JPH1072776A - Emulsion type laundering paste and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a laundering paste high in adsorbability to cellulose fibers and good in storage stability, and to provide a method for producing the same. SOLUTION: This emulsion type laundering paste comprises an emulsion having a par ticle diameter of 0.1-1.0μm and produced by preliminarily copolymerizing (a) a polymerizable unsaturated group-having quaternary ammonium salt with (b) vinyl acetate and (c) a monomer capable of being copolymerized with the vinyl acetate (b) in an amount of 1-50wt.% based on the whole amount of the used monomers, adding the remaining components (b) and (c) and subsequently emulsion-polymerizing the mixture. The method for producing the emulsion type laundering paste comprises the above-mentioned processes.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laundry paste comprising a cationic emulsion having a high degree of cationization, and more particularly, has a high adsorptivity to cellulosic fibers, provides sufficient firmness even when used in a small amount, and has excellent storage stability. And a method for producing the same.

[0002]

2. Description of the Related Art Starch has been conventionally used for household laundry paste, but various studies have been made to make it easier to use, and at present, many products are based on vinyl acetate synthetic resin emulsions. Occupy. This is because the paste can be glued simply by diluting it with water and immersing the clothes at the time of use, and does not require heat treatment for dissolution like starch.In the finish, the emulsion system is thicker than the starch-like feel of paper. The reason is that a certain feeling is felt, and a recent feeling of a casual-oriented and thick feeling is preferred. Vinyl acetate emulsions using ordinary water-soluble polymers as protective colloids
Compared to other resin compositions, the particle size is relatively large and is easily adsorbed to the fibers during gluing, and vinyl acetate has the advantage of being familiar with cellulose fibers. However,
Gluing is performed with a low concentration (high bath ratio) by diluting with water.
With conventional vinyl acetate emulsions having a large particle size, sufficient adsorption cannot be obtained, and not only hardness is not sufficient,
Due to the large particle size, there was a drawback that the viscosity increased during storage and the fluidity became poor, and particles precipitated at the bottom of the container.

In order to solve this problem, various studies have been made to improve the adsorption efficiency even when used at a low concentration. One of them is to cationize the emulsion,
This is to selectively adsorb to a negatively charged cellulose substrate. Various studies have been conducted on the cationization of this emulsion, for example, emulsion polymerization using a cationic surfactant as an emulsifier, blending of a cationic water-soluble polymer with a nonionic emulsion, Emulsion polymerization using a water-soluble polymer as a protective colloid is known. However, the method using a cationic surfactant has a problem that free surface activity not present on the particle surface pollutes the environment as a waste liquid and adversely affects the human body via the processed base material. In the method in which the cationic water-soluble polymer is blended with the nonionic emulsion, good adsorption is not recognized because the particle surface cannot be cationized. In the emulsion polymerization method using a cationic water-soluble polymer as a protective colloid, the cationic polymer is adsorbed on the particle surface at the emulsion stage, but the degree of cationization is not sufficiently high due to the structure of the cationic water-soluble polymer. In addition, there is a problem that only the water-soluble polymer, which is a protective colloid, selectively adsorbs to the cellulose fiber, and the emulsion particles themselves do not adsorb to the substrate.

[0004]

As a result of studying to solve the drawbacks of the conventional cationic emulsion-based laundry paste, the use of a cationic polymer and a specific polymerization method allows a high degree of cationization and an appropriate degree of cationization. An emulsion having a particle size was obtained, and it was found that these problems could be solved.

[0005]

Means for Solving the Problems The present invention provides: (1) an aqueous solution of one or more cationic polymer protective colloids selected from cationic starch, cationic cellulose and cationic polyvinyl alcohol;
A quaternary ammonium salt having a polymerizable unsaturated group, (b) vinyl acetate in an amount of 1 to 50% by weight of the total amount used, and (c)
An emulsion type emulsion comprising a monomer copolymerizable with vinyl acetate, which is initially polymerized, and then the remaining components (b) and (c) are added and emulsion-polymerized to a particle size of 0.1 to 1.0 μm. Laundry paste. 2. 2. The emulsion type laundry paste according to item 1, wherein the monomer of the component (c) is one or more selected from vinyl esters other than vinyl acetate, (meth) acrylic acid esters, and unsaturated carboxylic acids. 3. The amount of the cationic polymer protective colloid used is (b)
0.5 to 5.0% by weight based on the total amount of the component and the component (c)
3. The emulsion-type laundry paste according to paragraph 1 or 2. 4. The quaternary ammonium salt having a polymerizable unsaturated group as the component (a) is used in an amount of 1.0 to 20% by weight based on the total amount of the components (b) and (c). An emulsion-type laundry paste according to any one of the preceding claims. 5. In an aqueous solution of one or more cationic polymer protective colloids selected from cationic starch, cationic cellulose and cationic polyvinyl alcohol, (a)
A quaternary ammonium salt having a polymerizable unsaturated group as a component, a part of vinyl acetate as a component (b), and a monomer copolymerizable with a component (b) as a component (c) are initially used. Polymerized,
Then, the remaining components (b) and (c) are added and emulsion-polymerized to form an emulsion having a particle size of 0.1 to 1.0 μm, thereby producing a washing paste. About.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION In a reactor, an aqueous solution of one or more cationic polymer protective colloids selected from cationic starch, cationic cellulose and cationic polyvinyl alcohol is charged, and the temperature is raised. Fourth
A quaternary ammonium salt, vinyl acetate and a monomer copolymerizable with vinyl acetate are added, and initial polymerization is carried out with a polymerization initiator. Next, the remaining mixture of vinyl acetate and a monomer copolymerizable with vinyl acetate is added dropwise, an appropriate polymerization initiator is added thereto, and emulsion polymerization is performed to obtain an emulsion-type laundry paste having a particle diameter of 0.1 to 1.0 μm. Can be Initial polymerization of a quaternary ammonium salt having a polymerizable unsaturated group, 1 to 50% by weight of the total amount of vinyl acetate, and a monomer copolymerizable with vinyl acetate in a cationic polymer protective colloid aqueous solution Then, the remaining vinyl acetate and the monomer copolymerizable with vinyl acetate are added dropwise to carry out emulsion polymerization to perform a two-stage polymerization step, whereby the particle surface is cationized and a polymerization system using a protective colloid is used. As a relatively small particle size of 0.1 to 1.0
A μm emulsion is obtained.

The quaternary ammonium salt having a polymerizable unsaturated group of the component (a) used in the present invention is a compound represented by the formula (I). When it is used for the initial polymerization, it is relatively oriented on the particle surface due to its hydrophilicity, and contributes to cationization of the particle surface and also contributes to the stability of the particle. Compounds having the structural formula of formula (I) include compounds of formula (I)

[0008]

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(Wherein R and R 'each have 1 to 2 carbon atoms)
Represents an alkyl group having 0 carbon atoms, and R ″ has 1 to 1 carbon atoms.
R represents an alkyl group having 20 or an aromatic or alicyclic group having 6 to 15 carbon atoms, and R "" is an aliphatic hydrocarbon group having 2 to 6 carbon atoms and having one ethylene bond. And X represents a base or a bromine atom. As specific examples, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-acryloxypropyltrimethylammonium chloride, 2-hydroxy-3-methacryloxypropyltriethylammonium bromide,
2-hydroxy-3-methacryloxypropyltributylammonium chloride, 2-hydroxy-3-
Examples thereof include methacryloxypropylmethylethylbutylammonium chloride, 2-hydroxy-3-methacryloxypropyldimethylphenylammonium chloride, and 2-hydroxy-3-methacryloxypropyldimethylcyclohexylammonium chloride. These can be used alone or in combination of two or more. Among them, 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride is particularly preferred. The amount used is 1 to 20% by weight based on the total amount of the components (b) and (c). If the amount is less than 1 part by weight, the degree of cationization does not increase and the polymerization stability is insufficient. If the amount is more than 20 parts by weight, unreacted substances remain and the stability of the emulsion becomes poor.

The component (c) used in the present invention, ie, a monomer copolymerizable with vinyl acetate, includes vinyl esters other than vinyl acetate, alkyl (meth) acrylates,
Examples of the unsaturated carboxylic acid include vinyl propionate and vinyl as vinyl esters other than vinyl acetate, and Veova (vinyl ester of saturated carboxylic acid, manufactured by Shell Chemical Co., Ltd.), and ethyl acrylate as (meth) acrylate. Methyl methacrylate, n-butyl acrylate, t-butyl acrylate, 2-ethylhexyl acrylate, and the like, and among them, one having 1 carbon atom
(Meth) acrylic acid esters having from 4 to 4 alkyl groups are preferred. Examples of the unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, maleic acid and the like.
Other than these, ethylene, vinyl chloride, styrene, acrylonitrile, methacrylamide, N-methylolacrylamide, divinylbenzene, ethylene glycol dimethacrylate, hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, acetoacetoxyethyl methacrylate and the like can also be used. . Preferred as the component (c) are ethyl acrylate, methacrylic acid, and a combination of ethyl acrylate and methacrylic acid.

Examples of the cationic polymer used as the protective colloid include cationic starch, cationic polyvinyl alcohol, and cationic cellulose, and one or more of these are used. Specifically, as the cationic starch or the cationic cellulose, for example, those represented by the formula (11) are preferable. Equation (11)

[0012]

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(Where A is a starch residue or a cellulose residue, R is an alkylene group or a hydroxyalkylene group,
R ₁ , R ₂ , and R ₃ are the same or different and may form a heterocyclic ring containing an alkyl group, an aryl group, an aralkyl group or a nitrogen atom in the formula. X is an anion such as chlorine, bromine, iodine, sulfuric acid, sulfonic acid, methylsulfuric acid, phosphoric acid, nitric acid, and 1 is a positive integer;

As the cationic polyvinyl alcohol, for example, those represented by the formula (111) are preferable. Formula (I
II)

[0015]

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Wherein R ¹ is a hydrogen atom or a lower alkyl group, D is an alkyl group connecting the nitrogen atom of B to the amide group, and B is a group represented by the formula (IV) or (V) Formula (IV)

[0017]

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(Wherein R ² , R ³ and R ⁴ are lower alkyl groups) Formula (V)

[0019]

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[0020] (during ^{R 2} formula ^wherein, R 3, ^{R 4} is a lower alkyl group, X represents a group of negative forming the ammonium nitrogen and salt.) These water-soluble polymers 5-20% aqueous solution Used in When used in a dilute aqueous solution of 5% or less, the non-volatile content of the emulsion becomes low, the viscosity of the emulsion becomes low, and the particles tend to settle. On the other hand, if it is used with a high non-volatile content of 20% or more, the viscosity of the aqueous solution becomes too high and stable polymerization cannot be performed. Preferably it is around 10%.

Examples of the polymerization initiator include 2,2-azobis (2-amidinopropane), hydrogen peroxide, t-butyl peroxide, cumene hydroperoxide, t-butyl peroxide, methyl ethyl ketone hydroperoxide, and cyclohexanone. Examples thereof include hydroperoxide, peracetic acid, and perbenzoic acid, and are preferably used in the range of 0.01 to 5.0% by weight based on the total amount of the components (b) and (c). The polymerization reaction is an initial polymerization,
It is carried out in two stages of the subsequent polymerization. In the initial polymerization, a quaternary ammonium salt having a polymerizable unsaturated group of the component (a), one part of vinyl acetate of the component (b) and vinyl acetate of the component (c) are copolymerized in the presence of a cationic polymer aqueous solution. A polymerizable monomer is charged. This is very important in adjusting the particle size of the emulsion of the initial polymerization. The particles formed in the initial polymerization grow in the subsequent polymerization to become final particles. In other words, basically no new particles are generated in the subsequent polymerization, and the number of particles in the initial polymerization is maintained until the subsequent polymerization. Therefore, if the number of particles is determined in the initial polymerization and the amount of the monomer is adjusted in the subsequent polymerization, particles having a specific diameter are naturally obtained.

Component (b) used in the initial polymerization, (c)
The amount of the component is 1 to 1 with respect to the total amount of the component (b) and the component (c).
50% by weight. If the amount is less than 1% by weight, the polymerization stability is poor and a good emulsion cannot be obtained. If it exceeds 50% by weight, the particle size becomes too large, the stability of the emulsion becomes poor, and the control of the reaction becomes difficult. Preferably it is 1.0 to 10.0% by weight. The second stage polymerization is carried out by adding a monomer copolymerizable with the remaining vinyl acetate of component (b) and vinyl acetate of component (c). For more information,
The monomers of component (b) and component (c) are individually or mixed and polymerized by dropping. If necessary, additives such as an antifoaming agent, a preservative, a thickener, a pH adjuster, a plasticizer, a fluorescent brightener, a fragrance, a pigment, an antifreezing agent, and a lubricant such as silicone may be added to the obtained emulsion. be able to.

[0023]

【Example】

Example 1 To a separable flask equipped with a stirrer, a monomer metering device, a thermometer and a cold flow cooler, 1.0 part by weight of cationic starch was added together with 30 parts by weight of ion-exchanged water.
2. C. to dissolve, cool to 60.degree.
0 parts by weight, and after heating to 70 ° C, 2-hydroxy-3
-8.0 parts by weight of methacryloxypropyltrimethylammonium chloride, 2.0 parts by weight of vinyl acetate and 0.5 parts by weight of ethyl acrylate were charged, and 2,2'-azobis (2-amidicyclopropane) hydrochloride was used as an initiator. 0.2% by weight of a 5% aqueous solution was added to carry out initial polymerization for 30 minutes. Subsequently, a mixture of 38 parts by weight of vinyl acetate and 9.5 parts by weight of ethyl acrylate and 0.2 part by weight of 2,2'-azobis (2-amidicyclopropane) hydrochloride in 5 parts
% Aqueous solution was continuously dropped over 5 hours. 80 after dropping
The reaction was completed by aging at 1 ° C. for 1 hour.

Example 2 Example 1 was repeated except that 1.0 part by weight of cationic starch was changed to 1.0 part by weight of cationic hydroxyethyl cellulose.
Same as.

Example 3 The procedure of Example 1 was repeated, except that 1.0 part by weight of the cationic starch was changed to 1.0 part by weight of the cationic polyvinyl alcohol.

Example 4 2.0 parts by weight of vinyl acetate and 0.5 parts by weight of ethyl acrylate used for the initial polymerization were replaced by 2.0 parts by weight of vinyl acetate, 0.25 parts by weight of ethyl acrylate, and 0.1 part by weight of methacrylic acid.
25 parts by weight and the subsequent polymerization of vinyl acetate 38
Example 1 was repeated except that the mixture of parts by weight and 9.5 parts by weight of ethyl acrylate was changed to a mixture of 38 parts by weight of vinyl acetate, 4.75 parts by weight of ethyl acrylate, and 4.75 parts by weight of methacrylic acid.

Example 5 Polymerization was carried out by changing 2.0 parts by weight of vinyl acetate and 0.5 parts by weight of ethyl acrylate used for the initial polymerization to 4.0 parts by weight of vinyl acetate and 1.0 parts by weight of ethyl acrylate. 38 parts by weight of vinyl acetate and 9.5 ethyl acrylate
Example 1 was repeated except that the parts by weight were changed to 36 parts by weight of vinyl acetate and 9.0 parts by weight of ethyl acrylate.

Example 6 2.0 parts by weight of vinyl acetate and 0.5 parts by weight of ethyl acrylate used for the initial polymerization were converted to 1.5 parts by weight of vinyl acetate, 0.5 parts by weight of butyl acrylate, and 0.25 parts by weight of methyl acrylate. And 0.25 parts by weight of methacrylic acid, followed by 38 parts by weight of vinyl acetate and 9.5 parts by weight of ethyl acrylate for the subsequent polymerization, 28.5 parts by weight of vinyl acetate,
Example 1 was repeated except that 9.5 parts by weight of butyl acrylate, 4.75 parts by weight of ethyl acrylate and 4.75 parts by weight of methacrylic acid were used.

Example 7 The procedure of Example 1 was repeated, except that 8.0 parts by weight of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride was changed to 6.0 parts by weight.

Example 8 Example 1 was repeated except that 8.0 parts by weight of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride was changed to 10.0 parts by weight.

Comparative Example 1 To a separable flask equipped with a stirrer, a monomer metering device, a thermometer and a cold flow cooler, 1.0 part by weight of cationic starch was added together with 30 parts by weight of ion-exchanged water.
° C, and cooled to 60 ° C. Then, 6.0 parts by weight of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride and 3.0 parts by weight of ethanol were added, and after heating to 70 ° C, 2,2 Polymerization was started by adding 0.2% by weight of '-azobis (2-amidicyclopropane) hydrochloride as a 5% aqueous solution, followed by polymerization for 2 hours to obtain an aqueous resin solution in which cationic starch and a cationic vinyl polymer coexist. Was. A 5% aqueous solution of a mixture of 40 parts by weight of vinyl acetate and 10 parts by weight of ethyl acrylate and 0.2 part by weight of 2,2'-azobis (2-amidicyclopropane) hydrochloride was continuously dropped over 5 hours. After completion of the dropwise addition, the mixture was aged at 80 ° C. for 1 hour to complete the reaction.

Comparative Example 2 The procedure of Example 1 was repeated except that 1.0 part by weight of the cationic starch was changed to 8.0 parts by weight.

Comparative Example 3 Example 1 was repeated except that 8.0 parts by weight of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride was changed to 1.0 part by weight.

Comparative Example 4 The procedure of Example 1 was repeated except that 8.0 parts by weight of 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride was changed to 15.0 parts by weight.

Evaluation 1. Measurement of Particle Size The average particle size was measured with a centrifugal sedimentation type particle size measuring device. 2. 1 Gluing method A commercially available cotton broad # 40 was used, and a commercially available laundry detergent “Enzyme Top” (manufactured by Lion Corporation) was used for washing for 15 minutes with warm water at 50 ° C. for 15 minutes using a household electric washing machine. This was repeatedly used as a test cloth. Next, using a rounder meter manufactured by Daiei Kagaku Seiki Co., Ltd., 250 cc of water and 0.1 g of a solid content were added into a stainless steel pot and uniformly dispersed. About 12 g of test cloth was put in this dispersion, treated for 3 minutes, dehydrated for 30 seconds, and air-dried overnight. Thereafter, ironing was performed and evaluation was performed. 2. 2 Measurement of adsorption rate In the gluing method described above, the absorbance of the residual liquid after the gluing was measured at a wavelength of 550 nm. Separately, a calibration curve of the solid content of the dispersion and the absorbance of each emulsion was obtained for each emulsion, and the solid content of the liquid after gluing and hunting was obtained to produce an adsorption rate, which was determined according to the following criteria. : 50% or more Δ: 25 to 50% ×: 25% or less 2.3 Measurement of Bending Resistance 1. The test cloth created by the gluing method of JIS-L
The bending stiffness was measured by the -1096 (1990) cantilever method, and the stiffness was determined according to the following criteria. ◎: Softness of 50 mm or more Δ: Softness of 45 to 50 x: Softness of less than 45 mm The untreated cloth is 39 mm. 3. Storage stability The resulting emulsion was stored at 50 ° C for 4 weeks and observed for sedimentation of the particles. : No separation △: water separation of less than 2 mm at the top ×: water separation of 2 mm or more at the top The results are shown in Tables 1 and 2.

[0036]

[Table 1]

[0037]

[Table 2]

[0038]

Industrial Applicability The present invention has high adsorptivity to cellulosic fibers, good storage stability, and exhibits excellent effects as laundry paste.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Masakatsu Yamamoto 353-7, Chihama, Oto-cho, Ogasa-gun, Shizuoka Prefecture Inside the Shizuoka Research Laboratories, Ltd. (72) Inventor Naoichi Murase 353, Chihama, Daito-cho, Ogasa-gun, Shizuoka Prefecture -7 Heist Synthesis Co., Ltd. Shizuoka Research Laboratory

Claims (5)

[Claims] 1. A quaternary ammonium having a polymerizable unsaturated group in an aqueous solution of one or more cationic polymer protective colloids selected from cationic starch, cationic cellulose, and cationic polyvinyl alcohol. The salt and a monomer copolymerizable with (b) vinyl acetate and (c) vinyl acetate in an amount of 1 to 50% by weight of the total amount used are subjected to initial polymerization, and then the remaining component (b) and (c) An emulsion-type laundry paste comprising an emulsion having a particle size of 0.1 to 1.0 [mu] m and emulsion-polymerized by adding components. 2. The method according to claim 1, wherein the monomer of the component (c) is at least one selected from vinyl esters other than vinyl acetate, (meth) acrylates, and unsaturated carboxylic acids. Emulsion type laundry paste. 3. The amount of the cationic polymer protective colloid used is 0.5 to 5.0 based on the total amount of the components (b) and (c).
The emulsion-type laundry paste according to claim 1 or 2, which is 0% by weight. 4. The use amount of the quaternary ammonium salt having a polymerizable unsaturated group of the component (a) is 1.0 to 20% by weight based on the total amount of the components (b) and (c). Item 4. The emulsion-type laundry paste according to any one of Items 1 to 3. 5. An aqueous solution of one or more cationic polymer protective colloids selected from cationic starch, cationic cellulose, and cationic polyvinyl alcohol, having a polymerizable unsaturated group as component (a). The quaternary ammonium salt, 1 part of the total amount of vinyl acetate of the component (b) and the monomer copolymerizable with the component (b) as the component (c) are initially polymerized, and then the remaining component (b) And a component (c), which is emulsion-polymerized to form an emulsion having a particle size of 0.1 to 1.0 [mu] m.