 8 and Comparative Examples 5 and 6, cotton plaid #40 was glued, and the upholstery hardness and cleaning rate were evaluated. The results are shown in Table 2.

The test method used was as follows.

Gluing method: Add 0.669 of the resin content of the emulsions obtained in the Examples and Comparative Examples to 300 mJ of tap water and disperse well.
4g of cotton braid #40 was dipped into it. Next, I put it in a strong washing toughness tester for 5 minutes, dehydrated it for 1 minute in a household washer-extractor, air-dried it, and put it in an iPen press to 20°0.
．． It was stored in a 65% constant temperature and humidity room.

Artificial contamination and washing method: A starched cotton plaid #40 was immersed in an artificial contamination solution for 10 minutes and then air-dried to prepare a contaminated cloth, and then a commercially available detergent (
Kao soap cap and two knee beads) 0.13% aqueous solution (25'
The contaminated cloth was washed for 10 minutes in a domestic washing machine filled with j)), rinsed for 5 minutes, and air-dried. The artificially contaminated liquid used consisted of 1 g of butter, 39 g of liquid paraffin, 0.8 g of carbon black, and 500 g of carbon tetrachloride.

Upholstery hardness: Measured by cantilever method.

Cleaning efficiency: The reflectance was measured using a search unit of a photoelectric gloss meter To-108D (manufactured by Tokyo Denshoku Kin), and the cleaning efficiency was calculated using the following formula.

Claims (1)

[Claims] 1. Emulsion copolymerization of B (1) a vinyl monomer and (2) an unsaturated carboxylic acid in the presence of A (1) a chain transfer agent and (2) a water-soluble cationic polymer. A cationic, non-accumulative laundry glue whose main ingredient is a copolymer emulsion. 2. The cationic non-accumulative laundry starch according to claim 1, wherein the chain transfer agent is an alcohol chain transfer agent and/or a carbonyl chain transfer agent. 6 Is the water-soluble cationic polymer cationic starch, cationic cellulose, or cationic? The cationic non-accumulative laundry starch according to claim 1 or 2, which is one or more selected from the group of ribinyl alcohol and other cationic polymer electrolytes. 4. The cationic non-accumulative laundry starch according to claim 1, 2 or 3, wherein the vinyl monomer is a lower fatty acid vinyl ester. 5 The unsaturated carboxylic acid is selected from the group of acrylic acid, methacrylic acid, crotonic acid, maleic acid, and itaconic acid.
The cationic non-accumulative laundry starch according to claim 1, 2, 3 or 4, which is one or more types. 6 Emulsify B (1) vinyl monomer and (2) unsaturated carbic acid in the presence of A (1) chain transfer agent, (2) water-soluble thione gelimer, and (8) water-soluble retaining colloid. A cationic non-accumulative laundry starch whose main ingredient is a copolymer emulsion. 7. The cationic non-accumulative laundry starch according to claim 6, wherein the chain transfer agent is an alcohol chain transfer agent and/or a carbonyl chain transfer agent. 8. Claim 6, wherein the water-soluble cationic polymer is one or more selected from the group of cationic starch, cationic heptalulose, cationic polyvinyl alcohol, and other cationic polymer electrolytes. Or the seventh
Cationic non-accumulative laundry starch as described in Section 1. 9. The cationic non-accumulative laundry starch according to claim 6, 7, or 8, wherein the water-soluble protective near-pide is polyvinyl alcohol and/or a nonionic 7-alcohol derivative. 10. The cationic non-accumulative laundry starch according to claim 6, 7, 8 or 9, wherein the vinyl yarn monoplane is a lower fatty acid vinyl ester. 11 Unsaturated carboxylic acid is acrylic acid, methacrylic acid,
The cationic non-containing compound according to claim 6, 7, 8, 9, or 10 is one or more selected from the group of crotonic acid, maleic acid, and itafonic acid. Accumulative laundry glue 0