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WO1997036936A1 - Composition de resine hydrodispersable a reticulation spontanee - Google Patents

Composition de resine hydrodispersable a reticulation spontanee Download PDF

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Publication number
WO1997036936A1
WO1997036936A1 PCT/JP1997/001132 JP9701132W WO9736936A1 WO 1997036936 A1 WO1997036936 A1 WO 1997036936A1 JP 9701132 W JP9701132 W JP 9701132W WO 9736936 A1 WO9736936 A1 WO 9736936A1
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Prior art keywords
water
weight
parts
resin
reactive
Prior art date
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Ceased
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PCT/JP1997/001132
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English (en)
Japanese (ja)
Inventor
Masakazu Watanabe
Satoshi Suzuki
Hiroshi Miwa
Teruaki Kuwajima
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Nippon Paint Co Ltd
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Nippon Paint Co Ltd
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Publication of WO1997036936A1 publication Critical patent/WO1997036936A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06
    • C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups

Definitions

  • the present invention relates to a water-dispersible resin composition, and particularly to a water-dispersible resin composition suitably used for a coating composition.
  • Paints generally include colorants, such as dyes and pigments, a binder for securing the same to the painted surface, and a liquid medium for evenly coating them. Since the binder is a high molecular weight polymer or resin, it is inherently insoluble in water, but many organic solvents such as thinners have been used as the liquid medium in paints containing such water insoluble binders. Was.
  • the cause of poor stability of the water-dispersible paint is mainly due to poor dispersion stability of the water-dispersible resin composition used for the water-dispersible paint.
  • Japanese Patent Application Laid-Open No. 52-47029 discloses that a mixture of an alkoxymethylacrylamide, an a, ⁇ -: a ethylenically unsaturated carboxylic acid and another copolymerizable ethylenically unsaturated monomer is used as a water-soluble resin.
  • a water-dispersible resin composition obtained by neutralizing a copolymer obtained by polymerization in the presence of water.
  • the obtained resin composition has poor water dispersion stability. For this reason, the paint using this is inferior in the workability of coating, and sagging easily occurs.
  • Japanese Patent Application Laid-Open No. 3-504138 discloses that a monomer mixture containing an acrylic monomer having a carboxyl group and a monomer mixture containing an acrylyl monomer having a carboxyl group are alternately polymerized and neutralized. Although a dispersible resin composition is disclosed, this resin composition has poor water dispersion stability because the compatibility between a polymer having an acid value and a polymer having no acid value is insufficient. For this reason, paints using this do not exhibit sufficient structural viscosity. C In addition, they are poor in chemical resistance and water resistance.
  • the present invention has been made to solve the above-mentioned conventional problems, and its object is to form a coating film having excellent transparency, smoothness, chemical resistance, water resistance and mechanical strength.
  • An object of the present invention is to provide a water-dispersible resin composition capable of realizing an aqueous coating having dispersion stability and a method for producing the same.
  • the present invention provides: (a) 5 to 95% by weight of a reactive water-insoluble resin containing a functional group and having a solubility in water of 1 or less, and
  • a method for producing a self-crosslinkable water-dispersible resin composition which comprises a step of neutralizing the obtained resin composition by adding a neutralizing agent, thereby achieving the above object.
  • FIG. 1 is a cross-sectional view showing an example of a multilayer coating film formed using the coating composition of the present invention.
  • a reactive water-insoluble resin alone preferably a solution obtained by dissolving a reactive water-insoluble resin in an organic solvent is heated to a temperature equal to or lower than the boiling point of the organic solvent, specifically, Heat to about 60 to 150 ° C, preferably S0 to 12 (TC.
  • the reactive water-insoluble resin is a resin containing a functional group and having a solubility of 1 g or less in 100 g of water.
  • a water-insoluble resin By using a water-insoluble resin, a coating film having excellent water resistance is provided in comparison with the case of using a water-soluble resin, and a more robust coating film is provided because the functional groups contained in the resin are bridged. That is, a coating film having excellent chemical resistance and mechanical strength is provided.
  • This reactive water-insoluble resin is not particularly limited as long as it is a non-volatile liquid at the polymerization temperature and is used by those skilled in the art as a coating binder, but preferably has a molecular weight of 300 to 100,000, more preferably 1,000 to 10,000. If the c molecular weight having 50,000 is less than 300, the resin becomes volatile and may be lost by heating, and if it exceeds 100000, liquefaction may not occur even at the polymerization temperature.
  • the functional group is preferably an amino group, an epoxy group, an isocyanate group, or the like substituted with a hydroquinone methyl group or an alkyne methyl group.
  • the reactivity of these functional groups during polymerization can be arbitrarily controlled by selecting the polymerization temperature, the type of polymerization solvent and the amount of solvent, etc. This is because a solid cured film can be obtained under the above drying conditions, and the liquid state here means that the reactive water-insoluble resin must be liquid alone at the polymerization temperature. It is not desirable, and it suffices if it is dissolved in a polymerization medium appropriately selected from various organic solvents and is liquid.
  • aminoblast resins, epoxy resins and isocyanate resins are particularly preferred. Since these resins have a reactive functional group in the main chain skeleton of the resin, the coating film obtained by reacting with the acryl resin when the obtained aqueous resin dispersion is cured, has an acryl skeleton and these non-acryl groups. It can have a regular structure with the size of the polymer as a unit, having alternating resin skeletons. For this reason, the obtained coating film has excellent mechanical strength such as scratch resistance, impact resistance, and workability.
  • the reactive water-insoluble resin used in the present invention two or more resins of the same kind and having different characteristic values (for example, molecular weight and functional group content) can be used in combination.
  • Aminoplast refers to a resin synthesized by a condensation reaction between a compound containing an amino group and formaldehyde.
  • the compound containing an amino group include heterocyclic compounds such as benzoguanamine and benzotriazole, and urea.
  • Preferred aminoblasts for use in the present invention are those in which at least 50%, preferably 70%, of the above amino groups are substituted. If the substitution amount is less than 50%, a uniform polymerization reaction does not occur. When the substitution amount is 70% or more, the stability of the obtained dispersion is particularly excellent.
  • aminoblasts include Cymel 303, Simel 370, Cymel 325, Cymel 712, Cymel 701, Cymel 235, Simel 238, Cymel 285, Cymel 254, Cymel 202, Mycoat 506, Mycoat manufactured by Mitsui Cytec.
  • Epoxy resin refers to a resin containing an epoxy group in the molecule.
  • Preferred epoxy resins for use in the present invention have an epoxy equivalent of 100-750,000, preferably 100-50,000. If the epoxy equivalent is less than 100, the polymerization reaction may not proceed uniformly. If the epoxy equivalent is more than 75,000, the curability when the obtained dispersion is cured as a film decreases.
  • epoxy resins include glycidyl ethers such as 1,6-hexanediol diglycidyl ether, preferably trimethylolpropane triglycidyl ether, bisphenol A-diglindyl ether and hydrogenated bisphenol A-diglindyl ether.
  • Glycidyl esters such as adivic acid, diglycidyl ester, hydrogenated diglindyl phthalate, diglycidyl phthalate and preferably triglycidyl trimellitate, and 3,4-epoxycyclohexylmethyl-3,4-epoxy Aliphatic epoxy such as cyclohexane carboxylate, bis- (3,4-epoxycyclohexyl) adipate and vinyl chloride hexene quinde.
  • ERL-42210 JCC 4299 (manufactured by UCC), Epolite 1600 (manufactured by Kyoeisha Yushi Sii) and 4000 (manufactured by Kyoeisha Yushi), Denacol EX-301, 622, 512 and 421 (Nagase Kasei) Epl004, Ep drawing, Epl009, EplOlO (oiled shell) Epoxy), resins such as YD-014, YD-017 YD-019, YD-7019, YD-020N. YD-020H.
  • ZX-1449-4 manufactured by Toto Kasei Co., Ltd.
  • Epicort 1255HX-30C manufactured by Yuka Shell Epoxy PKHH.
  • PKHJ, PKHC Enoxyso A commercially available product such as a so-called phenoquine resin such as a shell
  • An isocyanate resin is a resin containing two or more isocyanate groups in a molecule.
  • Preferred isocyanate resins for use in the present invention are those having an isocyanate equivalent of 100 to 10,000, particularly 100 to 5,000. If the isocyanate equivalent is less than 100, the polymerization reaction may not proceed uniformly. If the equivalent is more than 10,000, the curability of the obtained hardened body as a film is reduced.
  • isocyanate resins examples include toluidine diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, 1,3- (isocyanoxymethyl) cyclohexane, and trimethyl methacrylate.
  • Xamethylene diisocyanate preferably diphenylmethane diisocyanate, lysine diisocyanate, methylene-bis (cyclohexyl isocyanate), isophorone diisocyanate, trimethyl hexamethylene diisocyanate And, particularly preferably, trimers of these isoneates, such as tri (toluidine diisocyanate) and tri (hexamethylene diisocyanate), or adducts thereof with polyols.
  • the reactive water-insoluble resin is preferably 10-95% by weight, based on the total weight of the starting mixture. It is preferably used in an amount of 25 to 95% by weight, more preferably 55 to 95% by weight. If the amount of the reactive water-insoluble resin is less than 10% by weight, no improvement in smoothness, chemical resistance and mechanical strength is observed. If the content exceeds 95% by weight, the dispersion stability of the paint and the curability of the paint film deteriorate.
  • Preferred organic solvents for use as the polymerization medium are so-called hydrogen bonding organic solvents. It is known that a hydrogen bonding solvent can solvate the reagent by hydrogen bonding and inhibit the substitution reaction (S.H.PINE ORGANIC CHEMISTRY McGraw-Hill (1387)). Therefore, when a monomer having a reactive functional group is polymerized in the presence of a reactive water-insoluble resin, the reaction between the resin and the functional group derived from the monomer is prevented, thereby causing non-uniform polymerization due to gelation. This is because the polymerization reaction can be prevented and the polymerization reaction can be effectively advanced.
  • the hydrogen-bonding solvent can promote the dispersion of the resin by solvating with water by hydrogen bonding at the time of dispersion in water. Therefore, the amount of the hydrogen-bonding organic solvent is preferably at least 5 equivalents of the monomer functional group serving as the reagent. It is more preferably at least 10 equivalents. Hydrogen-bonding organic solvents are described in J.N.Israeli Atabili, "Intermolecular and Surface Forces” (translated by Tamotsu Kondo and Hiroyuki Oshima, McGraw-Hill Publishing, 1991). An organic solvent that can form hydrogen atom-mediated “bonding” between an electronegative atom (oxygen, nitrogen, fluorine, chlorine) and a hydrogen atom covalently bonded to the electronegative atom.
  • the coupling moment is large and contains hydrogen, such as 0-H (oxygen-hydrogen bond), N-H (nitrogen-hydrogen bond), and F-H (fluorine-hydrogen bond).
  • hydrogen such as 0-H (oxygen-hydrogen bond), N-H (nitrogen-hydrogen bond), and F-H (fluorine-hydrogen bond).
  • the organic solvent is also used for adjusting the viscosity during the polymerization, and is preferably used in an amount of 10 to 400 parts by weight, particularly 20 to 200 parts by weight based on 100 parts by weight of the starting mixture. If the amount of the organic solvent is less than 10 parts by weight, the viscosity of the resin composition obtained by polymerization becomes too large, and the polymerization does not proceed uniformly. If it exceeds 400 parts by weight, the molecular weight becomes too small, and the dispersion stability of the obtained resin composition deteriorates.
  • organic solvent used for adjusting the viscosity at the time of polymerization various organic solvents not included in the above-mentioned hydrogen-bonding organic solvent are preferable, and 50% by weight or less of the hydrogen-bonding solvent is more preferable. Can be used in an amount of 30% by weight or less. If the content is more than 50% by weight, the solvation effect of the hydrogen bonding solvent may be lost, and the polymerization reaction may not proceed uniformly.
  • solvents examples include aromatic hydrocarbons such as benzene, tonolene, xylene, etc., esters such as ethyl acetate, butyl acetate, methoxypropanol, methyl ethyl ketone, methyl isobutyl ketone, etc. Such ketones are mentioned.
  • the monomer mixture is added to the heated reactive water-insoluble resin or the reactive water-insoluble resin solution, and the resulting starting mixture is polymerized in the presence of a polymerization initiator.
  • the polymerization is preferably carried out for 1 to 8 hours, particularly for 1 to 4 hours.
  • the monomer mixture and the polymerization initiator are simultaneously added dropwise to the reactive water-insoluble resin solution for 0.5-5 hours, preferably 1-3 hours, and then 0-4 hours, preferably Maintain the polymerization temperature for 1-2 hours.
  • the polymerization temperature is preferably a temperature lower than the boiling point of the organic solvent used. If the polymerization temperature exceeds the boiling point, the solvated reactive functional group may desolvate, causing a heterogeneous reaction such as gelation.
  • the monomer mixture used in the present invention comprises a reactive ethylenically unsaturated monomer, an ethylenically unsaturated monomer having a carboxyl group, and other ethylenically unsaturated monomers.
  • the reactive ethylenically unsaturated monomer refers to an ethylenically unsaturated monomer having a functional group that reacts with the functional group of the reactive water-insoluble resin. This varies depending on the type of reactive water-insoluble resin used.
  • aminoplast when aminoplast is used as the reactive water-insoluble resin, an ethylenically unsaturated monomer having a hydroxyl group is used.
  • an epoxy resin is used as the reactive water-insoluble resin, an ethylenically unsaturated monomer having a carboxyl group or a hydroxy group is used.
  • an isocyanate resin is used as the reactive water-insoluble resin, an ethylenically unsaturated monomer having a hydroquinyl group or a hydroxyl group is used.
  • the amount of the ethylenically unsaturated monomer having a functional group to be used is determined based on the functional group equivalent of the reactive water-insoluble resin.
  • the preferred use amount is 0.1 to 50 times the functional group equivalent of the resin. If the ratio is less than 0.1, no cross-linking occurs when the obtained aqueous dispersion is cured, so that the curability when the dispersion is cured as a film is reduced. I do. If the ratio is 50 times or more, a reaction may occur between the monomer and the water-insoluble resin at the time of polymerization even when a predetermined hydrogen bonding organic solvent is used, and the polymerization may not proceed uniformly.
  • Examples of the reactive ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid, and itaconic acid, and their half-esterified products, ethyl maleate, Examples include ethyl fumarate, ethyl itaconic ester, mono (meth) acryloyl quinethyl ester succinate and mono (meth) acryloyl quinethyl ester phthalate, and mixtures thereof.
  • the ethylenically unsaturated monomer having a carboxyl group also plays a role in providing water-dispersibility to the reactive water-insoluble resin in neutralization.
  • the ethylenically unsaturated monomer having a carboxyl group is an essential component in the water-dispersible resin composition of the present invention.
  • the styrene unsaturated monomer having a carboxyl group preferably has up to 6 carbon atoms in the molecule. This is because if the number of carbon atoms in the molecule exceeds 6, hydrophilicity is not sufficiently provided.
  • examples include (meth) acryloyl quinethyl ester and mono (meth) acryloyl oxethyl ester of phthalic acid and mixtures thereof.
  • the ethylenically unsaturated monomer having a carboxyl group is used in an amount of 2 to 90% by weight, preferably 4 to 80% by weight, and more preferably 15 to 50% by weight, based on the total amount of the monomer compound.
  • amount of the ethylenically unsaturated monomer having a carboquinol group is less than double S%, dispersibility becomes poor, and 90% by weight If the ratio exceeds the above, the polymerization may not proceed uniformly.
  • the ethylenically unsaturated group having a carboxyl group is preferably from 75 to 90% by weight, based on the total amount of the monomer mixture.
  • ethylenically unsaturated monomers that do not inhibit the water dispersibility imparted to the reactive water-insoluble resin by the carboxyl group-containing monomer and can coexist with the carboxyl group and the functional group of the reactive water-insoluble resin
  • the ethylenically unsaturated monomer having an amide group preferably has up to 12 carbon atoms in the molecule. If the number of carbon atoms in the molecule exceeds 12, the obtained resin will not be provided with good hydrophilicity.
  • acrylamide, methacrylamide, N-isopropylacrylamide, N-butylacrylamide, N, N-dibutylacrylamide or hydroquinmethylacrylamide, (Meth) acrylamides such as methoxymethyl acrylamide and butoxymethyl acrylamide are used.
  • Preferred (meth) acrylamides are acrylamide, methacrylamide and mixtures thereof.
  • the ethylenically unsaturated monomers having amide groups are used in an amount of 1 to 50% by weight, preferably 10 to 30% by weight, based on the total amount of the monomer mixture. If the amount of the ethylenically unsaturated monomer having an amide group is less than 1% by weight, the dispersibility becomes poor, and if it exceeds 50% by weight, the polymerization may not proceed uniformly.
  • ethylenically unsaturated monomers other than the ethylenically unsaturated monomer having an amide group do not inhibit the water dispersibility of the resin composition obtained after the polymerization. It is not particularly limited as long as it is one.
  • Styrene polymethylstyrene, acrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate and 2-ethyl hexyl acrylate) and methacrylates (eg, methyl methacrylate, methacrylic acid)
  • Non-functional monomers such as ethyl acrylate, butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, 2-ethylhexyl methacrylate, and propyl methacrylate) are other ethylenically unsaturated monomers. Can be used.
  • the non-functional monomer is used in an amount of 10 to 93% by weight, preferably 30 to 90% by weight, based on the total amount of the monomer mixture. If the amount of the nonfunctional monomer is less than 10% by weight, the polymerization does not proceed uniformly, and if it exceeds 93% by weight, the dispersibility is poor.
  • the above-mentioned monomer mixture comprising a reactive ethylenically unsaturated monomer, a carboxyl group-containing ethylenically unsaturated monomer and other ethylenically unsaturated monomers is preferably from 5 to 95% by weight, based on the total amount of the starting mixture. Is used in an amount of 5 to 75% by weight, more preferably 5 to 45% by weight.
  • the polymerization initiator used in the present invention is not particularly limited as long as it is generally used as a radical polymerization initiator, and examples thereof include organic peroxides such as benzoyl peroxide, t-butylperoxide and cumenehydroxide, and azobissilane. Examples include valazoic acid and azo compounds such as azobisisobutyronitrile.
  • the resin composition obtained after completion of the polymerization preferably has an acid value of 10 to 300, particularly preferably 20 to 200. If the acid value is less than 10, the water dispersibility may be poor. If the acid value is more than -300, the viscosity during water dispersion may be too high, and the dispersing operation may not be performed. Acid value is to increase or decrease the amount of monomer having carboxyl group 7/6
  • a neutralizing agent is added to neutralize at least a part of the carboxyl groups contained in the resin composition. Thereby, water dispersibility is imparted to the resin composition, and the water dispersible resin composition of the present invention is obtained.
  • the neutralizing agent used in the present invention is not particularly limited as long as it is used by those skilled in the art to neutralize the acidic group contained therein when preparing the aqueous or water-dispersible resin composition.
  • organic amines such as monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine, jetanolamine and dimethylethanolamine, and sodium hydroxide
  • inorganic bases such as potassium hydroxide and lithium hydroxide.
  • the amount of the neutralizing agent can be used in the methods commonly used by those skilled in the art for preparing an acid-functional water-dispersible resin, but is preferably based on the resin solid content before neutralization.
  • the obtained self-crosslinkable water-dispersible resin composition of the present invention is well dispersed in an aqueous medium to form a stable dispersion.
  • the aqueous medium refers to water or a mixed solution of water and a water-miscible solvent.
  • water and the water-miscible organic solvent are defined as 100/0 to 60/100 from the viewpoint of reducing the amount of the volatile organic solvent contained in the composition. It is preferable to mix them in a weight ratio of 40, especially 100/0 to 80/20.
  • Preferred water-miscible organic solvents include those described above as the organic solvent during the polymerization step.
  • a self-crosslinkable water-dispersible resin composition exhibiting good dispersion stability can be obtained by blending the obtained aqueous resin dispersion with a pigment and other additives well known to those skilled in the art.
  • the self-crosslinkable water-dispersible resin composition thus obtained may be used as it is, or the solid content may be adjusted, or an appropriate component may be further added.
  • an aqueous coating composition can be obtained.
  • a crosslinking agent known to those skilled in the art to bridge functional groups or carboquinol groups present in the dispersed resin may be added as an auxiliary curing agent.
  • at least one selected from the group consisting of an epoxy resin, an aminoblast, a fuanol resin, and a block isocyanate can be used.
  • the phenolic resin is a phenolic catalyst comprising at least one phenolic component selected from the group consisting of phenolic, phenolic having an alkyl substituent having 1 to 12 carbon atoms, bisphenol A and bisphenol F and formaldehyde. And a novolak-type phenol resin obtained by reacting the above-mentioned phenol component with formaldehyde with an acid catalyst.
  • phenolic resins are commercially available and include, for example, Shownol BKM-2620, C-908. CS-394, CKS-380. ARL-080 (all manufactured by Showa Polymer Co., Ltd.) and the like.
  • the block isocyanate a resin obtained by blocking an isocyanate resin used as a reactive water-insoluble resin with various active hydrogen-containing compounds, for example, an alcohol, an amine, an oxime or the like can be used.
  • a pigment, a modifier and the like may be added.
  • the pigment an appropriate amount of an appropriate inorganic pigment, organic pigment or metal pigment (for example, aluminum pigment) can be used.
  • examples of the modifying agent include an ultraviolet ray inhibitor, an antifoaming agent, and a surface preparation agent.
  • the known volimar emulsion resin, water-soluble acryl resin, polyester, alkyd resin, and epoxy resin of the present invention can also be used. It can be added to the citrus water-dispersible resin composition.
  • the aqueous coating composition of the present invention can be applied to a substrate to form a coating film.
  • the object to which the aqueous coating composition of the present invention is applied is not particularly limited, and examples thereof include metal materials such as iron and aluminum, plastics, paper, and wood.
  • the method of application is not limited, and can be applied by a conventionally known method such as spray coating, roll coater coating, electrodeposition coating, immersion coating, or brush coating.
  • a multilayer coating film having a good appearance can be formed.
  • An example of a preferred multilayer coating is shown in FIG.
  • a multilayer coating film 1 is provided on an object 2 such as a car body.
  • a base layer such as an electrodeposition layer and an intermediate coating layer is provided on the surface of the work 2, but is not shown here.
  • the multilayer coating film 1 is mainly composed of a base coating film 3 provided on the workpiece 2 and a clear coating film 4 provided on the base coating 3.
  • Multi-layer coatings are applied in a so-called two-coat / one-bake method, in which a base paint is applied, and then the clear paint is applied repeatedly without curing, and the base paint and clear paint are combined and cured. Preferably, it is formed.
  • the base coating film 3 is formed by brushing, spraying, electrostatic coating, flowing coating, immersion coating, and roller coating using the aqueous coating composition of the present invention containing a pigment and the above-mentioned usual additives. It is generally formed to a thickness of 10-30, preferably 10-20 m, by methods well known to those skilled in the art. If necessary, the base coating 3 can be treated before forming the clear coating 4 thereon, in order to obtain a good-looking multi-use coating 1. For example, the appearance of the multi-layer coating film 1 obtained by performing the so-called preheat treatment in which the provided base coating film 3 is heated at 50 to: L00 ° C for 2 to 3 minutes is further improved.
  • the clear coating 4 is generally made to a thickness of 20 to 80 m, preferably 20 to 60 ⁇ , using a solvent-based or aqueous so-called clear coating known to those skilled in the art, in the same manner as the base coating 3. Formed.
  • the clear coating film 4 is formed using a clear coating prepared with the aqueous coating composition of the present invention.
  • the clear coating film 4 is formed by using an aqueous clear coating material, it is not necessary to use a solvent for forming the multilayer coating film 1, so that the problem of environmental pollution hardly occurs.
  • a clear paint containing the water-dispersible resin composition of the present invention is used as the clear paint, the workability, appearance and adhesion of the coating are further improved in the case of ⁇ .
  • the base coating film 3 and the clear coating film 4 are hardened to obtain the multilayer coating film 1. Curing is performed by heating at a temperature of 100 to 200 ° C for 15 to 60 minutes.
  • an electrodeposition coating film having good anticorrosion properties can be formed.
  • preferable coating film forming methods include water-dispersible resin compositions and water-based paint compositions containing pigments, such as steel sheets used for automobile bodies and aluminum steel sheets used for aluminum sashes. After immersing the coating, compressing it as an electrode and precipitating the resin composition, baking and curing at 80 to 150 ° C for 5 to 30 minutes can be mentioned. The thickness of the coated film is adjusted depending on the energizing time and the current value, but is preferably 5 to 40 microns from the viewpoint of the corrosion resistance of the steel sheet.
  • a monomer mixture consisting of 30 parts of styrene, 17 parts of ethyl acrylate, 15 parts of 2-methacrylic acid, 15 parts of hydroquinethyl, 10 parts of butyl acrylate, and 28 parts of methacrylic acid, and (azosopthyronitrile) 2
  • the department was charged.
  • the monomer mixture and the initiator were added dropwise over 3 hours while maintaining the temperature at 75 ° C. After the dropwise addition, the mixture was kept at 75 for 2 hours.
  • the obtained resin solution was transparent.
  • 29 parts of dimethylethynolamine and 569 parts of deionized water were added and dissolved to obtain an opaque and sticky resin solution.
  • the obtained resin solution had a solid content of 34% and an acid value of the solid content of 53.8.
  • a dropping funnel was charged with a monomer mixture comprising 30 parts of styrene, 17 parts of ethyl acrylate, 15 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 28 parts of methacrylic acid and 3 parts of azoisobutyronitrile. While maintaining the temperature at 90 °, the dropping of the monomer mixture and the initiator was started at such a speed that the dropping was completed in 3 hours. And the polymerization operation could not be performed.
  • Mycoat 504 Melamine resin manufactured by Mitsui Cyanamid, 100% solids
  • toluene (boiling point ⁇ ) C) 50 parts were charged and the temperature was raised to 110 ° C.
  • a monomer mixture consisting of 20 parts of styrene, 20 parts of 2-ethylhexyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 20 parts of butyl acrylate, and 20 parts of methacrylic acid was added to the dropping funnel and PB0 (Chem. 3 parts of polymerization initiator “butyl butyl 0 J) were charged.
  • the dropping of the monomer mixture and the initiator was started at such a speed that the dropping was completed in 3 hours while maintaining the temperature at 90 ° C.
  • the contents of the kolben began to become cloudy, and one hour after the start, solids were deposited on the inner wall of the kolben and on the stirrer, preventing uniform polymerization.
  • Evolat 4000 made by Kyozhu Oil, Epoxy resin, Epoxy equivalent: approx. 250
  • a dropping funnel was charged with a monomer mixture consisting of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid, and 3 parts of PB0.
  • the monomer mixture and the initiator were added dropwise over 3 hours while maintaining the temperature at n5 ° C. After the dropwise addition, the temperature was further maintained at 115 ° C for 2 hours.
  • the obtained resin solution was transparent.
  • the product was diluted with deionized water using a No. 4 hood cup for 30 seconds, and then left standing at 40 ° C. for 10 days.
  • HEMA (Crylic acid 2 Hishi EA: 7 K! Jrt acid i-tyl TEA: Lietylamine BP0: Zoy M-Sai Necite '
  • a 300-part Evolat 4000 (made by Kyoeisha Yushi, epoxy resin, epoxy equivalent: approx. 250) and 2-metoxyl were added to a 11-hole corvette equipped with an agitator, a chamber inlet tube, a temperature controller, a condenser, and a dropping funnel. 100 parts of propanol (boiling point: 120 eC ) was charged, and the temperature was raised to 130 ° C.
  • a dropping funnel was charged with a monomer mixture composed of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid and 3 parts of PB0 '.
  • the monomer mixture and the initiator were added dropwise over 3 hours while maintaining the temperature at 13 CTC. After dropping, the temperature was kept at 130 for 2 hours. The resulting resin solution was opaque.
  • a monomer mixture consisting of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydro ⁇ -quijectyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid, and 3 parts. While maintaining the temperature at 80 ° C, the monomer mixture and the initiator were added dropwise over 2 hours. After the dropwise addition, the mixture was kept at 80 mm for 0.5 hour. The obtained resin solution was transparent.
  • the product was diluted with deionized water using a No. 4 Ford cup for 30 seconds, and then left at 40 for 10 days.
  • HEMA 2-methineuric acid i EA: Acrylic acid ⁇ ⁇ TEA: Tori I 7min ST: Styrene EHMA Crylic acid *
  • Desmodur W manufactured by Sumitomo Bayer Urethane, 4, 4 "-methylenebis (cyclohexyl isocyanate, isocyanate) provided in a 11-hole corbane equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and dropping funnel Equivalent 140) 100 parts and 100 parts of t-butyl alcohol (boiling point: 83 ° C) were charged, and the temperature was raised to 90 ° C.
  • a dropping funnel was charged with a monomer mixture consisting of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroquinethyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid, and 3 parts of AIBN. While maintaining the temperature at 90 ° C., the dropping was started at such a speed that the dropping of the monomer mixture and the initiator was completed in 2 hours. However, 15 minutes after the start of the dropwise addition, the contents of the kolben gelled, making it impossible to stir the mixture, making it impossible to continue the polymerization reaction.
  • Desmodur W manufactured by Sumitomo Bayer Urethane Co., Ltd., 4, 4'-methylenebiscyclohexane isocyanate (11), equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and dropping funnel 100 parts of an isocyanate equivalent and 100 parts of toluene (boiling point lirC) were charged, and the temperature was raised to 80 ° C.
  • a dropping funnel was charged with a monomer mixture consisting of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroquinethyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid, and 3 parts of AIBN. While maintaining the temperature at 80 ° C, the dropwise addition was started at such a speed that the addition of the monomer mixture and the initiator was completed in 2 hours. However, 10 minutes after the start of the dropwise addition, the contents of the kolben gelled and became unable to stir, making it impossible to continue the polymerization reaction.
  • a dropping funnel was charged with 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid, and 3 parts of PB03. While keeping the temperature at 11 C, In 3 hours, the monomer mixture and the initiator were added dropwise. After the dropwise addition, the temperature was further maintained at 115 ° C for 2 hours. The obtained resin solution was transparent. The solid content of the obtained resin solution was 49.8%, and the acid value of the solid content was 130.
  • t-butyl alcohol (boiling point: 83 ° C) was charged to 11 corbens equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and dropping funnel, and the temperature was raised to 80 ° C.
  • a dropping funnel was charged with a monomer mixture consisting of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid, and 3 parts of AIBN '.
  • the monomer mixture and the initiator were added dropwise over 2 hours while maintaining the temperature at 80 ° C. After the dropwise addition, the mixture was further kept at 8 CTC for 0.5 hour.
  • the obtained resin solution was transparent.
  • the solid content of the obtained resin solution was 50%, and the acid value of the solid content was 130.
  • Example 2 The aqueous resin dispersion obtained in Example 1 was diluted with deionized water with a No. 4 feed force for 30 seconds. The resulting diluted solution was left standing at 40 ° C for 10 days and visually evaluated. No change in appearance such as sedimentation occurred. The fall time of this stored solution in a No. 4 Ford cup was measured. As a result, the viscosity was 32 seconds, and the viscosity increase by the aging test was 2 seconds.
  • the diluent was applied to an iron plate using a Barco overnight to a film thickness of 40 microns, and the coating film obtained by baking at 140 ° C for 20 minutes was evaluated by the following operation.
  • the good gloss of the coating film indicates that its transparency and smoothness are good.
  • rubbing test is a test to expand the coating film by MEK, apply mechanical load such as gauze friction, and scratch it, and easily check the curability of the coating film and the resistance to mechanical load. Therefore, the absence of any change in the coating as a result of this test indicates that the coating has excellent curability and mechanical strength.
  • the Na ⁇ H spot test is a simple test of the resistance of the coating film to water, and as a result of this test, no change in the coating film is observed. It shows that the properties are good.
  • the iron plate on which the resin was applied was measured at a reflection angle of 2 ( ⁇ ) using a digital bending angle altimeter “UGV-5K” (manufactured by Suga Test Instruments Co., Ltd.).
  • Example 24 The dispersions obtained in Examples 2 to 14 were diluted with water in the same manner as in Example 15, and the diluted liquids obtained in the same manner as in Example 15 were evaluated.
  • Example 24 to 286 parts of the aqueous resin dispersion obtained in Example 10, 6 parts of Shonor CKS-394 (Showa Polymer Co., Ltd., a resole type phenol resin) was added, and the mixture was added with deionized water. No. 4 Ford cup diluted to 30 seconds was used.
  • a diluent was obtained in the same manner as in Example 15, except that the resin mixture obtained in Production Examples 4, 5, and 6 was used, and 2-methoxib D-Panol was used instead of deionized water. This was evaluated in the same manner as in Example 15, and the results obtained are shown in Table 4.
  • Example I No change + 2 150> 100 No change Example 23 No change 10 3 143 84 Stained Example 24 No change + 2 1 12> 100 No change Example 25 No change 1 1 147> 100 No change Example 26 No change + 4 150> 10D No change Example 27 No change + 5 147> 100 No change Example 28 No change + 4 153 77 No change Comparative example 10 No change -1- 1 1 125 70 e example ⁇ ⁇ no change + 20 109 68 moment ratio example ⁇ t gelation M undetermined 100 75 stain
  • Water-dispersible resin composition capable of forming a coating film having excellent transparency, smoothness, chemical resistance, water resistance and mechanical strength, and realizing an aqueous coating material having good coating workability and dispersion stability, and a method for producing the same was provided.

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  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne une composition de résine hydrodispersable à réticulation spontanée, capable de constituer un matériau de revêtement à l'eau formant un film de revêtement remarquable en raison de sa transparence, de son lissé et de sa résistance aux contraintes chimiques et mécaniques. Cette résine présente une excellente aptitude à l'application ainsi qu'une stabilité en dispersion satisfaisante. Le procédé d'obtention, qui comporte plusieurs opérations, consiste d'abord en une polymérisation des radicaux d'un mélange initial en présence d'un amorceur et d'une liaison hydrogène formant un solvant organique, et ce, à une température égale ou inférieure au point d'ébullition du solvant organique. Le mélange initial est constitué: (a) pour 5 % à 95 % de sa masse d'une résine de réaction non hydrosoluble contenant un groupe fonctionnel de réaction et dont la solubilité dans l'eau est égale ou inférieure à 1, et (b) pour 5 % à 95 % de sa masse d'un mélange monomère composé, pour 0,5 % à 50 % de sa masse d'un monomère de réaction (1) insaturé en éthylène et portant un groupe fonctionnel capable de réagir avec le groupe fonctionnel mentionné en (a), pour 1 % à 40 % de sa masse d'un monomère (2) insaturé en éthylène et portant un groupe carboxyle, et pour 10 % à 98 % de sa masse d'un autre monomère (3) insaturé en éthylène, la masse totale des composants (1) à (3) ne devant toutefois pas excéder 100 %. Le procédé consiste enfin à ajouter à la composition de résine résultante un agent de neutralisation ayant pour objet de neutraliser la composition de résine considérée.
PCT/JP1997/001132 1996-04-02 1997-04-02 Composition de resine hydrodispersable a reticulation spontanee Ceased WO1997036936A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP7992496 1996-04-02
JP8/79924 1996-04-02

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WO1997036936A1 true WO1997036936A1 (fr) 1997-10-09

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130086008A (ko) * 2012-01-20 2013-07-30 테사 소시에타스 유로파에아 폴리아크릴레이트용 가교제-촉진제 시스템
WO2020100790A1 (fr) * 2018-11-13 2020-05-22 昭和電工株式会社 Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5319394A (en) * 1976-08-09 1978-02-22 Nippon Paint Co Ltd Thermosetting resin compositions and coating compositions containing same
JPH08231616A (ja) * 1994-12-27 1996-09-10 Asahi Chem Ind Co Ltd 硬化性水性樹脂組成物

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5319394A (en) * 1976-08-09 1978-02-22 Nippon Paint Co Ltd Thermosetting resin compositions and coating compositions containing same
JPH08231616A (ja) * 1994-12-27 1996-09-10 Asahi Chem Ind Co Ltd 硬化性水性樹脂組成物

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130086008A (ko) * 2012-01-20 2013-07-30 테사 소시에타스 유로파에아 폴리아크릴레이트용 가교제-촉진제 시스템
JP2013147653A (ja) * 2012-01-20 2013-08-01 Tesa Se ポリアクリレート用の架橋剤−促進剤系
WO2020100790A1 (fr) * 2018-11-13 2020-05-22 昭和電工株式会社 Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse
JPWO2020100790A1 (ja) * 2018-11-13 2021-09-02 昭和電工株式会社 水性樹脂エマルジョン及びその製造方法、並びに水性樹脂組成物

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