JPS5813658A - Preparation of cationic emulsion - Google Patents

Abstract

PURPOSE:To obtain an emulsion in which a nonionic and anionic water-soluble high polymers are adsorbed to particles, by emulsion polymerizing a vinyl monomer in the presence of the nonionic and anionic water-soluble high polymers, and adding a specific amount of a cationic water-soluble high polymer thereto. CONSTITUTION:A vinyl monomer, e.g. a vinyl ester of a fatty acid or (meth) acrylic ester, is emulsion polymerized in the presence of a nonionic water- soluble high polymer, e.g. PVA having a saponification degree of 70-100%, and an anionic water-soluble high polymer, preferably a high polymer having a content of anionic functional groups of 0.3-1.0 millimoles based on one g high polymer, to give a high polymeric emulsion. A cationic water-soluble high polymer in an amount of 1.5 times or more that of the anionic high polymer is then added to the resultant emulsion. Preferably, 0.1-0.5wt%, based on the vinyl monomer, anionic high polymer is used, and 0.3-3wt%, based on the resultant emulsion, cationic high polymer is added thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for producing cationic emulsions whose particle surfaces are positively charged and are stable.

Conventionally, synthetic polymer emulsions obtained by emulsion polymerization of divinyl monomers have been used for a variety of purposes, such as adhesives, textile treatment agents, and textile fabrics. However, emulsions that use an anionic or nonionic compound 1 as an emulsifier or protective colloid during emulsion synthesis.
Njouko is charged with a normal member. As a result, the performance of the resulting emulgene is 11C, and currently it cannot be said that it fully satisfies the various requirements required in many applications such as paints and single-layer agents. .

Incidentally, in recent years, a method has been proposed for producing a cationic emulsion by carrying out emulsion polymerization using a cationic surfactant or a cationic molecular compound #II as an emulsifier or colloid. This cationic emulsion carbon r1 Tanizaki+sn, synthetic resin powder or ore, etc., generally has a surface of 4, which is a member, but also shows a cationic compound ewt-mixture. - Because it can be washed away, fiber treatment salts, - adhesives, asfa □ modifiers, etc.
J91 Samurai can be given ICP-like performance.

The present inventors have now developed a method for producing a cationic emulsion spray with positively charged particle surfaces! 1! In this research, a polymer emulsion obtained by emulsion polymerization of a vinyl monomer in the presence of a nonionic water-soluble polymer compound and an anionic water-soluble polymer compound has a cationic water-soluble polymer compound. It has been discovered that by adding a polymer compound, the adsorption power to 'N' to a negatively charged substance can be completely improved, and the present invention has been completed.

That is, the method for producing a cationic emulsion according to the present invention involves adding a vinyl monomer to milk in the presence of a nonionic water-soluble polymer compound IL+ and an anionic water-soluble polymer compound.
Adding the cationic water-soluble polymer compound to the polymer emulsion obtained by polymerization at least 1.5 times the amount of the anionic water-soluble polymer compound is defined as %.

Examples of vinyl monomers used in the method of the present invention include fatty acid vinyl esters such as vinyl acetate and propionic vinyl; ethyl acrylate, ethyl acrylate, butyl acrylate, and acrylic
Acrylic acid esters such as 2-ethyl silyl; methacrylic acid esters such as methyl methacrylate, methyl methacrylate, and methacryloptele;
These can be used alone or as a combination of two or more insects.

Furthermore, ethylene, styrene, vinyl chloride, etc. which can be copolymerized with these vinyl monomers can also be used simultaneously as copolymerizing components.

The amount of the vinyl monomer to be used is appropriately selected depending on the purpose of use of the cationic engineered emulsion obtained, but it is preferable to use it in an amount of 20 to 118 bO to 118, which is beneficial to the final emulsion. Mashih0 Invention 41CJll'Vh As a nonionic water-soluble polymer compound for convenience use, for example, the degree of chlorination is 70 to 10.
Modified starches such as 0% polyvinyl alcohol, desutrines, diethyl starch in hydrochloride or hydroxyglobil starch;
Examples include methylcellulose, and dorotendipropylcellulose, which are a mixture of VhFi2- or higher, which is a single delta insect, and Cf! can be used. Non-ionic water!
The amount of polymer compound used is 0 based on the final emulsion carbon.
．． It is preferable to use it in a range of 5 to 5 liters.

The anionic water-soluble polymer compound used in the present invention includes, for example, anion-modified polyvinyl alcohol having syl groups trx and ms in the carboxyl group (fulcaricinated product of a copolymer of Nisder acrylate and vinyl acetate,
Examples include carboxyl dimethylated polyvinyl alcohol. ), gum arabic, carboxymethylcellulose with a low degree of polymerization and low degree of substitution, anionic water-soluble polymer compounds derived from hydroxyethylated starch or dipropylated starch ( For example, by the reaction of diethylcellulose and sodium monochloroacetate in hydrochloride), etc., are melted, and these alone can be dissolved in 1. ,
The tank can be used as a mixed tank for two or more tanks.

It is important that the anionic water-soluble polymer compound used in the method of the present invention has appropriate anionic properties.
Anionic official 11! The content of groups is 90% per gram of polymer.
A preferred range of Ii is 1 to 2 mmol, preferably 0.2 to 1.5 mmol, and more preferably 0.3 to 1.0 mmol.

In the present invention, a cationic water-bathable molecular compound is added to the negatively charged Molecular Emul 217 particles using an anionic water-soluble molecular compound, and the cationic polymer is added to the particles of the cationic polymer. The feature is to make the suction as uniform as possible and to form a slope. Therefore, the content of anionic groups is 0
．． The anionic polymer compound #IFi of less than 1 mmol has insufficient compatibility with the cationic water-soluble polymer compound added later, and the adsorption of the cationic water-soluble II 116 molecular compound onto the emulsion 17 particles is insufficient. However, the performance as a catholytic emulsion deteriorates, which is not preferable.

On the other hand, when an anionic polymer compound # having an anionic group of 1044 violet groups exceeds 2 ml, 1.i. This is undesirable because it causes aggregation of the emulsion and the stability of the emulgene is significantly reduced.

The amount of the anionic water-soluble polymer compound to be used is appropriately changed depending on its anionic property, but is 0.05-1.0jjil, preferably 0.1-0jjil, relative to the vinyl monomer.
．． Used in the range of 51 Jlt. If the amount of anionic polymer compound used exceeds this 1liai, #
The same m- as mentioned above is not preferred.

Examples of the cationic water-soluble polymer compound used in the method VC of the present invention include the following.

(1) Cation-modified hydroxyethylcercose,
Cationically modified starch, cationically modified guar gum, e.g. Eva, human O-? An 814th-grade ammonium group represented by the formula of Shishita was introduced by the reaction of diethylcellulose, starch and guar gum with ammonium chloride in glycicyltrial or dipropyltrialkylammonium chloride in 3-halogeno-2-hydro. Cation modified products can be mentioned.

(In the formula, -R1, R, and R8 represent the same or different alkyl groups or alkyl groups having 1 to 4 carbon atoms, and X represents a monovalent anion.) (1) In the following structural formula Monomers of cationic acrylic esters, methacrylic esters, Okimi acryland or substituted methacrylamides, and co-monomers with acrylamide as shown.

4 Ckl, -C (iii) A polymer of diallyldimethylammonium talloride and a copolymer thereof with acrylamide.

The primary cationic polymer compounds can be used alone or in any mixture.

The amount of cationic polymer compound added depends on the amount of anionic polymer compound used in emulsion manufacturing. However, it is necessary to add 1.5 times more by weight than 6J, and usually 0.1 to 5J to Emulgene.
I is voluminous, preferably 0.3 to 3j. If the amount of the cationic polymer compound added is 1.5 of the amount of the 7-ionic polymer compound removed, the retention i of the resulting cationic emulsion will decrease, and the cationic This is not preferable because a 1 m addition of 1 m of Karasumolecular compound results in the production of 1 m of shemardine. If the amount of the cationic polymer compound 1 added to the emulsion carbon is less than 0.1%, the formation of young fruit will be insufficient, but if it is added in excess of 5Jtilfi, the effect 4 will be almost saturated. This is disadvantageous when considering the thickening of the emulsion and the strength of the emulsion.

In the present invention, the emulsification of the vinyl monomer □ carried out in the presence of a nonionic water-soluble molecular compound and an anionic water-soluble polymeric compound can also be carried out in the absence of an emulsifier. Diethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl phenyl ether, etc. in polio as necessary.
Non-ionic n uii rl a >IJ'? , carboxybetaine, sulfobemaine, amphoteric interfacial agents such as carboxylic acid intermediates, and long-alkyl compounds. It can be suitably carried out using a cationic surfactant such as &ammonium weir. There is no particular restriction on the amount of these emulsifiers added, but they are generally used in an amount of 0.05 to 5 J:m% based on 1 part of the vinyl monomer. 6. .

In the present invention, as a one-polymer initiator that can be conveniently used when emulsion polymerizing a vinyl monopolymer, any hydrostatic physical initiator that can be used in ordinary emulsion polymerization, such as hyperstable potassium, Examples include ammonium, aqueous peroxide, t-butyl hydroperoxide, azo-bis(i-tubyramidine hydrochloride) which gives cationic and cationic radical fragments among cumene and dropol.Polymerization initiators There is no particular restriction on the amount used, but it is generally 0.01 to JJl relative to the vinyl monomer.

In the present invention, the stage reaction conditions for emulsion polymerization of vinyl monomers in A can be based on general conditions, such as reaction @!
f is 40 to 100°C, preferably 50 to 90°C, and the pH
is 3-9, preferably 4-8. l1 of the reaction solution
In order to adjust the full Qi, a pH buffering agent such as sodium carbonate, sodium bicarbonate, sodium diphosphate, monobasic sodium phosphate, etc. can be used as appropriate.

After the above-mentioned emulsification is completed, the emulsification point is reached: ').

Then, if necessary, remove the alcohol according to a conventional method and add other common additives (for example, slenderizers such as dibutyl 7-talate and dibutyl adipate, ethylene glycol and furopyrene gel). Freeze stabilizers such as Recall, preservatives, antifoaming agents, etc.) can be added.

The emulsion 17 obtained by emulsion polymerization using a molecular compound is sewn with a cationic molecular compound wt to produce an emulgene. By carrying out emulsion polymerization and 2:1 polymerization using a γ-tanion-based molecular compound, a colloidal layer of anionic molecules is formed on the surface of the resulting particles, resulting in the addition of cationic polymers. Compound emul 98
7. Emul 2 has strong and uniform adsorption to particles.
17 particles are efficiently charged positively. As a result, the emulgene produced according to the present invention has a high affinity for negatively charged **tC. Therefore, for example, when the emulsion according to the invention is used as a #S material for general household use, as a result of dispersing the first part with a large amount of water, such as when rinsing laundry, -shinozaka Even in cases where the at. There is an advantage. Additionally, this engineered resin can also be used by lumberjacks, such as as an adhesive for modifying asphalt emulsions.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative 1FIl, but it goes without saying that the technical information d of the present invention is not limited to the following Examples.

Example 1 A temperature needle, a stirrer, a cooling device, a nitrogen introduction device, and a quantitative dropping device (500 units) were installed.
In a ruffled flask, add polyvinyl alcohol (saponified g8
5 buns, polymerization J! [1400) 59, anion-modified polyvinyl alcohol (acrylic acid group t amount 5 mo, degree of oxidation 98-1, [1800) 0.5P and I#y5
5m water 85ft, UDt, woe 11#.

This mixture was cooled to t-400 ml, and then 0.5 r of ethylecinonyl phenyl ether in poliomyelate (amount of 50 mol in ethylene chloride) and 0.5 r of sodium carbonate were added.
A solution of 5F dissolved in ion-exchanged water 109 was added, stirred for a while to make a homogeneous solution, and then mixed with vinyl acetate 7-10
After stirring for 20 minutes while introducing bulk, warm the mixture in a 70°C water bath. When the internal temperature reached 60CK, 0.29t of potassium persulfate and 1 (l) of ionized dust water
A 9N pongee solution was added. After polymerization starts 1
After 0 minutes, 90 t of vinyl acetate monomer was added continuously over 2#I#-columns.

After the continuous addition was completed, the mixture was aged at 80C for 14 hours to complete the first reaction. After cooling with Kenono, add 50j of ion exchange water.
Cation modification and doroya diethyl *JaH-A C'
llJ&'4i1 amount 1.8tlL1*, -E-chiL/7o, the number of moles of citrate in the water glucose unit Todoroki 91
．． 7% K, 21 to 1111 volumes of water K (25C) 25
epm) Add water sg dissolved in 31i'11 with f7%, heat in 50L portions, stir for 30 minutes, and form a cationic emulsion layer □. . . Engineering x Jl/-/W 7 f
)'mW'p+? It was a work, □, 5 weight. The solid content of this emulsion was &03 and the pH after diluting was 7.0.
The charged particles of the particles were defined using electrophoresis 4° AT (Hitachi).

The particle has a positive I/c4I charge, and its electrophoresis is 4 degrees.
．． 2 Cs·tym/1 m-V).

Furthermore, the resulting emulsion was tested for freeze stability and high stability according to JIS-6828-1977, and it was confirmed that the resulting emulsion was stable.

Implementation f12 -C emulsion polymerization was carried out in the same manner as in Example 1, and the amount of cation-modified hydroflate diethylcellulose (夷m?11 and 5J-) added to the obtained 92-margin carbonate was varied, The compatibility with the emulsion carbonate, the stability and electrophoresis of the resulting cationic emulsion were measured. 311 results
Shown in the table.

Margin below: 1 □"1.: IEl Table Book II & 11 Stability II The state of the emulsion seal III after being left at 160C twice was observed with the naked eye.

1111 Table 19, If the amount of cation-modified hydroxycellulose is small, leave it at room temperature even if the emulsion layer does not come together according to #A of cation-modified diethyl lulose in hydroxy cellulose. It is clear that the stability of the process error is extremely sensitive, as shown in Figure 9.

Example 3 Substitute for anion-modified polyvinyl alcohol in Example 1]
Carboxylic dimethyl starch with different substitution positions o, syt
Milk immersion was carried out in the same manner as in Example 1 except that the following ingredients were used. Click on the obtained engineering margin #: yfR human cI-
? Diethyl cellulose (same as illJIIH) 3] (
Solid content) was dissolved in ion-exchanged water (1&c) and 9 #! liquids were added and mixed at 50°C, and the @- property of η-thione-modified human oral diethyl cellulose to emulsion carbonate was tested.Results Table 2 shows the anion group ff.
In the case of an emulsion prepared using a large amount of multi-anionic polymer compound, the addition of a cationic polymer compound can improve the emulsion's #Ill! I know that happens.

Comparative Example 1 Polyvinyl alcohol (saponified 11B59
To, polymerization #1400) 511 & ion exchange water 85F
The mixture was incubated at 80°C. This liquid was cooled to 40°C,
Next^, polyoxyethylene nonylphenyl ether (ethylene oxide semi-uniformly distributed/JO 7 L number 50) o, s17!
and sodium carbonate 0.511! Aeon 5H Keisui 1
Add the bath solution containing dissolved S to 09, stir for a while to make a homogeneous solution, add 10ft of vinyl acetate monomer, continue stirring for 20 minutes while introducing 1i1 element, and then add 1JIJ@ in a bath at 70C. f, beginning circle. When the temperature of 1 is 60℃, potassium persulfate is mixed with acetic acid and nil monomer 9.
0 fl kAd's Km271J Shimaru. Four consecutive additions are completed.
Thereafter, the polymerization reaction was completed at 14 degrees Celsius at SO.degree. Leave to cool to room temperature, then add 5 liters of ion-exchanged water to an aqueous solution prepared by dissolving 3 liters of Kanon-denatured hydrogyf diethyl luulose (used in Example 1) with IJid Sugi-bun. kj
The mixture was heated to 50°C and stirred for 30 minutes to obtain a cationic emulsion carbonate. The solid content of this emulgene is 41.2 μm J1 excellent, Teiden state is positive, and electrophoresis is 4
R was 4.1 (μmV-·V).

Ratio example 2 @ Place needle, stirrer, Rflt cold! 4 devices, nitrogen injection tube and quantitative lit)'dtle p+tff 500a#)
In a 5zo seven-parallel flask, add polyvinyl alcohol (
Polymerization degree: 85%, polymerization degree: 1400%) and 50% of ion-exchanged water were added, dissolved at 80°C, and the following Example 1 was prepared.
Emulsification was carried out in the same manner as above. The resulting emulsion was mixed with anion-modified polyvinyl alcohol (same as Example 1 and 2) for 30 minutes at 50°C.Next, cation-modified human Q#1 ethyl cellulose C'A11tjtH
1) 32 (solid content) t-An aqueous solution dissolved in 5 of ion-exchanged water was added, and the mixture was further stirred for 30 minutes to obtain a cationic emulsion. Once the 1st form of this engineering Marji 1 was 41.5 degrees, the electric wire stopped, and the electric wire WhiA degree was 4.0 (μ・Country/-・V).

Comparison Oka 3 50011j 50011j equipped with temperature needle, stirrer, nitrogen inlet and metered dropping device = IK, Bo! 71: 'Nyl alcohol (saponification + at 85%, -polymerization 111400) 5F, anion-modified polyvinyl alcohol (same as Example 1) 0.5y, Kanon-modified and diethylcellulose in mud (4mSame as J1) in solid content 3 liters of water and 135 r of ion-exchanged water were added, and the mixture was heated at 80°C. This liquid was cooled, and then polyoxyethylene nonylphenyl ether (average addition of 7 m
50) 0.5f! and 0.5 y' of sodium carbonate
t ion exchange water 1 (add Sat dissolved in 1, stir for a while to form a homogeneous solution L7, $ 10 vinyl monomer)
After stirring was continued for 20 minutes while introducing bulk, 9 portions 1 was started in a water bath at 70°C. When the temperature inside reached 60℃, add 0.2f of potassium chloride to 102℃ of ion-exchanged water.
Added SM Saze-Kyu Initiator #I Enemy to. Vinyl acetate monomer 9 (
Continuously add l. It has been 80 years since the end of the
The mixture was aged at ℃ for 1 hour to complete the polymerization reaction. The solid content of this emulsion carbon was 41.4 μtS, the electrification state S was positive, and the electrophoretic excitation degree was 3.9 (jl·1/rigid·V).

Test Example 1 The emulgenes obtained in Example 12 and Comparative 111-3 were subjected to the horizontal loading test shown below. The results are shown in Section 3 along with the results of the ridge table determined by the arrival of the light absorbing band.

[Test with 1] Water at 25°C was poured into 4 mini-haulers (manufactured by Matsu F Denki Sangyo Co., Ltd.) for 3 hours.
and the emulsion tank solid content aR is 0.05J [JI
To make it look like E, I made a rug with g, and made it with cotton broadcloth (60
(Wear) Add 150F and run the washing machine for 3 minutes to apply the glue. Next, use a dehydrator (using the Toshiba dehydrator tank next to Wash 4).
Dehydrated for 0 seconds, air dried in 9-1, ironed, JIS-L
-1079-1976, Cm and t were measured by the cantilever method (the value is large @b).

C adsorption rate! 1111 constant] In the above-mentioned test, the absorbance of the drained liquid after one dimension of the shelf was determined to be 6
Measured with a 00 WrI & wave probe (Hitachi 1111 with Kokoken needle for f). Separately each emulsion m 7 If(-:)V
A calibration curve of the solid content "art" of the fractional liquid and the absorbance was determined, and the solid content # degree of the waste liquid after the completion of horizontal loading was determined to calculate the adsorption rate.

Grave 3 Table 3 From Table 3, a technical malushi obtained by carrying out emulsion polymerization using an anionic polymer compound.

The cationic emulsion vs.
It is clear that even when using a large amount of water, such as double-double water, it adsorbs well and is excellent in forming young fruit with glue.

Example 4 Emulsification was carried out in the same manner as in Example 1 except for converting the anion-modified polyvinyl alcohol into fi(]-f.
To the obtained emulsion carbonate was added an aqueous solution of 7 ethyl cellulose (same as in Example 1) dissolved in 31 (solid content) t-ion-exchanged water at 50 C/J.
The cationic properties when crystallized and the phase properties of emulsion carbon of diethyl cellulose in the slurry were tested. As a result t
In the same manner as in Test Example 1, the horizontal loading test was carried out using cotton broadcloth (60 Homare Q) and the adsorption rate was determined. The results are also shown in Table 4.

From Table 4 below, we can see that the addition cap of the anion l1168 child compound is too large and the emulsion 1 is agglomerated due to the addition of the cation polymer 1, and the addition amount of the 19 anion polymer compound is small V
In case k, it is clear that the adsorption force to the cloth is not sufficient.

Example 5 Polyvinyl alcohol (degree of oxidation: 98 or better, degree of polymerization: 1800) was added to a 500-500-meter flask equipped with a MiL-equipped temperature needle, stirrer, reflux condenser, nitrogen inlet tube, and foot dropper. Diethyl cellulose Cg in hydro
Water/lucose single w-ap cytoaddition mole I* in ethylene
L8~2. O, 2'A varicella hemorrhoid liquid viscosity (25℃) 30op
s) 3N, gum arabic 0.2P# and ion exchange water 8
Add 0.52 liters of sodium carbonate to 1 liter of ion-exchanged water. Cool this solution to 40°C.
To#! Add the dissolved solution, stir for a while, add vinyl acetate monomer 1 (71O), continue stirring for 20 minutes while introducing nitrogen, and then start heating in a 70°C water bath.

At the time of death when the internal temperature reaches 60°C, 4Iil#l potassium 0.
311 was dissolved in 15N of ion-exchanged water, and then the M initiator layer solution was added. 90v of vinyl acetate monomer was added uniformly over a period of 2 hours starting 10 minutes after the beginning of the first cup. This 4
After the further addition was completed, the mixture was aged at 80° C. for 1 hour, and the reaction mixture was placed on a stand. After stepping up to M temperature, cation-modified guar gum (nitrogen content 2.6 liters, 11 water #liquid viscosity R43
cps) 2 jl is #interpreted into 50jl of ion salt water f! A cationic emulsion was obtained by adding a trace and stirring at 50 Ct for ffimmL for 30 minutes. One cedar portion of this emulsion carbon has an amount of 41.0 ffi and an electrophoresis speed of t.
The value is +5.3 (μ・-71M1・V), and the freeze-restorability and stability tests were also good, which is rare. Patent Attorney -- Kazuyuki Patent Attorney Ishi 1) Kei 5P Danshi Akiyuki Yamaguchi, 1'l:, Procedural Amendment (Voluntary) September 1, 1981 President of the Japan Patent Office Haruki Shima 1, Indication of the case 1981 Patent Application No. 1099642, Title of invention: Method for producing cationic Mardiben O3, Relationship with the case of the person making the amendment Name of patent applicant (676) Lion Corporation 4, Agent.

(3 others) b) Column 6 of “Detailed Description of the Invention” of the specification to be amended, contents of the amendment a) Page 11 of the specification, line 16, “Vinyl monomer 1
"for vinyl monomers" is corrected to "for vinyl monomers."

4) In the 17th line of the 24th purchase, amend "together with the results" to "together with the results."

that's all

Claims (1)

[Claims] 1. Nonionic water-soluble polymer compound and anionic water #
1.5 of the Anionic Water-Soluble Polymer Compound Book ft1II is added to the polymer emulsion produced by emulsion polymerization of a vinyl monomer in the presence of a polyvalent polymer compound. A method for producing a cationic emulsion characterized by adding more than double the weight. 2. The nonionic water-soluble polymer compound is Ken Kasei 70~
Claim No. 1, which is at least one compound selected from the group consisting of 100% polyvinyl alcohol, desutratin, ethyl acetate, diethylcellulose, methylcellulose, and hydroxyprobil 7A/r:1-su. 1 Product description method. 3.7 Anionic water-soluble^ molecular compound has modified polyvinyl alcohol, gum arabic, low polymerization and low substitution position of dimethyl cellulose in carboxyl and diethyl in hydro, which has t-substituent on carboxyl group. When it is selected from the group of anionic water-soluble polymers derived from dipropyl cellulose or Fif starch and is at least a type of compound, the 11 ml of ffi* required,! J or the method described in the second product. 4. The cationic polymer compound is cationically modified hydrodiethyl cellulose, cationically modified starch, cationically modified guar gum, cationic (methanoacrylate or feramide polymer or copolymer with acrylamide, and diallyldimethylammonium chloride) Claim III: A tomb comprising at least seven types of compounds selected from the evaluation of polymers or copolymers with acrylamide;
The method described in Section 2 or ll3JJi.