[go: up one dir, main page]
More Web Proxy on the site http://driver.im/

WO1997036936A1 - Self-cross-linkable water dispersible resin composition - Google Patents

Self-cross-linkable water dispersible resin composition Download PDF

Info

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
Authority
WO
WIPO (PCT)
Prior art keywords
water
weight
parts
resin
reactive
Prior art date
Application number
PCT/JP1997/001132
Other languages
French (fr)
Japanese (ja)
Inventor
Masakazu Watanabe
Satoshi Suzuki
Hiroshi Miwa
Teruaki Kuwajima
Original Assignee
Nippon Paint Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Paint Co., Ltd. filed Critical Nippon Paint Co., Ltd.
Publication of WO1997036936A1 publication Critical patent/WO1997036936A1/en

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • C09D133/04Homopolymers or copolymers of esters
    • C09D133/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062Copolymers with monomers not covered by C09D133/06
    • C09D133/066Copolymers 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.

Landscapes

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

Abstract

A self-cross-linkable water dispersible resin composition capable of realizing a water-base coating material which forms a coating film having excellent transparency, smoothness, chemical resistance and mechanical strength, ensures excellent applicability and has a satisfactory dispersion stability is produced by the process comprising the steps of: conducting a radical polymerization of a starting mixture in the presence of a polymerization initiator and a hydrogen bond forming organic solvent at or below the boiling point of the organic solvent, the starting mixture comprising: (a) 5 to 95 % by weight of a reactive water insoluble resin containing a reactive functional group and having a water solubility of 1 or below, and (b) 5 to 95 % by weight of a monomer mixture comprising 0.5 to 50 % by weight of a reactive ethylenically unsaturated monomer having a functional group capable of reacting with the above functional group (1), 1 to 40 % by weight of an ethylenically unsaturated monomer having a carboxyl group (2) and 10 to 98.5 % by weight of another ethylenically unsaturated monomer (3) (provided that the total of components (1) to (3) is 100 % by weight), and adding a neutralizer to the resultant resin composition to thereby neutralize the same.

Description

明細書  Specification
自己架橋性水分散性樹脂組成物  Self-crosslinkable water-dispersible resin composition
発明の属する技術分野  Technical field to which the invention belongs
本発明は水分散性樹脂組成物に関し、 特に、 塗料組成物に好適に用いう る水分散性樹脂組成物に関する。  The present invention relates to a water-dispersible resin composition, and particularly to a water-dispersible resin composition suitably used for a coating composition.
従来の技術  Conventional technology
塗料は染料及び顔料のような着色剤とこれを塗装面に固着するバインダ 一とこれらを均一に被覆するための液体媒体とを一般に含む。 バインダー は高分子量のポリマーもしくは樹脂であるので本来非水溶性のものが多い が、 このような非水溶性バインダ一を含有する塗料にはシンナーのような 有機溶媒が液体媒体として主に用いられてきた。  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.
しかし、 近年では、 環境に悪影響を与えず、 作業者に無害な水性塗料へ の需要が高まっている。 これまでにも、 多くの水溶性または水分散性塗料 が報告されてきたが、 水溶性塗料には本質的に耐水性に劣る欠点が有り、 水分散性塗料には塗料組成物の安定性が悪い欠点がある。  However, in recent years, there has been an increasing demand for water-based paints that do not adversely affect the environment and are harmless to workers. Many water-soluble or water-dispersible paints have been reported so far, but water-soluble paints have inherently poor water resistance, and water-dispersible paints have poor stability of the paint composition. There are bad drawbacks.
水分散性塗料の安定性不良の原因は、 主に水分散性塗料に用いる水分散 性樹脂組成物の分散安定性が乏しいことにある。  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.
例えば、 特開昭 52- 47029号公報には、 アルコキシメチルアクリルアミ ド と a , β - : aチレン性不飽和カルボン酸とその他の共重合性ェチレン性不飽 和モノマーとの混合物を水溶性樹脂の存在下重合して得られる共重合体を 中和した水分散性樹脂組成物が開示されている。 しかしながら、 この系で は水溶性樹脂と共重合体との相溶性が不十分なので得られる樹脂組成物は 水分散安定性に劣る。 そのために、 これを用いた塗料は塗装作業性に劣り、 タレが生じ易い。 さらに、 得られる塗膜は透明性、 平滑性、 耐薬品性、 耐 水性及び機械強度に劣る。 また、 特開平 3- 504138号公報には、 カルボキシル基を有するアクリルモ ノマーを含有するモノマー混合物とカルボキシル基を有するァクリルモノ マーを含有するモノマー混合物とを交互に重合し中和することにより得ら れる水分散性樹脂組成物が開示されているが、 酸価を持つポリマーと持た ないポリマーとの相溶性が不十分なので、 この樹脂組成物は水分散安定性 に劣る。 そのために、 これを用いた塗料では構造粘性が十分に発現しない c また、 耐薬品性、 耐水性に劣る。 For example, Japanese Patent Application Laid-Open No. 52-47029 discloses that a mixture of an alkoxymethylacrylamide, an a, β-: a ethylenically unsaturated carboxylic acid and another copolymerizable ethylenically unsaturated monomer is used as a water-soluble resin. Discloses a water-dispersible resin composition obtained by neutralizing a copolymer obtained by polymerization in the presence of water. However, in this system, since the compatibility between the water-soluble resin and the copolymer is insufficient, 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. Furthermore, the resulting coating film is inferior in transparency, smoothness, chemical resistance, water resistance and mechanical strength. 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.
発明の要旨  Summary of the Invention
本発明は上記従来の問題を解決するものであり、 その目的とするところ は、 透明性、 平滑性、 耐薬品性、 耐水性及び機械強度に優れる塗膜を形成 し、 良好な塗装作業性及び分散安定性を有する水性塗料を実現しうる水分 散性樹脂組成物及びその製造方法を提供することにある。  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.
本発明は、 (a)官能基を含み水に対する溶解度が 1以下である反応性非 水溶性榭脂 5〜95重量%、 及び  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
(b) (1)該官能基と反応する官能基を有する反応性エチレン性不飽和モノ マー 0. 5〜50重量%と、 (2)カルボキシル基を有するェチレン性不飽和モノ マー 1〜40重量%と、 (3)その他のェチレン性不飽和モノマー 10〜98. 5重 量%とからなる、 モノマー混合物 (但し、 成分ひ)〜(3)の合計量は 100重量 %である。 )5 ~95重量%、  (b) (1) 0.5 to 50% by weight of a reactive ethylenically unsaturated monomer having a functional group which reacts with the functional group, and (2) 1 to 40% by weight of an ethylenic unsaturated monomer having a carboxyl group %, And (3) 10 to 98.5% by weight of the other ethylenically unsaturated monomer, and the total amount of the monomer mixture (wherein the components (1) to (3)) is 100% by weight. ) 5 to 95% by weight,
を含有する出発混合物を、 重合開始剤及び水素結合性有機溶媒の存在下に その有機溶媒の沸点以下の温度でラジカル重台する工程;及び Radically stacking a starting mixture containing at a temperature below the boiling point of the organic solvent in the presence of a polymerization initiator and a hydrogen-bonding organic solvent; and
得られる樹脂組成物を、 中和剤を加えることにより中和する工程: を包含する自己架橋性水分散性樹脂組成物の製造方法を提供するものであ り、 そのことにより上記目的が達成される。  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. You.
図面の簡単な説明 図 1は、 本発明の塗料組成物を用いて形成した多層塗膜の例を示す断面 図である。 BRIEF DESCRIPTION OF THE FIGURES FIG. 1 is a cross-sectional view showing an example of a multilayer coating film formed using the coating composition of the present invention.
1…多層塗膜  1 ... Multilayer coating
2…被塗装物  2 ... workpiece
3…ベース塗膜  3 ... Base coating
4…クリヤー塗膜  4 ... Clear coating
発明の実施の形態  Embodiment of the Invention
本発明の方法における好ましい態様では、 まず、 反応性非水溶性樹脂単 独、 好ましくは反応性非水溶性樹脂を有機溶媒に溶解した溶液をその有機 溶媒の沸点以下の温度、 具体的には、 約 60~150°C、 好ましくは S0〜12(TC に加熱する。  In a preferred embodiment of the method of the present invention, first, 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.
反応性非水溶性樹脂とは、 官能基を含み水 100gに対し 1 g以下の溶解性 を有する榭脂をいう。 非水溶性榭脂を用いることにより水溶性樹脂を用い た場合と比絞して耐水性に優れる塗膜が提供され、 またこれに含まれる官 能基が架橘するのでより堅牢な塗膜、 すなわち耐薬品性及び機械強度に優 れる塗膜が提供される。  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. 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.
この反応性非水溶性樹脂は、 重合温度において不揮発性液状であつて塗 料用バインダ一として当業者に用いられるものであれば特に限定されない が、 好ましくは分子量 300〜100000、 より好ましくは 1000~50000を有する c 分子量が 300を下回ると樹脂が揮発性となり加熱により失われる場合が生 じ、 100000を上回ると重合温度においても液化しない場合が生じる。 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.
また、 官能基はヒ ドロキンメチル基またはアルコキンメチル基で置換さ れたァミノ基、 エポキシ基及びイソシァネート基等が好ましい。 これらの 官能基は重合温度、 重合溶剤種及び溶剤量等の選択により重合時の反応性 を任意に制御することができ、 重合時の不均一化を起こさない上に、 通常 の乾燥条件で架橘させることができ、 堅牢な硬化膜が得られるからである 尚、 ここで液状とは必ずしも反応性非水溶性樹脂が単独で重合温度にお いて液体でなければならないことを恵味するものではなく、 種々の有機溶 媒から適宜選択される重合媒体に溶解されて液状であれば足りる。 Further, 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.
一般に、 アミノブラスト、 エポキシ樹脂及びイソシァネート樹脂、 およ びヒ ドロキシメチルァミノ基、 アルコキシメチルァミノ基、 エポキシ基ま たはィソシァネート基を含むモノマーを共重合したァク リル樹脂等が本発 明に好ましく用いられるが、 アミノブラスト樹脂、 エポキシ樹脂及びイソ シァネー 卜樹脂が特に好ましい。 これらは樹脂の主鎖骨格に反応性官能基 を有することから、 得られた水性樹脂分散体の硬化時にァクリル榭脂と反 応して得られる塗膜は、 ァク リル骨格とこれらの非ァクリル樹脂骨格を交 互に持つという、 高分子の大きさを単位とする規則的な構造を有すること ができる。 このため、 得られる塗膜は、 耐すりきず性、 耐衝撃性、 加工性 等の機械強度に優れるからである。  Generally, amino blast, epoxy resin and isocyanate resin, and acrylic resin obtained by copolymerizing a monomer containing a hydroxymethylamino group, an alkoxymethylamino group, an epoxy group or an isocyanate group, etc. Although clearly preferred, 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.
尚、 本発明において用いられる反応性非水溶性樹脂は、 同じ種類のもの で異なる特性値 (例えば、 分子量や官能基量) を有する樹脂を、 2以上、 混合して用いることができる。  As 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.
アミノプラス卜とは、 アミノ基を含む化合物とホルムアルデヒ ドとの縮 合反応により合成される榭脂をいう。 アミノ基を含む化合物としては、 ベ ンゾグァナミ ン及びべンゾトリアゾールのような複素環化台物、 及び尿素 等が挙げられる。  Aminoplast refers to a resin synthesized by a condensation reaction between a compound containing an amino group and formaldehyde. Examples of the compound containing an amino group include heterocyclic compounds such as benzoguanamine and benzotriazole, and urea.
本発明で用いるのに好ましいァミノブラストは、 上記ァミノ基のうち少 なくとも 50%、 好ましくは 70%が置換されているものである。 置換量が 50 %を下回ると均一な重合反応が生じないからである。 置換量が 70%以上で あると得られる分散体の安定性が特に優れる。 アミノブラストの例としては、 三井サイテック社製のサイメル 303、 サ ィメル 370、 サイメル 325、 サイメル 712、 サイメル 701、 サイメル 235、 サ ィメル 238、 サイメル 285、 サイメル 254、 サイメル 202、 マイコー 卜 506、 マイコー卜 508及びユーバン 20-N60、 及び日立化成社製のメラン 255のよう なべンゾトリアゾール骨格を有するもの;三井サイテツク社製のサイメル 1123、 マイコー ト 105、 サイメル 1128及びマイコート 130のようなべンゾグ ァナミン骨格を有するもの;及び三井サイテツク社製の UFR65及び UFR300 のような尿素骨格を有するもの:が挙げられる。 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. Examples of 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. Those having a benzotriazole skeleton such as 508 and Uban 20-N60, and Melan 255 manufactured by Hitachi Chemical; a benzoguanamine skeleton such as Cymel 1123, Mycoat 105, Cymel 1128 and Mycoat 130 manufactured by Mitsui Cytec. And those having a urea skeleton such as UFR65 and UFR300 manufactured by Mitsui Cytec.
エポキシ樹脂とは、 分子内にェポキシ基を含んでいる榭脂をいう。  Epoxy resin refers to a resin containing an epoxy group in the molecule.
本発明で用いるのに好ましいエポキシ樹脂は、 エポキシ当量が 100〜750 00、 好ましくは 100〜50000のものである。 エポキシ当量が 100を下回ると 重合反応が均一に進行しない場合があり、 75000を上回ると得られる分散 体を膜として硬化させる際の硬化性が低下する。  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.
エポキシ樹脂の例としては、 1, 6-へキサンジオールジグリシジルエーテ ル、 好ましくはトリメチロールプロパントリグリシジルエーテル、 ビスフェ ノール A-ジグリンジルエーテル及び水添ビスフヱノール A-ジグリンジルェ 一テルのようなグリシジルエーテル、 ァジビン酸、 ジグリシジルエステル、 水添フタル酸ジグリンジルエステル、 フタル酸ジグリシジルエステル及び 好ましくはトリメリツ ト酸トリグリシジルエステルのようなグリシジルェ ステル、 及び 3, 4-エポキシシクロへキンルメチル -3, 4 -エポキシシクロへ キサンカルボキシレート、 ビス- (3, 4-エポキシシク口へキンル)ァジぺー ト及びビニルンクロへキセンジ才キンドのような脂琛式ェポキシ等が挙げ られる。 ERL-42210JCC社製)、 同 4299(UCC社製)、 ェポライ 卜 1600(共栄社 油脂 Sii)及び同 4000(共栄社油脂製)、 デナコール EX- 301、 同 622、 同 512及 び同 421 (ナガセ化成社製)、 Epl004, Ep画、 Epl009、 EplOlO (油化シェル エポキシ社製)、 YD- 014、 YD-017 YD-019、 YD-7019、 YD-020N. YD-020H. YDF- 170、 YDF- 2001(以上東都化成社製)のような樹脂、 および YP- 50、 YP-5 0S、 Z¾-1449-2. ZX-1449-4(以上東都化成社製)、 ェピコ—ト 1255HX-30C油 化シェルエポキシ社製〕、 PKHH. PKHJ、 PKHC (フエノキシァソシェ一 卜)の ようないわゆるフエノキン樹脂等のような市販品も用いうる。 Examples of 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. YDF-170, YDF-2001 (all manufactured by Toto Kasei) and YP- 50, YP-500S, Z¾-1449-2. ZX-1449-4 (manufactured by Toto Kasei Co., Ltd.), Epicort 1255HX-30C manufactured by Yuka Shell Epoxy), PKHH. PKHJ, PKHC (Fenoxyso A commercially available product such as a so-called phenoquine resin such as a shell) can also be used.
イソシァネー卜樹脂とは分子内にイソシァネー 卜基を 2個以上含む樹脂 をいう。  An isocyanate resin is a resin containing two or more isocyanate groups in a molecule.
本発明で用いるのに好ましいィソシァネート樹脂は、 ィソシァネー卜当 量が 100~ 10000、 特に 100〜5000のものである。 イソシァネー 卜当量が 100 を下回ると重合反応が均一に進行しない場合があり、 10000を上回ると得 られる分歡体を膜として硬化させる際の硬化性が低下する。  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.
イソシァネー ト樹脂の例としては、 トルイジンジイソシァネ一 卜、 キシ リ レンジイソシァネート、 へキサメチレンジイソシァネート、 1, 3- (ィソ シアナ一トメチル)シク口へキサン、 ト リメチルへキサメチレンジィソシ ァネ—ト、 好ましくはジフエニルメタンジィソンァネー ト、 リ ジンジィソ シァネー 卜、 メチレン-ビス(ンクロへキシルイソシァネー ト)、 イソホロ ンジィソシァネー ト、 トリメチルへキサメチレンジィソシァネー 卜、 特に 好ましくは、 これらのイソンァネー トの三量体、 例えば、 トリ(トルイジ ンジイソシァネート)、 ト リ(へキサメチレンジイソシァネー ト)など、 ま たはこれらとポリオールとの付加物、 例えばト リメチロールプロパンと ト ルイジンジイソシァネート、 キンリ レンジイソシァネー ト、 へキサメチレ ンジイソシァネ一ト、 1, 3 -(ィソシアナ一 トメチル)シク口へキサンまたは トリメチルへキサメチレンジイソンァネー トとの 1 : 3の付加物などが挙 げられる。  Examples of isocyanate resins 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. For example, trimethylolpropane and toluidine diisocyanate, Natick DOO, to Kisamechire Njiisoshiane Ichito, 1, 3 - (Isoshiana one Tomechiru) to consequent opening hexane or trimethyl with hexamethylene diisopropyl Son § Natick sheet 1: such as 3 adduct can be mentioned up.
反応性非水溶性樹脂は出発混合物の全量を基準にして 10〜95重量%、 好 ましくは 25~95重量%、 更に好ましくは 55〜95重量%の量で用いられる。 反応性非水溶性樹脂の量が 10重量%を下回ると平滑性、 耐薬品性及び機械 δ勺強度の改善が見られない。 95重量%を上回ると塗料の分散安定性及び塗 膜の硬化性が悪くなる。 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.
重合媒体として使用するのに好ましい有機溶媒は、 いわゆる水素結合性 有機溶媒(protic organic solvent)である。 水素結合性溶剤は、 水素結合 により求該試薬を溶媒和し、 求該置換反応を阻害することができる(S. H. P ine ORGANIC CHEMISTRY McGraw-Hill(1387))ことが知られている。 従って、 反応性非水溶性榭脂の存在下、 反応性官能基を有するモノマーを重合する 際に、 樹脂とモノマーに由来する官能基間の反応を妨げることでゲル化に よる重合の不均一化を妨げることができ、 重合反応を有効に進行させるこ とができるからである。 さらに、 水素結合性溶媒は水分散時に水と水素結 合により溶媒和することにより、 樹脂の分散を促進することができるため である。 このため、 水素結合性有機溶媒量は求該試薬となるモノマー官能 基の 5当量以上であることが好ましい。 より好ましくは 10当量以上である。 尚、 水素結合性有機溶媒とは、 J . N. イスラエルァチビリ著、 「分子 間力と表面力」 (近藤保、 大島広行訳、 マグロウヒル出版、 1 9 9 1年)に 記載されるように、 電気的に陰性な原子 (酸素、 窒素、 フッ素、 塩素)と電 気的に陰性な原子と共有結合した水素原子間に生ずる、 水素原子媒介「結 合」を生ずることができるような有機溶媒、 すなわち、 桔合モーメン ト力 大きく、 かつ水素を含む結合、 例えば、 0— H (酸素水素結合)、 N— H (窒 素水素結合)、 F— H (フッ素水素結合)を含むことで近接した分子同士が 配列できるような有機溶媒をいう。  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. Further, 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. That is, 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). Refers to an organic solvent that allows the aligned molecules to be aligned.
具体的には、 メタノール、 エタノール、 プロパノール、 イ ソプ パノー ル、 エトキンエタノール、 エ トキシブロパノール及びメ トキンブロパノー ル、 n-ブタノール、 sec-ブタノール、 t-ブタノール、 2-ェチルへキサノー ル、 エチレングリコーノレ、 へキシレングリ コーノレ、 メチノレセロソノレブ、 ェ チルセ口ソルブ、 ブチルセ口ソルブ及びへキンルセ口ソルブのようなアル コール、 及びァセトアミ ド、 N-メチルァセトアミ ド及び N-メチルホルムァ ミ ドのようなアミ ドが挙げられる。 Specifically, methanol, ethanol, propanol, isopanol, ethoxyquinethanol, ethoxypropanol and methokinepropanol , N-butanol, sec-butanol, t-butanol, 2-ethylhexanol, ethylene glycolone, hexyleneglyconele, methinoresellosonolebu, ethylseolsolve, butylseolsolve, and quinlosesolve Alcohols, and amides such as acetoamide, N-methylacetamide and N-methylformamide.
特に好ましいものは、 メタノール、 エタノール、 プロパノール、 イソプ ロパノール、 n-ブタノール、 sec-ブタノール、 t-ブ夕ノール、 メチルセ口 ソルブ、 ェチルセ口ソルブ、 メ 卜キンプロパノール及びエトキンブロパノ ールのような沸点 1 5 0 °C以下のアルコールである。 これらは塗装時に迅 速に放散されるため、 硬化反応を阻害することがなく、 特に硬化性の優れ た塗膜を得ることができるためである。  Particularly preferred are those having a boiling point such as methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, t-butanol, methylseptolsolve, ethylsulfolsolve, metkinpropanol and ethokinepropanol. Alcohol below 0 ° C. This is because they are quickly released at the time of painting, so that the curing reaction is not hindered, and a coating film having particularly excellent curability can be obtained.
有機溶媒は重合時の粘度調整のためにも用いられ、 出発混合物 100重量 都に対して 10~400重量部、 特に 20〜200重量部の量で用いることが好まし い。 有機溶媒の量が 10重量部を下回ると重合して得られる樹脂組成物の粘 度が大きくなりすぎて重合が均一に進行しない。 400重量部を上回ると分 子量が小さくなりすぎて得られる樹脂組成物の分散安定性が悪化する。  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.
尚、 重合時の粘度調整のために用いられる有機溶媒としては、 上述の水 素結合性有機溶媒に含まれない各種有機溶媒も、 好ましくは水素結合性溶 媒の 5 0重量%以下、 さらに好ましくは 3 0重量%以下使用しうる。 5 0 重量%以上では、 水素結合性溶媒の溶媒和効果を坊げ、 重合反応が均一に 進行しない場合がある。  As the 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.
これらの溶媒の例としては、 ベンゼン、 トノレェン、 キシレン等のような 芳香族系炭化水素、 酢酸ェチル、 酢酸プチル、 メ トキシプロバノール等の ようなエステル、 メチルェチルケトン、 メチルイソブチルケ トン等のよう なケトンが挙げられる。 ついで、 加熱された反応性非水溶性樹脂もしくは反応性非水溶性榭脂溶 液にモノマー混合物を加え、 得られる出発混合物を重合開始剤の存在下重 合させる。 重合は 1 ~ 8時間、 特に 1〜4時間行うことが好ましい。 好ま しい態様では、 モノマー混合物と重合開始剤とを同時に反応性非水溶性榭 脂溶液に、 0. 5— 5時間、 好ましくは 1 ~ 3時間かけて滴下し、 その後、 0〜4時間、 好ましくは 1〜2時間重合温度を維持する。 重合温度は用い る有機溶媒の沸点を下回る温度とすることが好ましい。 重合温度が沸点を 越えると溶媒和された反応性官能基が脱溶媒和し、 ゲル化などの不均一化 反応を生ずることがありうるからである。 Examples of these solvents 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. Next, 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. In a preferred embodiment, 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.
本発明で用いるモノマ一混合物は、 反応性エチレン性不飽和モノマー、 カルボキシル基を有するエチレン性不飽和モノマー、 及びその他のェチレ ン性不飽和モノマーからなる。  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.
反応性ェチレン性不飽和モノマーとは、 反応性非水溶性樹脂の官能基と 反応する官能基を有するエチレン性不飽和モノマーをいう。 これは、 用い る反応性非水溶性樹脂の種類により種々異なる。  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.
例えば、 反応性非水溶性樹脂としてアミノプラストを用いる場合は、 ヒ ドロキシル基を有するエチレン性不飽和モノマーを用いる。 反応性非水溶 性樹脂としてエポキシ樹脂を用いる場合は、 カルボキシル基又はヒ ドロキ シル基を有するエチレン性不飽和モノマーを用いる。 また、 反応性非水溶 性榭脂としてィソシァネート樹脂を用いる場合は、 ヒドロキンル基又は力 ルポキシル基を有するエチレン性不飽和モノマーを用いる。  For example, when aminoplast is used as the reactive water-insoluble resin, an ethylenically unsaturated monomer having a hydroxyl group is used. When 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. When 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.
官能基を有するエチレン性不飽和モノマーの使用量は、 反応性非水溶性 樹脂の官能基当量に基づいて決定される。 好ましい使用量は、 樹脂の官能 基当量の 0. 1~50倍である。 0. 1倍以下であれば得られる水性分散体の硬化 時に架橋が生じないため、 分散体を膜として硬化させる際の硬化性が低下 する。 また、 50倍以上であれば、 所定の水素結合性有機溶媒を用いたとし ても重合時にモノマーと非水溶性榭脂間に反応が生じ、 重合が均一に進行 しない場合がある。 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.
カルボキシル基を有する反応性エチレン性不飽和モノマーの例には、 ァ クリル酸、 メタクリル酸、 エタクリル酸、 クロトン酸、 マレイン酸、 フマ ル酸及びィタコン酸及びそれらのハーフエステル化物、 マレイン酸ェチル エステル、 フマル酸ェチルエステル、 ィタコン酸ェチルエステル、 コハク 酸モノ(メタ)ァクリロイルォキンェチルエステル及びフタル酸モノ(メタ) ァクリロイルォキンェチルエステル及びこれらの混合物が挙げられる。 カルボキシル基を有するエチレン性不飽和モノマーは、 中和において反 応性非水溶性樹脂に水分散性を提供する役割も果たす。 したがって、 カル ボキシル基を有するェチレン性不飽和モノマ一は本発明の水分散性樹脂組 成物における必須の成分である。 カルボキシル基を有するヱチレン性不飽 和モノマーは分子中に炭素 6個までを有するものが好ましい。 分子中の炭 素数が 6個を上回ると親水性が良好に提供されないからである。  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. Therefore, 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.
具体的には、 ァクリル酸、 メタクリル酸、 エタクリル酸、 クロ トン酸、 マレイン酸、 フマル酸及びィタコン酸及びそれらのハ一フェステル化物、 マレイン酸ェチルエステル、 フマル酸ェチルエステル、 ィタコン酸ェチル エステル、 コハク酸モノ(メタ)ァクリロイルォキンェチルエステル及びフ タル酸モノ(メ夕)ァクリロイルォキシェチルエステル及びこれらの混合物 が举げられる。  Specifically, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid and itaconic acid and their polyesters, methyl ester maleate, ethyl ester fumarate, ethyl ester itaconate, monosuccinate Examples include (meth) acryloyl quinethyl ester and mono (meth) acryloyl oxethyl ester of phthalic acid and mixtures thereof.
カルボキシル基を有するェチレン性不飽和モノマーはモノマー泯合物の 全量を基準にして 2〜90重量%、 好ましくは 4 ~80重量%、 さらに好まし くは 15〜50重量%の量で用いられる。 カルボキンル基を有するエチレン性 不飽和モノマーの量が 2重 S %を下回ると分散性が不良となり、 90重量% を上回ると重合が均一に進行しない場合が生じる。 特に、 数平均分子量 10 000を上回るような高分子量の反応性非水溶性樹脂を、 出発混合物の 50重 量%を上回るような量で多量に用いる場合には、 カルボキシル基を有する エチレン性不飽和モノマーの Sは、 モノマー混合物の全量を基準にして、 75〜90重量%であることが好ましい。 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. When the 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. In particular, when a large amount of a high-molecular-weight reactive water-insoluble resin having a number average molecular weight of more than 10,000 is used in an amount of more than 50% by weight of the starting mixture, the ethylenically unsaturated group having a carboxyl group The S of the monomer is preferably from 75 to 90% by weight, based on the total amount of the monomer mixture.
その他のエチレン性不飽和モノマーは、 カルボキシル基含有モノマーに より反応性非水溶性樹脂に付与される水分散性を阻害せず、 カルボキシル 基及び反応性非水溶性樹脂の官能基と共存しうるものであれば特に限定さ れないが、 アミ ド基を有するエチレン性不飽和モノマーが好ましい。 アミ ド基を有するエチレン性不飽和モノマーは分子中に炭素原子 12個までを有 するものが好ましい。 分子中の炭素数が 12個を上回ると得られる樹脂に親 水性が良好に提供されない。  Other 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 There is no particular limitation so long as it is an ethylenically unsaturated monomer having an amide group. 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.
具体的には、 アク リルアミ ド、 メタクリルアミ ド、 N-イソプロピルァク リルァミ ド、 N-ブチルァクリルァミ ド、 N, N-ジブチルァクリルァミ ドまた はヒドロキンメチルァクリルアミ ド、 メ トキシメチルァクリルァミ ド及び ブトキシメチルァクリルァミ ドのような(メタ)アクリルアミ ドが用いられ る。 好ましい(メタ)ァクリルァミ ドはァクリルァミ ド、 メタクリルアミ ド 及びこれらの混合物である。  Specifically, 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.
ァミ ド基を有するエチレン性不飽和モノマーはモノマー混合物の全量を 基準にして 1〜50重量%、 好ましくは 10〜30重量%の量で用いられる。 ァ ミ ド基を有するェチレン性不飽和モノマーの量が 1重量%を下回ると分散 性が不良となり、 50重量%を上回ると重合が均一に進行しない場合が生じ る。  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.
ァミ ド基を有するエチレン性不飽和モノマー以外のその他のエチレン性 不飽和モノマーは、 重合後に得られる樹脂組成物の水分散性を阻害しない ものであれば特に限定されない。 Other 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.
スチレン、 ひ-メチルスチレン、 アク リル酸エステル(例えば、 ァク リノレ 酸メチル、 アク リル酸ェチル、 アクリル酸ブチル及びアクリル酸 2-ェチル へキシル)及びメタクリル酸エステル(例えば、 メタクリル酸メチル、 メタ クリル酸ェチル、 メタクリル酸ブチル、 メタクリル酸イソブチル、 メタク リル酸 t-ブチル、 メタクリル酸 2-ェチルへキシル及びメタクリル酸ラゥリ ル)等のような非官能性モノマーをその他のエチレン性不飽和モノマーと して用いうる。  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.
非官能性モノマーはモノマー混合物の全量を基準にして 10〜93重 S%、 好ましくは 30〜90重量%の量で用いられる。 非官能性モノマーの量が 10重 量%を下回ると重合が均一に進行せず、 93重量%を上回ると分散性不良と なる。  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.
上述の反応性エチレン性不飽和モノマー、 カルボキシル基を有するェチ レン性不飽和モノマー及びその他のェチレン性不飽和モノマーからなるモ ノマー混合物は出発混合物の全量を基準にして 5〜95重量%、 好ましくは 5〜75重量%、 更に好ましくは 5 ~45重量%の量で用いられる。  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.
本発明に用いる重合開始剤はラジカル重合開始剤として一般に用いられ るものであれば特に限定されないが、 例えば、 過酸化べンゾィル、 t -プチ ルパーォキシド及びクメンハイ ドロパーォキシドのような有機過酸化物、 ァゾビスシァノ吉草酸及びァゾビスイソブチロニトリルのような有璣ァゾ 化合物等が挙げられる。  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.
重合終了後に得られる樹脂組成物は、 酸価 10〜300、 特に 20〜200を有す ることが好ましい。 酸価が 10を下回ると水分散性が不良となる場合があり- 300を上回ると水分散時の粘度が高くなりすぎ、 分散操作が実施できない 場合がある。 酸価はカルボキシル基を有するモノマーの量を増減すること 7/ 6 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
により調節される。 Is adjusted by
ついで、 中和剤を加えて樹脂組成物中に含まれるカルボキシル基の少な くとも一部を中和する。 そのことにより樹脂組成物に水分散性が付与され て本発明の水分散性樹脂組成物が得られる。  Next, 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.
本発明に用いる中和剤は水性もしくは水分散性樹脂組成物を調製する際 にその中に含まれる酸性基を中和するために当業者に用いられるものであ れば特に限定されないが、 具体的には、 モノメチルァミ ン、 ジメチルアミ ン、 トリメチルァミ ン、 卜リエチルァミ ン、 ジイソプロビルァミ ン、 モノ エタノールァミ ン、 ジェタノールァミン及びジメチルエタノールァミ ンの ような有機ァミ ン、 及び水酸化ナトリウム、 水酸化カリウム及び水酸化リ チウムのような無機塩基類等が挙げられる。  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. Typically, organic amines, such as monomethylamine, dimethylamine, trimethylamine, triethylamine, diisopropylamine, monoethanolamine, jetanolamine and dimethylethanolamine, and sodium hydroxide And inorganic bases such as potassium hydroxide and lithium hydroxide.
中和剤の使用量は酸官能性水分散性樹脂を調製するために当業者に通常 用いられる惫で用い得るが、 好ましくは中和前の樹脂固形分を基準にして 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.
2〜30重量%、 好ましくは 5〜20重量%の量である。 It is in an amount of 2 to 30% by weight, preferably 5 to 20% by weight.
得られる本発明の自己架橋性水分散性樹脂組成物は水性媒体に良好に分 散されて安定な分散体を形成する。 水性媒体とは、 水または水と水混和性 有接溶媒との混合溶液をいう。 水と水混和性有機溶媒との混合溶液を用い る場合は、 水と水混和性有機溶媒とは、 組成物に含有される揮発性有機溶 媒量を少なくする観点より 100/0〜60/40、 特に 100/0〜80/20の重 割合で 配合することが好ましい。 好ましい水混和性有機溶媒には重合工程の際に 有機溶媒として上述したものが挙げられる。  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. When a mixed solution of water and a water-miscible organic solvent is used, 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.
得られる水性樹脂分散体に、 顔料及びその他の当業者に周知の添加剤を 配合することにより良好な分散安定性を示す自己架橋性水分散性樹脂組成 物が得られる。 このよ όにして得られた自己架橋性水分散性樹脂組成物は そのままで、 または、 固形分を調整したり、 適当な成分を更に添加するこ とにより、 水性塗料組成物を得ることができる。 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. Thus, an aqueous coating composition can be obtained.
例えば、 分散された樹脂中に存在する官能基またはカルボキンル基を架 橋するとして当業者に知られている架橋剤を補助的な硬化剤として添加し てよい。 具体的には、 エポキシ樹脂、 アミノブラスト、 フユノール樹脂及 びブロックイソシァネー卜からなる群から選択される少なくとも 1種を用 いることができる。  For example, 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. Specifically, at least one selected from the group consisting of an epoxy resin, an aminoblast, a fuanol resin, and a block isocyanate can be used.
ここで、 エポキシ榭脂およびアミノブラストについては、 反応性非水溶 性樹脂として用いるものを使用することができる。 また、 フユノール樹脂 としては、 フユノール、 炭素数 1〜12のアルキル置換基を有するフエノー ル、 ビスフェノール Aおよびビスフ ノール Fからなる群から選択される 少なくとも一種のフエノール成分とホルムアルデヒ ドとをアル力リ触媒で 反応させて得られるレゾ一ル型フヱノール榭)!旨や、 上記フヱノール成分と ホルムアルデヒ ドとを酸触媒で反応させて得られるノボラック型フヱノー ル樹脂を例示することができる。  Here, as the epoxy resin and the aminoblast, those used as reactive water-insoluble resins 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.
これらのフヱノール樹脂は市販されており、 例えば、 ショウノール BKM- 2620、 C -908. C S-394, CKS-380. ARL- 080(いずれも昭和高分子社製)等 が举げられる。 一方、 ブロックイソシァネートとしては、 反応性非水溶性 樹脂として用いるイソシァネート樹脂を、 種々の活性水素含有化合物、 例 えば、 アルコール、 ァミン、 ォキシム等でブロック化したものを用いるこ とができる。  These 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. On the other hand, as 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.
また、 顔料や改質剤等を添加してもよい。 顔料は適常の無機顔料、 有機 顔料及び金属顔料(例えば、 アルミニゥム顔料)を適当量使用することがで きる。 一方、 改質剤の例としては紫外線防止剤、 消泡剤、 表面調製剤等が 挙げられる。 この他、 公知のボリマーェマルジヨ ン榭脂、 水溶性のァクリ ル榭脂、 ポリエステル、 アルキド樹脂及びエポキシ樹脂も本発明の自己架 橘性水分散性榭脂組成物に添加しうる。 Further, a pigment, a modifier and the like may be added. As the pigment, an appropriate amount of an appropriate inorganic pigment, organic pigment or metal pigment (for example, aluminum pigment) can be used. On the other hand, examples of the modifying agent include an ultraviolet ray inhibitor, an antifoaming agent, and a surface preparation agent. In addition, 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.
本発明の水性塗料組成物は、 被塗物に塗布して、 塗膜を形成することが できる。 本発明の水性塗料組成物を適用する被^物としては特に限定され ず、 鉄やアルミニウムなどの金厲素材やプラスチック、 紙、 木材などを例 として挙げることができる。 塗布の方法についても限定されず、 スブレー 塗装、 ロールコーター塗装、 電着塗装、 浸濱塗装、 刷毛塗りなど従来知ら れた方法により、 塗布可能である。  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.
本発明の水性塗料組成物を用いて、 良好な外観を有する多層塗膜を形成 することができる。 好ましい多層塗膜の例を図 1に示す。 図 1においては、 自動車の車体のような被 装物 2の上に多層塗膜 1が設けられている。 尚、 一般に、 被塗装物 2の表面には電着層及び中塗り層のような基層が設けら れているが、 ここでは非表示とする。  Using the aqueous coating composition of the present invention, a multilayer coating film having a good appearance can be formed. An example of a preferred multilayer coating is shown in FIG. In FIG. 1, a multilayer coating film 1 is provided on an object 2 such as a car body. In general, 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.
多層塗膜 1は、 被塗装物 2上に設けられたベース塗膜 3とベース塗膜 3 上に設けられたクリヤー塗膜 4とから主に構成される。 多層塗膜は、 ベー ス塗料を塗布した後、 これを硬化させずにクリヤー塗料を重ね塗りし、 ベ ース塗料とクリヤー塗料とを合わせて硬化させるいわゆる 2コート / 1ベ ーク塗装方法により形成することが好ましい。  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.
ベース塗膜 3は、 顔料及び上記通常の添加剤等を含有する本発明の水性 塗料組成物を用いて、 刷毛塗り、 スプレー塗布、 静電塗布、 流し塗り、 浸 漬塗り及びローラ塗りのような当業者に周知の方法により、 一般に 10〜30 好ましくは 10〜20 mの厚さに形成する。 優れた外観の多雇塗膜 1を 得るために、 必要に応じて、 その上にクリヤー塗膜 4を形成する前にべ一 ス塗膜 3を処理しうる。 例えば、 設けられたベース塗膜 3を 50〜: L00°Cで 2〜3分間加熱するいわゆるプレヒー卜処理を行うことにより得られる多 層塗膜 1の外観がさらに向上する。 クリヤー塗膜 4は当業者に知られている溶剤系または水性のいわゆるク リヤー塗料を用いて、 ベース塗膜 3と同様の方法により、 一般に 20〜80 m、 好ましくは 20〜60 πιの厚さに形成する。 好ましくは、 クリヤー塗膜 4 は、 本発明の水性塗料組成物で調製したク リヤー塗料を用いて形成する。 水性のクリヤー塗料を用いてクリヤー塗膜 4を形成する場合は多層塗膜 1を形成するために溶剤を使用する必要が無くなるため、 環境汚染の問題 が生じ難い。 クリヤー塗料として本発明の水分散性樹脂組成物を含むクリ ヤー塗料を用 L、る場合は塗装の作業性、 外観及び付着性がさらに良好とな る ο 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 πι, 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. Preferably, the clear coating film 4 is formed using a clear coating prepared with the aqueous coating composition of the present invention. When 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. When 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 ο.
クリヤー塗膜 4を形成した後に、 ベース塗膜 3及びクリヤー塗膜 4を硬 化させることにより、 多層塗膜 1が得られる。 硬化は、 一股に、 100〜200 °Cの温度で 15〜60分間加熱することにより行う。  After forming the clear coating film 4, 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.
本発明の水分散性樹脂組成物を用いて、 良好な防食性を有する電着塗膜 を形成することができる。 好ましい塗膜形成方法の例としては、 水分散性 樹脂組成物および顔料を含む水性塗料組成物に自動車車体に用いられるよ うな跌鋼性镧板、 アルミサッシ用などに用いられるアルミ鋼板などの披塗 物を浸潰、 電極として通罨し、 樹脂組成物を析出させた後、 80〜: 150°Cで 5〜30分焼き付け硬化させることが挙げられる。 塗装膜厚は通電時間およ び電流値により調整されるが、 5 ~40ミクロンとすることが鋼板の防食性 の観点から好ましい。  By using the water-dispersible resin composition of the present invention, an electrodeposition coating film having good anticorrosion properties can be formed. Examples of 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.
実施例  Example
以下の実施例により本発明をさらに詳細に説明するが、 本発明はこれら に限定されない。 尚、 特に断らない限り、 「部」及び「 」は重量基準である < 実施例 1  The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” and “” are based on weight. <Example 1
(自己架橋性水性樹脂組成物) 攪拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 サイメル 254(三井サイアナミ ド社製: メラ ミ ン樹脂、 固形分 80%)300部およびエタノール(沸点 78°C)100部を仕込み、 75°Cに昇 し 。 (Self-crosslinkable aqueous resin composition) In a 11-cube equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser and dropping funnel, 300 parts of Cymel 254 (Mitsui Cyanamid: melamine resin, solid content 80%) and ethanol (boiling point 78 °) C) Charge 100 parts and raise to 75 ° C.
滴下ロートにスチレン 30部、 アクリル酸ェチル 17部、 メ夕クリル酸 2— ヒ ドロキンェチル 15部、 アクリル酸ブチル 10部、 メタク リル酸 28部からな るモノマー混合物及び (ァゾィソプチロニトリル) 2部を仕込んだ。 温 度を 75°Cに保持しながら、 3時間でモノマー混合物と開始剤を滴下した。 滴下後、 さらに 75 で 2時間保持した。 得られた樹脂溶液は透明であった。 続いて、 ジメチルェチノールアミ ン 29部および脱イオン水 569部を加え、 溶解することにより、 不透明で粘ちような樹脂溶液を得た。 得られた樹脂 溶液の固形分は 34%、 固形分酸価は 53. 8であった。  To the dropping funnel, 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. Subsequently, 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.
このものを脱イオン水を用いて No. 4フォー ド力ップで 30秒に希釈後、 40 てで 10曰間静置後の伏態を目視判定したところ、 均一であった。  This was diluted with deionized water using a No. 4 feed force for 30 seconds, and then visually examined for rest after standing for 10 days at 40 days, and found to be uniform.
実施例 2〜 5  Examples 2 to 5
メラミ ン樹脂種、 水素結合性溶剤種、 重合温度およびモノマー配合を種 々変更し同様の実験を行った。 樹脂配合および得られた結果を表 1に示す。 Similar experiments were conducted by changing the melamine resin type, hydrogen bonding solvent type, polymerization temperature, and monomer composition. Table 1 shows the resin formulations and the results obtained.
メラミン 重合溶媒 モノマー 重合開 中和剤 脱イオン S合 重合時 固形分 酸 価 Melamine Polymerization solvent Monomer Polymerization open Neutralizer Deionization S-polymerization Solid content Acid value
¾脂 始剤 水 ; 度 の状態 (%) ¾Fat Initiator Water; Degree state (%)
(固形分) (沸点: t) AA HEMA ST NBA EA EHMA (で) (Solid content) (boiling point: t) AA HEMA ST NBA EA EHMA (in)
実施例 ! メル 254 Iタノール 28 15 30 10 17 η  Example! Mel 254 I Tanol 28 15 30 10 17 η
ΑΙ DN o y ib 13 4 D .0 ΑΙ DN o y ib 13 4 D .0
1 (80重量%) (78) 2 29 1 (80% by weight) (78) 2 29
300部 50部  300 parts 50 parts
メ7ノ i>ii z一 1干ノ 20 25 20 10 25 Wt 3 o ynu 1¾口月  7 7 i> ii z 1 dry 20 25 20 10 25 Wt 3 o ynu 1
2 (60重量%) ブ 0バノ-ル 3 22  2 (60% by weight) 0 Banol 3 22
300部 (120 )50部  300 parts (120) 50 parts
ΛΕ -iVi 20 15 30 10 25 AIBN 476.3 qn 40 ΛΕ -iVi 20 15 30 10 25 AIBN 476.3 qn 40
3 (100重量 ¾) ブ Dバノ 3 20.7 3 (100 weight ¾) D Dano 3 20.7
300部 (120)100部  300 parts (120) 100 parts
実施例 J-/ 20S Bプチ JVセ ブ 20 15 30 10 25 PBO TEA 377 140 透明 28 46.6 4 (60重量%) (171) 5 18  Example J- / 20S B Petite JV Cebu 20 15 30 10 25 PBO TEA 377 140 Transparent 28 46.6 4 (60% by weight) (171) 5 18
300部 200部  300 parts 200 parts
実施例 7-O-1504 n-ブタノ-ル 20 20 20 20 20 PBO DMEA 52了 110 透明 40 32.6 5 (100重量? 50部 3 20  Example 7-O-1504 n-Butanol 20 20 20 20 20 PBO DMEA 52 Finish 110 Transparent 40 32.6 5 (100 weight? 50 parts 3 20
300部 (118)  300 parts (118)
比較例 サイ 254 Iタノ—ル 28 15 30 10 17 AIBN 90 ゲ ιΗ匕  Comparative Example Rhino 254 I ethanol 28 15 30 10 17 AIBN 90
ひ 1 (80重量%) (78) 2 Hi 1 (80% by weight) (78) 2
300部 50部  300 parts 50 parts
比較例 マイコ - 504 20 20 20 20 20 PBO 110 白濁  Comparative Example Maiko-504 20 20 20 20 20 PBO 110 Cloudy
2 (100重虽! (Ill) 3 /  2 (100 j 虽! (Ill) 3 /
300部 分離  300 parts separated
MAA: クリル酸 NBA: 7クリ 酸ブチ f DMEA:ジ ルエタノ-ルァミン  MAA: Crylic acid NBA: 7 Butyric acid butyrate f DMEA: Diethanol-lamine
HEMA: クリル酸 2-ヒ oネシ ι EA:ァク! Ι 酸 ιί TEA: リ Iチル 7ミン  HEMA: 2-acrylic acid lia EA: aq!
ST:スチレン EHMA: パクリ 酸 2-1チルへ シル ST: Styrene EHMA: 2-acrylic acid acrylate
比較例 1 Comparative Example 1
攒拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 サイメル 254(三井サイアナミ ド社製: メラミン樹脂、 固形分 80 % ) 300部およびエタノール(沸点 78°C ) 50部を仕込み、 90てに昇温 した。  In a 11-Corben equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and dropping funnel, 300 parts of Cymel 254 (Mitsui Cyanamid Co., Ltd .: melamine resin, solid content 80%) and 300 parts of ethanol (boiling point 78 ° C) ) 50 parts were charged, and the temperature was raised to 90%.
滴下ロートにスチレン 30部、 アクリル酸ェチル 17部、 メタクリル酸 2— ヒ ドロキシェチル 15部、 ァクリル酸ブチル 10部、 メタクリル酸 28部からな るモノマー混合物及びァゾィソブチロニトリル 3部を仕込んだ。 温度を 90 てに保持しながら、 3時間で滴下が完了するような速さでモノマー混合物 と開始剤の滴下を始めたところ、 滴下開始から 1時間でコルベンの内容物 がゲル化し、 攬拌不能となり、 重合操作ができなくなった。  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.
比絞例 2  Example 2
搜拌器、 窒素導入管、 温度制御装置、 コンデンサ一、 滴下ロー トを備え た 1 1コルベンに、 マイコー卜 504(三井サイアナミ ド社製メラミン樹脂、 固形分 100 % ) 300部およびトルエン(沸点 Π C ) 50部を仕込み、 110°Cに昇 温した。  A 11-corbene equipped with a stirrer, a nitrogen inlet, a temperature controller, a condenser, and a dropping funnel, 300 parts of Mycoat 504 (Melamine resin manufactured by Mitsui Cyanamid, 100% solids) and toluene (boiling point 沸) C) 50 parts were charged and the temperature was raised to 110 ° C.
滴下ロートにスチレン 20部、 メタクリル酸 2—ェチルへキンル 20部、 メ タクリル酸 2—ヒドロキシェチル 20部、 アクリル酸ブチル 20部、 メタクリ ル酸 20部からなるモノマー混合物及び PB0 (化薬ァクゾ钍製重合開始剤「パ 一ブチル 0 J) 3部を仕込んだ。 温度を 90°Cに保持しながら、 3時間で滴下 が完了するような速さでモノマー混合物と開始剤の滴下を始めたところ、 滴下開始から 0. 5時間でコルベンの内容物が白濁し始めた。 開始から 1時 間でコルベン内壁、 攪拌器に固形分が析出し、 均一な重合ができなくなつ た。  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. However, 0.5 hours after the start of the dropping, 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.
実施例 6 (自己架橋性水性榭脂組成物) Example 6 (Self-crosslinkable aqueous resin composition)
授拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 エボラィ 卜 4000(共朱社油脂製、 エポキシ榭脂、 ェポキ シ当量約 250)300部および 2—メ トキシプロバノール (沸点 120て)100部を 仕込み、 115°Cに昇温した。  300 parts of Evolat 4000 (made by Kyozhu Oil, Epoxy resin, Epoxy equivalent: approx. 250) and 2 parts per 11-corbene equipped with a stirrer, nitrogen inlet tube, temperature control device, condenser and dropping funnel 100 parts of toxicpropanol (boiling point: 120) was charged and heated to 115 ° C.
滴下ロー トにスチレン 30部、 アク リル酸ェチル 25部、 メタク リル酸 2— ヒ ドロキシェチル 15部、 アクリル酸ブチル 10部、 メタクリル酸 20部からな るモノマー混合物および PB0 3部を仕込んだ。 温度を n5°Cに保持しながら、 3時間でモノマー混合物と開始剤を滴下した。 滴下後、 さらに 115°Cで 2 時間保持した。 得られた樹脂溶液は透明であった。  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.
铳いて、 ジメチルエタノールアミ ン 20. 7部および脱イオン水 476. 3部を 加え、 溶解することにより、 不透明で粘ちよ うな樹脂溶液を得た。 得られ た榭脂溶液の固形分は 40%、 固形分酸価は 33であった。  Then, 20.7 parts of dimethylethanolamine and 476.3 parts of deionized water were added and dissolved to obtain an opaque and viscous resin solution. The solid content of the obtained resin solution was 40%, and the acid value of the solid content was 33.
このものを脱イオン水を用いて No. 4フォ一ドカップで 30秒に希釈後、 40 °Cで 10日間静置後の状態を目視判定したところ、 均一であった。  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.
実施例 7〜10  Examples 7 to 10
エポキシ樹脂種、 水素結合性溶剤種、 重合温度およびモノマー配合を種 々変更し同様の実験を行った。 樹脂配合および得られた結果を表 2に示す。 The same experiment was conducted by changing the epoxy resin type, hydrogen bonding solvent type, polymerization temperature and monomer composition. Table 2 shows the resin formulation and the results obtained.
t t
Figure imgf000023_0001
Figure imgf000023_0001
HEMA: (ククリル酸 2 ヒ シ EA: 7ク !Jrt酸 iチル TEA: リェチルァミン BP0: ゾィ M-才ネサイト'  HEMA: (Crylic acid 2 Hishi EA: 7 K! Jrt acid i-tyl TEA: Lietylamine BP0: Zoy M-Sai Necite '
ST :スチレン EHMA : メタクリル酸 2 - ιίΛ シ ft ST: Styrene EHMA: Methacrylic acid 2-ft
比铰例 3 Comparative Example 3
攬拌器、 室素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 エボラィ ト 4000(共栄社油脂製、 エポキシ樹脂、 ェポキ シ当量約 250)300部および 2—メ 卜キシプロパノール(沸点 120eC)100部を 仕込み、 130°Cに昇温した。 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.
滴下ロートにスチレン 30部、 アクリル酸ェチル 25部、 メタクリル酸 2— ヒ ドロキシェチル 15部、 アクリル酸ブチル 10部、 メ夕クリル酸 20部からな るモノマー混合物及び PB0 3部を仕込んた'。 温度を 13CTCに保持しながら、 3時間でモノマー混合物と開始剤を滴下した。 滴下後、 さらに 130 で 2 時間保持した。 得られた樹脂溶液は不透明であった。  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.
続いて、 ジメチルエタノールァミ ン 22部および脱イオン水 475部を加え たところ、 コルベンの内壁及び攪拌器に白色の固体が析出し、 均一な水性 樹脂分散液が得られなかった。  Subsequently, when 22 parts of dimethylethanolamine and 475 parts of deionized water were added, white solids precipitated on the inner wall of the Kolben and on the stirrer, and a uniform aqueous resin dispersion could not be obtained.
比較例 4  Comparative Example 4
攪拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 YD- 017(東都化成社製、 エポキシ樹脂、 エポキシ当量約 2000)300部およびトルエン(沸点 11 Ο100部を仕込み、 90°Cに昇温した。 滴下ロートにスチレン 20部、 アクリル酸ェチル 25部、 メタクリル酸 2— ヒ ドロキシェチル 25部、 ァク リル酸ブチル 10部、 メタクリル酸 20部からな るモノマー混合物及び AIBN 3部を仕込んだ。 温度を 90°Cに保持しながら、 3時間でモノマー混合物と開始剤の滴下が完了するような速さで滴下を閒 始した。 滴下開始から 0. 5時間で内容物がゲル化、 攪拌が不可能となり、 重合操作ができなくなった。  In a 11-hole corbane equipped with a stirrer, nitrogen inlet tube, temperature controller, condenser, and dropping funnel, 300 parts of YD-017 (manufactured by Toto Kasei Co., Ltd., epoxy resin, epoxy equivalent about 2000) and toluene (boiling point: 11-100 The mixture was heated to 90 ° C. A monomer mixture comprising 20 parts of styrene, 25 parts of ethyl acrylate, 25 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 20 parts of methacrylic acid was added to the dropping funnel. 3 parts of AIBN were charged, and the dropping was started at such a speed that the dropping of the monomer mixture and the initiator was completed in 3 hours while maintaining the temperature at 90 ° C. The contents were 0.5 hours after the start of the dropping. The product gelled, stirring became impossible, and the polymerization operation became impossible.
実施例: 1  Example: 1
(自己架橋性水性樹脂組成物) 攬拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 デスモジュール W (住友バイエルウレタン社製、 4. 4' - メチレンビス(シクロへキンルイソシァネー ト、 イソシァネート当量 140) 1 00部および t一ブチルアルコール(沸点 83eC ) 100部を仕込み、 80 °Cに昇温し た。 (Self-crosslinkable aqueous resin composition) A 11-corbane equipped with an agitator, a nitrogen inlet tube, a temperature controller, a condenser, and a dropping funnel was fitted with Desmodur W (manufactured by Sumitomo Bayer Urethane, 4.4'-methylenebis (cyclohexane isocyanate, Isoshianeto eq 140) 1 00 parts of t one-butyl alcohol (boiling point 83 e C) and 100 parts, was heated to 80 ° C.
滴下ロートにスチレン 30部、 アクリル酸ェチル 25部、 メタクリル酸 2— ヒ ド αキジェチル 15部、 アクリル酸ブチル 10部、 メタク リル酸 20部からな るモノマー混台物および ΑΙΒΝ 3部を仕込んだ。 温度を 80°Cに保持しながら、 2時間でモノマー混台物と開始剤を滴下した。 滴下後、 さらに 80てで 0. 5 時間保持した。 得られた樹脂溶液は透明であった。  Into the dropping funnel were charged a monomer mixture consisting of 30 parts of styrene, 25 parts of ethyl acrylate, 15 parts of 2-hydroα-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.
続いて、 ジメチルエタノールアミン 20. 7および脱イオン水 676. 3部を加 え、 溶解することにより、 不透明で粘ちような樹脂溶液を得た。 得られた 樹脂溶液の固形分は 20%、 固形分酸価は 65. 7であった。  Subsequently, dimethylethanolamine 20.7 and 677.3 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 20% and an acid value of the solid content of 65.7.
このものを脱イオン水を用いて No. 4フォードカップで 30秒に希釈後、 40 てで 10日間静置後の状態を目視判定したところ、 均一であった。  The product was diluted with deionized water using a No. 4 Ford cup for 30 seconds, and then left at 40 for 10 days.
実施例 12〜14  Examples 12 to 14
イソシァネート樹脂種、 水素結合性溶剤種、 重合温度およびモノマー配 合を種々変更し同様の実験を行った。 樹脂配合および得られた結果を表 3 に示す。 Similar experiments were conducted with various changes in the isocyanate resin type, hydrogen bonding solvent type, polymerization temperature, and monomer combination. Table 3 shows the resin formulation and the results obtained.
Figure imgf000026_0001
Figure imgf000026_0001
HEMA:メクウリル酸 2-ヒ ネシ i EA:アクリル酸 ιίΑ TEA: トリ Iチ 7ミン ST:スチレン EHMA クリル酸 シ * HEMA: 2-methineuric acid i EA: Acrylic acid ι チ TEA: Tori I 7min ST: Styrene EHMA Crylic acid *
比較例 5 Comparative Example 5
攪拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 デスモジュール W (住友バイエルウレタン社製、 4, 4" - メチレンビス(シクロへキンルイソシァネート、 ィソシァネー卜当量 140) 1 00部および t一ブチルアルコール(沸点 83°C) 100部を仕込み、 90。Cに昇温し た。  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.
滴下ロートにスチレン 30部、 アクリル酸ェチル 25部、 メタクリル酸 2— ヒ ドロキンェチル 15部、 アクリル酸ブチル 10部、 メタクリル酸 20部からな るモノマー混合物及び AIBN 3部を仕込んだ。 温度を 90°Cに保持しながら、 2時間でモノマー混合物と開始剤の滴下が完了するような速さで滴下を開 始した。 ところが、 滴下開始 15分後にコルベンの内容物がゲル化し、 攬拌 不能となり、 重合反応の继続が不可能となった。  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.
比較例 6  Comparative Example 6
攪拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロー卜を備え た 1 1コルベンに、 デスモジュール W (住友バイエルウレタン社製、 4, 4' - メチレンビスシクロへキンルイソシァネー ト(ィソシァネー ト当量 140) 100 部およびトルエン(沸点 lirC) 100部を仕込み、 80°Cに昇温した。  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.
滴下ロートにスチレン 30部、 アクリル酸ェチル 25部、 メタクリル酸 2— ヒ ドロキンェチル 15部、 ァク リル酸ブチル 10部、 メタクリル酸 20部からな るモノマー混合物及び AIBN 3部を仕込んだ。 温度を 80°Cに保持しながら、 2時間でモノマー混合物と開始剤の滴下が完了するような速さで滴下を開 始した。 ところが、 滴下開始 10分後にコルベンの内容物がゲル化し、 攪拌 不能となり、 重合反応の継続が不可能となった。  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.
製造例 1  Production Example 1
ァクリル樹脂の製造 攪拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 エタノール(沸点 78eC) 100部を仕込み、 75°Cに昇温した c 滴下ロートにスチレン 30部、 アクリル酸ェチル 17部、 メタクリル酸 2— ヒ ドロキシェチル 15部、 ァクリル酸ブチル 10部、 メタク リル酸 28部からな るモノマー混合物及び AIBN 2部を仕込んだ。 温度を 75°Cに保持しながら、 3時間でモノマー混合物と開始剤を滴下した。 滴下後、 さらに 75てで 2時 間保持した。 得られた樹脂溶液は透明であった。 得られた樹脂溶液の固形 分は 39. 7 %、 固形分酸価は 183であった。 Manufacture of acrylic resin Stirrer, nitrogen inlet, temperature controller, condenser, 1 1 flask equipped with a dropping funnel, ethanol (boiling point 78 e C) and 100 parts, 30 parts of styrene c dropping funnel was heated to 75 ° C, A monomer mixture consisting of 17 parts of ethyl acrylate, 15 parts of 2-hydroxyl methacrylate, 10 parts of butyl acrylate, and 28 parts of methacrylic acid, and 2 parts of AIBN were charged. While maintaining the temperature at 75 ° C, the monomer mixture and the initiator were added dropwise over 3 hours. After the addition, the mixture was kept at 75 mm for 2 hours. The obtained resin solution was transparent. The solid content of the obtained resin solution was 39.7%, and the acid value of the solid content was 183.
比絞例 7  Example 7
メラ ミ ン分散液の製造  Production of melamine dispersion
製造例 1で得られた樹脂溶液 202部を製造例 1で用いたのと同じコルべ ンに加え、 75。Cに加熱した後、 ジメチルエタノールァミ ン 22部および脱ィ オン水 475部を加え、 溶解することにより、 透明で粘ちような樹脂溶液を 'こ  Add 202 parts of the resin solution obtained in Production Example 1 to the same kolben used in Production Example 1, and add 75. After heating to C, add 22 parts of dimethylethanolamine and 475 parts of deionized water and dissolve to form a clear, viscous resin solution.
続いて、 サイメル 254の 300部を 1時間で添加が完了するような速さで加 えたところ、 添加開始 20分で油状の樹脂が析出し始め、 均一な分散液が得 られなかった。  Subsequently, when 300 parts of Cymel 254 was added at such a speed that the addition was completed in one hour, an oily resin began to precipitate in 20 minutes after the addition, and a uniform dispersion could not be obtained.
製造例 2  Production Example 2
水性ァクリル樹脂の製造  Production of aqueous acryl resin
攪拌器、 窒素導入管、 温度制御装置、 コンデンサー、 滴下ロートを備え た 1 1コルベンに、 2 —メ トキシプロパノール(沸点 120°C) 100部を仕込み、 115°Cに昇温した。  100 parts of 2-methoxypropanol (boiling point: 120 ° C) was charged into a 1 1 colben equipped with a stirrer, a nitrogen inlet tube, a temperature controller, a condenser, and a dropping funnel, and the temperature was raised to 115 ° C.
滴下ロートにスチレン 30部、 アクリル酸ェチル 25部、 メタクリル酸 2— ヒ ドロキシェチル 15部、 ァク リル酸ブチル 10部、 メタク リル酸 20部からな るモノマー混合物及び PB0 3部を仕込んた'。 温度を 1 11 Cに保持しながら、 3時間でモノマー混合物と開始剤を滴下した。 滴下後、 さらに 115°Cで 2 時間保持した。 得られた樹脂溶液は透明であった。 得られた樹脂溶液の固 形分は 49. 8%、 固形分酸価は 130であった。 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.
比較例 8  Comparative Example 8
エポキシ樹脂分散液の製造  Production of epoxy resin dispersion
製造例 2で得られた榭脂溶液 203部を製造例 2で用いたのと同じコルべ ンに加え、 9CTCに加熱したのち、 ジメチルエタノールァミ ン 20. 7部および 脱イオン水 476. 3部を加え、 溶解することにより、 透明で粘ちような樹脂 溶液を得た。 続いて、 授拌しながらェポライ 卜 4000(共栄社油脂製、 ェポ キシ樹脂、 エポキシ当量約 250)300部を 1時間で添加が完了するような速 さで加えたところ、 添加開始 10分で油状の樹脂が析出し始め、 均一な分散 液が得られなかった。  203 parts of the resin solution obtained in Production Example 2 was added to the same kolben used in Production Example 2, heated to 9 CTC, then 20.7 parts of dimethylethanolamine and 477.3 of deionized water. A transparent and sticky resin solution was obtained by adding and dissolving the above solution. Subsequently, 300 parts of Epolite 4000 (made by Kyoeisha Oil & Fat Co., Ltd., epoxy resin, epoxy equivalent: about 250) were added with stirring at such a speed that the addition was completed in one hour. The resin began to precipitate, and a uniform dispersion could not be obtained.
製造例 3  Production Example 3
ァクリル樹脂の製造  Manufacture of acrylic resin
授拌器、 窒素導入管、 温度制御装置、 コンデンサ一、 滴下ロートを備え た 1 1コルベンに、 t—ブチルアルコール(沸点 83°C)100部を仕込み、 80°C に昇温した。 滴下ロートにスチレン 30部、 アクリル酸ェチル 25部、 メタ クリル酸 2—ヒ ドロキシェチル 15部、 アクリル酸ブチル 10部、 メタク リル 酸 20部からなるモノマー混合物及び AIBN' 3部を仕込んだ。 温度を 80°Cに保 持しながら、 2時間でモノマー混合物と開始剤を滴下した。 滴下後、 さら に 8CTCで 0. 5時間保持した。 得られた榭脂溶液は透明であつた。  100 parts of 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.
得られた榭脂溶液の固形分は 50%、 固形分酸価は 130であった。  The solid content of the obtained resin solution was 50%, and the acid value of the solid content was 130.
比校例 9  Comparative example 9
ィソシァネート樹脂分散液の製造  Production of isocyanate resin dispersion
製造例 3で得られた樹脂溶液 203部を製造例で用いたのと同じコルベン に加え、 80。Cに加熱したのち、 ジメチルェチノールアミ ン 20. 7部および脱 イオン水 676. 3部を加え、 溶解することにより、 透明で粘ちよ うな樹脂溶 液を得た。 続いて、 デスモジュール W (住友バイエルウレタン社製、 , 4' —メチレンビス(ンクロへキンルイソシァネート、 ィソシァネ一ト当量 140) 1D0部を、 1時間で添加が完了するような速さで加えたところ、 添加開始 δ分で内容物がゲル化し、 水性分散液が得られなかった。 203 parts of the resin solution obtained in Production Example 3 were the same as those used in Production Example. In addition to 80. After heating to C, 20.7 parts of dimethylethynolamine and 676.3 parts of deionized water were added and dissolved to obtain a transparent and viscous resin solution. Subsequently, 1D0 part of Desmodur W (manufactured by Sumitomo Bayer Urethane Co., Ltd.,, 4'-methylenebis (cyclohexylisocyanate, isocyanate equivalent 140)) was added at such a rate that the addition was completed in one hour. As a result, the contents gelled δ minutes after the start of the addition, and no aqueous dispersion was obtained.
製造例 4  Production Example 4
溶剤型榭脂混合溶液  Solvent type resin mixed solution
製造例 1で得られたァクリル榭脂 202部をエタノール 200部で希釈後、 ディ スパー攪拌しながらサイメル 254の 300部を添加、 続いて 2—メ トキシプロ パノール 298部で希釈した。 得られた樹脂混合液は均一透明、 固形分は 34 %であった。  After diluting 202 parts of the acryl resin obtained in Production Example 1 with 200 parts of ethanol, 300 parts of Cymel 254 was added with dispersing and stirring, and then diluted with 298 parts of 2-methoxypropanol. The resulting resin mixture was uniformly transparent and had a solid content of 34%.
製造例 5  Production Example 5
溶剤型榭脂混合溶液  Solvent type resin mixed solution
製造例 2で得られたァクリル樹脂 203部を 2—メ 卜キンプロパノール 200 部で希釈後、 デイスパー攪拌しながら、 ェポライ ト 4000の 300部を添加、 続いて 2 —メ 卜キンプロパノール 297部で希釈した。 得られた樹脂混合液 は均一透明、 固形分  After diluting 203 parts of the acrylyl resin obtained in Production Example 2 with 200 parts of 2-methokine propanol, add 300 parts of Epolite 4000 while dispersing and stirring, and then dilute with 297 parts of 2-methokine propanol. did. The resulting resin mixture is uniform and transparent, solid content
は 40%であった。 Was 40%.
製造例 6  Production Example 6
溶剤型樹脂混合溶液  Solvent type resin mixed solution
製造例 3で得られたァクリル樹脂 203部を 2—メ トキシプロパノール 200 部で希釈後、 ディスパー攪拌しながらデスモジュール Wの 100部を添加、 梡いて 2—メ トキンプロパノール 297部で希釈した。 得られた樹脂混合液 は均一透明、 固形分は 20%であった。 実施例 15 After diluting 203 parts of the acryl resin obtained in Production Example 3 with 200 parts of 2-methoxypropanol, 100 parts of Desmodur W was added with stirring with a disper, and then diluted with 297 parts of 2-methkinpropanol. The resulting resin mixture was uniformly transparent and had a solid content of 20%. Example 15
実施例 1で得られた水性樹脂分散液を脱イオン水を用いて No. 4フォ一ド 力ップで 30秒になるように希釈した。 得られた希釈液を 40°Cで 10日間静置 保存したものを目視評価したところ、 沈降などの外観変化を生じなかった また、 この狞蔵液を No. 4フォードカップでの落下時間を測定したところ 32 秒であり、 経時試験による粘度上昇は 2秒であった。  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.
—方、 希釈液をバーコ一夕一を用い、 膜厚が 40ミ クロンになるように鉄 板上に塗布し、 140°Cで 20分間焼き付け得られた塗膜を以下の操作により 評価した。  On the other hand, 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.
なお、 塗膜の光沢が良好であることは、 その透明性及び平滑性が良好で あることを示す。  The good gloss of the coating film indicates that its transparency and smoothness are good.
MEI (ラビングテス卜は MEKにより塗膜を膨涠させ、 ガーゼの摩擦という機 械的な負荷を与え、 擦り傷を付けるための試験であり、 塗膜の硬化性と機 械的負荷に対する耐性を簡便に検定するためのものである。 したがって、 この試験の結果、 塗膜の変化が観察されないことは、 塗膜の硬化性および 機械的強度が優れていることを示す。  MEI (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.
さらに、 Na〇Hスポッ トテストは、 アル力リ水に対する塗膜の耐性を 簡便に検定するものであり、 この試験の結果、 塗膜の変化が観察されない ことは、 塗膜の耐薬品性および耐水性が良好であることを示す。  In addition, the Na〇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.
光沢  Gloss
樹脂を塗布した鉄板をデジタル変角高度計「UGV- 5 K」(スガ試験機社製) を用いて 2(Γの反射角で測定した。  The iron plate on which the resin was applied was measured at a reflection angle of 2 (Γ) using a digital bending angle altimeter “UGV-5K” (manufactured by Suga Test Instruments Co., Ltd.).
M E Κラビングテス ト  M E Κ Loving test
8 cm角に切断したガーゼを 4つ折りにしたものをへッ ドの重さ 200 gの ハンマーにテープで張り付けた。 これに MEK 5 E1を滴下し含浸させた。 こ のハンマーを樹脂を塗布した鉄板上に置き、 水平方向に前後 10cm動かす操 作を繰り返した。 この操作より塗膜に傷が目視で見られるまでの繰り返し 回数を記録した。 A piece of gauze that had been cut into 8 cm squares, folded in four, was taped to a hammer with a head weight of 200 g. MEK 5 E1 was dripped into this and impregnated. This The hammer was placed on a steel plate coated with resin, and the operation of moving it back and forth 10 cm horizontally was repeated. From this operation, the number of repetitions until a scratch was visually observed on the coating film was recorded.
N a O Hスポッ トテスト  NaOH spot test
榭脂を塗布した鉄板上に 0. 1 Nの N a O H水溶液 5滴をスポィ 卜から滴下 し、 24時間後の塗膜の変化を目視観察した。  Five drops of a 0.1 N NaOH aqueous solution were dropped from a spot on the iron plate coated with the resin, and the change of the coating film after 24 hours was visually observed.
実施例 16〜28  Examples 16 to 28
実施例 2〜14で得られた分散液を実施例 15と同様に水希釈して得られた 希釈液に対し、 実施例 15と同様に評価した結果を表 4に示す。 なお、 実施 例 24においては、 実施例 10で得られた水性樹脂分散液 286部にショーノー ル CKS-394 昭和高分子社製レゾール型フ二ノール樹脂) 6部を加え、 脱ィ ォン水で No. 4フォードカップで 30秒になるように希釈したものを用いた。  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. In 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.
比較例 10〜12  Comparative Examples 10-12
製造例 4、 5、 6で得られた樹脂混合液を用い、 脱イオン水の代わりに 2—メ トキシブ Dパノールを用いること以外は実施例 15と同様にして希釈 液を得た。 このものを実施例 15と同様に評価して得られた結果を表 4に示 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.
貯蔵試联% 貯葳拭敏後 光 沢 M E Kラビンゲ NaOHX'†: の外観変化 の秒数変化 ^ (回数) テス 実施例 15 変化無し + 2 145 > 100 変化無し 実施例 15 変化無し + 1 151 > 100 変化無し 実施例 1了 変化無し 0 149 88 変化無し 実施例 18 変化無し 十 2 150 81 シ ミあり 実施例 19 変化無し + 2 146 > 100 変化無し 実施例 20 変化無し + 1 150 > 100 変化無し 実施例 21 変化無し + 3 147 > 100 変化無しStorage test% After storage wisdom Mitsawa MEK Labinge NaOHX '†: change in appearance change in seconds ^ (number of times) Test Example 15 No change + 2 145> 100 No change Example 15 No change + 1 151> 100 No change Example 1 Finish No change 0 149 88 No change Example 18 No change 10 2 150 81 Stained Example 19 No change + 2 146> 100 No change Example 20 No change + 1 150> 100 No change Example 21 No change + 3 147> 100 No change
5 施例 I 変化無し + 2 150 > 100 変化無し 実施例 23 変化無し 十 3 143 84 シ ミあり 実施例 24 変化無し + 2 1 12 > 100 変化無し 実施例 25 変化無し 一 1 147 > 100 変化無し 実施例 26 変化無し + 4 150 > 10D 変化無し 実施例 27 変化無し + 5 147 > 100 変化無し 実施例 28 変化無し + 4 153 77 変化無し 比較例 10 変化無し -1- 1 1 125 70 剝雜 比 e例 Π 変化無し + 20 109 68 刹雜 比お例 \ t ゲル化 M定不能 100 75 シ ミあり 5 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 無 し no change + 20 109 68 moment ratio example \ t gelation M undetermined 100 75 stain
発明の効果 The invention's effect
透明性、 平滑性、 耐薬品性、 耐水性及び機械強度に優れる塗膜を形成し、 良好な塗装作業性及び分散安定性を有する水性塗料を実現しうる水分散性 樹脂組成物及びその製造方法が提供された。  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.

Claims

請求の範囲 The scope of the claims
1 . (a)反応性官能基を含み水に対する溶解度が 1以下である反応性非 水溶性樹脂 5〜95重量%、 及び  1. (a) 5 to 95% by weight of a reactive water-insoluble resin containing a reactive functional group and having a solubility in water of 1 or less, and
(b) (1)該官能基と反応する官能基を有する反応性エチレン性不飽和モノ マ一 0. 5〜50重量%と、 (2)カルボキシル基を有するエチレン性不飽和モノ マー 1〜40重量%と、 (3)その他のェチレン性不飽和モノマー 10〜98. 5重 量%とからなる、 モノマー混合物(但し、 成分(] )〜(3)の合計量は 100重量 %である。 )5〜95重鲞%、  (b) (1) 0.5 to 50% by weight of a reactive ethylenically unsaturated monomer having a functional group which reacts with the functional group, and (2) 1 to 40% of an ethylenically unsaturated monomer having a carboxyl group. % By weight, and (3) 10 to 98.5% by weight of the other ethylenically unsaturated monomers, where the total amount of the components (]) to (3) is 100% by weight. 5 ~ 95 weight%,
を含有する出発混合物を、 重合開始剤及び水素結合性有機溶媒の存在下に その有機溶媒の沸点以下の温度でラジカル重合する工程;及び Radically polymerizing a starting mixture containing at a temperature not higher than the boiling point of the organic solvent in the presence of a polymerization initiator and a hydrogen bonding organic solvent; and
得られる樹脂組成物を、 中和剤を加えることにより中和する工程: を包含する自己架橋性水分散性樹脂組成物の製造方法。  A method for producing a self-crosslinkable water-dispersible resin composition, comprising: neutralizing the obtained resin composition by adding a neutralizing agent.
2 . 前記反応性非水溶性樹脂がァミノブラストである請求項 1記載の方 法。  2. The method according to claim 1, wherein the reactive water-insoluble resin is aminoblast.
3. 前記反応性非水溶性樹脂がエポキシ樹脂である請求項 1記載の方法 c 3. The method c according to claim 1, wherein the reactive water-insoluble resin is an epoxy resin.
4 . 前記反応性非水溶性樹脂がイソンァネー卜樹脂である請求項 1記載 の方法。 4. The method according to claim 1, wherein the reactive water-insoluble resin is an isocyanate resin.
5. 前記反応性エチレン性不飽和モノマーに含まれる官能基がカルボキ シル基である請求項 1〜4のいずれか記載の方法。  5. The method according to claim 1, wherein the functional group contained in the reactive ethylenically unsaturated monomer is a carboxyl group.
6. 前記反応性エチレン性不飽和モノマーに含まれる官能基がヒ ドロキ シル基である請求項 1〜4のいずれか記載の方法。  6. The method according to any one of claims 1 to 4, wherein the functional group contained in the reactive ethylenically unsaturated monomer is a hydroxyl group.
7 . 前記有機溶媒が沸点 1 5 0 °C以下のアルコールである請求項 1〜6 のいずれか記載の方法。  7. The method according to any one of claims 1 to 6, wherein the organic solvent is an alcohol having a boiling point of 150 ° C or lower.
8 . 請求項 1〜 7のいずれか ΐ己载の方法により得られる自己架橘性水分 散性樹脂組成物。 8. A self-crosslinking water-dispersible resin composition obtained by the method of any one of claims 1 to 7.
9. 請求項 8記載の水分散性樹脂組成物と水性媒体とを含む水性塗料組 成物。 9. An aqueous coating composition comprising the water-dispersible resin composition according to claim 8 and an aqueous medium.
1 0. さらに顔料を含む請求項 9記載の水性塗料組成物。  10. The aqueous coating composition according to claim 9, further comprising a pigment.
1 1. 請求項 8記載の水分散性樹脂組成物と水性媒体と顔料とを含むァ 二オン電着性塗料組成物。  1 1. An electrodeposition coating composition comprising the water-dispersible resin composition according to claim 8, an aqueous medium, and a pigment.
1 2. ベース塗料を塗布した後、 これを硬化させずにクリヤー塗料を重 ね^りし、 ベース塗料とクリヤー塗料とを合わせて硬化させる 2コー卜/ 1ベーク塗装方法において、 該ベース塗料が請求項 1 0記載の水性塗料組 成物である方法。  1 2. After applying the base paint, the clear paint is layered without curing, and the base paint and the clear paint are cured together. In the 2 coat / 1 bake coating method, the base paint is applied. A method which is the water-based paint composition according to claim 10.
1 3. 前記クリヤー塗料が溶剤系クリヤー塗料である請求項 1 2記載の 塗装方法。  13. The coating method according to claim 12, wherein the clear paint is a solvent-based clear paint.
1 4. 前記クリヤー塗料が水性クリヤー塗料である請求項 1 2記載の塗 法。  14. The coating method according to claim 12, wherein the clear paint is an aqueous clear paint.
1 5. 前記水性クリヤー塗料が請求項 9記載の水性塗料組成物である請 求項 1 2記載の塗装方法。  15. The coating method according to claim 12, wherein the aqueous clear paint is the aqueous paint composition according to claim 9.
1 6. ベース塗膜とクリヤー塗膜とを有する多層塗膜において、 該ベー ス塗膜が請求項 1 0記載の水性塗料組成物を用いて形成される多層塗膜。  16. A multilayer coating film having a base coating film and a clear coating film, wherein the base coating film is formed using the aqueous coating composition according to claim 10.
3 Three
PCT/JP1997/001132 1996-04-02 1997-04-02 Self-cross-linkable water dispersible resin composition WO1997036936A1 (en)

Applications Claiming Priority (2)

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

Publications (1)

Publication Number Publication Date
WO1997036936A1 true WO1997036936A1 (en) 1997-10-09

Family

ID=13703863

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1997/001132 WO1997036936A1 (en) 1996-04-02 1997-04-02 Self-cross-linkable water dispersible resin composition

Country Status (1)

Country Link
WO (1) WO1997036936A1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130086008A (en) * 2012-01-20 2013-07-30 테사 소시에타스 유로파에아 Crosslinker accelerator system for polyacrylates
WO2020100790A1 (en) * 2018-11-13 2020-05-22 昭和電工株式会社 Aqueous resin emulsion, method for producing same, and aqueous resin composition

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 (en) * 1994-12-27 1996-09-10 Asahi Chem Ind Co Ltd Curable water-based resin composition

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 (en) * 1994-12-27 1996-09-10 Asahi Chem Ind Co Ltd Curable water-based resin composition

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20130086008A (en) * 2012-01-20 2013-07-30 테사 소시에타스 유로파에아 Crosslinker accelerator system for polyacrylates
JP2013147653A (en) * 2012-01-20 2013-08-01 Tesa Se Cross-linking agent-accelerator system for polyacrylate
WO2020100790A1 (en) * 2018-11-13 2020-05-22 昭和電工株式会社 Aqueous resin emulsion, method for producing same, and aqueous resin composition
JPWO2020100790A1 (en) * 2018-11-13 2021-09-02 昭和電工株式会社 Aqueous resin emulsion and its production method, and aqueous resin composition

Similar Documents

Publication Publication Date Title
JP5219641B2 (en) Water-based resin composition, water-based coating composition, and method for coating plastic molded article
JP5294863B2 (en) Resin composition for aqueous paint and aqueous paint composition
JPH05271614A (en) Water-based pigmented coating composition and method for applying the same
EP0300612B1 (en) Basecoat compositions
US5166272A (en) Emulsion polymers and coating compositions prepared therefrom
EP0266152B1 (en) Method of painting
JP3071998B2 (en) Aqueous paint composition
JP2004307544A (en) Aqueous emulsion and water-based coating composition comprising the same
US7550206B2 (en) Phosphonic acid-modified microgel dispersion
EP0775175B1 (en) Water-dispersible acrylic graft copolymer, method for making it and water-based paint
JPS63179913A (en) Aqueous dispersion system of addition polymer
WO1997036936A1 (en) Self-cross-linkable water dispersible resin composition
JPH07247460A (en) Aqueous covering composition
JP3025367B2 (en) Resin composition for water-based paint
JP5260820B2 (en) Method for producing aqueous emulsion
JPS6213991B2 (en)
JP4829416B2 (en) Water-based coloring base thermosetting paint and coating film forming method using the same
JPH11319707A (en) Coating by using water coating-composition having high water-resistant secondary adhesion
JP2001139766A (en) Method for producing aqueous dispersion of thermoset resin, and water-based coating agent of thermoset resin
JP3982021B2 (en) Aqueous resin composition
JPS6158101B2 (en)
WO1994014905A1 (en) Water-base coating resin composition and water-base coating composition
JPH06279713A (en) Water spot filling agent and use thereof in method for preparation of multilayer coating
JPH06212049A (en) Water dispersing resin element for metallic coating and aqueous metallic coating using the same
JP2722603B2 (en) Paint composition

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): JP US

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FI FR GB GR IE IT LU MC NL PT SE

121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase