JPS5829802A - Production of aqueous emulsion - Google Patents

Abstract

PURPOSE:To obtain an aqueous emulsion having improved adhesiveness and improved blocking resistance and non-tackiness, by emulsion-polymerizing a polymerizable vinyl monomer in an aqueous medium in which a lubricant has been dissolved or dispersed. CONSTITUTION:In emulsion-polymerizing a polymerizable monomer, a lubricant is predissolved or predispersed in an aqueous medium to be used, and then the polymerizable vinyl monomer is emulsion-polymerized in the solvent. As the lubricant used, there can be mentioned one member or a mixture of at least two members selected from the following compounds (A)-(D):(A) an alcohol ester of an 8-22C fatty acid, (B) an acid amide of an 8-22C fatty acid, (C) a compound, HLB<=10, which is an adduct between a hydroxyl group-containing compound (A) and an alkylene oxide and (D) a compound, HLB<= about 15, which is an adduct between compound (B) and an alkylene oxide.

Description

[Detailed description of the invention] This iJ! ij1 This invention relates to a method for producing an aqueous emulsion, particularly to the production of an aqueous emulsion 0% useful as a vehicle component of an aqueous coating material that exhibits excellent adhesion to polyolefin films and the like.

In recent years, from the viewpoints of resource saving, low pollution, and occupational health, mI departments,
There is a call for water-based am agents for printing inks, coating agents, etc., and a shift from conventional solvent-based am agents to aqueous-based am agents using water or water and a miscible solvent is progressing.

However, when making a water-based coating agent for polyolefin films, etc., compared to the soluble type, adhesiveness, water resistance,
There are some types of aK that are not yet at the stage of being used in pottery because they do not have sufficient dryness or other resistance.

Regarding the vehicles conventionally used for aqueous treatment, there are two types: aqueous solution type and emulsilon type 04, which are used alone or in combination. Examples include aqueous alkaline solutions such as maleated rosin, styrene maleic resin, carboxyl group tuna acrylic resin, and carboxyl group-containing styrene acrylic resin, but the disadvantage is that solution 1f has a high percentage/& rounding resin content. However, on the other hand, the water-soluble soap type was rarely used alone due to insufficient adhesion and water resistance.

1. There are various types of emulsilon type vehicles such as styrene, styrene acrylic, 6-vinyl J, and SBR, which have the advantage of low viscosity even though they have a high resin content. Drying properties and water resistance are generally superior to water-welded types.

However, due to the volatilization of water during the formation of the Emulsilon coating film, the residual water in the ti11 layer has a negative effect on the adhesion to the polyolefin film, and at this point, the adhesion and 9. Water resistance is also poor.

Therefore, the above-mentioned lack of conventional water-based shavings! t&! Various 411F studies have been conducted to improve drying performance.
The use of binder to increase the ratio of Nippon Co., Ltd. ingredients, or the improvement of various types of drying equipment, and the selection of the vehicle to be used, or the addition of a water resistance improver O by each company, are being considered for water resistance.

On the other hand, as methods for improving adhesion, methods using polymers and emulsilon with a low minimum film formation rate, plasticizers, etc. have been investigated, and some have been shown to be effective! However, on the contrary, the blocking resistance and adhesiveness deteriorate, and it is not sufficient in tape removal tests.

Films such as polyolefin are weather resistant. *In IE, adhesive properties are required. However, if blocking or the like occurs at the coating knee, it becomes impossible to work, so anti-blocking properties and non-adhesive properties are particularly required.

Conventional solvent I! In the case of masturbation, it is known to add a rilling agent such as higher fatty acid ester to improve tape adhesion and blocking properties.

However, since all of these 'a' agents are water-insoluble and water-soluble, they can be directly applied to aqueous coatings.
It is difficult to add all of them to a single agent, so make them into an emulsion in advance to create a water-based coating! Deciding to add
Alternatively, there is a method of partially saponifying a lubricant consisting of sorbitan higher fatty acid ester, converting it into an emulsilon, and adding a friend (Special II Sho s3-! Hatake 641), and coating compositions with improved tape adhesion are also known. ing. However, these emulsilons have a very large particle size due to mechanical separation, and have a 1! The reason for this is that the distribution of the emulsilon in the aqueous 8117M is not uniform, and during storage, the emulsilon is deposited on the i7 surface and aggregates are formed, resulting in workability and storage stability. When applied to printing, fK has disadvantages such as poor suitability, especially gravure printing (in gravure printing, it causes plate jams).

The present inventors completed the present invention as a result of extensive research into improving the adhesion, blocking resistance, and non-adhesiveness of emulsilon type vehicles among the vehicle components of conventional aqueous H covering agents. It was natural to do so.

That is, the present invention relates to a method for producing aqueous emulsilone, which is characterized by emulsification and electropolymerization of polymerizable monomers. , The name temples used in - in the present invention include F (4) to (
It is possible to mention one kind or a mixture of two or more kinds of chemical compounds derived from fatty acids selected from the freshest of monuments.

(A Charcoal ester is 8 ~ Alcohol ester of fatty acid of Yixue (@ Charcoal l/1 & is 8 ~! Hiroshi's fatty acid steep amide (q
An addition reaction product between a compound (4) having a hydroxyl group and an alkylene oxide, and an addition reaction product between the compound (2) and an alkylene oquinide, and HL Composition of combination motive (b) 11. *Fatty acids have 8 to 2 carbon atoms! These include saturated or unsaturated fatty acids such as Cagril, Capric acid, Cucric acid, Myristic acid, Valmitic acid, Stearic acid, 12-hydroxystearin, Instearin, Oleic acid, Ricinoleic acid, Linoleic acid. Acids include phosphoric acid, eleostearin, castor tab fatty acid, erucic acid, and the like.

The number of carbon atoms in the above fatty acids is 12 to 2, particularly 141 to 2.
! The compound (6) (Q) is preferably obtained from saturated fatty acids.
B) is made from unsaturated fatty acids!
lI- is preferred.

Used to react with the above fatty acid to synthesize compound (4) F@
Specific examples of alcohols that can be used include ethanol, propatool, butanol, decanol, octatool, etc.
Alcohol, ethylene gelcol, diethylene 17
dihydric alcohols such as co-A/, -70 pyrene glycol, cyfropyrene glycol, butanediol, hequinanediol, neopentyl glycol, glycerin,
Trimethylolpropane, cycliserin, pentaerythritol, sorbitol, n! Examples include trihydric or higher alcohols such as Levitol and monosaccharide. The alcohol is preferably a polyhydric alcohol having a valence of 72 or more, particularly a polyhydric alcohol having a valence of 3 or more.

Compound 1d8cA) is an alcohol in which part or all of the hydroxyl groups are esterified with a fatty acid;
The amine used to synthesize compound (B) by reacting with the above fatty acid is an? ≧1, methylenediamine and ethylenediamine are mentioned, and compound (2) is synthesized by an acid amide reaction. Among these, fatty acid amides which are cleaved by reaction with ammonia are preferred.

Compound (C) Fi is an addition reaction product of 1-rukylene oxide such as ethylene oxide or propylene oxide to the remaining hydroxyl group of compound * (4), and H
The LB value is 10 or more, and #iP is Fia or less. In addition, when all the hydroxyl groups O of the alcohol are esterified in the compound (4), the compound derived from the compound is used.

Compound @ is a reaction product of compound @O#&amide group and the above alkylene oxide, and has an HLB value of Is or more, F1, preferably 12 or more, FO.

When the lubricant (in Q@, the value of 1Ll is higher than the above value), not only the water resistance deteriorates but also the adhesiveness is not good. In addition, HLB and ij Grth] 111
It is an interval value indicating a measure of the balance between hydrophilicity and hydrophilicity using the following formula.

Preferable examples of M= hexamolecule molecular weight among these compound motive factors (b) are shown below.

Compound (4) is ethylene glycol mono- or dispair, erythrium-9,7-mono- or dispear. di(1tri8.a, -t, sorbitan mono- or di-Etli) listearate,
Examples include mono- or di-tris-tetrastearate, tri-stearate, and their corresponding palmitates.

Compound (2) includes lafric acid amide, myristic acid amide, palmitic acid amide, stearic acid amide,
Examples include oleic acid amide, erucamide, methylenebisoleylamide, ethylenebisoleylamide, and the like.

Compound (Q) is compound (4) with 1 to 10 moles of ethylene oxide added, preferably #i1 to about 1 mole, and compound (B) is compound #I (6) added with ethylene oxide. One example is a 1-io cell, in which 6 moles of t-tIN are added.

These combinations 4iilt alone 4h! < is a mixture of two or more cypresses and ~10% by weight. If the amount used is less than α %, the effect will be small, and although it may be used in an amount of 30% or more, there will be little advantage.

I can do it with Jin.

In order to dissolve or disperse the metal compound, it is preferable to make the temperature higher than the melting point of the compound, and it can usually be carried out at a temperature of 60° C. or lower.

Further, emulsion polymerization is carried out under an inert gas atmosphere at 10-to-1.

°C, preferably 80-90 °C, preferably 150-80 °C
In the emulsion polymerization of the present invention, the polymerizable vinyl monomer can be placed at a temperature of Emulsifiers, polymerization initiators, and other warming agents other than the polymerizable vinyl hexamer can be optionally used.

Specific examples of polymerizable vinyl monomers include styrene, a
- Methyl styrene, vinyl acetate, fatty vinyl esters, acrylic acid and its alkyl esters (methyl acrylate, ethyl acrylate, ethyl acrylate, acryl ethylhexyl, tucryl acrylate, acryl stearyl acrylate, etc.) methacrylic acid and its alkyl esters Esters (butyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, tucryl methacrylate,
(methacrylate, stearyl, etc.), itaconic acid and its alkyl esters (digyl itaconate, itamoji shunji 2, etc.)
ethylhexyl, etc.), digtyl maleate, digtyl acrylate, 2-hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,
Examples include glycidyl methacrylate, acrylontolyl, acrylamide, N-methylolacrylamide, and the like.

In the production method of the present invention, it is better to use at least -#lK acrylic alkyl ester or methacrylic alkyl ester among these polymerizable vinyl monomers in terms of workability.

As the emulsifier, a polymer emulsifier, #I#active All, can be used.

Examples of polymer emulsifiers include Sheftsuku, carboxyl group-containing acrylic resin, carboxyl group-containing styrene acrylic resin, and carboxyl group-containing alkyd resin! II, anionic polymer emulsion which is an alkaline aqueous solution such as styrene maleic acid resin.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl nitrate, and anionic interfacial surfactants such as dodecylbenzene XA/hot soda. To improve water resistance, polymeric milk (alcoholic acid) is recommended.

As the polymerization initiator, potassium persulfate, anthonicum persulfate, aqueous peroxide, t,t'-azobis(!-amidinopropane) monosulfate, or a redox polymerization initiator is used. .

The resin content of the stirred hydrophilic emulsion is 80-10%.

Preferably containing 40 to 60% -b; convenient for use.

The aqueous emulsion obtained according to the present invention has excellent adhesion, sometimes adhesion of tape to d-lyolefin 74 lume, and anti-blocking property. It also has excellent thin frame properties such as transparency, water resistance, storage stability, and printability. These are considered to be the ninth sign that the lubricant is uniformly distributed in the emulsion carbon.

The aqueous emulgene according to the present invention is also useful as an aqueous printing ink, paint, or coating.

An example of 'liE will be shown below and its details will be explained.

Example 1 Stirring bowl, thermometer, reflux cooling pipe, and nitrogen gas inlet tf
1, 16 mole adduct of nonylphenol ethylene oxidite, 1 bf, m ion water 3...2 and glycerin monobalmite) 15F were placed in a j7 Tusco. Deionized water containing 2.0 ft.*ytm of ammonium sulfate was added. Then methyl methacrylate 161
A mixed monomer of F and butyl acrylate 227y was added dropwise over 3 hours. After the dropping was completed, the temperature was raised to 85'C, which was maintained at 70°C for 1 hour, and maintained for 1 hour.

After cooling to room temperature, the mixture was passed through a 200-mesh steel plate to obtain an emulsion. No ischemic dye was observed.Example 2 15 moles of ethylene oxide adduct of nonylphenol 16F, 281y of deionized water and 6 moles of ethylene oxide adduct of sorbitol hexastearate toyf:
Charged in the same equipment as in Example 1, and further added persulfated ammonicum 2. 70 p of deionized water containing Oy was added, and the temperature was raised to 76° C. while flowing 1 nitrogen gas. A mixture of 6Qf 2-ethylhexyl acrylate, 145y styrene, and 117' acrylic acid 141y was added dropwise over 2 hours, and the temperature was raised to 80°C and maintained for 1 hour. An emulsion was obtained by passing the emulsion through a 1,200 ml gilt copper tube cooled in a room + 1 iit.

xA Example 3 Sheftsk ammonia droplet layer (25%) 4ooy, 10 mole adduct of ethylene oxide of octylphenol 109, ammonium persulfate LOf't- deionized water 110f! and sorbitan monostear) 20fi
The mixture was placed in the same apparatus as in Example 1, and the temperature was raised to -5° C. while nitrogen gas was flowing. 2ethylhexyl acrylate 2(i
p, butyl acrylate 15y, methyl methacrylate 75
It took 2 hours for the mixed monomer consisting of y to be added dropwise at 66°C.
After keeping it for 1 hour, raise the temperature to 80℃ and hold it for 1 hour to make sure. Afterwards, he had a similar experience with Teisebaku and obtained Emulji training.

Example 4 Example 3 except that sorbitan tristearate 20y is used instead of sorbitan monostearate*
An emulsion layer was obtained in the same manner as in Example 3.

Containing WA Example 6 Same as Example 1111, and Shellac's aqueous ammonia solution (16%) l! @P, ethylene oxidite lS molar adduct of octylphenol! Oy, 148p of deionized water containing ammonia persulfate, y, and amyl oleate)
76° C. was added, and the temperature was raised to 66° C. while flowing nitrogen gas. 'A mixed monomer consisting of dimethylaminoethyl methacrylate 26f acrylic acid ethylhexyl 52y
After adding drops at 111 hours, a mixed monomer mixture consisting of 1 p of methacrylic methyl and 126 y of acrylic was added dropwise for 2 hours. @ Raise the temperature to O℃ 1
After holding for a period of time, the mixture was cooled and filtered to obtain an emulsion.

'*mn 藝田j1 In Example 3, instead of sorbitan monostearate, 4 mole adduct of ethylene oxide of stearin amide (1' = 6) ITF (1 for the total amount)
Example 3 and 14 birch were used except that 16 (e) was used.

Comparison Example In Example 3, emulsion carbon containing no sorbitan monostearate was synthesized in the same manner as in Example 3.

Examples of using the emulsion carbon obtained in Examples and Comparative Examples are shown below.

Usage example 1 Water-based printing ink annealing blue 10g 6 Ammonia solution of styrene acrylic resin with an acid value of 2 oo (◎%) 16%, Example and Jt [45% of the salt mixed in the example], Inglobil alcohol 20 A water-based printing ink containing 20g of water and 100 hooks was prepared, spread on polyglopylene film, and subjected to a ratio e test.9.

At the same time, an engineered ink prepared by partially converting sorbitan sonostearate was used, and the ink contained 4LI% of sorbitan sonostearate (the same amount as in the running ink using 1 liter of emulsion in Example 3). A real printing ink was created and compared.

The obtained M fruit is shown as wheat.

Evaluation method 1) Tape adhesion: Attach the tape to the ink** surface,
Check the appearance of the ink when it is suddenly removed, and it does not peel off at all. , % peeling Δ, all abrasive X.

I got #F* for being poor.

2) Rub resistance: The surface of the ink coating was rubbed hard several times, and the MS-like strength of the ink was evaluated as Ichimine, and the softness was evaluated in the same way as the tape adhesion.

S) Place the water-resistant two-color film in water at 25°C for 10 minutes.

After soaking, the test was carried out in the same manner as for kneading resistance.

Usage example 2 The above example, ratio 4m! The emulsion resin of Example 4 and the emulsion resin of Example 4 and 2 were emulsified with Nrubitan monostearate to 9g6, and the emulsion resin containing 9g6 was applied to a reinforced polyethylene film and used for peeling. In the same manner as above, tape adhesion was investigated.

Claims (1)

[Scope of Claims] A method for producing an aqueous emulsion, which comprises emulsifying an orthogonal vinyl sulfuric acid in an emulsion. (O) A special feature in which the lubricant is a compound selected from the group of (4) to (b) in F. A method for producing aqueous emulsion carbon. (A) Alcohol ester of fatty acid with carbon content of 8 to !8 (jl Alcohol ester of fatty acid with carbon content of s to 2)
It is an addition reaction product of a compound having a droxyl group and 1-rukylene oxide, and the compound (IILBIL) is 1 or less. Compound of 'knl & F (rich) 0.0% lubricant is added to polymerizable vinyl nitrate.
A method for producing an aqueous emulsion according to the scope of the patent Il claim, item 1 or item 2, characterized in that 1 to 1% sob@% is used.