JP3125061B2 - Room temperature curable composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to various kinds of coatings for interior and exterior of buildings, automobiles, household appliances, plastics, etc.
In particular, the present invention relates to a room temperature curable composition used for painting or the like requiring weather resistance and durability.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, the use of organic solvents has been changed from water-soluble or water-dispersible resins to pollution control or resource saving. Have been tried.

However, conventional water-based paints do not have crosslinkable functional groups, and are strongly affected by the surfactant used for polymerization, and the formed coating film has poor weather resistance, water resistance, and stain resistance. It had the drawback that the film properties were remarkably worse and the physical properties of the coating film were inferior to those of the solvent-based paint.

Therefore, a method has been proposed in which an emulsion having an alkoxysilyl group is applied to a coating material as a crosslinkable emulsion. However, the stability of alkoxysilyl groups that are easily hydrolyzed with water is insufficient,
There are problems that the film formability after long-term storage is reduced, the mechanical stability of the emulsion, and the gloss of the white enamel are inferior.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on the above problems, and as a result, introduced a vinyl monomer having a polyoxyethylene chain as a hydrophilic monomer and a polyether as a surfactant. By using an anionic surfactant having an oxyethylene chain, the stability of the hydrolyzable silyl group is remarkably improved, so that the hydrolyzable silyl group reacts during polymerization or storage, and the film forming property is reduced. That the mechanical stability of the emulsion,
They found that the gloss of white enamel was also good, and completed the present invention.

That is, the present invention relates to a vinyl monomer having a silyl group represented by the following general formula (I):
0 parts by weight, 0.1 to 10 parts by weight of a hydrophilic vinyl-based monomer (B) having a polyoxyethylene chain and another vinyl-based monomer (C) were added to make the whole 100 parts by weight. It is a room temperature curable composition containing an emulsion obtained by emulsion polymerization of a monomer using an anionic surfactant having a polyoxyethylene chain.

Embedded image (Wherein, R is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group; X is a halogen atom, or an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, or a phenoxy group) , A thioalkoxy group or an amino group, and y is an integer of 0 to 2. When each of X and R bonded to Si is two or more, they may be the same or different. May be.)

Hereinafter, vinyl monomers (A), (B),
(C) and the surfactant will be described sequentially.

The vinyl monomer having a silyl group (A) The vinyl monomer having a silyl group represented by the general formula (I) is not limited, but specific examples thereof include:

Embedded image

Embedded image

Embedded image And the like.

[0009] These silyl group-containing vinyl monomers are
One type may be used alone, or two or more types may be used in combination. In particular, it is preferable to use an alkoxysilyl group-containing vinyl monomer from the viewpoint of ease of handling, cost, and reaction by-products.

A hydrophilic vinyl having a polyoxyethylene chain
The monomer (B) is not limited to the hydrophilic vinyl monomer (B) having a polyoxyethylene chain, but is preferably an acrylate or methacrylate having a polyoxyethylene chain. , Blemmer PE-90, PE-
200, PE-350, PME-100, PME-20
0, PME-400, AE-350 (all manufactured by NOF Corporation), MA-30, MA-50, MA-100,
MA-150, RA-1120, RA-2614, RM
A-564, RMA-568, RMA-1114, MP
G130-MA (all manufactured by Nippon Emulsifier Co., Ltd.) and the like.

The number of oxyethylene units in the polyoxyethylene chain is preferably from 2 to 30. If it is less than 2, the mechanical stability and white enamel gloss of the emulsion are inferior. If it exceeds 30, the coating film becomes soft and easily stained.

Other Vinyl Monomer (C) The other vinyl monomer (C) is not limited and includes, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl ( Meta)
(Meth) acrylate monomers such as acrylate, benzyl (meth) acrylate, and cyclohexyl (meth) acrylate; trifluoroethyl (meth) acrylate, pentafluoropropyl (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,
2,3,3-tetrafluoropropyl methacrylate,
Fluorine-containing vinyl monomers such as β- (perfluorooctyl) ethyl (meth) acrylate; styrene, α-
Aromatic hydrocarbon-based vinyl monomers such as methylstyrene, chlorostyrene, 4-hydroxystyrene, and vinyltoluene; acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid,
Acids having a polymerizable carbon-carbon double bond, such as α, β-ethylenically unsaturated carboxylic acids such as fumaric acid and citraconic acid, styrenesulfonic acid, and vinylsulfonic acid, or salts thereof (alkali metal salts, ammonium Salts, amine salts, etc.); acid anhydrides such as maleic anhydride or half esters thereof with linear or branched alcohols having 1 to 20 carbon atoms; dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate And (meth) acrylates having an amino group such as diethylaminoethyl (meth) acrylate; (meth) acrylamide, α-ethyl (meth) acrylamide, N-
Butoxymethyl (meth) acrylamide, N, N-dimethylacrylamide, N-methylacrylamide, acryloylmorpholine, or hydrochloric acid or acetate thereof;
Vinyl esters and allyl compounds such as vinyl acetate, vinyl propionate and diallyl phthalate; vinyl monomers containing a nitrile group such as (meth) acrylonitrile; vinyl monomers containing an epoxy group such as glycidyl (meth) acrylate; Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2
-Hydroxyethyl vinyl ether, N-methylol (meth) acrylamide, hydroxystyrene, Alonix 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), Placec
lFA-1, PlacelFA-4, Placel
FM-1, PlacelFM-4 (all manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-20, HP-10,
HP-20 (above, manufactured by Nippon Shokubai Kagaku Co., Ltd.), Blemmer PP series, Blemmer PEP series, Blemmer AP-400, Blemmer NKH-5050, Blemmer GLM (all, manufactured by NOF Corporation), hydroxyl group-containing vinyl Hydroxyl-containing vinyl monomers such as modified hydroxyalkyl vinyl monomers; hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphate esters Vinyl compounds or vinyl compounds such as (meth) acrylates containing a urethane bond or a siloxane bond; macro-monomers AS-6, AN- manufactured by Toa Gosei Chemical Co., Ltd.
6, AA-6, AB-6, AK-5, and other vinyl monomers such as vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, N-vinyl imidazole, and vinyl sulfonic acid LA87, LA82, LA2 manufactured by Asahi Denka Kogyo Co., Ltd.
2, a polymerizable light stabilizer, a polymerizable ultraviolet absorber and the like.

[0013] The cycloalkyl methacrylate having an alkyl methacrylates and C ₄ or a cycloalkyl group having C ₄ or higher alkyl groups containing 60 or more parts by weight, is improved, especially stability of hydrolyzable silyl groups. In particular, n-butyl methacrylate and cyclohexyl methacrylate are preferable in terms of weather resistance, ease of adjusting the glass transition temperature (Tg) of the emulsion resin, and price.

By using a fluorine-containing vinyl monomer or a siloxane-containing vinyl monomer, water repellency is improved, and water resistance and durability are improved.

In addition, by using a monomer having two or more polymerizable unsaturated bonds, for example, polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate, etc., the resulting polymer is crosslinked. It is also possible to have a structure.

The proportion of the silyl group-containing vinyl monomer (A) used may be the total amount of vinyl monomers (A + B +
C) a silyl group-containing vinyl monomer in an amount of 1 to 30.
% (% By weight, the same applies hereinafter), and more preferably 2 to 20%. If the amount of the silyl group-containing vinyl monomer is less than 1%, the water resistance and weather resistance tend to be inferior, and if it exceeds 30%, the stability of the emulsion tends to decrease. The amount of the hydrophilic vinyl monomer (B) having a polyoxyethylene chain is 0.1 to 10%.
Is preferred. If it is less than 0.1%, the mechanical stability and gloss of the white enamel are low, and if it exceeds 10%, the coating film becomes soft and easily stained.

Next, the production of an emulsion polymer (emulsion) will be described.

As the emulsion polymerization method, various emulsion polymerization methods such as a batch polymerization method, a monomer dropping polymerization method, and an emulsion monomer dropping polymerization method can be appropriately selected and employed. In particular, stability during production is ensured. In this case, a monomer drop polymerization method and an emulsion monomer drop polymerization method are suitable.

Surfactant The hydrolyzable silyl group is stabilized by using an anionic surfactant having a polyoxyethylene chain as a surfactant that can be used in the above-mentioned production method. Specific examples of the anionic surfactant include Newcol-560SN,
Newcol-560SF (The above is Nippon Emulsifier Co., Ltd.)
Newcol-707SF, Nemol NC-35, Reveil WZ (manufactured by Kao Corporation), and other polyoxyethylene nonylphenyl ether sulfates.
ewcol-707SN, Newcol-723SF,
Polyoxyethylene allyl ether sulfate such as Newcol-740SF; Newcol-861S
Octylphenoxyethoxyethylsulfonate such as E; polyoxyethylene tridecyl ether sulfate such as Newcol-1305SN (all manufactured by Nippon Emulsifier Co., Ltd.).

In particular, the number of oxyethylene units in the polyoxyethylene chain is preferably 1 to 50 from the viewpoint of polymerization stability and stability of the hydrolyzable silyl group. Further, from the viewpoint of the water resistance of the coating film obtained from the emulsion, an anionic surfactant of an ammonium salt is preferred.

The anionic surfactant having a polyoxyethylene chain can be used in combination with another ionic surfactant or a nonionic surfactant.

The other ionic surfactant is not particularly limited, and examples thereof include sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate, and sodium isooctylbenzene sulfonate.

Examples of the nonionic surfactant include polyoxyethylenes such as polyoxyethylene nonyl phenyl ether and polyoxyethylene lauryl ether;
L-77, L-720, L-5410, L-7602,
Representative examples include nonionic surfactants containing silicon, such as L-7607 (all manufactured by Union Carbide).

The use of a reactive surfactant having a polymerizable double bond in one molecule does not obstruct the present invention. In particular, when a reactive surfactant having a polyoxyethylene group in the molecule is used, the water resistance is improved. As specific examples, Adeka Soap NE-10, NE
-20, NE-30, NE-40, SE-10N (all manufactured by Asahi Denka Kogyo KK), Antox-MS-60
(Manufactured by Nippon Emulsifier Co., Ltd.), Aqualon RN-20, RN
-30, RN-50, HS-10, HS-20, HS-
1025 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.).

The amount of the anionic surfactant having a polyoxyethylene chain is 0.01 to 20%, preferably 0.05 to 10%, based on the weight of all monomers. If it is less than 0.01%, the polymerization becomes unstable, and if it exceeds 20%, the water resistance decreases.

It is also possible to carry out polymerization using a water-soluble resin in combination. When this method is used, the water resistance of the coating film is improved. By introducing the silyl group represented by the general formula (I) into the water-soluble resin, the water resistance can be further increased.

In order to carry out the polymerization more stably, a temperature of 70.degree. C. or less, preferably 40.degree.
Perform at a temperature of ６５65 ° C. Further, for stabilizing the silyl group, it is preferable to adjust the pH during the polymerization.
8, more preferably adjusted to pH 6-7.

The redox catalysts include potassium persulfate, ammonium persulfate and sodium acid sulfite,
Rongalit combination, hydrogen peroxide and ascorbic acid combination, t-butyl hydroperoxide,
A combination of an organic peroxide such as benzoyl peroxide, cumene hydroperoxide, or p-menthane hydroperoxide with sodium acid sulfite, Rongalite, or the like is used. In particular, a combination of an organic peroxide and a reducing agent is preferable because polymerization can be stably performed. In order to stably obtain a catalytic activity, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be appropriately used in combination.

The amount of such a redox catalyst (initiator) to be used is from 0.01 to 0.01 based on the weight of all monomers.
It is preferably 10%, more preferably 0.05 to 5%.

The solid concentration in the emulsion according to the present invention is preferably 20 to 70%, more preferably 30 to 70%.
~ 60%. If the solids content exceeds 70%, the viscosity of the system will be significantly increased, and it will be difficult to remove the heat generated by the polymerization reaction, or it will take a long time to take out from the polymerization machine. When the solid content concentration is less than 20%, there is no problem in terms of polymerization operation, but the amount of resin generated by one polymerization operation is small, which is extremely disadvantageous from an economical point of view. If the concentration is less than 20%, the film thickness of the coating film becomes thin, and performance problems are caused, and disadvantages in application workability are caused.

The emulsion has an average particle size of 0.1.
Composed of ultrafine particles of about 02 to 0.7 μm,
As a result, it has excellent film forming ability.

The crosslinking is promoted by adding a curing agent when the composition of the present invention is applied. As the curing agent, an organometallic compound, an acidic catalyst, or a basic catalyst is used. In particular, organoaluminum compounds or organotin compounds are preferred in terms of curing activity, for example, dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, dioctyltin dimaleate,
Organotin compounds such as dibutyltin diacetate, dibutyltin dimethoxide, tributyltin sulphite, dibutyltin thioglycolate, tin octylate; aluminum isopropylate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), ethyl acetoacetate Organic aluminum compounds such as aluminum diisopropylate are exemplified.

These organometallic compounds are excellent in curing activity and storage stability by being emulsified in advance and added at the time of use. The amount used is preferably 0.01 to 10 parts, more preferably 0.1 to 5 parts, per 100 parts (parts by weight, hereinafter the same) of the solid content of the silyl group-containing emulsion as the organometallic compound. Is more preferable. 0.
If it is less than 01 parts, the curing activity is low, and if it exceeds 10 parts, the water resistance is reduced.

The obtained curable composition may, if necessary,
Pigments (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, and kaolin, and colored pigments such as carbon, red iron, cyanine blue, etc.) and coating agents, colloidal silica, plasticizers, solvents, dispersants, and the like commonly used in paints Additives such as thickeners, defoamers, preservatives, and ultraviolet absorbers, which are commonly used as components for coatings, may be mixed and used.

It is also possible to add a melamine resin and an isocyanate compound as a cross-linking agent to provide quick curability.

The composition of the present invention can be used for, for example,
For repair, for automotive such as clear on metallic coat, for direct application of metal such as aluminum and stainless steel, slate, concrete, tile, mortar, gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium silicate It is used as a direct coating for ceramics such as plates, tiles and bricks, as a coating for glass and stone, or as a top surface treatment agent. Further, it can be used as an adhesive or a pressure-sensitive adhesive.

It is also possible to blend with commercially available water-based paints, for example, acrylic paints,
Thermosetting acrylic paint, such as acrylic melamine paint,
Blending with alkyd paints, epoxy paints and fluororesin paints can improve the weather resistance, acid resistance and solvent resistance of these paints.

[0038]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited by these examples.

Examples 1 to 7, Comparative Examples 1 to 3 Initially, 40 parts of deionized water and 0.35 parts of Rongalite were charged into a reactor equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel. , A surfactant shown in Table 1, polyoxyethylene nonyl phenyl ether
0 parts, 0.5 parts of ammonium acetate, 0.2 parts of t-butyl hydroperoxide and 20 parts of 158 parts of a monomer emulsion having the composition shown in Table 2 were charged. Next, while introducing nitrogen gas, the temperature was raised to 50 ° C., and after heating for 1 hour, t-
A mixture of 0.5 part of butyl hydroperoxide and the remaining 138 parts of the monomer emulsion was added dropwise over 3 hours. Thereafter, polymerization was carried out for 1 hour, and the solid content was adjusted to 40% using deionized water to obtain an emulsion.

The obtained emulsion was evaluated by the following method. Table 3 shows the evaluation results.

[Evaluation method] Stability of methoxysilyl group (hydrolyzable silyl group) The synthesized emulsion was applied to a polyethylene sheet.
After standing at room temperature for one day, the coating film formed on the polyethylene sheet was peeled off, and the coating film was measured by infrared spectroscopy. The residual ratio of the methoxysilyl group to the charged methoxysilyl group-containing vinyl monomer ( %).

Long-term storage stability (appearance) The emulsion was stored at 50 ° C. for 1 month, and the state of the liquid (appearance) was visually observed.

Long-term storage stability (film formation at 5 ° C.) Each emulsion stored at 50 ° C. for one month was left at 5 ° C. overnight, applied on a glass plate, and the coated glass plate was left at 5 ° C. overnight. And the surface condition was observed.な し indicates that there was no abnormality, and X indicates that cracks occurred.

Mechanical Stability According to JIS K 6392, a test was carried out using a Marlon tester under a load of 15 kg for 5 minutes. The amount of agglomerates after the test was weighed and indicated as a ratio (ppm) to the amount of solids in the charged emulsion.

White Enamel Gloss Compounded according to the following formula and 1000
The mixture was dispersed at 1 rpm for 1 hour to obtain a pigment paste. 60 parts of the emulsion was added to 30 parts of the pigment paste, mixed, applied to a glass plate, allowed to stand at room temperature for one day, and then measured at 60 ° gloss with a gloss meter. Water 20 parts 14% ammonia water 0.3 parts Poise 521 (pigment wetting agent manufactured by Kao Corporation) 1 part SN deformer 381 (antifoaming agent manufactured by San Nopco Co.) 0.3 part 2% Tyrose H4000P (Thickener manufactured by Hoechst Japan KK) 6.5 parts Titanium oxide (pigment) 72 parts

0.4 g of dibutyltin dilaurate was added to 10 g of the water-resistant emulsion, mixed and applied to a polyethylene sheet. After drying at room temperature for 10 days, 1
After immersion for one day, the increased weight was shown as a percentage (%) with respect to the weight of the film before immersion.

[0047]

[Table 1]

[0048]

[Table 2]

[0049]

[Table 3]

[0050]

The cold-setting composition of the present invention has excellent stability of hydrolyzable silyl groups, and has greatly improved film formability after long-term storage. It is also excellent in mechanical stability and gloss of white enamel.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 43/04 C08F 230/08 C08L 33/06 C09D 133/06 C09D 143/04 C08F 2/26

Claims (8)

(57) [Claims] 1 to 30 parts by weight of a silyl group-containing vinyl monomer (A) represented by the following general formula (I), and a hydrophilic vinyl monomer (B) having a polyoxyethylene chain:
Emulsion polymerization of 1 to 10 parts by weight and another vinyl monomer (C) to give a total of 100 parts by weight of the vinyl monomer using an anionic surfactant having a polyoxyethylene chain. Room temperature curable composition containing the emulsion obtained by the above. Embedded image (Wherein, R is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group, and an aralkyl group; X is a halogen atom, or an alkoxy group, a hydroxy group, an acyloxy group, an aminoxy group, or a phenoxy group) , A thioalkoxy group or an amino group, and y is an integer of 0 to 2. When each of X and R bonded to Si is two or more, they may be the same or different. May be.) 2. A vinyl monomer having a silyl group (A)
Is an alkoxysilyl group-containing vinyl monomer. 3. The cold-setting composition according to claim 1, wherein the hydrophilic vinyl monomer (B) has 2 to 30 oxyethylene units in the polyoxyethylene chain. 4. As another vinyl monomer (C), C ₄
To any one of claims 1 to 3, characterized in that it comprises one or more 60 or more parts by weight of the cycloalkyl methacrylate having an alkyl methacrylates and C ₄ or more cycloalkyl groups having the above alkyl groups The room temperature curable composition according to the above. 5. The cold-setting composition according to claim 1, wherein an anionic surfactant having 1 to 50 oxyethylene units in the polyoxyethylene chain is used. 6. The cold-setting composition according to claim 1, wherein the anionic surfactant is an ammonium salt. 7. The method according to claim 1, further comprising a curing agent.
The cold-setting composition according to any one of Items 1 to 6. 8. The room temperature curable composition according to claim 7, wherein the curing agent is an organoaluminum compound or an organotin compound.