JPH02191654A - Emulsion composition - Google Patents

Abstract

PURPOSE:To obtain an emulsion composition consisting of a fluorine-containing synthetic resin emulsion having small granule size and synthetic resin emulsion having large granule size and containing no fluorine, enhanced in dispersibility of emulsion and improved in storage stability, etc. and suitable for water repelling, oil repelling and stainproofing uses, etc. CONSTITUTION:The aimed composition obtained by blending (A) 1-50 pts.wt. fluorine-containing synthetic emulsion obtained by subjecting a mixture consisting of A1: 0.5-60wt.% monomer having a salt producing group or polyalkylene oxide group and radical polymerizable unsaturated bond, A2: 5-99wt.% fluorine-containing monomer having radical polymerizable unsaturated bond and A3: 0-94.5wt.% monomer having radically polymerizable unsaturated bond other than the components A1 and A2 to solution polymerization in a specific solvent, adding a neutralizing agent to the reaction product and distilling the solvent and having 0.001-0.05mu average granule size with (B) 99-50 pts.wt. synthetic resin emulsion having 0.05-1mu average granule size and containing no fluorine.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to an emulsion composition containing a fluorine-containing synthetic resin emulsion. The present invention relates to a synthetic resin emulsion that contains both a synthetic resin emulsion that does not contain a synthetic resin emulsion and a synthetic resin emulsion that does not contain a synthetic resin emulsion that contains both.

[Prior art and problems to be solved by the invention] In the production of fluorine-containing fat emulsine, it is difficult to uniformly solubilize it by emulsion polymerization using a normal activator because the specific gravity of the fluorine-containing fat is large. Therefore, normal emulsion polymerization cannot be carried out, and special methods have been taken to improve this problem. That is, the use of fluorosurfactants and/or
Alternatively, relatively large amounts of water-soluble organic solvents such as methanol, ethanol, ethylene glycol, propylene glycol, acetone, and dioxane are used. These actions and effects are as described in US Pat. No. 3,062,765.

However, these water-soluble emulsions lack the chemical resistance, weather resistance, non-stick properties, and properties of fluorocarbons unless they use relatively large amounts of expensive fluorine monomers.
Water and oil repellency and fingerability may or may not be expressed.These characteristics are properties of the film surface, and their performance depends on the fluorine concentration present on the film surface. In the above water-soluble emulsion, the fluorine monomer is uniformly polymerized, so even when it is formed into a film, the fluorocarbon is evenly distributed in the film. Therefore, there is a problem that only a small amount of fluorocarbon acts effectively on the surface, and the presence of fluorocarbon on the adhesive surface of the base material also deteriorates the adhesion.

The purpose of the present invention is to solve the above-mentioned problems, to provide an emulsion that efficiently distributes fluorocarbon on the surface, is simpler and cheaper than conventional emulsions, and fully exhibits the characteristics of fluorocarbon.

[Means for Solving the Problems] As a result of intensive research to solve the many problems described above, the present inventor has developed both a fluorine-containing emulsion with a small particle size and a fluorine-free synthetic resin emulsion with a large particle size. It has been found that it is extremely effective to use a synthetic resin emulsion composition containing the following, and the present invention has been completed.

That is, the present invention provides a fluorine-containing synthetic resin emulsion 1 to 501 J (solid content) with an average particle diameter of o, ooi to 0.05μ and a fluorine-free synthetic resin emulsion 23299 to 50 with an average particle diameter of 0.05 to 140μ. The present invention provides an emulsion composition obtained by mixing parts by weight (solid content).

In addition, in the present invention, the average particle diameter refers to CO[ILTER
ELECTI? 0NIC3 INC C0IILTER
This is a value measured at 25°C using MODEL N4.

Below, a fluorine-containing synthetic resin emulsion with an average particle diameter of 06001 to 0.05μ is synthesized with a small particle diameter fluorine-containing synthetic resin emulsion, and a fluorine-free synthetic resin emulsion with an average particle diameter of 0.05 to 1.0μ is synthesized with a large particle diameter. It is called a resin emulsion.

In the present invention, the function of the fluorine-containing synthetic resin emulsion with a small particle size is particularly important.

The small particle size fluorine-containing synthetic resin emulsion used in the present invention can be produced by various methods, and typical production methods include, for example, the following.

(11 Patent of DuPont Company (Special Publication No. 49-369)
A method for producing acrylic hydrosil according to Publication No. 42).

(2) Special Publication No. 49-43381 and Special Publication No. 51-
A method disclosed in Japanese Patent No. 13192 in which maleated butadiene or a water-soluble alkyd resin is used in a relatively large amount to emulsify and disperse a nil monomer for graft polymerization.

(3) A method disclosed in Japanese Patent Publication No. 49-27127, in which a vinyl monomer is polymerized in an aqueous solution prepared by dissolving a highly concentrated shellac resin in aqueous ammonia.

(4) (A) Monomer 0 having a salt-forming group or a polyalkylene oxide group and a radically polymerizable unsaturated bond
．． 5 to 60% by weight, (B) 5 to 99.5% by weight of a fluorine-containing monomer having a radically polymerizable unsaturated bond, (C) Radically polymerizable, which does not fall under either (A) or (B). A monomer mixture consisting of 0 to 94.5% by weight of monomers having unsaturated bonds is solution-polymerized in an alcohol-based or ketone-based solvent, and then the resulting reaction product is treated with a neutralizing agent as required. The method involves adding water, distilling off the alcoholic or ketone solvent, and inverting the phase to an aqueous solvent.

(5) Others, such as Japanese Patent Publication No. 50-15027,
Special Publication No. 53-7479, Special Publication No. 53-748
A method for producing an aqueous urethane resin described in Publication No. 0, etc.

Methods (4) and (5) are advantageous as methods for producing fluorine-containing synthetic resin emulsilane with the smallest particle size;
Method 4) is particularly preferred.

The method (4) will be explained in more detail below.

In the present invention, the monomer composition for obtaining a small particle diameter fluorine-containing synthetic resin emulsion is 1. (A) a monomer having a salt-forming group or a polyalkylene oxide group and a radically polymerizable unsaturated bond; (hereinafter referred to as surface-active monomer) 0.5 to 60% by weight, (B) fluorine-containing monomer having a radically polymerizable unsaturated bond (hereinafter referred to as fluorine-containing monomer) 5 to 99.5% by weight %, and the remainder is surface active monomer,
It is a monomer having a radically polymerizable unsaturated bond other than a fluorine-containing monomer.

If the amount of surface active monomer is less than 0.5% by weight, a uniform and stable fluororesin aqueous emulsion silane cannot be obtained;
If it exceeds 0% by weight, a resin with water resistance of practical use cannot be obtained.

Furthermore, if the amount of the fluorine-containing monomer is less than 5% by weight, a resin that exhibits the practical characteristics of the fluorine-containing monomer cannot be obtained.

Surface-active monomers used in the present invention include anionic heavy monomers, cationic monomers, amphoteric monolayers, nonionic monomers, and the like. More specifically, as anionic monomers,
There are unsaturated carboxylic acid monomers, unsaturated sulfonic acid monomers, unsaturated phosphoric acid monomers, etc.Cationic monomers include unsaturated tertiary amine-containing monomers, unsaturated ammonium salt-containing monomers, etc. As a monomer, N
-(3-sulfopropyl)-N~mecchloryloxyethyl-N,N-dimethylammonium betaine, N-(
3-sulfopropyl)-N-methacrylamidoprobyl-N,N-dimethylammonium betaine, 1-(3
-sulfopropyl)-2-vinylpyridinium betaine, and nonionic monomers include unsaturated polyoxyethylene oxide monomers and unsaturated polyoxypropylene oxide monomers.

Specifically, among the anionic monomers, unsaturated carboxylic acid monomers include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid,
Examples include citraconic acid, anhydrides thereof, monoalkyl esters thereof, and vinyl ethers having a carboxyl group such as carboxyethyl vinyl ether and carboxypropyl vinyl ether.

Examples of unsaturated sulfonic acid monomers include styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 3-sulfopropyl (meth)acrylic acid ester, bis-(3-sulfopropyl)-itaconic acid ester, etc. and its salt. or,
Others include 2=sulfuric acid monoester of hydroxyethyl (meth)acrylic acid and its salts.

Unsaturated phosphoric acid monomers include vinylphosphonic acid, vinylphosphate, acid phosphoxyethyl (meth)
Acrylate, acid phosphoxypropyl (meth)acrylate, bis(methacryloyloxyethyl) phosphate, diphenyl-2-methacryloyloxyethyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, dibutyl-2-methacryloyloxyethyl phosphate, dibutyl -2-acryloyloxyethyl phosphate, dioctyl-2(meth)acryloyloxyethyl phosphate, and the like.

Examples of cationic monomers include unsaturated tertiary amine-containing monomers and unsaturated ammonium salt-containing monomers. Specifically, vinylpyridine, 2-methyl-5-vinylpyridine, 2-ethyl-5 - Monovinylpyridines such as vinylpyridine; Styrenes having a dialkylamino group such as N,N-dimethylaminostyrene, N,N-dimethylaminomethylstyrene; N,N-dimethylaminoethyl methacrylate, N,N-dimethylamino ethyl acrylate), N,N-diethylaminoethyl methacrylate, N,N-diethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylate,
NJ-dimethylaminobrobyl acrylate), N, N-
Esters having a dialkylamino group of acrylic acid or methacrylic acid such as diethylaminopropyl methacrylate, N,N-diethylaminopropyl acrylate; vinyl ethers having a dialkylamino group such as 2-dimethylaminoethyl vinyl ether 1liN-(N
'.

N-dimethylaminoethyl)methacrylamide, N-
(N',N'-dimethylaminoethyl)acrylamide, N-(N',N'-diethylaminoethyl)methacrylamide, N-(N',N"-diethylaminoethyl)acrylamide, N-(N",N") -dimethylaminopropyl)methacrylamide, N-(N″N +-dimethylaminopropyl)acrylamide, N-(N'
.

Ko-diethylaminopropyl) methacrylamide, N
- Acrylamides or methacrylamides having a dialkylamino group such as (N''Nl-diethylaminoprobyl) acrylamide, or alkyl halides (alkyl group having 1 to 18 carbon atoms, halogens such as chlorine, bromine, and iodine), halogens, etc. benzyl chloride or benzyl bromide, alkyl esters of alkyl or arylsulfonic acids such as methanesulfonic acid, benzenesulfonic acid or toluenesulfonic acid (the alkyl group has 1 to 18 carbon atoms), and dialkyl sulfates (the alkyl group has 1 to 18 carbon atoms); Examples include those which have been quaternized with a known quaternization side such as those having 1 to 4 carbon atoms.

Examples of nonionic monomers include esters of unsaturated carboxylic acid monomers and polyoxyalkylene glycols or polyoxyalkylene oxide adducts of lower alcohols, or allyl glycidyl ethers or glycidyl ethers of unsaturated carboxylic acid monomers and polyoxyalkylene glycols. There are reaction products of oxyalkylene glycol or lower alcohol with polyoxyalkylene oxide adducts, and for example, those shown by the following formula can be used.

CHx = CHCHtO-(CHzC[1g0),
1-LCI-COOR' OOH (wherein R1 is H, C) I, or -CLCIICIIzO-(CLC)IzO)--R"
, Hz is H or H is C11. ) C) 1ffi=c) I-Co-(C)1. cHffiO
), 1M.

CHl-CH-CO-(CH2CH1O), CH3°C
Hz=CH-CO-CHz(JCHzO(CHtCHz
O)-CH3゜OH (In the above formula, n is a number from 1 to 100) In the present invention, as the fluorine-containing monomer, (meth)acrylates having polyfluoroalkyl groups and perfluoroalkyl groups, vinyl esters, vinyl ether,
Known compounds such as malate, fumarate, and α-olefin can be mentioned. More preferred fluorine-containing monomers include those having a polyfluoroalkyl group or perfluoroalkyl group having 4 or more carbon atoms.

Examples of these compounds include, for example, CHz=CBCO*CmH<CthF+t, CHz=C
HCO*CJ4CsP+t+CHt -CtlCOgC
JnCl @F x r, CHl = C(C)L
s) COtC! ! (nCJ+s.

CHt −C(CHs)COzCtHaCJ + q,
CHl = C(CHs) C0tCdLC+ eF
z+.

C5FjvSOz(CJy)CHzCHzOCQCH-
CHt.

C@Fl? sOt (CHz)CHtCHtOCOC
(CHs)=CHt.

C,IP,5CON(CIHs)C)! ICHtOCO
C(CI=CHt.

CaF+1(CHx) r +0COC(CL) =C
Hz.

CJ'ryCToCHCToOCOC(CHff)
H! .

H (Ch)*CFO(CHz)sOcOcH=CHt.

CtFs(OChCFthOChCFtCON(CHz
>CHtCIIz.

Low CL=CtlCO0 CaF + tsOtN (CH*C11zOCOCH
= CL) Yi.

CIF 5OtN(CHz)(Cut)t. 0COCH
tCH=CTo.

C,F,,SO,N(C1l(S)CIIC)lIOG
OCI-CHCOOC,H,.

CJ'+5SOJ(CHs)CHtCHtOCOCH"
”C) IzlCJ+1SOtHHCHtCHxSOtC
I4=CH*.

CFj (cps) a (cut) zOcOc (
CH3) = Clt.

CFs(CFt)acHzOcOc(CHz)-CH□
Ch(Ch) h(C)It) gOcOc(CHs
)=CIf.

Ch (CFt) tsOtN(Cillt) (CH
,) gOcOcH=c)It.

CFz(Ch) vs OJ(C)It) (CHg)tO
cOc(CHff) -CHzlChCl (CFt)
+ocHzOcOc<CHs) =CHt.

C) If-CH-0-(CH, -(CF, -X.

~16, n is an integer from 0 to 2. ) CHz = CH-(C)l. 1- (CPri@-X
.

CHg=CH-(C11ri/-0-C-(CH2)--
(Ch)--X~16, n is an integer of 0-2, and P is an integer of 0-3. ]CJbm-+ (a is 1 to 18) or -(C
Ht) = - (CF, ) , -X, and ■ is 5 to 16
, n is an integer from 0 to 2. ) (In the formula, × is H, P, CI, CP, Y is H, F, CI,
CPS, Z are H, F, C1, CFj. ) There are also macromonomers of the monomers shown above. This macromonomer can be easily synthesized using a recipe known in the art.

For example, the above monomers are radically polymerized with thioglycolic acid, 2-mercaptoethanol, etc. in the presence of an initiator, and the resulting reaction product is reacted with glycidyl (meth)acrylate, isocyanate ethyl (meth)acrylate, etc. can be obtained by introducing a radically polymerizable unsaturated bond at one end.

The number average molecular weight of the macromonomer is desirably 10.000 or less, and if the molecular weight exceeds this molecular weight, the solubility in the solvent used for producing the self-dispersed fluororesin aqueous emulsion silane will be poor. Preferably, the number average molecular weight is 5,000 or less.

In addition, examples of monomers having radically polymerizable unsaturated bonds other than surface-active monomers and fluorine-containing monomers include (meth)acrylates, vinyl esters, vinyl ethers, malates, fumarates, α-olefins, and other known monomers. The following compounds can be mentioned.

Specific examples of these compounds include vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl caproate, vinyl laurate, vinyl versatate, and vinyl cyclohexanecarboxylate; methyl vinyl ether; and vinyl esters such as vinyl cyclohexanecarboxylate. vinyl ether,
n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, t-butyl vinyl ether, n-pentyl vinyl ether, n-hexyl vinyl ether, n-octyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, lauryl vinyl ether propylene, etc. Monoolefins, malates such as dimethyl maleate, diethyl maleate, dioctyl maleate, diolefins such as butadiene and isoprene, allyls such as allyl acetate, methyl (meth)acrylate, ethyl (meth)acrylate, (Meth) such as n-butyl acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-octyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, etc. In addition to monomers such as meth)acrylic acid esters, styrene monomers such as styrene and vinyltoluene, and monomers such as acrylonitrile, there are macromonomers of the monomers shown above.

This macromonomer can be easily synthesized using recipes known in the art. For example, the above monomers are radically polymerized with thioglycolic acid, 2-mercaptoethanol, etc. in the presence of an initiator, and the resulting reaction product is reacted with glycidyl (meth)acrylate, isocyanate ethyl (meth)acrylate, etc. It can be obtained by introducing a radically polymerizable unsaturated bond at one end.

The number average molecular weight of the macromonomer is preferably io, ooo or less; if the molecular weight is higher than this, the self-dispersed fluororesin aqueous emulsigone will have a high viscosity during the production, which will interfere with the phase inversion process, resulting in a stable self-dispersed fluororesin. Aqueous emulsigone cannot be obtained.

The monomer can be selected from one or more of the intermediates listed above.

In the present invention, examples of alcoholic solvents used for producing the fluororesin emulsion 5 include methanol, ethanol, n-propanol, isopropanol,
Examples include n-butanol, secondary butanol, tertiary butanol, isobutanol, diacetone alcohol, 2-iminoethanol, and isopropanol is preferred.

Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone, dipropyl ketone, methyl isobutyl ketone, and methyl isopropyl ketone, with methyl ethyl ketone being preferred.

These may be used alone or in a mixture of two or more. If necessary, a high boiling point hydrophilic organic solvent may be used in combination.

Examples of high-boiling hydrophilic organic solvents include phenoxyethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol 7-methyl ether, diethylene glycol diethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, 3-methyl-3- Examples include methoxybutanol.

In the present invention, a known radical initiator is used as the initiator for producing the self-dispersed gold fluororesin aqueous emulsion. For example, hydroperoxides represented by t-butyl hydroperoxide, di-L-peroxide
Dialkyl peroxides represented by butyl, diacyl peroxides represented by acetyl peroxide, peracid esters represented by t-butyl peracetate, ketone peroxides represented by methyl ethyl ketone peroxide, and 2,2
゛-Azobis(isobutyronitrile), 2,2°-azobis(2,4-dimethylacreonitrile), 1.1
'-azobis(cyclohexane-1-carbonitrile)
Examples include azo polymerization initiators represented by.

In order to obtain a uniform and stable self-dispersed fluororesin aqueous emulsion using each of the above raw materials, for example, prepare a reactor equipped with a stirrer, reflux condenser, dropping funnel, temperature 81, and a nitrogen gas introduction tube. and surface active monomer (A) 0.5-6
0% by weight and 1. 5 to 99.5% by weight of a fluorine-containing monomer (B) and 0 to 9465% by weight of a monomer (C) that does not fall under either (A) or CB) in an alcohol-based or ketone-based solvent. Examples include a solution polymerization method and a bulk polymerization method, but solution polymerization in an alcohol-based or ketone-based solvent is necessary to obtain the emulsion of the present invention.

As another formulation, for example, in the case of gaseous monomers such as ethylene, propylene, and tetrafluoroethylene, an autoclave is used, and the surfactant monomer (^) 0.5 to 60% is used.
% by weight, 5 to 99.5% by weight of the fluorine-containing monomer (B), and further θ to 94.5% by weight of the monomer (C) that does not fall under either (A) or (B). , obtained by solution polymerization in alcohol-based and ketone-based solvents.

The reaction product obtained by solution polymerization as described above is neutralized by adding a neutralizing agent such as caustic soda, triethylamine, or glycolic acid as necessary, and then water is added and the alcohol-based or ketone-based solvent is distilled off. The self-dispersing fluororesin aqueous emulsion according to the present invention can be obtained by phase inversion to an aqueous system.

The small particle diameter fluorine-containing synthetic resin emulsion thus obtained has almost complete transparency in transmitted light.
When irradiated with laser light, the Tyndall phenomenon characteristic of colloidal dispersions occurs, and the polymer concentration in the dispersion medium is usually 30%.
The number average molecular weight is preferably i,ooo to 200.000, and exhibits a considerably high viscosity at a concentration as low as 200.000%.

On the other hand, large-particle synthetic resin conjugates can be obtained by known formulations such as general emulsion polymerization methods.

For example, in emulsion polymerization, anionic surfactants and cationic surfactants are generally used to solubilize hydrophobic polymers in micelles to provide a polymerization site, and to stabilize the resulting emulsion. This is a method in which a nonionic surfactant is used alone or as a mixture in an amount of 0.5 to 5% by weight based on the raw material monomer. There is also a seed polymerization method in which an emulsion obtained by emulsion polymerization is used as a polymerization site to increase the particle size of the emulsion. The particle size of the emulsion obtained by these methods is 0.0
It is a translucent or white opaque, low viscosity colloidal dispersion with a diameter of 5 to 1.0 microns.

When a small particle diameter fluorine-containing synthetic resin emulsion and a large particle diameter synthetic resin emulsion are used alone, for example, in the case of a small particle diameter fluorine containing synthetic resin emulsion,
As mentioned above, it has a fairly high viscosity at low concentrations, and it is usually difficult to increase the concentration to 30% or more, but when made into a coating, it has the same coating forming properties as an organic solvent type, and the coating becomes dense. It is shiny. In addition, the characteristics of fluorocarbon, such as chemical resistance, weather resistance, non-adhesiveness, water and oil repellency, and sliding properties, are well recognized.

On the other hand, in the case of a large particle size synthetic resin emulsion, a highly concentrated product can be obtained due to its low viscosity as described above, but in general, as the particle size increases, the storage stability of the emulsion deteriorates. In addition, when made into a coating film, the coating film is rougher and less dense than a small particle size product, and has poor gloss, water resistance, adhesion, etc.
It has many problems.

However, when a small particle size fluorine-containing synthetic resin emulsion and a large particle size synthetic resin emulsion are blended as in the present invention, the emulsification and dispersion ability of the large particle size synthetic resin emulsion increases in terms of solution properties, and storage stability and mechanical Performance such as stability is greatly improved.

In addition, in terms of solid-state properties, when the material is flat and non-absorbent, it forms a close-packed structure during the film-forming process, which greatly improves the film-forming properties of the film, improving the density, gloss, and mechanical strength,
Many properties such as water resistance and adhesion are improved.

Furthermore, the characteristics of the fluorocarbon described above are not proportional to the mixing ratio of the small particle size fluorine-containing synthetic resin emulsion and the large particle size synthetic resin emulsion, but even if a small particle size is added, the small particle size fluorine-containing synthetic resin emulsion is Because the perfluoroalkyl group is oriented on the surface, it exhibits the same performance as when it is used alone.

Small particle size It is desirable that the particle size of the fluorine-containing synthetic resin emulsion be small; if the particle size exceeds 0.05μ, the above-mentioned effects and the rate of migration to the surface in contact with air will be slow, and perfluoroalkyl groups will be formed on the surface. Because it becomes difficult to orient,
The above-mentioned effects cannot be expected much.

In addition, the mixing ratio of the small particle diameter fluorine-containing synthetic resin emulsion and the large particle diameter synthetic resin emulsion is 1 to 50 parts by weight (solid content) of the small particle diameter fluorine containing synthetic resin emulsion and 99 to 50 parts by weight of the large particle diameter synthetic resin emulsion. Parts by weight (solid content) are desirable; if the small particle size fluorine-containing synthetic resin emulsion is less than 1 part by weight, the effect of increasing the emulsification and dispersion ability of the large particle size emulsion is small, and the storage stability of the emulsion is
9 In addition, a close-packed structure is created during the film-forming process to improve the film-forming properties of the coating film and to improve the performance of denseness, gloss, adhesion, mechanical strength, and water resistance. There is little effect on increasing it.

Furthermore, properties such as chemical resistance, weather resistance, non-adhesiveness, water and oil repellency, and sliding properties due to fluorine do not appear.

On the other hand, although there are few practical problems if only the small particle type fluorine-containing synthetic resin emulsion is used, it is economically disadvantageous because only the expensive fluororesin is used. In addition, it is often difficult to operate due to its low concentration and high viscosity.

Examples of uses of the Emulsita 2 composition of the present invention include:
Water and oil repellent antifouling applications, resin surface modifiers, positive photoresists, optical fibers, waterless planographic printing plates, contact/optical lenses, paint and ink applications, medical polymer materials, mold release applications, magnetic tapes / Can be used in fields such as coating and sliding properties of magnetic disks, cosmetics, recording materials, thermal recording paper, sizing agents, paper processing, OP varnish, powders, anti-caking agents, anti-mold agents, etc., fiber materials, Impregnated with non-woven fabric, paper, leather, rubber, wood, metal, asphalt, concrete, plaster, ALC board, ceramic siding material, glass, glass fiber, plastics, etc., or applied to these surfaces and dried. In addition to achieving performance improvement effects such as surface coating, adhesion, and texture improvement, it is also used in cathode ray tube filming liquids, coating agents for barcode labels (POS labels), civil engineering and construction, various binders, adhesives, It can be advantageously used in fields where paper processing agents, cement admixtures, and rubber latexes and resin emulsions are commonly used.

〔Example〕

EXAMPLES Next, the present invention will be specifically explained with reference to Examples, but it goes without saying that the present invention is not limited thereto. In addition, all parts and percentages in the examples are based on weight unless otherwise specified.

Reference Example-1 64 parts of isopropyl alcohol, 4 parts of ion-exchanged water, 14.8 parts of methyl methacrylate, i
ll, IH, 2)! , 41.2 parts of 2H-hebutadecafluorodecyl methacrylate and 8 parts of 2-acrylamide 1-2-methylpropanesulfonic acid were charged, and dissolved oxygen was removed by flowing nitrogen gas.

On the other hand, 36 parts of isopropyl alcohol from which dissolved oxygen has been removed, 36 parts of methyl methacrylate, and 0,807 parts of azobisisobutyronitrile are charged into the dropping funnel.

After heating 83 parts of the reactor to 3 DEG C., a solution of 0.13 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone was added, and 70 grams were added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile 0
．． A solution of 2 parts dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.
．． A solution of 1 part dissolved in 2 parts of methyl ethyl ketone was added, and the reaction was continued again for 6 hours to obtain a homogeneous copolymer.

Next, 15.5 parts of a 10% caustic soda aqueous solution was added to this copolymer to neutralize it, and then 300 parts of ion-exchanged water was added, and methyl ethyl ketone was distilled off under reduced pressure to reduce the particle size to 0.00.
A transparent self-dispersing fluororesin aqueous emulsion of 8μ was obtained. In addition, the particle size is C0ULTf! RBLfICTRO
NIC5INCI! C0ULTf! RMODELN4
This is the value measured at 25°C (the same applies below).

Reference Example-2 64 parts of isopropyl alcohol, 4 parts of ion-exchanged water, 14.8 parts of methyl methacrylate, 1
B. 41.2 parts of IH,2H,2H-hebutadecafluorodecyl methacrylate and 5 parts of 2-acrylamide 2-methylbropanesulfonic acid were charged, and dissolved oxygen was removed by flowing nitrogen gas.

Meanwhile, 36 parts of isopropyl alcohol from which dissolved oxygen has been removed, 36 parts of methyl methacrylate, and 0.07 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83±3°C, a solution of 0.13 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone is added, and a drop of 70 grams is added dropwise from the dropping funnel in accordance with the consumption rate of methyl methacrylate.

After dropping the monomer, azobisisobutyronitrile 0
．． A solution of 2 parts dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.
．． A solution of 1 part dissolved in 2 parts of methyl ethyl ketone was added, and the reaction was continued again for 6 hours to obtain a homogeneous copolymer.

Next, 9.7 parts of a 10% caustic soda aqueous solution was added to this copolymer to neutralize it, and then 300 parts of ion-exchanged water was added.
Methyl ethyl ketone was distilled off under reduced pressure, and the particle size was 0.047.
A translucent self-dispersing fluororesin aqueous emulsion of μ was obtained.

Reference Example 3 64 parts of isopropyl alcohol, 4 parts of ion exchange water, 14.8 parts of methyl methacrylate, I
Il, IH, 2H, 2) 41.2 parts of 1-hebutadecafluorodecyl methacrylate, 2-acrylamide-2
-Prepare 3 parts of methylpropane sulfonic acid,
Flow nitrogen gas to remove dissolved oxygen.

Meanwhile, 36 parts of isopropyl alcohol from which dissolved oxygen has been removed, 36 parts of methyl methacrylate, and 0.07 part of azobisisobutyronitrile are charged into the dropping funnel.

After heating the reactor to 83±3"C, add 0.13 parts of azobisisobutyronitrile dissolved in 2 parts of methyl ethyl ketone, and dropwise add 7-mer from the dropping funnel in accordance with the consumption rate of methyl methacrylate. .

After dropping the monomer, add abbisisobutyronitrile 0
．． A solution of 2 parts dissolved in 3 parts of methyl ethyl ketone was added, and the mixture was further aged for 2 hours.
．． A solution of 1 part dissolved in 2 parts of methyl ethyl ketone was added, and the reaction was continued again for 6 hours to obtain a homogeneous copolymer.

Next, 5.8 parts of a 10% caustic soda aqueous solution was added to this copolymer to neutralize it, and then 300 parts of ion-exchanged water was added.
Methyl ethyl ketone was distilled off under reduced pressure, and the particle size was 0.082.
A milky white self-dispersing fluororesin aqueous emulsion of μ was obtained.

Reference Example-4 Surfactant Emulgen 935 [35 mol adduct of nonylphenol ethylene oxide (manufactured by Kao ■)] 2 parts, Perex 5S-L (alkyl diphenyl ether disulfonate (manufactured by Kao ■)) 0.5 parts were added to a nitrogen introduction tube. , a stirrer, a reactor equipped with a temperature needle, and add 280 ml of ion-exchanged water.
parts, styrene/butyl acrylate) = 1. / 1
100 parts of the mixture was added, and the atmosphere was replaced with nitrogen at room temperature. Next, after adjusting the liquid temperature to 30°C, 5 parts of a 2% aqueous potassium persulfate solution was added and the reactor was immersed in an 80°C oil bath to initiate polymerization.

After a certain period of time, a portion of the reaction solution was sampled and its solid content was measured (drying at 150° C. for 3 hours) to determine the polymerization rate. Further, after polymerization for 2 hours, a milky white emulsion with a particle size of 0.11 μm was obtained.

Example-1 The emulsion obtained in Reference Example-1 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 50,150.

Example 2 The emulsion obtained in Reference Example 4 and the emulsion obtained in Reference Example 4 were blended at a resin weight ratio of 30/70.

Example-3 The emulsion obtained in Reference Example-1 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 10/90.

Example-4 The emulsion obtained in Reference Example-1 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 5/95.

Example 5 The emulsion obtained in Reference Example 1 and the emulsion in Reference Example 4 were blended at a resin weight ratio of 2/98.

Example-6 The emulsion obtained in 11 m-2 and the emulsion of Reference Example-4 were blended at a resin weight ratio of 50,150.

Example-7 The emulsion obtained in Reference Example-2 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 30/70.

Example-8 The emulsion obtained in Reference Example-2 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 10/90.

Example-9 The emulsion obtained in Reference Example-2 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 5/95.

Example-10 The emulsion obtained in Reference Example-2 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 2/98.

Comparative Example-1 The emulsion obtained in Reference Example-3 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 50,150.

Comparative Example-2 The emulsion obtained in Reference Example-3 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 30/70.

Comparative Example-3 The emulsion obtained in Reference Example-3 and the emulsion in Reference Example-4 were blended at a resin weight ratio of 5/95.

Example-1 to Example-10 and Comparative Example-1 to Comparative Example-3
The physical properties of the emulsion composition obtained were evaluated by the following method.

Further, the physical properties of the emulsions of Reference Example-1 and Reference Example-4 were evaluated in the same manner. The results are also shown in Table 1.

Method (1) Apply the emulsion composition on a water-repellent glass plate, dry it at 80°C overnight, and measure the resulting coating using an ermagoniometer contact angle measuring device (Model G-1). Contact angle was measured with distilled water.

(2) Adhesion (preparation of specimen) The viscosity of the emulsion composition was adjusted to 1 Qeps, and applied on an unpainted board of Kubota Fire Prevention #449 (150
The specimen was dried at 80°C for 2 hours and then left overnight.

Next, the base material test described in JiSK 5400-1979 "General Test Methods for Coatings" was conducted.

However, 2x2CI was cut at 4m+ intervals to make a total of 25 bases, and those with 100% adhesion were shown as 25/25.

(3) The emulsion composition was applied to a glossy glass plate, and after drying, it was measured with a glossy needle of Suga Test Instruments ■.

A few examples using the same gloss meter are shown for reference.

The larger the number, the better the gloss.

(4) The J-Full 952 composition was placed in a water-resistant Teflon-coated dish and the resulting film was immersed in water at 25°C for 4 days.
Observed changes in condition.

○ mark: The swelling rate of the coating film is within 5% and there is no change such as whitening △ mark: The swelling rate of the coating film is 5% to 10% and there is no change such as whitening, or there is slight whitening × mark: The coating film (5) Storage stability of emulsion The emulsion composition was placed in a mayonnaise bottle and left in a thermostat at 50'C, and changes in the state were observed.

× mark: 50'CX Sedimentation of coarse particles, thickening, and gum-up are observed within one week.

Δ mark: 50"CX Sedimentation of coarse particles, thickening, and gum-up are observed within 2 weeks.

O mark: Stable for 2 weeks or more at 50°C.

Claims (1)

[Scope of Claims] 1. Synthesis of 1 to 50 parts by weight (solid content) of a fluorine-containing synthetic resin emulsion with an average particle diameter of 0.001 to 0.05μ and a fluorine-free composition with an average particle diameter of 0.05 to 1.0μ An emulsion composition prepared by mixing 99 to 50 parts by weight (solid content) of a resin emulsion. 2. The fluorine-containing synthetic resin emulsion contains (A) 0.5 to 60% by weight of a monomer having a salt-forming group or a polyalkylene oxide group and a radically polymerizable unsaturated bond, (B) a radically polymerizable monomer. 5 to 99.5% by weight of a fluorine-containing monomer having an unsaturated bond; (C) 0 to 99.5% by weight of a monomer having a radically polymerizable unsaturated bond that does not fall under either (A) or (B); A monomer mixture consisting of 5% by weight is solution-polymerized in an alcohol-based or ketone-based solvent, and then a neutralizing agent is added as necessary to the resulting reaction product, water is added, and the alcohol-based or ketone-based solvent is polymerized. Claim 1: The product is manufactured by a method of distilling off the solvent.
The emulsion composition described.