JP3385371B2 - Room temperature curable composition - Google Patents

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 used for various coatings on, for example, building exteriors, automobiles, home electric appliances, plastics, etc., particularly coatings requiring weather resistance and durability.

[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 of the alkoxysilyl group is insufficient because it is easily hydrolyzed, and the film-forming property after long-term storage is lowered, and the mechanical properties of the emulsion are reduced. There were problems such as poor stability and poor gloss of white enamel.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have carried out multistage emulsion polymerization and carried out hydrolysis as a reactive silyl group introduced into the outermost shell of emulsion particles. Use stable polymerizable monomer containing alkoxysilyl group (dimethoxysilyl group, triethoxysilyl group, diethoxysilyl group, tripropoxysilyl group, dipropoxysilyl group, tributoxysilyl group, dibutoxysilyl group, etc.) Therefore, the stability of the silyl group is remarkably improved, and the silyl group does not react to decrease the film-forming property during polymerization or storage.
By introducing a hydrophilic group into the outermost shell part of the emulsion particles, it was found that the mechanical stability of the emulsion and the gloss of the white enamel were good, and the present invention was completed.

That is, the room temperature curable composition of the present invention is
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 monomer composition of the core portion in the emulsion particles is (A) components 1 to 30. % By weight, component (B) 60-9
9% by weight, and 0 to 39% by weight of the component (C), and the monomer 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 '), ) Component 60 to 99.5% by weight, component (C) 0 to 39.5% by weight, and component (D) 0.5 to 30% by weight.

[However, the above components (A) to (D) are as follows. That is, the component (A): a vinyl monomer having a silyl group represented by the following general formula (I)

[Chemical 2] (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 each bonded to Si are two or more, they may be the same group.

Component (A '): The silyl group is a dimethoxysilyl group, a triethoxysilyl group, a diethoxysilyl group, a tripropoxysilyl group, a dipropoxysilyl group,
At least one vinyl-based monomer which is a group selected from the group consisting of tributoxysilyl group and dibutoxysilyl group.
seed.

Component (B): an alkyl methacrylate having a C4 or more alkyl group, or a cycloalkyl methacrylate having the above alkyl methacrylate and a C4 or more cycloalkyl group.

Component (C): Other non-hydrophilic vinyl-based monomer other than the component (B).

Component (D): a vinyl-based unit having a polyoxyethylene chain
Quantum. ]

The "(meth) acrylamide" in the component (D) is "acrylamide or methacrylamide".
Means "N-methylol (meth) acrylamide"
Means "N-methylol acrylamide or N-methylol methacrylamide" (hereinafter the same).

The vinyl monomer (A) component, (A
The component '), the component (B), the component (C), and the component (D) will be sequentially described.

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

[Chemical 3]

[Chemical 4]

[Chemical 5] And so on.

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 monomer from the viewpoints of easy handling, cost and reaction by-products.

The silyl group-containing vinyl monomer (A) contains 1 to 30% by weight (hereinafter simply referred to as "%") in the core portion.
Copolymerized. If the core portion is less than 1%, the water resistance, durability, etc. are reduced, and if it exceeds 30%, the emulsion becomes unstable and gels during the core portion polymerization.

In the outermost shell portion, among the silyl group-containing vinyl monomers (A), dimethoxysilyl group, triethoxysilyl group, diethoxysilyl group, tripropoxysilyl group, dipropoxysilyl group, tributoxy group. At least one kind (A ′) selected from vinyl-based monomers having a silyl group and a dibutoxysilyl group is copolymerized by 0.1 to 30%. If the content of the outermost shell is less than 0.1%, the durability and water resistance will decrease due to the lack of crosslinking between particles.
If it is more than%, the emulsion becomes unstable.

Component (B) Component (B) is an alkyl methacrylate having an alkyl group of C4 (having 4 carbon atoms, the same applies below) or a cycloalkyl methacrylate having the alkyl methacrylate and a cycloalkyl group of C4 or more. is there.

There is no particular limitation on the alkyl methacrylate having a C4 or more alkyl group and the cycloalkyl methacrylate having a C4 or more cycloalkyl group. Specific examples thereof include n-butyl methacrylate and iso-
Examples thereof include butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate and isobornyl methacrylate.

Particularly, n-butyl methacrylate and cyclohexyl methacrylate are preferable in terms of price, weather resistance of the composition, balance between hardness and impact resistance, and ease of adjusting glass transition temperature (Tg) of emulsion resin.

The component (B) is copolymerized at 60 to 99% in the core portion and 60 to 99.5% in the outermost shell portion in the multistage emulsion polymerization. If it is less than 60%, the silyl group becomes unstable and the minimum film forming temperature rises.

Component (C) [Do not have hydrophilicity other than component (B)
Other vinyl-based monomer] The vinyl-based monomer (C) is not particularly limited. Specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate and iso-.
Butyl acrylate, tert-butyl acrylate,
(Meth) acrylate monomers such as benzyl (meth) acrylate and cyclohexyl acrylate; hexafluoropropylene, chlorotrifluoroethylene, vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, pentafluoropropylene, trifluoro (meth) acrylate , Fluorine-containing vinyl monomers such as pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate An aromatic hydrocarbon vinyl monomer such as styrene, α-methylstyrene, chlorostyrene, 4-hydroxystyrene, vinyltoluene; vinyl acetate, vinyl propionate,
Vinyl esters such as diallyl phthalate and allyl compounds; Nitrile group-containing vinyl monomers such as (meth) acrylonitrile; Epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-Hydroxypropyl (meth) acrylate, 2-Hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronix 5700 (manufactured by Toagosei Kagaku Co., Ltd.), PlaccelFA-1, Plac
celFA-4, PlaccelFM-1, Placc
elFM-4 (above, manufactured by Daicel Chemical Industries, Ltd.), HE-
10, HE-20, HP-10, HP-20 (Nippon Shokubai Kagaku Co., Ltd.), Blemmer PEP series, Blemmer NKH-5050, Blemmer GLM (above,
Nippon Oil & Fats Co., Ltd., hydroxyl-containing vinyl-based modified hydroxyalkyl vinyl-based monomers such as hydroxyl-containing vinyl-based monomers; (meth) acrylic acid hydroxyalkyl esters such as α, β-ethylenically unsaturated carboxylic acids Vinyl compounds such as condensation products of hydroxyalkyl esters with phosphoric acid or phosphoric acid esters, or vinyl-based monomers such as (meth) acrylates containing urethane bond or siloxane bond; Toa Gosei Chemical Co., Ltd. macro Monomers AS-6, AN-6, AA-6, AB-
6, compounds such as AK-5, vinyl methyl ether, vinyl chloride, vinylidene chloride, chloroprene, propylene, butadiene and other vinyl monomers, polymerization types such as LA87, LA82 and LA22 manufactured by Asahi Denka Co., Ltd. Examples thereof include light stabilizers and polymerization type ultraviolet absorbers.

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

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

The component (C) is copolymerized at 0 to 39% in the core portion and 0 to 39.5% in the outermost shell portion. Usage ratio is 3
If it exceeds 9% (core portion) or 39.5% (outermost shell portion), the hydrophilicity of the particles becomes high, and the problem that the reactive silyl group is easily hydrolyzed easily occurs. In addition,
The preferred range of component (C) is 0.1 for the core.
~ 38% and 0.1-39% for the shell.

Component (D) [hydrophilic vinyl monomer (D)] Emulsion particles have polyoxyethylene in the outermost shell.
Hydrophilic vinyl monomer consisting of vinyl monomer having chain
It is essential to copolymerize the monomer (D). Note that α,
β-ethylenically unsaturated carboxylic acid, styrene sulfonic acid, vinyl sulfonic acid, sodium styrene sulfonate, sodium 2-sulfoethyl methacrylate, 2-
Sulfoethylmethacrylate ammonium, (meth) acrylamide, N-methylol (meth) acrylamide, dialkylaminoalkylmethacrylate, dialkylaminoalkylmethacrylate hydrochloride, 2-aminoethylmethacrylate hydrochloride, vinyl-based monomer having polypropylene chain the hydrophilic vinyl-based monomer
It is also possible to mix and copolymerize.

Examples of 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 an acrylic acid ester or a 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 may be 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 so on.

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.

Next, the production of the emulsion polymer (emulsion particles) will be described. First, the mixture of the component (A), the component (B), and the component (C) is emulsion polymerized by a known emulsion polymerization method as the first stage, and the presence of the resulting polymer (which becomes the core portion) The emulsion polymerization from the second stage onward is sequentially performed below.

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 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, from the viewpoint of polymerization stability and stability of hydrolyzable silyl groups, it is preferable that the polyoxyethylene chain has 1 to 50 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 a reactive surfactant having a polyoxyethylene group in the molecule is used, water resistance is improved. As a specific example, ADEKA rear soap NE-1
0, NE-20, NE-30, NE-40, SE-10
N (above, Asahi Denka Kogyo KK), Antox-MS-
60 (manufactured by Nippon Emulsifier Co., Ltd.), Aqualon RN-20,
RN-30, RN-50, HS-10, HS-20, H
S-1025 (above, Daiichi Kogyo Seiyaku Co., Ltd. product) is 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 ° C., 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 ultra fine particles of about 02 to 1.0 μm,
As a result, it has excellent film forming performance.

Crosslinking is promoted by adding a curing agent when coating the composition of the present invention. 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 mainly containing an alkyl ether type surfactant and added before 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 the amine or the reaction product include monobutyl phosphate, dibutyl phosphate, isopropyl acid phosphate, di-2-ethylhexyl phosphate, and the like, and examples of the amine include hexyl. Examples thereof include amine, triethylamine, N, N-dimethyldodecylamine and 3-propanolamine. It is preferable to add 0.001 to 10 parts of these mixtures or reaction products to 100 parts of the solid content of the silyl group-containing emulsion, and particularly preferably 0.01 to 5 parts. If the curing agent is less than 0.01 part, the curing activity will be low, and if it exceeds 10 parts, the water resistance will be reduced.

If necessary, the obtained curable composition is
Pigments (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, etc., colored pigments such as carbon, red iron oxide, cyanine blue), film forming agents, colloidal silica, plasticizers, solvents, dispersants, etc. Additives such as thickeners, defoaming agents, preservatives, and ultraviolet absorbers that are commonly used as components for paints may be mixed and used.

It is also possible to add a melamine resin or an isocyanate compound as a cross-linking agent to obtain a quick-curing property.

The composition of the present invention is used for, for example, interior construction, automobiles such as metallic bases or clears on metallic bases, direct metal coating of aluminum, stainless steel, etc., slate, concrete, roof tile, mortar, gypsum board, asbestos. Slate, asbestos board, precast concrete, lightweight cellular concrete, calcium silicate board, tile, for direct coating of ceramics such as bricks, for glass,
It is used as a paint or top treatment agent for stone materials such as natural marble and granite. 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]

INDUSTRIAL APPLICABILITY The room temperature curable composition of the present invention has excellent stability of the silyl group, and the film-forming property after long-term storage is significantly improved. It is also excellent in mechanical stability, water resistance, durability, and white enamel luster.

[0058]

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

Examples 1 to 8 and Comparative Examples 1 to 4 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
20 parts, Rongalit 0.7 parts, Newcol-707
3 parts of SF, 0.6 part of ammonium acetate, 0.7 part of t-butyl hydroperoxide and the monomer composition liquid shown in the following [Table 1] were charged.

Next, the temperature was raised to 50 ° C. while introducing nitrogen gas and polymerization was carried out for 1 hour. Then, in Examples 1 to 6 and Comparative Examples 1 to 4, t-butyl hydroperoxide 0.3. Parts and the monomer emulsion shown in the following [Table 2] were added dropwise over 3 hours.

Examples 7 and 8 are three-stage polymerization. After the monomer emulsion of the core portion was polymerized for 1 hour, the second-stage monomer emulsion shown in [Table 2] and t-butyl hydroperoxide 0 were used. .2 parts was added dropwise over 2 hours, and the outermost shell monomer emulsion and t-butyl hydroperoxide were added.
One part was added dropwise over 1 hour.

Then, after 1 hour of 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").

The obtained emulsion was evaluated by the following methods. The results are shown in [Table 3] below.

[0064]

[Table 1]

[0065]

[Table 2]

[0066]

[Table 3]

[Evaluation Method] 1. Stability of alkoxysilyl groups (hydrolyzable silyl groups)
Sex synthesized emulsion was coated on a polyethylene sheet,
After left at room temperature for 1 day, the coating film formed on the polyethylene sheet was peeled off, and the infrared spectroscopic measurement of this coating film was performed. The residual ratio (%) of the alkoxysilyl group to the charged vinyl monomer containing an alkoxysilyl group was measured. ) Was asked.

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

3. 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 (film-forming aid manufactured by Chisso Corporation) per 100 parts of each emulsion solid content. Was added and left overnight at 5 ° C to coat on a glass plate, and the coated glass plate was kept at 5 ° C for 1 hour.
It was left overnight and the surface condition was observed. ○: No problem △: Some small cracks were observed ×: Cracks were generated on the entire surface.

[0070] 4. Mechanical Stability According to JIS K 6392, a test was carried out for 5 minutes with a load of 15 kg using a Marlon tester. The amount of agglomerates after the test was measured and expressed as a ratio (ppm) with respect to the solid content in the charged emulsion.

5. White enamel luster Blended in the formulation shown in [Table 4] below, and dispersed using a sand mill at 1,000 rpm for 1 hour to obtain a pigment paste.

[0072]

[Table 4]

To 30 parts of this pigment paste, 60 parts of emulsion, 2.4 parts of CS-12 (see above), 3 parts of propylene glycol and SN deformer 381 were added.
02 parts, 4 parts 20% UH420 (thickener manufactured by Asahi Denka Kogyo Co., Ltd.) and 2.0 parts 2% chillose H4000P were added and mixed, then coated on a glass plate and left at room temperature for 1 day. After that, 60 ° gloss was measured with a gloss meter.

6. Water resistance 0.4 parts of CS-12 with respect to 10 g of emulsion, and Examples 1 to 7 and Comparative Examples 1 to 4 below [Table 5].
In (Formulation 1), 0.04 g of dibutyltin dilaurate emulsified with a homogenizer as a solid content was added and mixed, and in Example 8, 0.4 g of the solution shown in (Formulation 2) of [Table 6] below was added and mixed. .

This mixture was applied to a polyethylene sheet, dried at room temperature for 10 days, and then immersed in water at room temperature for 1 day, and the increased weight was shown as a ratio to the weight of the film before immersion.

[0076]

[Table 5]

[0077]

[Table 6]

─────────────────────────────────────────────────── ─── Continuation of front page (56) Reference JP-A-1-315451 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 51/00-51/10

Claims (7)

(57) [Claims] 1. 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 monomer composition of the core part in the emulsion particles is ) Component 1 to 30% by weight, component (B) 60 to 99% by weight, and component (C) 0 to 39% by weight, and the monomer composition of the outermost shell part in the shell part of the emulsion particles is: Component A ') is 0.1 to 30% by weight, component (B) is 60 to 99.5% by weight, component (C) is 0 to 39.5% by weight, and component (D) is 0.5 to 30% by weight. A room temperature curable composition characterized by the above. [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). [Chemical 1] (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. ) Component: the silyl group is a dimethoxysilyl group,
At least one vinyl monomer that is a group selected from the group consisting of triethoxysilyl group, diethoxysilyl group, tripropoxysilyl group, dipropoxysilyl group, tributoxysilyl group, and dibutoxysilyl group. Component (B): alkyl methacrylate having an alkyl group of C4 or more, or the above alkyl methacrylate and C
A cycloalkyl methacrylate having 4 or more cycloalkyl groups. Component (C): Other non-hydrophilic vinyl-based monomer other than the component (B). Component (D): a vinyl-based unit having a polyoxyethylene chain
Quantum. ] 2. The room temperature curable composition according to claim 1, wherein the silyl group in the component (A) is an alkoxysilyl group. 3. The room temperature curable composition according to claim 1, wherein the silyl group in the component (A) is a trimethoxysilyl group. 4. The emulsion particles are obtained by copolymerizing with an anionic surfactant having a polyoxyethylene chain .
Room temperature curing composition as claimed in any one of 3. 5. The method according to claim 1, further comprising a curing agent .
4. The room temperature curable composition according to any one of 4 above. 6. The room temperature curing according to claim 5 , wherein the curing agent is obtained by emulsifying an organic aluminum compound or an organic tin compound with a surfactant containing an alkyl ether type surfactant as a main component. Sex composition. Claim wherein said curing agent which is a mixture or reaction product of acidic phosphate and amine
Room temperature curing composition as described in 5.