JPH0820617A - Cold-setting composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful for a building exterior, having excellent stability of silyl group, extremely improved in film-forming properties after long-term storage, excellent in durability (weather resistance and white enamel luster), by using a chain transfer agent in a core part of emulsion particles prepared by multi-stage emulsion polymerization. CONSTITUTION:In this composition containing emulsion particles each comprising (A) core part and (B) shell part obtained by multi-stage emulsion polymerization, the composition contains particles composed of the component A consisting of (i) 0.5-30wt.% of a silyl group-containing vinyl-based monomer of the formula (R is a 1-10C alkyl, an aryl or an aralkyl; X is a halogen, an alkoxy, hydroxy, an acyloxy, phenoxy, a thioalkoxy or amino; (y) is 0-2), (ii) 0.01-10wt.% of a chain transfer agent and (iii) 60-99.49wt.% of a vinyl-based carrier except the component (i), and the shell part B consists of 0.1-30wt.% of the component (i), 0-10wt.% of the component (ii), (iv) 30-99.4wt.% of a vinyl-based monomer except the component (i) and a component (v) and 0.5-30wt.% of an alpha,beta-ethylenic unsaturated carboxylic acid as the component (v).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a room temperature curable composition containing emulsion particles, and more specifically, it is required to have various coatings for building exteriors, automobiles, household appliances, plastics, etc., particularly weather resistance and durability. The present invention relates to a room temperature curable composition containing emulsion particles used for coating or the like.

[0002]

2. Description of the Related Art In recent years, in the field of paints and adhesives, from the viewpoint of pollution control or resource saving, from organic solvent to water-soluble or water-dispersible resin (hereinafter collectively referred to as "organic solvent"). Is called "water-based paint").

However, since the conventional water-based paint does not have a crosslinkable functional group, as a result, it is strongly influenced by the surfactant used for polymerization, and the formed coating film has weather resistance, water resistance and stain resistance. It has a drawback that the properties are remarkably deteriorated and the physical properties of the coating film are inferior to those of the solvent-based paint.

Various attempts have been proposed to improve this drawback. One of them has been proposed to apply an emulsion of a polymer having an alkoxysilyl group as a crosslinkable functional group to a coating material. (JP-A-3-227312
(See the official gazette).

Although some problems have been solved by this, the stability is insufficient because the alkoxysilyl group is easily hydrolyzed, and the film formability after long-term storage is deteriorated (mechanical stability of emulsion). There is a problem that the glossiness of the white enamel is inferior, the weather resistance of the cured product (for example, a coating film) is not yet satisfactory, and the gloss is easily deteriorated.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have found that by using a chain transfer agent in the core portion of emulsion particles produced by multistage emulsion polymerization, polymerization The present invention has been completed by finding that the silyl group does not react to reduce the film-forming property during storage or during storage, that the gloss of white enamel is improved, and that the weather resistance is also improved. Came to do.

That is, the room temperature curable composition of the present invention is
A room temperature curable composition containing emulsion particles in which a core part and a shell part are formed by multistage emulsion polymerization, wherein the composition of the core part in the emulsion particles is
Component (A) 0.5 to 30% by weight, Component (B) 0.01 to
10% by weight, and 60 to 99.49% by weight of the component (C), and the composition of the outermost shell portion in the shell portion of the emulsion particles is 0.1 to 30% by weight of the component (A) and the component (B). The composition comprises 0 to 10% by weight, component (C ') 30 to 99.4% by weight, and component (D) 0.5 to 30% by weight.

[However, the above components (A) to (D) are as follows.

Component (A): A vinyl monomer having a silyl group represented by the following general formula (I).

Embedded image (In the formula, 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, a phenoxy group and a thio group. A group selected from an alkoxy group and an amino group, y is an integer of 0 to 2. When X and R bonded to Si are each 2 or more, they may be the same group.) (B) Component: chain transfer agent (C) component: vinyl-based monomer other than component (A) (C ') component: component (A), vinyl-based monomer other than component (D) (D) component: α, β-ethylenically unsaturated carboxylic acid, styrene sulfonic acid, vinyl sulfonic acid, sodium styrene sulfonate, 2-sulfoethyl methacrylate sodium, 2-sulfoethyl methacrylate ammonium, (meth) acrylic acid De, N-methylol (meta)
Acrylamide, dialkylaminoalkylmethacrylate, dialkylaminoalkylmethacrylate hydrochloride, 2-aminoethylmethacrylate hydrochloride, diacetone (meth) acrylamide, vinyl monomer having polyoxyethylene chain and vinyl monomer having polyoxypropylene chain At least one hydrophilic vinyl-based monomer selected from the group consisting of monomers. In addition, in this specification, "(meth) acryl-" means "acryl- and methacryl-." For example, "(meth) acrylamide" means "acrylamide and methacrylamide," and "N-methylol (meth) acrylamide" means "N-methylol acrylamide and N-methylol methacrylamide (the same applies hereinafter). .

Hereinafter, the vinyl-based monomer (A) component, (B)
The component, the component (C), the component (C ′), and the component (D) will be sequentially described.

Component (A) [vinyl-based monomer having a silyl group
Polymer] A vinyl monomer having a silyl group represented by the general formula (I) (hereinafter, also referred to as "silyl group-containing vinyl monomer")
There is no particular limitation. As a concrete example,

Embedded image

[Chemical 4]

Embedded image And the like.

The silyl group-containing vinyl monomer (A)
May be used alone or in combination of two or more. In particular, it is preferable to use an alkoxysilyl group-containing vinyl-based monomer from the viewpoints of easy handling, cost, and reaction by-products, and triethoxysilyl group- and diethoxysilyl group-containing vinyl-based monomers are stable. Is particularly preferable in terms of.

The silyl group-containing vinyl monomer (A) is copolymerized in the core portion in an amount of 0.5 to 30% by weight (hereinafter simply referred to as "%"). If the core portion is less than 0.5%, the water resistance and durability are deteriorated, and if it exceeds 30%, the emulsion becomes unstable and gels during the core portion polymerization.

The outermost shell of the shell is copolymerized by 0.1 to 30%. If it is less than 0.1%, the water resistance and durability will be reduced, and if it exceeds 30%, the emulsion will become unstable and gel during the polymerization.

Component (B) [Chain Transfer Agent] The component (B) is a chain transfer agent, and includes mercaptan, sulfide benzene, isopropylbenzene, chloroform,
Examples thereof include carbon tetrabromide and ferric chloride. In particular, among mercaptans, in terms of price, odor and efficiency, n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-
Mercaptopropylmethyldimethoxysilane and γ-mercaptopropylmethyldiethoxysilane are preferred. Further, an alkoxysilyl group-containing mercaptan is preferable as a method for introducing a crosslinkable alkoxysilyl group.

The chain transfer agent (B) component is 0.01 to 10% copolymerized in the core portion in the multistage emulsion polymerization,
It may or may not be used in the outermost shell portion.
When used, it is 0.01 to 10% copolymerized. When it exceeds 10%, coloring of the film or deterioration of water resistance and durability are recognized.

There is no particular limitation as long as it is a vinyl-based monomer other than the component (C) and the component (A). The component (D) is also included in the component (C).
Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, iso-butyl (meth) acrylate, ter.
(Meth) acrylate monomers such as t-butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate; hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene ,
Pentafluoropropylene, trifluoro (meth) acrylate, pentafluoro (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 vinyl monomers such as methylstyrene, chlorostyrene, 4-hydroxystyrene and vinyltoluene; vinyl esters such as vinyl acetate, vinyl propionate, diallyl phthalate and allyl compounds; (meth)
Nitrile group-containing vinyl monomers such as acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; formyl styrene and vinyl methyl ketone, vinyl ethyl ketone, vinyl butyl ketone, etc., having 4 to 7 carbon atoms Vinyl alkyl ketone; 2-
Hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronix 5700 (manufactured by Toa Gosei Kagaku Co., Ltd.), PlaccelF
A-1, PlaccelFA-4, PlaccelFM
-1, Placcel FM-4 (above, Daicel Chemical Industries Ltd.), HE-10, HE-20, HP-10, H
P-20 (above, Nippon Shokubai Chemical Co., Ltd.), Blemmer PEP series, Blemmer NKH-5050, Blemmer GLM (above, Nippon Oil & Fats Co., Ltd.), hydroxyl groups containing hydroxyl group-modified hydroxyalkyl vinyl monomers, etc. Vinyl-containing monomer: vinyl compound as a condensation product of hydroxyalkyl esters of α, β-ethylenically unsaturated carboxylic acids such as hydroxyalkyl esters of (meth) acrylic acid and phosphoric acid or phosphoric acid esters Alternatively, vinyl-based monomers such as (meth) acrylate having a urethane bond or a siloxane bond; AS-6 and AN- which are macromonomers manufactured by Toagosei Co., Ltd.
6, compounds such as AA-6, AB-6, AK-5, vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene, other vinyl monomers, LA87 manufactured by Asahi Denka Co., Ltd. , LA82, L
Examples include polymerization type light stabilizers such as A22 and polymerization type ultraviolet absorbers.

Also, a silicone macromer having a polymerizable double bond can be copolymerized. For example, X-22-164
Methacryloxy group-containing reactive silicone oil such as B, X-22-164C, X-22-5002 (manufactured by Shin-Etsu Silicone Co., Ltd.), KR211, KR212, KR2.
No. 13, KR9218 (manufactured by Shin-Etsu Silicone Co., Ltd.) and the like, a silicone varnish containing a double bond and a hydroxyl group obtained by reacting a silicone varnish for modification with a vinyl monomer containing a reactive silyl group such as component (A). A reaction product of the contained cyclic or linear siloxane and a compound having an isocyanate group and a polymerizable double bond in one molecule such as m-isopropenyl-α, α dimethylbenzyl isocyanate or methacryloyl isocyanate.

Further, by using the fluorine-containing vinyl monomer and the siloxane-containing vinyl monomer, the water repellency is improved, and the water resistance and durability are improved.

In addition to this, for example, it is produced by using a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol dimethacrylate, ethylene glycol diacrylate, triallyl cyanurate and allyl methacrylate. It is also possible that the polymer has a crosslinked structure. The component (C) is copolymerized at 60 to 99.49% in the core portion.

The component (C) contains 50% or more of an alkyl methacrylate having an alkyl group of C4 (having 4 carbon atoms, the same shall apply hereinafter), or the alkyl methacrylate and a cycloalkyl methacrylate having a cycloalkyl group of C4 or more. As a result, the stability of the silyl group is improved and the weather resistance is also improved.

Specific examples include n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate,
Isodecyl methacrylate, lauryl methacrylate,
Examples thereof include tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate and the like.

Component (D) [hydrophilic vinyl monomer] The outermost shell of the emulsion particles contains α, β-ethylenically unsaturated carboxylic acid, styrene sulfonic acid, vinyl sulfonic acid, sodium styrene sulfonate, and 2 -Sodium sulfoethyl methacrylate, 2-sulfoethyl methacrylate ammonium, (meth) acrylamide, N
-Methylol (meth) acrylamide, dialkylaminoalkylmethacrylate, dialkylaminoalkylmethacrylate hydrochloride, 2-aminoethylmethacrylate hydrochloride, diacetone (meth) acrylamide, vinyl monomer having polyoxyethylene chain and polypropylene chain It is essential to copolymerize a hydrophilic vinyl monomer (D) selected from vinyl monomers.

Examples of the α, β-ethylenically unsaturated carboxylic acid include (meth) acrylic acid, maleic acid, itaconic acid,
Examples include crotonic acid, fumaric acid, and citraconic acid.

Examples of the dialkylaminoalkyl methacrylate and the dialkylaminoalkyl methacrylate hydrochloride include dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate and its hydrochloride.

The vinyl monomer having a polyoxyethylene chain is not limited, but acrylic acid ester or methacrylic acid ester having a polyoxyethylene chain is preferable, and specific examples thereof include Bremmer PE-90 and PE-2.
00, 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 (above, Nippon Emulsifier Co., Ltd. product) etc. are mentioned.

The vinyl-based monomer having a polyoxypropylene chain is not limited, but Bremmer PP-1000, P-1000
P-500, PP-800, AP-400 (above, manufactured by NOF CORPORATION), RS-30 (manufactured by Sanyo Kasei Co., Ltd.)
And the like.

Particularly, when a vinyl monomer having a polyoxyethylene chain is used as the component (D), the stability of the silyl group is remarkably improved, the film-forming property is not deteriorated, and the mechanical stability of the emulsion is The gloss of white enamel is also good. The oxyethylene unit of this polyoxyethylene chain is 2-3
0 is preferred. If it is less than 2, the emulsion is inferior in mechanical stability and white enamel gloss, and if it is more than 30, the coating film becomes soft and is easily stained.

Component (D) is copolymerized at 0.5 to 30%. If it is less than 0.5%, the mechanical stability and white enamel gloss are poor, and if it exceeds 30%, the water resistance is lowered.

Component (C ′ ) Component (C ′) is a vinyl-based monomer obtained by removing the components (A) and (D) from the component (C). By containing 50% or more of the alkyl methacrylate having a C4 or more alkyl group or the alkyl methacrylate and the cycloalkyl methacrylate having a C4 or more cycloalkyl group as the component (C '), the stability of the silyl group is improved, and The weather resistance is also improved.

Next, the production of the emulsion polymer (emulsion particles) will be described. First, a mixture (monomer emulsion) composed of the component (A), the component (B), and the component (C).
As the first stage, the emulsion polymerization is carried out by a known emulsion polymerization method, and the emulsion polymerization of the second stage and thereafter is successively carried out in the presence of the obtained polymer (which becomes the core portion).

At this time, the emulsion polymerization in the second and subsequent stages may be carried out with the same monomer composition as in the first stage or with different compositions. Then, the polymer of the final stage monomer composition becomes the outermost shell portion.

In the present invention, it is essential that the component (D) is contained in an amount of 0.5 to 30% in the total amount of the monomers in the outermost shell portion.

The multistage emulsion polymerization is preferably a 2-4 stage emulsion polymerization, and the weight ratio of the core portion to the other portions is 1.
It is preferable to polymerize so as to be in the range of 0:90 to 90:10. The polymer obtained by such a method is referred to as the multilayer polymer of the present invention.

During polymerization, the silyl group is stabilized by using an anionic (anionic) surfactant having a polyoxyethylene chain as the surfactant. Specific examples of the anionic surfactant include Newcol-5.
Polyoxyethylene nonylphenyl ether sulfate such as 60SN, Newcol-560SF (all manufactured by Nippon Emulsifier Co., Ltd.), Emar NC-35, Revere WZ (all manufactured by Kao Corporation); Newcol-707
SF, Newcol-707SN, Newcol-72
3SF, polyoxyethylene allyl ether sulphate such as Newcol-740SF; Newcol-
Examples include octylphenoxyethoxyethyl sulfonate such as 861SE; polyoxyethylene tridecyl ether sulfate such as Newcol-1305SN (manufactured by Nippon Emulsifier Co., Ltd.).

Particularly, in view of polymerization stability and stability of hydrolyzable silyl group, it is preferable that the polyoxyethylene chain has 1 to 70 oxyethylene units. Further, from the viewpoint of water resistance of the coating film obtained from the emulsion, an anionic surfactant of ammonium salt is preferable.

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

Other ionic surfactants are not particularly limited, and examples thereof include sulfonates such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate, and sodium isooctylbenzene sulfonate.

As the nonionic surfactant, polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether;
L-77, L-720, L-5410, L-7602,
Representative examples include nonionic surfactants containing silicon such as L-7607 (above, manufactured by Union Carbide Co.).

The use of a reactive surfactant having a polymerizable double bond in one molecule as the surfactant does not interfere with the present invention. In particular, when an anionic reactive surfactant having both a polymerizable double bond and a polyoxyethylene chain in the molecule is used, the water resistance is improved. As a specific example, ADEKA rear soap NE-10, NE-20, NE-
30, NE-40, SE-10N (above, Asahi Denka Kogyo KK), Antox-MS-60 (Nippon Emulsifier KK), Aqualon RN-20, RN-30, RN
-50, HS-10, HS-20, HS-1025 (above, Dai-ichi Kogyo Seiyaku Co., Ltd. product) are mentioned.

The amount of the anionic surfactant having a polyoxyethylene chain used is 0.
It is 01 to 20%, preferably 0.05 to 10%.
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 polymerize by 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 (1) into the water-soluble resin, the water resistance can be further enhanced.

In order to carry out the polymerization more stably, a temperature of 70 ° C. or lower, preferably 40, using a redox catalyst.
Perform at ~ 65 ° C. Further, for stabilizing the silyl group, the pH during the polymerization is preferably 5 to 8, and more preferably 6 to 7.

As the redox catalyst, potassium persulfate, ammonium persulfate and acidic sodium 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 acidic sodium sulfite or Rongalit is used. In particular, a combination of an organic peroxide and a reducing agent is preferable from the viewpoint of stable polymerization. Further, 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 in order to stably obtain the catalytic activity.

The amount of such a redox catalyst (initiator) used is 0.01 to 1 based on the weight of all monomers.
0% is preferable, and 0.05 to 5% is more preferable.

The solid content concentration in the emulsion of the present invention is preferably 20 to 70%, more preferably 30 to 70%.
60%. If the solid content concentration exceeds 70%, the viscosity of the system remarkably increases, which makes it difficult to remove the heat generated by the polymerization reaction, and it takes a long time to take it out of the polymerization machine. Also, the solid content concentration is 2
When it is less than 0%, no problem occurs in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is extremely disadvantageous from the economical point of view. , The coating film is not running low,
There is a problem in use such as performance deterioration and disadvantage in coating workability.

The emulsion has an average particle size of 0.
It is composed of fine particles of about 02 to 1.0 μm, and as a result, has excellent film forming performance.

Crosslinking is promoted by adding a curing agent when the composition of the present invention is applied. As the curing agent, an organic metal compound, an acidic catalyst or a basic catalyst is used. In particular, a mixture or reaction product of an organoaluminum compound or an organotin compound or an acidic phosphoric acid ester and an amine is preferable in terms of curing activity, and examples of the organometallic compound include dibutyltin dilaurate, dibutyltin malate, dioctyltin dilaurate and dibutyltin acetate. , Organotin compounds such as dibutyltin dimethoxide, tributyltin sulphite, dibutyltin thioglycolate, tin octylate; aluminum isopropylate, aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), ethylacetoacetate aluminum diisopropylate Examples thereof include organic aluminum compounds such as rate.

These organometallic compounds are excellent in curing activity and storage stability when they are emulsified with a surfactant containing an alkyl ether type surfactant as a main component and added at the time of use. The amount of the organometallic compound used is preferably 0.01 to 10 parts, and more preferably 0.1 to 5 parts, per 100 parts by weight of the solid content of the silyl group-containing emulsion (parts by weight, the same applies hereinafter). More preferably.
Examples of the acidic phosphoric acid ester mixture of the acidic phosphoric acid ester and ammonia or amine or the reaction product include, for example, monobutyl phosphate, dibutyl phosphate, and the like.
Examples of the amine include isopropyl acid phosphate and di-2-ethylhexyl phosphate.
For example, hexylamine, triethylamine, N, N-
Examples thereof include dimethyldodecylamine and 3-propanolamine. Also, a block type of a sulfonic acid group-containing compound, specifically, NAC manufactured by King Industry
UREX49-110, 3525, 5225, 592
5,554,2500X can also be used. These mixtures or reactants are preferably added in an amount of 0.001 to 10 parts, and particularly preferably 0.01 to 6 parts, per 100 parts of the solid content of the silyl group-containing emulsion as an active ingredient. If the curing agent is less than 0.01 part, the curing activity is low and 10
If it exceeds the amount, the water resistance will decrease. When a mixture or reaction product of an acidic phosphoric acid ester and ammonia or an amine, or a block type of a sulfonic acid group-containing compound is used, the composition is stable even in the presence of a curing agent, and one liquefaction is possible.

The resulting curable composition may, if necessary,
Pigments usually used in paints (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, etc., colored pigments such as carbon, red iron oxide, cyanine blue etc.) can be used. Titanium dioxide is the most used among the pigments and is important.

When titanium dioxide is added to the silyl group-containing emulsion, the gloss and weather resistance are improved by using titanium dioxide having an isoelectric point of 7 or more.

Specifically, JR901, JR603, J
R602 (Taika Co., Ltd.) and the like can be mentioned. Further, additives such as film-forming agents, colloidal silica, plasticizers, solvents, dispersants, thickeners, defoamers, preservatives and ultraviolet absorbers which are usually used as components for paints are mixed and used. It doesn't matter.

Other crosslinking methods can also be used in combination. For example, a method of introducing a reactive group such as a hydroxyl group or a carboxyl group into emulsion particles and using melamine or isocyanate as a crosslinking agent. A method using epoxy crosslinking in which an epoxy group and an amino group or a carboxyl group are combined. As a copolymerization component, a carbonyl group-containing vinyl monomer is used to introduce a carbonyl group into the emulsion particles,
As a cross-linking agent, there may be mentioned a cross-linking method in which a polyhydrazide compound having at least two hydrazide groups per molecule is contained in the resin dispersion liquid. Of these, the method of introducing a carbonyl group is preferable in terms of stability of the composition and durability of the coating film.

As the carbonyl group-containing vinyl monomer, for example, vinyl alkyl having 4 to 7 carbon atoms such as acrolein, diacetone (meth) acrylamide, formyl styrene, vinyl methyl ketone, vinyl ethyl ketone and vinyl butyl ketone. Examples include ketones. The carbonyl group-containing vinyl monomer is blended as the component (C) or the component (D). Examples of the polyhydrazide compound include succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide and the like. Further, a crosslinking method in which a carboxyl group is introduced into the emulsion by copolymerizing (meth) acrylic acid or the like and an oxazoline group is used as a crosslinking agent may be used.

The composition of the present invention is used, for example, for interior construction, automobiles such as metallic bases or clears on metallic bases, direct metal coating of aluminum, stainless steel, silver, etc., slate, concrete, roof tile, mortar,
As a paint or top treatment for gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium silicate board, ceramics direct coating for ceramics, glass, natural marble, stone materials such as granite Used. It can also be used as an adhesive or a pressure-sensitive adhesive.

It is also possible to blend with a commercially available water-based paint, for example, a thermosetting acrylic paint such as an acrylic resin or an acrylic melamine resin,
It can be blended with alkyd paint, epoxy paint and fluororesin paint to improve weather resistance, acid resistance and solvent resistance of these paints.

[0057]

EFFECTS OF THE INVENTION The room temperature curable composition of the present invention has excellent stability of the silyl group, greatly improves the film-forming property after long-term storage, and has durability (weather resistance) and white enamel gloss. Are better.

[0058]

EXAMPLES The present invention will be described below based on examples, but the present invention is not limited thereto.

Synthesis Examples 1 to 7 A reactor equipped with a stirrer, a reflux condenser, a nitrogen gas introducing pipe and a dropping funnel was initially charged with deionized water 1
60 parts, Rongalit 1.4 parts, Newcol-707
4 parts of SF, 1.2 parts of ammonium acetate, 0.5 part of t-butyl hydroperoxide and the monomer composition liquid shown in the following [Table 1] were charged.

Next, while introducing nitrogen gas, the temperature was raised to 50 ° C., polymerization was carried out for 1 hour, 1.0 part of t-butyl hydroperoxide was dissolved in 30 g of pure water, and the solution was continuously added over 3 hours. Added to. For the monomer emulsion, the additional monomer emulsion 1 shown in [Table 1] [Table 2]
The additional monomer emulsion 2 was added dropwise for 90 minutes and the additional monomer emulsion 3 was added for 60 minutes over a total of 3 hours to obtain emulsion particles having a multilayer structure.

Then, after 1 hour of post-polymerization, the pH was adjusted to 7 with aqueous ammonia, and the solid content concentration was adjusted to 4 with deionized water.
It was adjusted to be 0% to obtain a room temperature curable composition containing emulsion particles (hereinafter, simply referred to as "emulsion").

[0062]

[Table 1]

[0063]

[Table 2]

White enamel was prepared using the emulsions obtained in Examples 1 to 8 and Comparative Examples 1 and 2 and Synthesis Examples 1 to 7. The method of making white enamel is as follows. That is, the components shown in the following [Table 3] were blended in the proportions shown in the same table, and the mixture was mixed with a sand mill at 1,000
The pigment paste was obtained by dispersing at rpm for 1 hour.

[Table 3] Emulsion 60 to 30 parts of the obtained pigment paste
Part, CS-12 (film-forming aid manufactured by Chisso Corporation) 2.4
Part, propylene glycol 3 parts, SN deformer 3
81 0.02 part, 20% UH420 (thickener manufactured by Asahi Denka Co., Ltd.) 4 parts, and 2% chillose H400.
2.0 parts of 0P was added and mixed to obtain white enamel.

Thereafter, a dibutyltin dilaurate emulsion prepared by the following [Table 4] formulation was added to the white enamel as a curing agent in the proportion shown in [Table 5] below, and then applied to the article to be coated.

Then, the glossiness, the weather resistance (sunshine weatherometer), and the storage stability of the emulsion after standing at room temperature for 2 weeks were evaluated. The results are also shown in [Table 5].

[0067]

[Table 4]

[0068]

[Table 5]

The evaluation method of each physical property is as follows.

White enamel gloss curing agent-added white enamel was applied to a glass plate, and after 2 weeks at room temperature, 60 ° gloss was measured with a gloss meter. The larger the number, the better the gloss.

The above-mentioned coating material was applied to a weather-resistant slate plate, left at room temperature for 2 weeks, and then subjected to a sunshine weatherometer test to obtain 3,000.
The gloss retention rate after 0 hours was obtained. The larger the value, the better the weather resistance.

Long-term storage stability (5 ° C. film-forming property) The emulsion was stored at 50 ° C. for 1 month, and then 10 parts of CS-12 (manufactured by Chisso Corporation) for 100 parts of each emulsion solid content. Auxiliary agent) is added, the mixture is left to stand at 5 ° C. overnight and coated on a glass plate.
It was left overnight and the surface condition was observed. ○: No problem △: Partially small cracks are observed ×: Cracks occur on the entire surface

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Claims (16)

[Claims] 1. A room temperature curable composition containing emulsion particles in which a core portion and a shell portion are formed by multistage emulsion polymerization, wherein the composition of the core portion in the emulsion particles is (A) component 0. 0.5 to 30% by weight, component (B) 0.01 to 10% by weight, and component (C) 60 to 99.49% by weight, and the composition of the outermost shell part in the shell part of the emulsion particles is: Component (A) 0.1 to 30% by weight, component (B) 0 to 10% by weight, component (C ') 30 to 99.4% by weight, and component (D) 0.5 to 30% by weight. A characteristic room temperature curable composition. [However, the components (A) to (D) are as follows. Component (A): A vinyl monomer having a silyl group represented by the following general formula (I). Embedded image (In the formula, 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, a phenoxy group and a thio group. A group selected from an alkoxy group and an amino group, y is an integer of 0 to 2. When X and R bonded to Si are each 2 or more, they may be the same group.) (B) Component: chain transfer agent (C) component: vinyl-based monomer other than component (A) (C ') component: component (A), vinyl-based monomer other than component (D) (D) component: α, β-ethylenically unsaturated carboxylic acid, styrene sulfonic acid, vinyl sulfonic acid, sodium styrene sulfonate, 2-sulfoethyl methacrylate sodium, 2-sulfoethyl methacrylate ammonium, (meth) acrylic acid De, N-methylol (meta)
Acrylamide, dialkylaminoalkylmethacrylate, dialkylaminoalkylmethacrylate hydrochloride, 2-aminoethylmethacrylate hydrochloride, diacetone (meth) acrylamide, vinyl monomer having polyoxyethylene chain and vinyl monomer having polyoxypropylene chain At least one hydrophilic vinyl-based monomer selected from the group consisting of monomers. ] 2. The composition according to claim 1, wherein the silyl group in the component (A) is an alkoxysilyl group. 3. The component (A) contains a compound containing one of a triethoxysilyl group and a diethoxysilyl group, or a compound containing a triethoxysilyl group and a diethoxysilyl group in one molecule. The composition according to claim 2, wherein the composition is a mixture of contained compounds. 4. A chain transfer agent which is the component (B) is a mercaptan compound.
The composition according to any one of 1. 5. The mercaptan compound is n-dodecyl mercaptan, t-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane,
γ-mercaptopropylmethyldimethoxysilane and γ
-The composition according to claim 4, which is a mixture of one or more selected from the group consisting of mercaptopropylmethyldiethoxysilane. 6. The component (C) or the component (C ′),
50% by weight or more of an alkyl methacrylate having an alkyl group having 4 or more carbon atoms, or 50% by weight or more of the alkyl methacrylate and a cycloalkyl methacrylate having a C4 or more cycloalkyl group.
6. The composition according to any one of 5 to 5. 7. The composition according to any one of claims 1 to 6, wherein the component (D) is a vinyl monomer having a polyoxyethylene chain. 8. The emulsion particles are obtained by copolymerizing with an anionic surfactant having a polyoxyethylene chain.
7. The composition according to any one of 7. 9. The composition according to claim 8, wherein the anionic surfactant also has a polymerizable double bond. 10. A polyhydrazide compound having a carbonyl group introduced into the emulsion particles and having at least two hydrazide groups per molecule as a cross-linking agent is blended. The composition according to claim 1. 11. The composition according to claim 1, which contains a curing agent. 12. The composition according to claim 11, wherein the curing agent is obtained by emulsifying an organoaluminum compound or an organotin compound with a surfactant mainly containing an alkyl ether type surfactant. 13. The composition according to claim 11, wherein the curing agent is a mixture or reaction product of an acidic phosphoric acid ester and an amine. 14. The composition according to claim 11, wherein the curing agent is a sulfonic acid group-containing compound, and the sulfonyl group is reacted and blocked. 15. The composition according to claim 1, which contains titanium dioxide having an isoelectric point of 7 or more. 16. The method according to claim 1, which is used as a paint.
16. The composition according to any one of to 15.