WO2010050387A1 - Matériau de revêtement aqueux résistant à l’eau - Google Patents

Matériau de revêtement aqueux résistant à l’eau Download PDF

Info

Publication number
WO2010050387A1
WO2010050387A1 PCT/JP2009/068095 JP2009068095W WO2010050387A1 WO 2010050387 A1 WO2010050387 A1 WO 2010050387A1 JP 2009068095 W JP2009068095 W JP 2009068095W WO 2010050387 A1 WO2010050387 A1 WO 2010050387A1
Authority
WO
WIPO (PCT)
Prior art keywords
water
coating material
resistant coating
group
vinyl
Prior art date
Application number
PCT/JP2009/068095
Other languages
English (en)
Japanese (ja)
Inventor
明宏 権野
彩 児玉
Original Assignee
協和発酵ケミカル株式会社
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 協和発酵ケミカル株式会社 filed Critical 協和発酵ケミカル株式会社
Publication of WO2010050387A1 publication Critical patent/WO2010050387A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a water-resistant coating material useful for applications such as paints, adhesives or inks.
  • an aqueous emulsion resin In order to respond to strict environmental regulations, an aqueous emulsion resin is desired.
  • Tg glass transition temperature
  • the decrease in Tg deteriorates various physical properties such as water resistance, blocking resistance, and contamination resistance.
  • a carbonyl group-containing emulsion obtained by copolymerizing a monomer having a carbonyl group has at least two hydrazide groups in the molecule.
  • An aqueous emulsion resin comprising a compound is disclosed (Patent Document 1).
  • This water-based emulsion paint can be formed at a relatively low temperature by designing a resin having a low Tg, and the emulsion particles are cross-linked after film formation to improve water resistance, blocking resistance and stain resistance. Can do. However, under actual use conditions, the blocking resistance and stain resistance were good, but the water resistance and wet abrasion resistance were not sufficient.
  • An object of the present invention is to provide a water-resistant coating material having excellent water resistance and the like.
  • the present invention provides the following (1) to (10).
  • a water-resistant coating material containing at least the following components (A) to (D).
  • a vinyl monomer (a) containing at least one carbonyl group (wherein the carbonyl group is other than a carboxyl group, a carbamoyl group or an ester group) and another copolymerizable copolymer Vinyl copolymer (a) obtained from a raw material containing a vinyl monomer (b) having various carboxyl groups
  • B) Neutralizing agent containing a water-soluble organic amine having 1 to 6 carbon atoms
  • C A hydrazide derivative having two or more hydrazide groups or a hydrazide derivative in which the hydrazide group is protected with a low molecular carbonyl compound (D) aqueous
  • the raw material of the vinyl copolymer (a) is 0.50 to 50% by weight of a vinyl monomer containing at least one carbonyl group, and 0.001% of a vinyl monomer having a carboxyl group.
  • the water-soluble organic amine having 1 to 6 carbon atoms is 0.2 to 1 equivalent with respect to the carboxyl group, and ammonia is 0.5 to 1.5 equivalent with respect to the carboxyl group (2) or (3)
  • the water-resistant coating material according to the description (6) The water-resistant coating material according to any one of (1) to (5), wherein the component (B) contains one or more amines selected from the group consisting of alkylamines having 1 to 6 carbon atoms or dialkylamines .
  • the present invention provides a water-resistant coating material having excellent water resistance and the like.
  • the raw material for the production of the component (A) vinyl copolymer (a) is a vinyl monomer (a) containing at least one carbonyl group (hereinafter sometimes referred to as monomer (a)). ] Is used.
  • This monomer (a) is a component that enables crosslinking by being introduced into a polymer, and at least one carbonyl group (wherein the carbonyl group is other than a carboxyl group, a carbamoyl group, or an ester group) And a monomer having a polymerizable double bond.
  • the monomer (a) examples include acrolein, diacetone (meth) acrylamide, formylstyrene, vinyl methyl ketone, vinyl isobutyl ketone, (meth) acrylamide pivalin aldehyde, diacetone (meth) acrylate, and acetonyl (meth).
  • R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom or lower alkyl
  • R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom or lower alkyl
  • R 1 , R 2 , R 3 and R 4 are alkyl having 1 to 4 carbon atoms
  • the alkyl having 1 to 4 carbon atoms include linear or branched ones, and more specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like.
  • the monomer (a) acrolein, diacetone acrylamide or vinyl methyl ketone is preferable.
  • the monomer (a) can be used not only in one type but also in two or more types, and the vinyl copolymer obtained in this case is also included in the vinyl copolymer of the component (A). It is.
  • the monomer (a) is preferably contained in an amount of 0.5 to 50% by weight in the total vinyl polymer raw material.
  • the vinyl monomer (b) having a copolymerizable carboxyl group used in the production of the vinyl copolymer (a) includes at least in the molecule. Any one having one polymerizable double bond can be selected according to the purpose. Specific examples of the monomer (b) include ⁇ , ⁇ -ethylenically unsaturated groups such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, crotonic acid, fumaric acid, and citraconic acid.
  • Unsaturated carboxylic acid vinyl sulfonic acids such as carboxylic acid, linseed oil fatty acid, tall oil fatty acid or dehydrated castor oil fatty acid, sulfonated vinyl monomers such as styrene sulfonic acid, methylacrylamide propane sulfonic acid and their salts, fumaric acid
  • vinyl monomers obtained by the reaction of polymerizable double bond-containing carboxylic acids such as maleic acid, maleic anhydride, linseed oil fatty acid, tall oil fatty acid, and dehydrated castor oil fatty acid with an epoxy resin or an epoxy compound.
  • the raw material of the vinyl copolymer (a) may contain a vinyl monomer other than those mentioned above [hereinafter sometimes referred to as the monomer (c)].
  • a vinyl monomer other than those mentioned above hereinafter sometimes referred to as the monomer (c)].
  • methyl (meth) acrylate represents methyl acrylate and methyl methacrylate.
  • the monomer (b) is preferably contained in the total vinyl polymer raw material in an amount of 0.05 to 2% by weight. Since the crosslinking reaction of the carbonyl group and the hydrazide group proceeds by an acid catalyst mechanism, when the monomer (b) is 0.05% by weight or more, the crosslinking reaction proceeds by the acid catalyst mechanism and the physical properties of the coating film are improved. Moreover, in 2 weight% or less, storage stability, film forming property, and water resistance are improved.
  • the vinyl copolymer (a) may be combined with other polymers as necessary.
  • other polymers include, for example, alkyd resin, polyester resin, acrylic resin, epoxy resin, polyurethane resin, nylon resin, polydimethylsiloxane, polyvinyl alcohol, polyvinylamine, polybutadiene resin, melamine resin, phenol resin, water-soluble A cellulose ether etc. are mention
  • the polymer those having a weight average molecular weight of 500 to 200,000 are preferably used.
  • the component (A) may contain the following polymer as necessary.
  • the polymer include, for example, alkyd resin, polyester resin, acrylic resin, epoxy resin, polyurethane resin, nylon resin, polydimethylsiloxane, polyvinyl alcohol, polyvinylamine, polybutadiene resin, melamine resin, phenol resin, and water-soluble cellulose. Ether and the like.
  • the polymer those having a weight average molecular weight of 500 to 200,000 are preferably used.
  • inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide
  • inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide
  • ammonia is contained.
  • the blending amount of the neutralizing agent is preferably 0.5 to 1.5 equivalents based on the total carboxyl groups.
  • inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide
  • ammonia is contained.
  • the blending amount of the neutralizing agent is preferably 0.5 to 1.5 equivalents based on the total carboxyl groups.
  • water-soluble organic amine having 1 to 6 carbon atoms contained in the component (B) include methylamine, ethylamine, isopropylamine, propylamine, n-butylamine, isobutylamine, tert-butylamine, sec-butylamine, and amylamine.
  • Dimethylamine, methylethylamine, diethylamine, diisopropylamine, dimethylethanolamine and 2-amino-2-methyl-1-propanol are preferred, and isopropylamine, propylamine and n-butylamine are preferred in terms of water resistance and the like.
  • N-Butylamine is more preferable.
  • 2-amino-2-methyl-1-propanol, aminoethylethanolamine, 3-amino-1-propanol, diethanolamine, methylethanolamine, methyldiethanolamine, diethylethanolamine, 3-methoxypropylamine and 3-ethoxypropylamine are In view of water resistance, non-toxicity, odor and the like. Of these, water-soluble organic amines having 1 to 5 carbon atoms are preferred.
  • Component (B) includes cyclohexylamine, allylamine, monoethanolamine, monoisopropanolamine, N- (2-hydroxypropyl) -ethylenediamine, 2-amino-1-butanol, 3-amino-2-butanol, 2-amino -1-propanol, 1-amino-2-methyl-2-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, tris (Hydroxyethyl) -aminomethane, primary amines such as aminobenzyl alcohol, diallylamine, diethylamine, diisopropylamine, ethylethanolamine, 2-propylaminoethanol, butylethanolamine, butylmethanolamine, N-acetylethanolamine, diisopropano Secondary amines such as ruamine, triethanolamine, ethyl
  • the water-soluble organic amine having 1 to 6 carbon atoms can be used alone or in combination of two or more.
  • the blending amount of the water-soluble organic amine having 1 to 6 carbon atoms is preferably included in the range of 0.2 to 1.0 molar equivalent with respect to the carboxyl group.
  • the component (C) hydrazide derivative include two or more hydrazide groups in one molecule, and more specifically, carbohydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, glutaric acid dihydrazide.
  • aliphatic water-soluble dihydrazines having 0 to 4 carbon atoms such as hydrazine, ethylene-1,2-dihydrazine, propylene-1,3-dihydrazine, butylene-1,4-dihydrazine, and dihydrazine Or trihydrazine-triazine, thiocarbohydrazide or N, N′-diaminoguanidine-triazine, 2-hydrazinopyridine-5-carboxylic acid hydrazide, 3-chloro-hydrazinopyridine-5-carboxylic acid hydrazide, 6-chloro- Hydrazine-pyridine derivatives such as 2-hydrazinopyridine-4-carboxylic acid hydrazide, 2,5-dihydrazinopyridine-4-carboxylic acid, bis-thiosemicarbazide, bishydrazine of alkylenebisacrylamide, dihydrazine alkane, 1, 4-
  • the hydrazide derivative of component (C) is preferably a dihydrazide compound of a dicarboxylic acid having 4 to 12 carbon atoms.
  • a dihydrazide compound of a dicarboxylic acid having 4 to 12 carbon atoms succinic acid dihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide, etc. Of these, adipic acid dihydrazide is particularly preferable.
  • the coating material of the present invention is used for a one-pack type paint or adhesive, the hydrazide group of the hydrazide derivative is protected with a low molecular carbonyl compound as component (C) in order to improve the storage stability. It may be used as a derivative.
  • the low molecular carbonyl compound is preferably one having 3 to 10 carbon atoms.
  • the hydrazide group (or hydrazide group protected with a carbonyl compound) of the hydrazide derivative of component (C) is 0.1 to 5 moles relative to the carbonyl group in the vinyl copolymer of component (A). It is preferably used so as to be equivalent, more preferably 0.2 to 2 molar equivalents, and even more preferably 0.5 to 1.0 molar equivalents.
  • the hydrazide group is 0.1 molar equivalent or more with respect to the carbonyl group, a coating film is more easily formed, and the water resistance is excellent.
  • the hydrazide group is 5 molar equivalents or less with respect to the carbonyl group, the coating film properties such as water resistance are further improved.
  • the vinyl copolymer (a) of the component (A) is prepared by, for example, the monomer (a) and the monomer by a known polymerization method such as a suspension polymerization method, a solution polymerization method, an emulsion polymerization method, or a bulk polymerization method.
  • a known polymerization method such as a suspension polymerization method, a solution polymerization method, an emulsion polymerization method, or a bulk polymerization method.
  • B If necessary, it can be produced by copolymerizing a raw material containing the monomer (c), but when using an emulsion polymerization method, the polymerization reaction solution containing the copolymer is used as an aqueous dispersion as it is. Since it can be used, it is preferable.
  • emulsion polymerization method a known method can be used, and emulsion polymerization is usually carried out by a method using an emulsifier and a polymerization initiator. Also, a method of obtaining a core-shell type dispersion by changing the monomer composition between layers of a known multilayer emulsion polymerization dispersion, or power feed type polymerization in which the monomer composition is gradually changed can be used.
  • the emulsifier include anionic, cationic, and nonionic emulsifiers, and polymer emulsifiers.
  • anionic surfactants such as higher alcohol sulfates, alkylbenzene sulfonates, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenol ether sulfates, polyoxyethylene alkyl phenol ethers, ethylene oxides.
  • Nonionic surfactants such as propylene oxide block polymers and sorbitan derivatives are exemplified, but the invention is not limited thereto.
  • the polymer emulsifier include polyvinyl alcohol and hydroxyethyl cellulose. The amount of the emulsifier can be appropriately set depending on the conditions such as the type of the monomer and is not particularly limited, but is usually 0.1 to 10% with respect to the amount of the total vinyl monomer used. Is preferred.
  • the polymerization initiator examples include persulfates such as potassium persulfate and ammonium persulfate, peroxides such as hydrogen peroxide, benzoyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, azobisisobutyro An azo compound such as nitrile is used. Further, a redox initiator in which a reducing component such as a metal ion having a reducing action, sodium sulfite, or mercaptan is combined with the above polymerization initiator is preferable. Usually, the polymerization initiator is preferably used in an amount of 0.1 to 5.0 mol% based on the amount of all vinyl monomers used.
  • a chain transfer agent such as n-dodecyl mercaptan, tert-dodecyl mercaptan, ⁇ -methylstyrene dimer may be used as necessary.
  • the polymerization temperature is not particularly limited, but is usually 40 to 100 ° C., preferably 60 to 90 ° C.
  • a solvent in the case of manufacturing a vinyl-type copolymer (a) by a solution polymerization method all can be used if it can melt
  • this solvent include, for example, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, glycols such as ethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, propylene glycol methyl ether, ethyl acetate, butyl acetate And the like, and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • alcohols such as methanol, ethanol, propanol, isopropanol
  • butanol glycols such as ethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, propylene glycol methyl ether, ethyl acetate, butyl acetate And the like
  • ketones such as methyl ethyl ketone and methyl isobutyl ketone
  • the reaction temperature in the solution polymerization method is preferably 40 ° C. to the boiling point of the solvent.
  • a polymerization initiator similar to the above or a chain transfer agent similar to the above may be used.
  • the vinyl copolymer (a) is preferably present in a state dispersed in water (aqueous dispersion) or dissolved in water or a mixture of water and a solvent (water-soluble resin). .
  • the glass transition temperature (Tg) of the vinyl copolymer is ⁇ 40 to 100 ° C. More preferably, it is preferably ⁇ 30 to 50 ° C., more preferably ⁇ 20 to 20 ° C.
  • Tg is ⁇ 40 ° C. or higher, the coating film has more excellent hardness and blocking resistance.
  • the Tg of the vinyl copolymer (a) can be adjusted by changing the type and ratio of the vinyl monomer.
  • the aqueous dispersion or water-soluble resin of component (A) is obtained after a polymerization reaction for copolymerizing the monomer (a) and the monomer (b) and, if necessary, the monomer (c), It can be obtained by adding component (D) and, if necessary, an emulsifier to the polymerization reaction solution.
  • any solvent can be used as long as the polymer is stable in the water-soluble resin or aqueous dispersion.
  • the solvent in this case include the same solvents as those used in the solution polymerization method, and the amount used is not particularly limited, but it is preferably 30% by weight or less based on water.
  • the water-resistant coating material of the present invention is obtained by adding the component (C) to the aqueous dispersion or water-soluble resin obtained by a known method from the component (A), the component (B) and the component (D), for example. And can be obtained by mixing.
  • Component (A) is preferably contained in an amount of 20 to 70% by weight in the water-resistant coating material of the present invention.
  • the aqueous medium of component (D) include water or a mixture of water and an organic solvent.
  • the organic solvent include alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, glycols such as ethyl cellosolve, cellosolve acetate, butyl cellosolve, butyl carbitol, and propylene glycol methyl ether, and acetic acid such as ethyl acetate and butyl acetate.
  • esters examples include esters, ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the amount of the organic solvent used is preferably 30% by weight or less based on water.
  • the aqueous medium is preferably contained in an amount of 30 to 80% by weight in the water-resistant coating material of the present invention.
  • the emulsifier As the emulsifier, the aforementioned anionic, cationic or nonionic, or a polymer emulsifier can be used.
  • the emulsifier is preferably used in an amount of 0.1 to 10% by weight based on the component (A) in the present invention.
  • the water-resistant coating material of the present invention is cured by drying at room temperature to about 100 ° C.
  • the water-resistant coating material of the present invention can also be obtained by drying an aqueous resin as it is, but various colorants such as organic pigments and inorganic pigments, ultraviolet absorbers, pigment dispersants, leveling agents, thickeners, etc. Can be added and used as necessary.
  • various colorants such as organic pigments and inorganic pigments, ultraviolet absorbers, pigment dispersants, leveling agents, thickeners, etc.
  • dispersing the pigment it may be dispersed with a paint shaker, a disper, a ball mill or the like using a pigment dispersant, but a commercially available processed pigment may be used.
  • a film-forming aid can be added to improve the film-forming property, but the blending amount is preferably as small as possible.
  • the water-resistant coating material of the present invention can be used for paints, adhesives or inks. When used as a paint, it has a low viscosity and can be applied to conventional brush coating, spray coating, and the like. As an object to be coated, it can be used for metals, wood, plastics, inorganic materials, gypsum board, concrete, asphalt, etc., and is suitable for use mainly for interior and exterior of buildings. When used for building applications, in addition to water resistance, wet abrasion resistance can also be improved.
  • Reference Example 1 Synthesis of aqueous dispersion 560 g of deionized water was placed in a 2 L separable flask equipped with a temperature controller, a reflux tube, a nitrogen tube and a stirring motor, and the temperature was raised to 80 ° C. in a water bath.
  • An initiator solution in which was mixed and dissolved was added to conduct initial polymerization. 15 minutes after charging the initiator solution, an initiator solution prepared by mixing and dissolving 1.87 g of ammonium persulfate and 370 g of deionized water was added to the remaining 98% of the vinyl monomer mixture, and the mixture was stirred to prepare. The pre-emulsion was added dropwise over 3 hours. After completion of dropping, the mixture was further aged at 80 ° C. for 2 hours. After aging, the mixture was cooled to 30 ° C.
  • Example 1 a 50% by weight isopropylamine aqueous solution was used in the same procedure as in Example 1 except that 0.50 g (0.5 molar equivalent based on the carboxyl group of methacrylic acid) was used instead of 0.30 g.
  • Coating material 2 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.24% by weight (excluding the neutralizing agent ammonia).
  • Example 2 The same procedure as in Example 1 except that 0.30 g of a 50% aqueous propylamine solution (0.3 molar equivalents relative to the carboxyl group of methacrylic acid) was used in place of 0.30 g of the 50% by weight isopropylamine aqueous solution in Example 1.
  • the water-resistant coating material 3 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.14% by weight (excluding the neutralizing agent ammonia).
  • Example 3 a 50 wt% propylamine aqueous solution was used in the same procedure as in Example 3 except that 0.50 g (0.5 molar equivalent based on the carboxyl group of methacrylic acid) was used instead of 0.30 g.
  • Coating material 4 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.24% by weight (excluding the neutralizing agent ammonia).
  • Example 1 A procedure similar to that in Example 1 except that 0.37 g of 50% n-butylamine (0.3 molar equivalent based on the carboxyl group of methacrylic acid) was used instead of 0.30 g of the 50 wt% isopropylamine aqueous solution in Example 1.
  • the water-resistant coating material 5 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.18% by weight (excluding the neutralizing agent ammonia).
  • Example 5 the same procedure as in Example 5 was performed, except that 0.61 g (0.5 molar equivalent based on the carboxyl group of methacrylic acid) was used instead of 0.37 g of the 50 wt% n-butylamine aqueous solution.
  • a water resistant coating material 6 was prepared. The water-soluble amine content in the water-resistant coating material was 0.29% by weight (excluding the neutralizing agent ammonia).
  • Example 2 A procedure similar to that of Example 1 was used except that 0.16 g of a 70% aqueous ethylamine solution (0.3 molar equivalents relative to the carboxyl group of methacrylic acid) was used instead of 0.30 g of the 50% by weight isopropylamine aqueous solution in Example 1.
  • the water-resistant coating material 7 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.08% by weight (excluding the neutralizing agent ammonia).
  • Example 7 the same procedure as in Example 7 was used except that 0.27 g (0.5 molar equivalents relative to the carboxyl group of methacrylic acid) was used instead of 0.16 g of the 70% by weight ethylamine aqueous solution.
  • Material 8 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.13% by weight (excluding the neutralizing agent ammonia).
  • Example 2 The same procedure as in Example 1 was used except that 0.37 g of a 50% diethylamine aqueous solution (0.3 molar equivalents relative to the carboxyl group of methacrylic acid) was used instead of 0.30 g of the 50% by weight isopropylamine aqueous solution in Example 1.
  • the water-resistant coating material 9 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.18% by weight (excluding the neutralizing agent ammonia).
  • Example 9 a 50 wt% aqueous solution of diethylamine was used in the same procedure as in Example 9 except that 0.61 g (0.5 molar equivalent based on the carboxyl group of methacrylic acid) was used instead of 0.37 g.
  • a coating material 10 was prepared.
  • the water-soluble amine content in the water-resistant coating material was 0.29% by weight (excluding the neutralizing agent ammonia).
  • Comparative Example 1 To 100 parts of the aqueous dispersion obtained in Reference Example 1, 3.79 g of a 10% by weight aqueous solution of adipic acid dihydrazide (ADH) (the hydrazide group was 0 with respect to 1 mol of the carbonyl group in the aqueous dispersion obtained in Reference Example 1). .8 molar equivalent) was added to obtain a water-resistant coating material 11. The ammonia content in the water-resistant coating material was 0.14% by weight.
  • ADH adipic acid dihydrazide
  • the water-resistant coating material was obtained by drying the water-resistant coating material obtained in Examples 1 to 10 and Comparative Example 1 at 23 ° C. and 50% humidity for 7 days, and subjected to the following test method.
  • the water resistance of the coating film was evaluated by the water absorption rate and the degree of whitening. The evaluation method is described below.
  • Water absorption rate Each of the water-resistant coating materials of Examples 1 to 10 and Comparative Example 1 was applied to a glass plate using a 0.5 mm applicator. This was dried at 23 ° C. and 50% humidity for 7 days (dry film thickness of about 150 ⁇ m).
  • the coating film was peeled off from the glass plate, cut into a square of about 4 cm, weighed, immersed in distilled water, and allowed to stand at 23 ° C.
  • the water-resistant coating materials obtained from Examples 1 to 10 are superior in water resistance to those obtained from Comparative Example 1.
  • the present invention provides a water-resistant coating material having excellent water resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (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

L’invention concerne un matériau de revêtement résistant à l’eau qui contient au moins les composants suivants : (A) un copolymère vinylique (a) obtenu à partir d’un matériau brut qui contient un monomère vinylique (a) contenant au moins un groupe carboxyle (à condition que la fraction du groupe carboxyle ne soit pas un groupe carboxyle, un groupe carbamoyle ou un  groupe ester) et un autre monomère vinylique copolymérisable (b) comprenant un groupe carboxyle ; (B) un agent de neutralisation contenant une amine organique soluble dans l’eau contenant 1 à 6 atomes de carbone ; (C) un dérivé hydrazide comprenant deux groupes hydrazide ou plus ou un autre dérivé hydrazide obtenu par protection des groupes hydrazide du dérivé hydrazide précité et un composé carbonyle de faible poids moléculaire ; (et D) un milieu aqueux.
PCT/JP2009/068095 2008-10-31 2009-10-21 Matériau de revêtement aqueux résistant à l’eau WO2010050387A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2008-281730 2008-10-31
JP2008281730 2008-10-31

Publications (1)

Publication Number Publication Date
WO2010050387A1 true WO2010050387A1 (fr) 2010-05-06

Family

ID=42128752

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2009/068095 WO2010050387A1 (fr) 2008-10-31 2009-10-21 Matériau de revêtement aqueux résistant à l’eau

Country Status (1)

Country Link
WO (1) WO2010050387A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4749500B1 (ja) * 2010-09-06 2011-08-17 ハニー化成株式会社 水性表面処理剤組成物

Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130450A (ja) * 1996-10-30 1998-05-19 Jsr Corp 水系分散体
JPH11349828A (ja) * 1998-06-08 1999-12-21 Toyo Ink Mfg Co Ltd 樹脂組成物および水性樹脂組成物ならびにその硬化物
JP2000198856A (ja) * 1998-10-19 2000-07-18 Vianova Resins Ag 自己架橋性コポリマ―水性分散物、その製造方法および塗料用バインダ―としての用途
JP2000265023A (ja) * 1999-03-12 2000-09-26 Unitika Chem Co Ltd 耐水性樹脂組成物
JP2001302966A (ja) * 2000-04-26 2001-10-31 Dainippon Toryo Co Ltd 水性塗料組成物
JP2001522922A (ja) * 1997-11-10 2001-11-20 ビーエーエスエフ アクチェンゲゼルシャフト カルボニルポリマー分散液、顔料およびポリアミンよりなる水性組成物
JP2002003778A (ja) * 2000-06-20 2002-01-09 Dainippon Toryo Co Ltd 水性塗料用樹脂組成物
JP2003286450A (ja) * 2002-01-25 2003-10-10 Nippon Paint Co Ltd 水性塗料組成物及び複層塗膜形成方法
JP2005029685A (ja) * 2003-07-14 2005-02-03 Mitsubishi Rayon Co Ltd 軟質下地保護用水性被覆材
JP2005307163A (ja) * 2004-03-24 2005-11-04 Nippon Paint Co Ltd エマルション樹脂および水性塗料組成物
JP2007291212A (ja) * 2006-04-24 2007-11-08 Mitsubishi Rayon Co Ltd 水系塗料用組成物、その製造方法および被膜
JP2008239779A (ja) * 2007-03-27 2008-10-09 Dainippon Toryo Co Ltd 低汚染性水性被覆組成物及びその被覆物

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10130450A (ja) * 1996-10-30 1998-05-19 Jsr Corp 水系分散体
JP2001522922A (ja) * 1997-11-10 2001-11-20 ビーエーエスエフ アクチェンゲゼルシャフト カルボニルポリマー分散液、顔料およびポリアミンよりなる水性組成物
JPH11349828A (ja) * 1998-06-08 1999-12-21 Toyo Ink Mfg Co Ltd 樹脂組成物および水性樹脂組成物ならびにその硬化物
JP2000198856A (ja) * 1998-10-19 2000-07-18 Vianova Resins Ag 自己架橋性コポリマ―水性分散物、その製造方法および塗料用バインダ―としての用途
JP2000265023A (ja) * 1999-03-12 2000-09-26 Unitika Chem Co Ltd 耐水性樹脂組成物
JP2001302966A (ja) * 2000-04-26 2001-10-31 Dainippon Toryo Co Ltd 水性塗料組成物
JP2002003778A (ja) * 2000-06-20 2002-01-09 Dainippon Toryo Co Ltd 水性塗料用樹脂組成物
JP2003286450A (ja) * 2002-01-25 2003-10-10 Nippon Paint Co Ltd 水性塗料組成物及び複層塗膜形成方法
JP2005029685A (ja) * 2003-07-14 2005-02-03 Mitsubishi Rayon Co Ltd 軟質下地保護用水性被覆材
JP2005307163A (ja) * 2004-03-24 2005-11-04 Nippon Paint Co Ltd エマルション樹脂および水性塗料組成物
JP2007291212A (ja) * 2006-04-24 2007-11-08 Mitsubishi Rayon Co Ltd 水系塗料用組成物、その製造方法および被膜
JP2008239779A (ja) * 2007-03-27 2008-10-09 Dainippon Toryo Co Ltd 低汚染性水性被覆組成物及びその被覆物

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4749500B1 (ja) * 2010-09-06 2011-08-17 ハニー化成株式会社 水性表面処理剤組成物

Similar Documents

Publication Publication Date Title
US7235603B2 (en) Ambient curable polymer
JP5016817B2 (ja) 水性樹脂分散体の製造方法
CN1676560A (zh) 水分散型丙烯酸树脂组合物
JP5100948B2 (ja) 樹脂組成物
JP4179632B2 (ja) 水をベースとする光沢ラッカーで使用するための水性ポリマー分散物
JP5043391B2 (ja) 硬化型水性樹脂組成物
JP4781562B2 (ja) 水性インク組成物用水性エマルション組成物
JP2007297491A (ja) 硬化型水性樹脂組成物
WO2010050387A1 (fr) Matériau de revêtement aqueux résistant à l’eau
JPH07247460A (ja) 水性被覆材組成物
JP5048966B2 (ja) 水系塗料用組成物、その製造方法および被膜
JP5336816B2 (ja) 水性被覆材およびエマルションの製造方法
JP4673010B2 (ja) 硬化型水性樹脂組成物
CN114316160A (zh) 一种丙烯酸乳液聚合物及基于聚合物的水性涂料制备方法
JP2006321889A (ja) 一液常温硬化型組成物
JP4333012B2 (ja) 水性樹脂分散体およびその製造法
JP5348729B2 (ja) 水性樹脂分散体の製造方法
JP2001335670A (ja) 水性樹脂組成物及び架橋剤
JP2010138256A (ja) エマルションの製造方法、及び水性被覆材
JP4948047B2 (ja) 酸化硬化型塗料
JP6102972B2 (ja) エマルションの製造方法、及び水性被覆材の製造方法
JP4608259B2 (ja) 水性樹脂組成物
JP2000191881A (ja) 樹脂組成物
JP5618131B2 (ja) エマルションの製造方法
JP2006316151A (ja) ヒドラジド基含有共重合体、製造方法及び該共重合体を含む樹脂組成物

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09823499

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 09823499

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP