JP3093566B2 - Core-shell type microemulsion having functionality - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a core-shell type microemulsion having functions such as ultraviolet ray prevention, fragrance, fungicide, rust prevention and fragrance and used for coating agents, inks, cosmetics and the like. .

[0002]

2. Description of the Related Art Conventionally, a so-called functional coating composition having a function of absorbing ultraviolet rays, a function of preventing mold, a function of preventing rust, etc., other than a coating composition for the purpose of aesthetics and protection, exhibits the above-mentioned functionality. Compound as filler
This is usually kneaded with a resin component as a binder and dispersed in a solvent or water as a dispersion medium. On the other hand, from the viewpoints of global environmental problems, human body protection, and safety against fire, it is true that the above functional coating agent is also desired to be made water-based and is moving in this direction.

When the functional coating agent is made aqueous,
The technical problem depends on how a functional compound having a remarkable chemical property can be wrapped in a binder and dispersed in water. If this is not complete, it will ooze out of the wrapped-in binder during storage over time, degrading storage stability or making the formed film non-uniform, rendering it impractical. Therefore, in order to overcome this problem, an interfacial polymerization method (JP-A-59-159177, JP-A-5-159177)
9-172653), a coacervation method (Japanese Unexamined Patent Publication No.
1-254243, 56-49312), in situ
Although microencapsulation methods such as a u polymerization method (JP-A-59-162943) and a double emulsion method have been attempted,
In any case, the particle size is too large or the compatibility with other resin systems is insufficient, so that it has not been practically used as a functional coating agent.

[0004] Further, an attempt to disperse a functional compound in the particles constituting the emulsion using an ordinary emulsifier during polymerization has been lacking in emulsifying power, so that the compound was not incorporated into the particles and the polymerization stability was lost. The fact is that it cannot be manufactured.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a microemulsion as an aqueous coating agent having functions such as ultraviolet protection, anti-mold, rust-prevention, and aromatic properties, which enables storage stability and uniform film formation. Is to provide.

[0006]

Means for Solving the Problems As a means for solving the above-mentioned technical problems, the present inventors have proposed to disperse the functional compound during polymerization into a core of a core / shell type emulsion from which stable fine particles can be obtained. The present inventors were able to complete the present invention as a result of intensive studies on the means for confining. In the emulsion, the core component is an acrylate / methacrylate ester containing 20% or less of one kind of a functional compound, a copolymer of 80 to 100% of other monomers, and the shell component is an acrylate ester or a methacrylate ester. , Other monomers 6
0 to 95% and αβ ethylenically unsaturated carboxylic acid 40 to 5
Parts of a water-soluble copolymer having a Mw of 5,000 to 100,000 and a core / shell ratio of 1/10 to 10/1 having an average particle size of 0.3.
It is a core / shell type functional microemulsion having a value of μ or less.

The functional core-shell emulsion of the present invention is obtained by neutralizing a water-soluble resin obtained by various synthetic methods with an amine or ammonia, and dissolving a functional compound in a solution dispersed in water. It is synthesized by dropping a monomer solution. At this time, it is presumed that the hydrophobic monomer containing the functional compound gradually enters the shell polymer dispersed in water and polymerizes. For this reason, it is excellent in polymerization stability, and becomes a form in which the functional compound is uniformly dispersed in the core polymer.

Acrylic esters and methacrylic esters are used as monomers for producing the polymer of the core portion, and other monomers may be added in some cases.

Examples of the acrylate monomer and the methacrylate monomer include acrylic acid or C ₁ -C ₁₂ alkyl esters of methacrylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, and the like.
Isobutyl acrylate, 2-ethylhexyl acrylate,
Decyl acrylate, dodecyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, laurel methacrylate, laurel methacrylate, 2-ethylhexyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, etc .; glycidyl acrylate, Glycidyl methacrylate: dimethylaminoethyl methacrylate and the like.
More than one species is used.

Examples of other monomers include acrylamide, methacrylamide, N-methylacrylamide,
Monoethylenically unsaturated amides such as N-vinylpyrrolidone; esters of monoethylenically unsaturated alcohols such as vinyl acetate, vinyl propionate and allyl acetate; monoethylenically unsaturated nitriles such as acrylonitrile and methacrylonitrile; styrene, α -Aromatic monoethylenically unsaturated monomers such as methylstyrene; vinyl ethyl ether;
Monoethylenically unsaturated ether monomers such as vinyl ethyl ether and allyl ethyl ether; monoethylenically unsaturated alcohols such as allyl alcohol; and halogen-containing monomers such as vinyl chloride and vinylidene chloride. Next, examples of the functional compound include an ultraviolet absorber, a fragrance, a fungicide, a rust inhibitor, and an antifouling agent.

Examples of the ultraviolet absorber include salicylic acid-based ultraviolet absorbers such as phenyl salicylate, p-tertbutylphenyl salicylate and p-octylphenyl salicylate, dihydrobenzoquinone, 2-hydroxy-4-methoxy-4-octoxy. Benzophenone, 2
-Hydroxydodecylbenzophenone, 2-2'-dihydroxy-4-dinitroxybenzophenone, 2-2 '
Benzophenone-based ultraviolet absorbers such as -dihydroxy-4-4'-dimethoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfobenzoquinone, bis (2-methoxy-4-hydroxy-5-benzoylphenyl) methane; (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-
5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-ter
t-butylphenyl) benzotriazole, 2- (2 ′
-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole, 2- [2′-hydroxy-3 ′ -(3 ", 4",
5 ", 6" -tetrahydrophthalimidomethyl) -5 '
-Methylphenyl] benzotriazole, benzotriazole-based ultraviolet absorption such as 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] Agents, methoxydibenzoylmethane, octyl methoxycinnamate and the like.

Examples of fragrances include methyl anthranilate, benzyl benzoate, methyl benzoate, isoamyl isovalerate, ethyl isovalerate, γ-undelactone, ethylene brassate, calaxokud, dimethylbenzurecarbitol acetate, acetic acid Hydryl, linalyl acetate, isoamyl salicylate, benzyl salicylate, cyclopentadecanolide, dimethylbenzylcarbinol, tetrahydrolinalool, β-naphthylethyl ether, nonalactone, vanillin, isoamyl propionate, benzyl propionate, p-methylacetophenone, etc. Can be

Examples of the fungicide include N-trichloroethylthiophthalimide, diiodomethylsulfone,
2,4-triazolylbenzimidazole, 3,4,5
Tribromosalicylanilide, 2-n-octyl-4-
Isothiazolin-3-one, 2,3,5,6-tetrachloro-4-methylsulfopyridine, tetrachloroisophthalonitrile and the like can be mentioned.

Examples of rust preventives and antifouling agents include ethyl cinnamate, tributyltin chloride and the like. The proportion of the functional compound in the core part in the copolymer monomer is as follows:
Although it depends on the solubility in the functional compound and the copolymer monomer, from the polymerization stability, 20% by weight or less, preferably
1% to 5% by weight is desirable.

The polymer in the shell portion is composed of 60 to 95% by weight of the above-mentioned acrylate monomer, methacrylate ester monomer and other monomers and 40 to 5% by weight of αβ monoethylenically unsaturated carboxylic acid. Be composed. Examples of the αβ monoethylenically unsaturated carboxylic acid include acrylic acid, methacrylic acid, crotonic acid, fumaric acid, and maleic acid.

The copolymer of the shell portion has a molecular weight of 3,000 to 200,000, preferably 5,000 to 40,000. If the molecular weight is less than 3,000, the stability of the shell is lacking, the functional compound is precipitated, and the polymerization becomes impossible. If the molecular weight exceeds 200,000, the viscosity when dispersed in water can increase the solid content of the core / shell emulsion. Absent.

The acid value of the shell is preferably from 20 to 250. When the acid value is 20 or less, the stability at the time of dispersion in water is poor, and a functional compound is precipitated. When the acid value exceeds 250, the solubility becomes strong and micelles are not formed, so that polymerization is not possible. As the shell component, known water-dispersible water-soluble alkyds, polyesters, polyurethanes, and water-soluble maleated butadiene can also be used.

The core / shell ratio varies depending on the core composition, the shell composition and the type of the functional compound.
5/95 ratio. Preferably, 40/60 to 90/10
Is desirable. When the shell amount is 5% by weight or less, the polymerization stability is lacking, and the precipitation of the functional compound and the destruction of the emulsion occur during the polymerization as in the case of the emulsion using a usual emulsifier. On the other hand, if the shell content exceeds 90%, the viscosity at the time of dispersion increases, and an emulsion having a high solid content cannot be obtained.

[0019]

【Example】

(Example 1) (Synthesis of shell water-soluble resin) 300 parts of isopropyl alcohol was charged into a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen reflux glass tube, and a stirrer. A solution consisting of 80 parts of acrylic acid, 240 parts of ethyl acrylate, 80 parts of methyl methacrylate and 12 parts of AIBN was dropped at a uniform rate over 4 hours. A after 2 hours and 4 hours respectively
0.5 parts of IBN was added, and stirring was continued for another 3 hours to complete the reaction. After completion of the reaction, 68 parts of 28% ammonia water and 532 parts of pure water were added to obtain an aqueous dispersion. from here,
By distillation, 300 parts were distilled off, and most of the isopropyl alcohol was removed to obtain an aqueous dispersion having a nonvolatile content of 40%.

(Synthesis of Functional (Ultraviolet Absorbing) Core-Shell Emulsion) In a five-necked flask equipped with a reflux condenser, a thermometer, a nitrogen reflux glass tube and a stirrer, 150 parts (solids) 60 parts), 460 parts of ion-exchanged water, and 0.8 parts of sodium thiosulfate were charged, and stirring was started.
Until heated. Here, 96 parts of methyl methacrylate,
64 parts of ethyl acrylate and 96 parts of 2-ethylhexyl acrylate and butyl methoxybenzoylmethane (PAR
SOL1789: U manufactured by GIVAUDAN-ROUSE
A mixture of 6.4 parts of V filter) and 6.4 parts of octyl methoxycinnamate (PARSOLMCX) was added dropwise over 4 hours. At the same time, a solution comprising 3.2 parts of ammonium persulfate and 70 parts of ion-exchanged water was added dropwise over 5 hours. After further aging for 2 hours, the reaction was terminated. Nonvolatile 40
% Emulsion was obtained.

The stability of the functional (ultraviolet absorbing) core-shell type emulsion synthesized by the above method after storage at 40 ° C. for 12 months was good, and no generation of precipitates was observed. Also, the presence of coarse particles of 1 micron or more was not observed in the crush gauge. The above functional core-shell type emulsion was coated on a glass plate with a bar coater (coating amount: 10 g / m ² ), dried, and then recorded with a self-recording spectrophotometer U-320.
0 (manufactured by Hitachi, Ltd.), and the chart of FIG. 1 was obtained. The absorption at 390 nm is 90% or more;
It can be seen that UV-A waves (320 to 400 nm) having strong permeability are absorbed.

(Examples 2 to 10) Monomer composition, core /
Polymerization was carried out by changing the shell ratio and the amount of the functional compound as shown in Tables 1 and 2, and a stable emulsion was obtained as in Example 1.

[0023]

[Table 1]

[0024]

[Table 2]

(Comparative Examples 1 to 5) Polymerization was carried out by changing the monomer composition, the core / shell ratio, and the amount of the functional compound as shown in Table 3. However, during the reaction, coarse particles were generated and agglomerated. I couldn't get a good emulsion.

[0026]

[Table 3]

(Example 11) The above functionalities (UV absorption and
Using an (aromatic) core-shell type microemulsion, an eyeliner was prototyped with the following composition. (Formulation example) Liquid film type eyeliner Carbon black 4.8 Titanium dioxide 2.2 Polyoxyethylene sorbitan monostearate 1.0 Deionized water 21.0 Propylene glycol 5.4 Carboxymethylcellulose 0.6 Functional core Shell type emulsion (Example 6) 65.0 Preservative appropriate amount

(Preparation method) Polyoxyethylene monostearate is dissolved in ion-exchanged water, and carbon black and titanium dioxide are mixed therein and dispersed using a colloid mill. To this, propylene glycol, carboxymethyl cellulose, and an aqueous composite polymer emulsion,
A preservative is added to form a film-type eyeliner. The above functional emulsions include foundations, eye shadows, eye liners, eyebrow, eye makeup cosmetics such as mascara, packs, lipsticks, blushers, sunscreens, body paints, nail enamels, barrier creams, coloring for hair It is widely applied to skin cosmetics such as cosmetics and leg makeup cosmetics, and hair cosmetics.

Example 12 A gloss coating for gloss processing of paper was prepared using the above-mentioned functional (ultraviolet absorbing) core-shell emulsion with the following composition, and was applied to coated paper by a roll coater. A uniform coating film was formed, gloss was improved, and no decrease in physical properties was observed. (Formulation example) 3MV-100 * 36.0 Functional core-shell emulsion (Example 7) 48.0 Propylene glycol 2.5 Butyl cellosolve 1.0 JW-26 ** 3.0 Chemipal W-200 ** * 0.5 Formaster JK **** 0.1 Isopropyl alcohol 2.4 Ion exchange water 6.5 * ST-acrylic water-soluble resin (solid content 30%) manufactured by Taisei Kako ** Water dispersion manufactured by Johnson Polymer Type micro wax *** Water dispersion type wax manufactured by Mitsui Petrochemical Industries **** Sannopco defoamer

(Physical Properties) Gloss ○ Adhesion (cellotape / scratch) ○ Light resistance (fade meter) ○ Friction resistance (Gakushin type) ○ Blocking resistance ○ (80% RH ・ 300 g / cm ²・ 24Hr) m Secondary adhesion (Life Bond AV-650) ○

[Brief description of the drawings]

FIG. 1 is an ultraviolet spectrum diagram of a coating film comprising an emulsion of Example 1 of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08F 265/06 A61K 7/00 A61K 7/42 C09D 151/00

Claims (6)

(57) [Claims] 1. The core component comprises at least one functional compound.
Polymer of acrylic acid ester and / or methacrylic acid ester containing not more than 20% by weight of seed, 60 to 95% by weight of acrylic acid and / or methacrylic acid ester as shell component and αβ monoethylenically unsaturated carboxylic acid 40 And a core / shell ratio in the range of 10/1 to 1/10 and a particle size of 0.1 to 5% by weight.
A core-shell type microemulsion having a size of 3 μ or less. 2. The microemulsion according to claim 1, wherein the functional compound is an ultraviolet absorber. 3. A coating agent containing the emulsion according to claim 1. 4. A cosmetic comprising the emulsion according to claim 1. 5. A coating agent comprising the microemulsion according to claim 2. 6. A cosmetic containing the microemulsion according to claim 2.