JP5288679B2 - Contamination resistance imparting composition, coating composition, and coating film obtained from the coating composition - Google Patents

Description

  The present invention relates to a stain resistance imparting composition that exhibits stain resistance when added to a paint, a paint composition using the composition, and a coating film obtained from the composition.

In recent years, in the field of paints, from the viewpoint of pollution control or resource saving, attempts have been made to switch from using organic solvents to water-soluble or water-dispersed resins. However, water-based paints tended to be inferior in coating film performance compared to solvent-based paints. Under such circumstances, water-based paints are also required to have the same coating film properties as solvent-based paints, and in particular, it is required to provide high performance such as stain resistance.

As a method for imparting stain resistance to a paint, a method of blending an organosilicate in the paint is known (for example, see Patent Document 1).
By this method, the hydrophilicity of the formed coating film is improved, and it is effective in preventing the adhesion of oily contaminants, and the adhered contaminants can be washed away with water droplets such as rain. However, when the above method is applied to an aqueous paint, there is a problem that the miscibility of the organosilicate into the aqueous paint is poor and the surface gloss is lowered.
On the other hand, a method of adding a mixture of an organosilicate and an emulsifier is disclosed as a method for improving the miscibility of an organosilicate in an aqueous paint (see, for example, Patent Document 2).

By this method, the miscibility with water-based paints was improved, and the extreme reduction in surface gloss was solved. However, organosilicate is easily hydrolyzed, and when a paint containing organosilicate that has been hydrolyzed is applied, there is a problem that the stain resistance of the coating film cannot be obtained. Whether the stain resistance is manifested cannot be distinguished by just looking at the paint before application, and it has been empirically estimated from the elapsed time after the organosilicate is blended. However, the actual situation is that this time varies considerably depending on the type of paint.
This application is characterized by preventing the hydrolysis of organosilicates, maintaining the pot life, and making paints that no longer exhibit stain resistance not usable or hesitate to use. It is.
WO94 / 06870 Publication Japanese Patent Laid-Open No. 10-17850

  The problem to be solved by the present invention is to provide a stain resistance imparting agent and a water-based paint that form a stain-resistant and high gloss coating film while maintaining the hydrophilic function of the coating film within the pot life. It is.

Pot life can be maintained for a specific period of time by adding a uniform mixture of organosilicate compound, polyoxyalkylene group-containing compound, organotin compound, amine compound, and alcohol to the water-based paint, and stain resistance can be stably imparted. I found a way.

That is, this application
(A) Organosilicate compound represented by general formula (1) or partial hydrolysis condensate thereof Si— (OR) ₄ ... General formula (1)
(Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms),
(B) a polyoxyalkylene group-containing compound,
(C) an organic tin compound,
(D) An antifouling composition comprising an amine compound (E) alcohol (claim 1).
The component (D) is an alkanolamine compound, and the stain resistance imparting composition according to claim 1 (claim 2).
· (C) Sulfur-containing organotin compound (R ¹ ) (R ² ) Sn (S—R ³ ) (S—R ⁴ ) in which the component is represented by the general formula (2) (2)
Wherein R ¹ and R ² are the same or different and are linear or branched alkyl groups having 1 to 8 carbon atoms, R ³ and R ⁴ are linear or branched alkyl groups having 1 to 20 carbon atoms and alkenyl groups. The composition for imparting contamination resistance according to claim 1 or 2, wherein the composition is a hydrocarbon group selected from the group (Claim 3).
-(B) component is a polyoxypropylene group containing compound, The contamination-resistance imparting composition of any one of Claims 1-3 characterized by the above-mentioned (Claim 4).
-The terminal of (B) component is 1 type, or 2 or more types chosen from a hydroxyl group, an ether group, an ester group, an allyl group, and a (meth) acryl group, In any one of Claims 1-4 characterized by the above-mentioned. The composition for imparting stain resistance according to claim 5 (Claim 5).
The component (E) is 2,2,4-trimethylpentanediol-1,3-monoisobutyrate, the stain resistance-imparting composition according to any one of claims 1 to 5, Claim 6).
-Furthermore, (F) Carbodiimide compound is mix | blended as needed, The contamination-resistance imparting composition of any one of Claims 1-6 (Claim 7).
A coating composition containing the stain resistance-imparting composition according to any one of claims 1 to 7 and a binder component (claim 8).
The coating composition according to claim 8, wherein the binder is an emulsion of a synthetic resin (claim 9).
10. The coating composition according to claim 9, wherein the emulsion of the synthetic resin is an emulsion of an alkoxysilyl group-containing polymer (claim 10).
The coating composition according to claim 9 or 10, wherein the synthetic resin emulsion is an emulsion of a polyoxyalkylene group-containing polymer (claim 11).
The coating composition according to any one of claims 8 to 11, wherein the polyoxyalkylene compound (B) is 5 to 300 parts per 100 parts by weight of the organosilicate compound (A). Item 12).
-The coating film obtained from the coating composition of any one of Claims 7-12 (Claim 13).
This is due to the above configuration.

The stain resistance-imparting composition of the present invention can be produced at a low cost with a simple operation. Moreover, the stain resistance imparting composition of the present invention is added to the aqueous coating material, thereby forming a coating material and a coating film excellent in stain resistance imparting and gloss immediately after mixing and after pot life. Moreover, the formed coating film improves water resistance, weather resistance, and adhesion. Further, after 24 hours in the pot life, the paint becomes hesitant to use, and it becomes possible not to use a paint having a poor degree of expression of the above characteristics.

In the paint application work, it is usual to predict the amount of paint required per day before the morning work and to mix the catalyst and other materials. In rare cases, when the paint left after the previous day was used, the hydrolysis of the organosilicate progressed, and there was a case where a part with different stain resistance appeared, which was an aesthetic problem. The present invention can prevent such a problem in advance.
This application prevents the rapid hydrolysis / condensation of organosilicates, maintains the pot life, and the hydrolysis / condensation proceeds so much that the paint does not exhibit stain resistance or has poor stain resistance performance. Or, it can be in a state of hesitation in using it.
In order to achieve such a situation, it is necessary to use the paint prepared in the morning of the work day in a stable manner on the day of the work and not to use it on the next day. As a guide, 24 hours can be considered as a guide. If possible, 20 hours or 15 hours are preferable.

Hereinafter, the present invention will be described in detail based on an embodiment thereof.
(Organosilicate)
The organosilicate compound (A) usable in the present invention is a compound containing a hydrolyzable silicon group, and is a compound represented by the following general formula (1) or a partially decomposed condensate thereof.
Si- (OR) ₄ ... General formula (1)
(Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms)
Specific compounds include tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-i-propoxysilane, tetra-n-butoxysilane, tetra-i-butoxysilane, tetra-t-butoxysilane and the like The partial hydrolysis-condensation product can be illustrated. Of these, methyl silicate 51, ethyl silicate 45, ethyl silicate 40, ethyl silicate 48 (manufactured by Colcoat Co., Ltd.), silicate 45, and silicate 40 (manufactured by Tama Chemical Industry Co., Ltd.) are preferable. The said compound may be single 1 type, and may use 2 or more types together.

  Organosilicates containing different alkoxysilyl groups in the same molecule can also be used. For example, methyl ethyl silicate, methyl propyl silicate, methyl butyl silicate, ethyl propyl silicate, propyl butyl silicate and the like. The ratio of these substituents can be arbitrarily changed between 0 to 100%. Moreover, although it described that the partial hydrolysis and condensate of these silicates can also be used, about 1-20 are preferable for a condensation degree. A more preferable range of the condensation degree is 3-15.

  In the organosilicate compound, compounds having 1 to 4 carbon atoms in the alkoxysilyl group are exemplified, but it is generally known that the reactivity improves as the carbon number decreases. When added to a water-based paint, an organosilicate having a small number of carbon atoms, such as methyl silicate, is highly reactive, and the time until gelation of the paint, that is, the pot life is shortened. On the other hand, when butyl silicate having a large number of carbon atoms is used, the stain resistance imparting rate is lowered and the pot life is lengthened. Considering the balance between the contamination resistance and the pot life, when the alkyl part of the alkoxysilyl group has 1 carbon and 2, 3 or 4 carbons, the carbon number is 2 and the carbon number is 3 or 4 is preferably mixed, and an average of 1.5 to 2.8 carbon atoms is preferable. That is, an equimolar mixture of methyl silicate and ethyl silicate, or a silicate having the same number of methyl groups and ethyl groups in the same molecule can be calculated as 1.5 carbon atoms.

(Polyoxyalkylene group-containing compound)
The polyoxyalkylene group-containing compound (B) in the present invention functions as a hydrophilic group site and can uniformly disperse the resulting stain resistance-imparting composition in the aqueous paint.
Specific examples of the polyoxyalkylene group include a polyoxyethylene group, a polyoxypropylene group, a polyoxyalkylene group in which an oxyethylene group and an oxypropylene group are blocked or randomly bonded, the polyoxyethylene group, the polyoxypropylene group, and the polyoxyalkylene group. Examples of the oxyalkylene group further include a group in which an oxyoxybutylene group is contained in a block or random bond.

  In particular, the compatibility with the organosilicate compound (A) is good, and even if the amount of the alcohol (E) used is reduced, the resulting stain resistance-imparting composition tends to be a uniform solution. The group is particularly preferred. This can greatly contribute to the reduction of the volatile solvent (VOC) in the final paint.

  Furthermore, it is preferable that the terminal of the polyoxyalkylene group is low in reactivity with the amine compound (D) or has no reactivity in order to ensure the storage stability of the stain resistance-imparting composition. Therefore, the terminal of the polyoxyalkylene group is preferably a hydroxyl group, an ether group, an ester group, an allyl group, or a (meth) acryl group.

  Specific examples of the compound in which the terminal of the polyoxyalkylene group is a hydroxyl group include polyalkylene glycol derivatives such as polyethylene glycol and polypropylene glycol with various addition amounts, and block types represented by the Pronon series such as Pronon 102 and Pronon 201 (above) And bisphenol A derivatives such as UNIOR DA-400, UNIOR DB-400, UNIOR DB-530 (and above, manufactured by NOF Corporation), and the like.

  Specific examples of the compound in which the end of the polyoxyalkylene group is an ether group include various polyalkylene glycol alkyl ethers such as polyethylene glycol oleyl ether and polyethylene glycol dimethyl ether.

  Specific examples of the compound in which the end of the polyoxyalkylene group is an ester group include polyalkylene glycol alkyl esters such as polyethylene glycol monooctyl ester, polypropylene glycol monostearyl ester, and polypropylene glycol distearyl ester.

  Specific examples of the compound in which the end of the polyoxyalkylene group is an allyl group include various polyalkylene glycol allyls such as UNIOX PKA-5006, UNIOR PKA-5014, UNIOR PKA-5017 (above, manufactured by NOF Corporation). Ether.

  Specific examples of the compound in which the end of the polyoxyalkylene group is a (meth) acrylic group include polyalkylene glycols (meth) such as Blemmer PP series, Blemmer PME series, and Blemmer PDE series (above, manufactured by NOF Corporation). An acrylate is mentioned.

These may be used alone or in combination of two or more.
The amount of the polyoxyalkylene group-containing compound used is preferably 5 to 300 parts, more preferably 10 to 150 parts, per 100 parts by weight of the organosilicate compound (A).
If the amount is less than 5 parts by weight, the stain resistance imparting composition is not uniformly dispersed in the water-based paint, and the gloss value of the formed coating film is lowered. Tack and hardness tend to decrease.

(Organic tin compounds)
Examples of the organotin compound as component (C) in the present invention include dioctyltin bis (2-ethylhexyl maleate), dioctyltin oxide or a condensate of dibutyltin oxide and silicate, dibutyltin dioctate, and dibutyl. Tin dilaurate, dibutyltin distearate, dibutyltin diacetylacetonate, dibutyltin bis (ethyl maleate), dibutyltin bis (butyl maleate), dibutyltin bis (2-ethylhexyl maleate), dibutyl There are tin bis (oleyl maleate), stannous octoate, tin stearate, and di-n-butyltin rallate oxide. Examples of tin compounds having S atoms in the molecule include dibutyltin bisisononyl-3-mercaptopropionate, dioctyltin bisisononyl-3-mercaptopropionate, octylbutyltin bisisononyl-3-mercaptopropionate, Examples thereof include dibutyltin bisisooctylthiogluconate, dioctyltin bisisooctylthiogluconate, and octylbutyltin bisisooctylthiogluconate.

Among them, dibutyltin thioglycolate, dibutyltin bisisononyl 3-mercaptopropionate, dibutyltin bisisooctylthioglycolate, dibutyltin bis-2-ethylhexyl thioglycolate, dimethyltin bisdodecyl mercaptide, dibutyltin bisdodecylmercapa Peptide, dioctyltin bisdodecyl mercaptide, dimethyltin bis (octylthioglycolate) salt, etc. are preferred because the contact angle and pot life can be easily balanced.
Furthermore, the sulfur-containing organotin compound (R ¹ ) (R ² ) Sn represented by the general formula (2) is used because the contact angle is lowered even when using a paint after pot life after stability in water. ^{(S-R 3) (S} -R 4) ··· formula (2)
Wherein R ¹ and R ² are the same or different and are linear or branched alkyl groups having 1 to 8 carbon atoms, R ³ and R ⁴ are linear or branched alkyl groups having 1 to 20 carbon atoms and alkenyl groups. In particular, dibutyltin bisdodecyl mercaptide, dioctyltin bisdodecyl mercaptide, and the like.

  These may be used alone or in combination of two or more.

Component (C) can be blended in an amount of 0.05 to 20 parts by weight, preferably 0.05 to 10 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the organosilicate compound (A). It is. When the blending amount is less than 0.05 parts by weight, the effect of imparting stain resistance is low, and when it exceeds 20 parts by weight, the stability of the blend decreases. When added to a water-based paint, the amount of (C) present increases, and the weather resistance of the coating film decreases.
(Amine compound)
The amine compound as the component (D) in the present invention is preferably an alkanolamine compound, and specific examples include monoethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, dimethylpropanolamine and the like.
These may be used alone or in combination of two or more.
Component (D) can be added in an amount of 0.1 to 20 parts by weight, preferably 0.5 to 20 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of organosilicate compound (A). . If the blending amount is less than 0.1 parts by weight, for example, it is difficult to gel the paint even if time elapses until the next day, and if it exceeds 20 parts by weight, the water resistance of the coating film tends to decrease. .

(alcohol)
Specific examples of the alcohols as the component (E) in the present invention include alkyl alcohols such as methanol, ethanol, isopropanol and butanol, alkylene glycol derivatives such as ethylene glycol and propylene glycol, or ethylene. Alkylene glycol alkyl ether derivatives such as glycol monobutyl ether and propylene glycol monomethyl ether, or 2,2,4-trimethylpentane-1,3-diol, 2,2,4-trimethylpentanediol-1.3-monobutyrate, etc. Examples include various alkyl-substituted aliphatic polyhydric alcohol derivatives.
These may be used alone or in combination of two or more.

  Among them, since the transparency of the resulting stain resistance imparting composition is improved or the film-thickness of the coating composition is improved, an alkylene glycol alkyl ether derivative or an alkyl-substituted aliphatic polyhydric alcohol derivative is preferable. In particular, 2,2,4-trimethylpentanediol-1.3-monobutyrate is preferable.

  (E) A component can be mix | blended 1-100 weight part with respect to 100 weight part of organosilicate compounds (A), Preferably it is 5-70 weight part, More preferably, it is 10-50 weight part. When the blending amount is less than 1 part by weight, the transparency of the resulting stain resistance-imparting composition is lowered.

(Carbodiimide group-containing compound)
When the carbodiimide group-containing compound which is the component (F) in the present invention is blended, the appearance and gloss of the coating film can be further improved. Examples of the component (F) include water-soluble or self-emulsifying carbodiimide compounds described in JP-A-8-59303.

  These are 2,4-tolylene diisocyanate (2,4-TDI), 2,6-tolylene diisocyanate (2,6-TDI), 4,4'-diphenylmethane diisocyanate (MDI), xylylene diisocyanate (XDI) , Isophorone diisocyanate (IPDI), methylcyclohexyl diisocyanate (H6TDI), 4,4′-dicyclohexylmethane diisocyanate (H12MDI), 1,3-bis (isocyanatomethyl) cyclohexane (H6XDI), tetramethylxylylene diisocyanate (TMXDI), 2,2,4-trimethylhexamethylene diisocyanate (TMHDI), hexamethylene diisocyanate (HDI), norbornene diisocyanate (NBDI), 2,4,6-triisopropylpheny Ludiisocyanate (TIDI), 1,12-diisocyanate dodecane (DDI), 2,4, -bis- (8-isocyanatooctyl) -1,3-dioctylcyclobutane (OCDI), n-pentane-1,4-diisocyanate, etc. One or more of these polyfunctional isocyanates is subjected to a carbon dioxide condensation reaction to form a carbodiimide, and the residual isocyanate group at the end is sealed with a hydrophilic group.

  Examples of the hydrophilic group to be sealed include a residue of an alkyl sulfonate, a quaternary salt of a residue of a dialkylamino alcohol, a residue of a polyoxyalkylene whose end is blocked with an alkoxy group.

  These are, for example, Nisshinbo Co., Ltd. Carbodilite V-02, V-04, V-06, V-02-L2, E-01, E-02, E-03, E-04, E- 05 and so on.

  Moreover, there are V-02B, V-04B, Elastostab H01 and the like that do not contain water.

In the stain resistance-imparting composition of the present invention, it is preferable not to contain water in order to allow the reactive functional group and the organosilicate to coexist. When water is contained, these are used after dehydration or water. It is desirable to use those that do not contain.
When the component (F) is used, it can be blended in an amount of 50 parts by weight or less, preferably 30 parts by weight or less, based on 100 parts by weight of the organosilicate compound (A). If it exceeds 50 parts by weight, the initial tack and hardness of the coating film will decrease.

(Dehydrating agent)
Since organosilicate has a dehydrating action, a dehydrating agent (G) is not usually required in a stain-imparting composition, but an organosilicate or a water-soluble and / or water-dispersed curing agent that is particularly highly reactive with water is used. When using, it is preferable to mix | blend a dehydrating agent.

  Examples of the dehydrating agent include trialkyl orthoformate such as trimethyl orthoformate, triethyl orthoformate or tributyl orthoformate; trialkyl orthoacetate such as trimethyl orthoacetate, triethyl orthoacetate or tributyl orthoacetate; or trimethyl orthoborate and orthoboric acid. Orthocarboxylic acid esters such as trialkyl orthoborate such as triethyl and tributyl orthoborate.

  In addition, there are isocyanates such as benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate, p-chlorophenyl isocyanate, etc., but various monovalents such as benzenesulfonyl isocyanate, tosyl isocyanate, phenyl isocyanate or p-chlorophenyl isocyanate are preferable. Isocyanates and the like.

(Preparation method of stain resistance imparting composition)
As a method for producing the stain resistance-imparting composition of the present invention, the above components (A) to (E), and in some cases (F) and (G) can be obtained by simply mixing and stirring. It is. Further, as another method, it is possible to cope with heating to such an extent that physical properties are not affected. When the temperature is higher than 100 ° C. or when moisture is mixed, the condensation reaction of the component (A) occurs, and the stain resistance imparting composition itself may be thickened and gelled. In addition, even if it does not gel, it may be deteriorated in functions such as a decrease in stain resistance and a decrease in gloss of the coating film formed by adding to the water-based paint.

(Emulsion of synthetic resin)
Examples of synthetic resin emulsions that can be used in the present invention include, but are not limited to, acrylic resin emulsions, urethane resin emulsions, fluorine resin emulsions, epoxy resin emulsions, polyester resin emulsions, alkyd resin emulsions, and melamine resin emulsions. I don't mean. These may be used alone or in combination of two or more. Among these, acrylic resin emulsion is advantageous because of its high cost and high degree of freedom in resin design.
As the acrylic resin emulsion, those obtained by radical copolymerization of an acrylic monomer and a monomer copolymerizable with the acrylic monomer can be used.

  The monomer that can be used is not particularly limited, but specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl acrylate, iso-butyl acrylate, tert-butyl acrylate, and benzyl. (Meth) acrylate, cyclohexyl acrylate, n-butyl methacrylate, iso-butyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, isodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, etc. (Meth) acrylate monomers; aromatic hydrocarbon vinyl monomers such as styrene, α-methylstyrene, chlorostyrene, vinyltoluene Vinyl compounds such as vinyl acetate and vinyl propionate; nitrile group-containing vinyl monomers such as (meth) acrylonitrile; epoxy group-containing vinyl monomers such as glycidyl (meth) acrylate; 2-hydroxypropyl (meta) ) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl vinyl ether, hydroxystyrene, Aronics 5700 (manufactured by Toa Gosei Chemical Co., Ltd.), pelcelFA-1, pelcelFA-4, lacquerFM-1, lacquerFM-4 (and above) , Manufactured by Daicel Chemical Industries, Ltd.), HE-10, HE-20, HP-10, HP-20 (above, manufactured by Nippon Shokubai Co., Ltd.), Bremer PEP series, Bremer NKH-5050, Bremermer GLM (above Nippon Oil & Fats) (Made by) Hydroxyl group-containing vinyl monomers such as acid group-containing vinyl-modified hydroxyalkyl vinyl monomers; AS-6, AN-6, AA-6, AB-6, AK which are macromonomers manufactured by Toa Synthetic Chemical Co., Ltd. And compounds such as -5, vinyl methyl ether, propylene, butadiene and the like.

  Furthermore, a hydrophilic vinyl monomer capable of improving the stability of the emulsion can also be used. Examples of the vinyl monomer having a hydrophilic group that can be used include sodium styrenesulfonate, sodium 2-sulfoethyl methacrylate, 2-sulfoethyl methacrylate ammonium, and vinyl monomers having a polyoxyalkylene chain.

  Although there is no limitation in the vinyl-type monomer which has a polyoxyalkylene chain, the acrylic acid ester or methacrylic acid ester which has a polyoxyalkylene chain is preferable, and as a specific example, Nippon Oil & Fats Co., Ltd. Blemmer PE-90, PE- 200, PE-350, AE-90, AE-200, AE-350, PP-500, PP-800, PP-1000, AP-400, AP-550, AP-800, 700PEP-350B, 10PEP-550B, 55PET-400, 30PET-800, 55PET-800, 30PPT-800, 50PPT-800, 70PPT-800, PME-100, PME-200, PME-400, PME-1000, PME-4000, AME-400, 50POEP- 800B, 50AOEP-800B, AE , AET, APT, PLE, ALE, PSE, ASE, PKE, AKE, PNE, ANE, PNP, ANP, PNEP-600, Kyoeisha Chemical Co., Ltd. light ester 130MA, 041MA, MTG, light acrylate EC-A, MTG -A, 130A, DPM-A, P-200A, NP-4EA, NP-8EA, EHDG-A, MA-30 manufactured by Nippon Emulsifier Co., Ltd., MA-50, MA-100, MA-150, RMA-1120 , RMA-564, RMA-568, RMA-506, MPG130-MA, Antox MS-60, MPG-130MA, RMA-150M, RMA-300M, RMA-450M, RA-1020, RA-1120, RA-1820, NK-ESTER M-20G, M-40G, M manufactured by Shin-Nakamura Chemical Co., Ltd. 90G, M-230G, AMP-10G, AMP-20G, AMP-60G, AM-90G, LA, Sanyo Chemical Industries Co., Ltd. ELEMINOL RS-30 and the like.

  Uses a monomer having two or more polymerizable unsaturated bonds such as polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) acrylate, triallyl cyanurate, allyl (meth) acrylate, divinylbenzene, diallyl phthalate It is also possible to do. In this case, the generated particles have a structure having cross-linking, and the water resistance of the formed coating film is improved.

  Moreover, trifluoro (meth) acrylate, pentafluoro (meth) acrylate, perfluorocyclohexyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl methacrylate, β- (perfluorooctyl) ethyl (meth) acrylate, etc. Fluorine-containing acrylic resin emulsions having high water and oil repellency can be prepared by using the above-mentioned fluorine-containing vinyl monomers.

  Moreover, a crosslinked acrylic resin emulsion in which a carbonyl group-containing vinyl monomer is copolymerized with the above monomer and a compound containing a hydrazine and / or hydrazide group is blended can also be produced. The water resistance of the coating film obtained from such a crosslinked acrylic resin emulsion is very good.

  Furthermore, an acrylic resin emulsion containing a hydrolyzable silyl group can be prepared by copolymerizing the monomer and a monomer having a hydrolyzable silyl group.

  As the monomer containing a hydrolyzable silyl group, an alkoxysilyl group-containing vinyl monomer is preferable from the viewpoint of ease of handling, cost, and the difficulty of producing a reaction byproduct. Specific examples of the alkoxysilane-containing vinyl monomer include vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyltris (2-methoxyethoxy) silane, vinyltriisopropoxysilane, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ -(Meth) acryloxypropyltri-n-propoxysilane, γ- (meth) acryloxypropyltriisopropoxysilane, vinyltriacetoxysilane, β- (meth) acryloxyethyltrimethoxysilane and the like. These hydrolyzable silyl group-containing vinyl monomers may be used alone or in combination of two or more.

  Γ- (Meth) acryloxypropylmethyldimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropylmethyldiethoxysilane, γ from the viewpoint of storage stability in the case of water-based paint -(Meth) acryloxypropyltri-n-propoxysilane and γ- (meth) acryloxypropyltriisopropoxysilane are particularly preferred.

The hydrolyzable silyl group-containing monomer is desirably copolymerized using 0.1 to 50 parts by weight in 100 parts by weight of all monomers. If it is less than 0.1 parts by weight, the water resistance and durability are lowered, and if it exceeds 50 parts by weight, the emulsion becomes unstable, and 0.5 to 20 parts by weight is more preferable.
When the compound (C) that promotes hydrolysis / condensation of the alkoxysilane compound of the present invention is mixed with the alkoxysilyl group-containing acrylic emulsion obtained as described above, the crosslinking reaction proceeds, and the water resistance / The coating film has good weather resistance.

  The acrylic resin emulsion that can be used in the present invention can be obtained by adopting a usual method, but an emulsion polymerization method is preferred in consideration of the particle size and stability of the emulsion.

  The emulsion polymerization method is not particularly limited, and can be appropriately selected from various emulsion polymerization methods such as a batch polymerization method, a monomer dropping polymerization method, and an emulsion monomer dropping polymerization method. In particular, in order to ensure the stability of the emulsion at the time of production, a monomer dropping polymerization method and an emulsion monomer dropping polymerization method are preferred.

  In emulsion polymerization, commonly used ionic or nonionic surfactants can be used.

  Examples of the ionic surfactant include an anionic surfactant having a polyoxyethylene chain such as polyoxyethylene nonylphenyl ether sulfate, polyoxyethylene allyl ether sulfate, octylphenoxyethoxyethyl sulfonate, polyoxyethylene tridecyl ether sulfate, and the like. Sulfonic acid salts such as sodium lauryl sulfonate, sodium dodecylbenzene sulfonate and sodium isooctylbenzene sulfonate; ammonium salts such as imidazoline laurate and ammonium hydroxide are typical examples. An anionic surfactant having an oxyethylene chain is preferred.

  Examples of the nonionic surfactant include polyethylene glycol nonylphenyl ether; polyoxyethylenes such as polyoxyethylene nonylphenyl ether and polyoxyethylene lauryl ether; L-77, L-720, L-5410, L Representative examples include nonionic surfactants containing silicone such as −7602 and L-7607 (manufactured by Union Carbide).

  In the present invention, it is preferable to use a reactive surfactant having a polymerizable double bond in one molecule as the surfactant in terms of water resistance and weather resistance. In particular, when a reactive surfactant having a polyoxyalkylene group in the molecule is used, the mechanical stability can be improved.

  Specific examples of such reactive surfactants include, for example, Adeka Soap ER-10, ER-20, ER-30, ER-40, SR-10, SR-20, SR- manufactured by Asahi Denka Kogyo Co., Ltd. 1025, NE-10, NE-20, NE-30, NE-40, SE-10N), Nippon Emulsifier Co., Ltd. Antox-MS-60, RMA-1120, RMA-564, RMA-568, RMA-506 , Aqualon KH-05, KH-10, RN-20, RN-30, RN-50, RN-2025, HS-10, HS-20, HS-1025, BC05, BC10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. BC0515, BC1025, Sanyo Chemical Industries Co., Ltd. Eleminol JS-2, Eleminol RS-30, Kao Co., Ltd. Latemul S-180, S-180A, PD-104, PD 420, such as PD-430 and the like.

  Of these, non-alkylphenol-based ones are desirable in consideration of the environment.

  The surfactants can be used alone or in admixture of two or more, and the amount used is 10 parts by weight or less, preferably 0.5 to 8 parts by weight based on 100 parts by weight of the total amount of monomers. is there.

  Although there is no limitation in particular as a polymerization initiator, In order to perform superposition | polymerization more stably, it is desirable to use a redox system as a polymerization initiator. Further, in order to maintain the stability of the mixed solution during the polymerization and perform the polymerization stably, the temperature is 70 ° C. or lower, preferably 40 to 65 ° C., and the pH is preferably adjusted to 5 to 9.

  Examples of the initiator used in the redox system include potassium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide, and the like. Examples thereof include acidic sodium sulfite, Rongalite, Bruggolite FF-6 (manufactured by Bruggamann Chemical US), thiourea dioxide, L-ascorbic acid and the like. In particular, a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, cumene hydroperoxide and the like and Rongalite, Bruggolite FF-6 or thiourea dioxide is preferable.

  Note that the reducing agent is particularly preferably Bruggolite FF-6 or thiourea dioxide which does not generate formaldehyde in consideration of the environment.

  The amount of the polymerization initiator used is 0.01 to 10 parts, preferably 0.05 to 5 parts by weight based on 100 parts by weight of the total amount of monomers. When the amount of the polymerization initiator used is less than 0.01 parts by weight, the polymerization may be difficult to proceed. When the amount exceeds 10 parts by weight, the molecular weight of the produced polymer tends to decrease. is there.

  In order to stably impart the catalytic activity of the polymerization initiator, a compound containing a divalent iron ion such as iron sulfate and a chelating agent such as disodium ethylenediaminetetraacetate may be used. The amount of the chelating agent used is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 100 parts by weight of the total amount of monomers.

  Chain transfer agents can be added to control the molecular weight of the polymer. Known chain transfer agents such as n-dodecyl mercaptan, tert-dodecyl mercaptan, n-butyl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Examples include mercaptan compounds such as γ-mercaptopropylmethyldiethoxysilane, organic halides such as chloroform and carbon tetrachloride, sulfide benzene, isopropylbenzene, and ferric chloride.

  The resin solid content concentration in the acrylic resin emulsion is preferably 20 to 70% by weight, and more preferably 30 to 60% by weight. When the resin solid content concentration exceeds 70% by weight, the concentration of the system increases remarkably, making it difficult to remove the heat generated by the polymerization reaction or taking a long time to remove from the polymerization vessel. There is a tendency to become necessary. Further, when the resin solid content concentration is less than 20% by weight, there is no problem in terms of polymerization operation, but the amount of resin produced by one polymerization operation is small, which is disadvantageous in terms of economy.

  The acrylic resin emulsion used in the present invention preferably has an average particle size of about 0.02 to 1.0 μm. The average particle size can be adjusted by the amount of the emulsifier charged in the initial stage of polymerization.

  These acrylic resin emulsions are commercially available from various companies, for example, Dainippon Ink & Chemicals Co., Ltd. Boncoat, Watersol, Nippon Shokubai Co., Ltd. Acre Reset, Udouble, Showa High Polymer Co., Ltd. Polysol, Japan NS Co., Ltd. Yodosol, Kanebinol, Asahi Kasei Kogyo Co., Ltd. Polytron, Polydurex, Chuo Rika Kogyo Co., Ltd. Rikabond, Nippon Acrylic Co., Ltd. Primal, BASF Dispersion Co., Ltd., Acronal, Clariant Polymer ( Movinyl, Inc., Kaneka Zemrak, Kanevirak, Inc.

  Urethane resin emulsions include those in which urethane resin is dispersed in water, and those in which urethane resin is given a hydrophilic group and made self-dispersing, and those in which hydrophobic urethane resin is forcibly emulsified with an emulsifier, etc. Any of them can be used.

  These are commercially available from various companies. For example, Superflex 90, 107M, 110, 126, 130, 150, 150HS, 160, 300, 361, 370, 410, 420, 460, manufactured by Daiichi Kogyo Seiyaku Co., Ltd. 460S, 500, 600, E-2000, E-2500, E-4000, E-4500, E-4700, R-5000, Elastron BN-08, BN-11, BN-50D, NeoRez R-960 made by Avecia KK R-972, R-9637, R-9679, AX-311, R-966, R-967, R-9603, R-600, R-9320, R-9617, R-9621, NeoPac R-9000, R-9699, Takelac W-615, W-6010, W-6020, W-6 manufactured by Mitsui Takeda Chemical Co., Ltd. 061, W-511, W-405, W-7004, W-605, W-512A6, W-635, W-635C, WS-7000, WS-5000, WS-5070X, WS-4000, XW-75- Asahi Denka Kogyo Co., Ltd. Adekabon titer HUX-290H, HUX-290K, HUK-290N, HUX-395D, HUX-394, HUX-232, HUX-240, HUX-320, HUX-350, HUX- 380, HUX-381, HUX-388, HUX-380A, HUX-386, HUX-401, HUX-750, HUX-670, HUX-680, HUX-575, HUX-580, and the like.

  The urethane resin emulsion can be used alone or in a mixed system with other resin emulsions. In particular, a mixed system with an acrylic resin emulsion is useful in terms of ease of coating design and cost.

  As the fluororesin emulsion, a dispersion of a fluoroolefin polymer and / or a copolymer of a monomer copolymerizable with the fluoroolefin in water can be used.

  Examples of the fluoroolefin include vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, tetrafluoroethylene, pentafluoropropylene, hexafluoropropylene and the like.

  Monomers that can be copolymerized with fluoroolefins include olefins such as ethylene and propylene, vinyl ethers such as ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether, butyl vinyl ester, octyl vinyl ester, vinyl acetate, and versatic acid. Vinyl esters such as vinyl (Japan Epoxy Resin Co., Ltd. Veova 10, Veova 9, Veova 11), aromatic vinyl compounds such as styrene and vinyl toluene, allyl ethers such as ethyl allyl ether, and allyl such as butyl allyl ester Examples thereof include compounds and (meth) acrylic acid esters.

  These are commercially available from various companies, and examples thereof include Lumiflon manufactured by Asahi Glass Co., Ltd., Zaffle manufactured by Daikin Industries, Ltd., Cefral Coat manufactured by Central Glass Co., Ltd., and Fluonate manufactured by Dainippon Ink & Chemicals, Inc.

  If necessary, pigments that are usually used in paints (white pigments such as titanium dioxide, calcium carbonate, barium carbonate, kaolin, and colored pigments such as carbon, bengara, and cyanine blue) are used in the synthetic resin emulsion that can be used in the present invention. Can be used. Titanium dioxide is the most used and important among the pigments. Gloss and weather resistance are improved by using titanium dioxide surface-treated with alumina or zirconia. Also for ordinary coatings such as film-forming aids, colloidal silica, plasticizers, solvents, dispersants, thickeners, antifoaming agents, antiseptics, fungicides, algaeproofing agents, ultraviolet absorbers, light stabilizers, etc. Additives used as ingredients can also be blended.

(Addition of antifouling composition to water-based paint)
As a method for mixing the stain resistance-imparting composition and the aqueous paint in the present invention, the stain-resistance imparting composition may be added directly to the aqueous paint. It is possible to add a stain resistance-imparting composition to a synthetic resin emulsion in advance and add a paint compounding agent to make a water-based paint. A method of adding a stain resistance-imparting composition can be mentioned. This method is preferable because there is little change in physical properties of the coating film when the coating is applied. With this method, it is possible to stably form a coating film having excellent stain resistance and high gloss. It is also possible to use both the above methods in combination. That is, this is a method of further adding a stain resistance imparting composition to a water-based paint obtained by adding a stain resistance imparting composition to a synthetic resin emulsion before coating.

  The mixing ratio of the water-based paint and the stain resistance-imparting composition is such that the organosilicate compound (A) is 2 to 40 parts by weight with respect to 100 parts by weight of the resin solid content in the water-based paint. It is preferable to do. If the component (A) is less than 2 parts by weight, the stain resistance performance is not sufficiently exhibited, and if it exceeds 40 parts by weight, the compatibility between the resin in the aqueous paint and the organosilicate compound decreases. There is a tendency to see a decrease in gloss. Furthermore, the usage-amount of a preferable organosilicate compound (A) is 3-20 weight part.

  The water-based paint imparted with stain resistance of the present invention is, for example, for interior and exterior of buildings, for automobiles such as metallic base or clear on metallic base, for direct coating of metals such as aluminum and stainless steel, slate, concrete, roof tile, mortar, Gypsum board, asbestos slate, asbestos board, precast concrete, lightweight cellular concrete, calcium oxalate board, tiles, bricks and other ceramics direct coating, glass, natural marble, granite and other stone paints or top treatments Used. In addition to direct coating, water-based or solvent-based primer, acrylic rubber, multi-layer finish top coat, flexible top finish coat, water-based inorganic base materials such as concrete Alternatively, it can be used for coating on a solvent-based permeable water absorption preventing material.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto.
(Manufacturing method of stain resistance imparting composition: Production Examples 1 to 10) The components shown in Table 1 in the container equipped with a stirrer, a reflux condenser, and a nitrogen gas inlet tube are (B), (E), (F). , (A), (C), (G), and (D) were added while stirring in the order (if there was an unused component, the component was not charged and the next component was charged). In addition, it is preferable that the component (D) is mixed with a part of the component (E) in advance and then added, since it can be mixed more uniformly.
After completion of the addition, the mixture was stirred for 30 minutes to obtain the stain resistance imparting compositions of Production Examples 1-10. The obtained stain resistance-imparting composition was put in a transparent container, visually checked for separation / sedimentation, and the one without separation / sedimentation was marked as ◯.

Methyl silicate 51: Methyl silicate partial hydrolysis condensate (silica residual ratio 51%) (manufactured by Colcoat Co., Ltd.)
Silicate 45: ethyl silicate partial hydrolysis condensate (silica residual ratio 45%) (manufactured by Tama Chemical Co., Ltd.)
Ethyl silicate 40: Ethyl silicate partial hydrolysis condensate (silica residual ratio 40%) (manufactured by Colcoat Co., Ltd.)
UNIOR DB-530: Polypropylene glycol bisphenol A ether (manufactured by NOF Corporation)
Unisafe PKA-5014: Polypropylene glycol allyl ether (manufactured by NOF Corporation)
Unisafe NKL-9520: Polypropylene glycol distearate (Nippon Yushi Co., Ltd.)
New Coal 562: Polyethylene glycol nonylphenyl ether (manufactured by Nippon Emulsifier Co., Ltd.)
UNIOX PKA-5006: Methoxypolyethylene glycol allyl ether (manufactured by NOF Corporation)
Carbodilite V-04B: Water-soluble polycarbodiimide (manufactured by Nisshinbo Co., Ltd.)
Additive TI: Monofunctional isocyanate (manufactured by Sumika Bayer Urethane Co., Ltd.).

(Synthesis Example 1 of alkoxysilyl group-containing acrylic emulsion)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen gas inlet tube and a dropping funnel, 200 parts by weight of deionized water, 0.16 parts by weight of Newcol-707SF (manufactured by Nippon Emulsifier Co., Ltd .: 30% active ingredient), Sodium hydrogen carbonate 0.05 part by weight was charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas. After the temperature increase, 12 parts by weight of the monomer mixture shown in the core part of Table 2 (Em-1), 0.14 parts by weight of t-butyl hydroperoxide, and 0.4 parts by weight of Rongalite were added, and the initial period was 30 minutes. Polymerization was performed. The remaining 268 parts by weight of the monomer mixture is 9.7 parts by weight of Aqualon BC0515 (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 15%), Aqualon RN2025 (Daiichi Kogyo Seiyaku Co., Ltd .: active ingredient 20%) 2 .7 parts by weight and 66 parts by weight of deionized water and emulsified monomer emulsion and 0.20 parts by weight of t-butyl hydroperoxide were added at a constant rate over 145 minutes. Polymerization was performed after 1 hour after the addition was completed.

  Furthermore, a monomer emulsion obtained by emulsifying by adding 6.0 parts by weight of Aqualon BC0515, 1.6 parts by weight of Aqualon RN2025 and 27 parts by weight of deionized water to 120 parts by weight of the monomer mixture shown in the shell part of Table 2 (Em-1), 0.15 parts by weight of t-butyl hydroperoxide was added at a constant rate over 65 minutes. Polymerization was performed after 1 hour after the addition was completed. After adding 1.0 part of sodium hydrogen carbonate to the obtained synthetic resin emulsion, the solid part was adjusted to 50% with deionized water (Em-1).

(Synthesis example 2 of alkoxysilyl group-containing acrylic emulsion)
In a reaction vessel equipped with a stirrer, reflux condenser, nitrogen gas inlet tube and dropping funnel, 200 parts by weight of deionized water, 1.0 part by weight of Newcol-707SF (manufactured by Nippon Emulsifier Co., Ltd.), 0. 05 parts by weight were charged, and the temperature was raised to 50 ° C. while introducing nitrogen gas. After the temperature rise, 20 parts by weight of the monomer mixture shown in the core part of Table 2 (Em-2), 0.14 parts by weight of t-butyl hydroperoxide, 0.5 parts by weight of Bruggolite FF-6 are added, Initial polymerization was performed for 30 minutes. The remaining 180 parts by weight of the monomer mixture is 3 parts by weight of Adeka Soap SR-10 (Asahi Denka Kogyo Co., Ltd .: active ingredient 100%), Adeka Soap ER-20 (Asahi Denka Kogyo Co., Ltd .: active ingredient) 75%) A monomer emulsion obtained by adding 1.9 parts by weight and 64 parts by weight of deionized water and emulsifying and 0.14 parts by weight of t-butyl hydroperoxide were added at a constant rate over 100 minutes. Polymerization was performed after 1 hour after the addition was completed.

  Furthermore, 200 parts by weight of the monomer mixture shown in the shell part of Table 2 (Em-2), 3.0 parts by weight of ADEKA rear soap SR-10, 1.9 parts by weight of ADEKA rear soap ER-20, and 64 parts by weight of deionized water A monomer emulsion obtained by adding a part and emulsified monomer and 0.21 part by weight of t-butyl hydroperoxide were added at a constant rate over 110 minutes. Polymerization was performed after 1 hour after the addition was completed. After adding 1.0 part of sodium hydrogen carbonate to the obtained synthetic resin emulsion, the solid part was adjusted to 50% with deionized water (Em-2).

(Creation of paint)
Using the synthesized resin emulsion, paints were prepared with the formulation (parts by weight) shown in Table 4 using the pigment pace shown in Table 3. (AS-1 to 2).

(Evaluation of the physical properties)
-Coating film preparation The antifouling property-imparting composition of the present invention was added to the water-based paint produced by the formulation shown in Table 4, and stirred (parts by weight). The glass plate was coated with a 6 mil applicator and cured at room temperature for 7 days. Table 5 shows the physical property evaluation results.

-Measurement of water contact angle of coating film The water contact angle of the coating film, which is an index of stain resistance, was measured using a contact angle measuring machine (Kyowa Interface Science Co., Ltd .: CA-S150 type). The evaluation was carried out after curing the prepared sample and immersing it in water for 7 days.

-Paint state after 24 hours of pot life The above paint was lightly covered with aluminum foil and allowed to stand at room temperature for 24 hours. The state of the paint after standing was visually observed.
A: Gelled state B: Vigorous thickening, almost no fluidity C: No change or slightly thickened, but possible to paint ・ 60 ° gloss above curing sample (added) 60 ° gloss immediately after) was measured with a gloss meter Multi Gross268 (manufactured by Minolta Co., Ltd.).

The stain resistance-imparting composition of the present invention can be produced at a low cost with a simple operation. Further, by adding the stain resistance-imparting composition of the present invention to the aqueous coating material, the coating material becomes substantially unhealthy after 24 hours of pot life, and as shown in the examples, for example. In addition, a coating film having hydrophilicity is formed without increasing the contact angle even after 6 hours of pot life. The formed coating film can improve water resistance, weather resistance, and adhesion.

Claims (11)

(A) Organosilicate compound represented by general formula (1) or partially hydrolyzed condensate thereof Si- (OR) ₄ ... General formula (1)
(Wherein R is the same or different and is an alkyl group having 1 to 4 carbon atoms),
(B) a polyoxyalkylene compound having at least one selected from the group consisting of a hydroxyl group, an alkyl ether group , an alkyl ester group , an allyl group, and a (meth) acryl group at the end;
(C) an organic tin compound,
(D) an alkanolamine compound,
(E) added to a coating composition containing a binder component comprising at least one alcohol selected from the group consisting of alkyl alcohols, alkylene glycols, alkylene glycol alkyl ethers, and alkyl group-substituted aliphatic polyhydric alcohols. Contamination resistance-imparting composition used for (C) Sulfur-containing organotin compound whose component is represented by the general formula (2) (R ¹ ) (R ² ) Sn (S—R ³ ) (S—R ⁴ )... General formula (2)
Wherein R ¹ and R ² are the same or different and are linear or branched alkyl groups having 1 to 8 carbon atoms, R ³ and R ⁴ are linear or branched alkyl groups having 1 to 20 carbon atoms and alkenyl groups. The composition for imparting stain resistance according to claim 1, wherein the composition is a hydrocarbon group selected from The component (B) is a polyoxypropylene compound having at least one selected from the group consisting of a hydroxyl group, an alkyl ether group , an alkyl ester group , an allyl group, and a (meth) acryl group at the terminal. Item 3. The composition for imparting stain resistance according to Item 1 or 2. The composition for imparting stain resistance according to any one of claims 1 to 3, wherein the component (E) is 2,2,4-trimethylpentanediol-1,3-monoisobutyrate. Furthermore, the contamination | pollution resistance provision composition of any one of Claims 1-4 by which a carbodiimide compound is mix | blended as needed. A coating composition containing the stain resistance-imparting composition according to any one of claims 1 to 5 and a binder component. The coating composition according to claim 6, wherein the binder component is an emulsion of a synthetic resin. The coating composition according to claim 7, wherein the emulsion of the synthetic resin is an emulsion of an alkoxysilyl group-containing polymer. 9. The coating composition according to claim 7, wherein the synthetic resin emulsion is an emulsion of a polyoxyalkylene group-containing polymer. The said polyoxyalkylene compound (B) is 5-300 weight part with respect to 100 weight part of organosilicate compounds (A), The coating composition of any one of Claims 6-9 characterized by the above-mentioned. The coating film obtained from the coating composition of any one of Claims 6-10.