CN100348632C - Crosslinked microparticle, hydrophilic treatment agent, method for coating hydrophilic capsule and hydrophilic capsule - Google Patents

Crosslinked microparticle, hydrophilic treatment agent, method for coating hydrophilic capsule and hydrophilic capsule Download PDF

Info

Publication number
CN100348632C
CN100348632C CNB2004100479671A CN200410047967A CN100348632C CN 100348632 C CN100348632 C CN 100348632C CN B2004100479671 A CNB2004100479671 A CN B2004100479671A CN 200410047967 A CN200410047967 A CN 200410047967A CN 100348632 C CN100348632 C CN 100348632C
Authority
CN
China
Prior art keywords
hydrophilic
monomer
resin
quality
acid
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
CNB2004100479671A
Other languages
Chinese (zh)
Other versions
CN1572804A (en
Inventor
饭田美和
印部俊雄
牛尾朗
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nippon Paint Surf Chemicals Co Ltd
Nippon Paint Holdings Co Ltd
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 CN1572804A publication Critical patent/CN1572804A/en
Application granted granted Critical
Publication of CN100348632C publication Critical patent/CN100348632C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F216/00—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—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 an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • C08F216/14—Monomers containing only one unsaturated aliphatic radical
    • C08F216/1416—Monomers containing oxygen in addition to the ether oxygen, e.g. allyl glycidyl ether
    • C08F216/1425—Monomers containing side chains of polyether groups
    • C08F216/1433—Monomers containing side chains of polyethylene oxide groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/305—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/306—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and polyethylene oxide chain in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F226/00—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/06—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 a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a heterocyclic ring containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/24—Homopolymers or copolymers of amides or imides
    • C09D133/26—Homopolymers or copolymers of acrylamide or methacrylamide

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The invention provides crosslinkable microparticles, which form a hydrophilic coating layer having excellent hydrophilicity, hydrophilicity maintenance after the adhesion of contaminants and adhesion on metallic surfaces such as aluminum or aluminum alloy.The crosslinkable microparticles are obtained by the copolymerization of monomer components comprising: (a) 30-95 wt% of a monomer represented by the following formula 1; (b) 5-60 wt% of a monomer having a polyoxyalkylene chain and polymerizable double bond; and (c) 0-50 wt% of other polymerizable monomers. In formula 1, R1 represents H or methyl group, and R2 represents CH2 or C2H4. Particularly.

Description

The coating method of crosslinkable microparticles, hydrophilic finishing agent, hydrophilic coating film and hydrophilic coating film
Technical field
The present invention relates to the coating method and the hydrophilic coating film of crosslinkable microparticles, hydrophilic finishing agent, hydrophilic coating film.
Background technology
At metal material surface, carrying out various surface treatments.Especially aluminium and alloy thereof, it is in light weight, and has excellent processibility and thermal conductivity, thereby it is widely used in heat exchanger.
During refrigeration such as air-conditioning, scatterer for its heat exchanger, airborne attachment of moisture forms water of condensation in spreader surface, because this water droplet causes filling, the result has increased ventilation resistance, the exchange efficiency of heat exchanger is descended, also exist in addition because of producing noise, the water droplet problem such as pollute of dispersing.In order to prevent that such problem from taking place, be to carry out hydrophilicity-imparting treatment on the surface of scatterer all the time.
In recent years, as the performance requriements to hydrophilicity-imparting treatment, the hydrophilic persistence that is stained with under the pollution substance situation becomes important.This is because have various indoor suspended solids in the environment for use of air-conditioning etc., comprising plastics such as Palmiticacid, stearic acid, paraffinic acid with lubricator, pollution substance such as phthalic acid di-isooctyl, in this case, these materials stick to spreader surface, and wetting ability is significantly reduced.
As hydrophilicity-imparting treatment, disclose the composition (for example consulting patent documentation 1) of the polymkeric substance that is used for hydrophilicity-imparting treatment, said composition contains polymer such as acrylic acid polymer, forms the polymers such as polyethylene oxide of hydrogen bond with this polymer.This is a technology of improving hydrophilic persistence, but this technology is not considered the persistence under the pollution substance adhesion situation such as Palmiticacid, and about concerning the persistence of pollution substance, this technology is inadequate.In addition, it also is inadequate for the adaptation under the attachment of moisture state.
In addition, also disclose the hydrophilic surface treatment agent that contains carboxymethyl cellulose salt, N hydroxymethyl acrylamide, polyacrylic acid and polyethylene oxide, and the hydrophilic surface treating water solution (for example consulting patent documentation 2,3) that contains aqueous high molecular compound, water-base resin and the N hydroxymethyl acrylamide of being with polyoxyalkylene chain.In these hydrophilic surface treated substances, N hydroxymethyl acrylamide is sneaked into wherein as monomer, under the adherent situation of pollution substance, hydrophilic persistence is inadequate.
In addition, the monoene class monomer, (methyl) acrylic amide monoene class monomer, N hydroxymethyl acrylamide etc. that also disclose by the band polyoxyalkylene chain have N-methylol and the bridging property unsaturated monomer of the two keys of polymerizability and the hydrophilic cross-linking polymer particles (consulting patent documentation 4～6) that other monomers obtain.
These disclosed technology are not considered hydrophilic persistence under the pollution substance adhesion situations such as Palmiticacid.In addition, for N hydroxymethyl acrylamide etc., it only is to wish that particle takes place crosslinked and the blended composition, and the amount ratio of N hydroxymethyl acrylamide etc. is less, and resulting like this hydrophilic cross-linking polymer particles can not satisfy hydrophilic persistence under pollution substance adhesion situation.
Patent documentation 1 spy opens flat 6-322292 communique (page 2)
Patent documentation 2 spies open flat 6-322552 communique (page 2)
Patent documentation 3 spies open flat 7-102189 communique (page 2)
Patent documentation 4 spies open flat 8-120003 communique (page 2)
Patent documentation 5 spies open 2000-248225 communique (page 2)
Patent documentation 6 spies open 2002-302644 communique (page 2)
Summary of the invention
In view of described situation, the purpose of this invention is to provide crosslinkable microparticles and hydrophilic finishing agent, institute's crosslinkable microparticles that provides and hydrophilic finishing agent are applicable to metal, especially aluminium and alloy thereof, the wetting ability excellence of the hydrophilic coating film of its formation, especially under pollutant adheres to, the hydrophilic persistence excellence of described hydrophilic coating film, and also the adaptation of described hydrophilic coating film is also excellent.
The present invention relates to crosslinkable microparticles, it is characterized by, it is obtained by the monomer component copolymerization, and described monomer component is made up of the have polyoxyalkylene chain and the monomer (b) of the two keys of polymerizability and other polymerizable monomer (c) of 0～50 quality % as shown in the formula the monomer (a) shown in (1), 5 quality %～60 quality % of 30 quality %～95 quality %.
Figure C20041004796700051
(in the formula, R 1Expression hydrogen or methyl; R 2Expression CH 2Perhaps C 2H 4)
Preferred described monomer (b) is the compound with following formula (2) and/or following formula (3) expression.
Figure C20041004796700061
(R in the formula 3And R 4Identical or different, expression hydrogen or methyl; R 5Expression hydrogen, methyl, SO 4H, SO 4Na or SO 4NH 4N represents 6～300 integer);
Figure C20041004796700062
(in the formula, R 6And R 8Identical or different, expression hydrogen or methyl; R 9Expression hydrogen, methyl, SO 4H, SO 4Na or SO 4NH 4R 7Expression CH 2Perhaps
Figure C20041004796700063
M represents 6～300 integer).
Preferred described monomer (b) is to contain the compound of polyoxyalkylene chain more than or equal to 50 quality %.
Preferred described other polymerizable monomer (c) contains (methyl) vinylformic acid.
The present invention relates to hydrophilic finishing agent, it is characterized by, it contains described crosslinkable microparticles and hydrophilic resin.
Preferred described hydrophilic resin be selected from by acid number more than or equal to 200 or the group formed more than or equal to 200 acrylic resin, polyvinyl alcohol, carboxymethyl cellulose and their modified resin of hydroxyl value at least a kind of material.
The proportion optimization of described crosslinkable microparticles and described hydrophilic resin is 1/99 to 80/20.
The present invention relates to the coating method of hydrophilic coating film, it is characterized by, it comprises the operation that is coated with described hydrophilic finishing agent.
The invention still further relates to hydrophilic coating film, it is characterized by, it is that coating method by described hydrophilic coating film forms.
Embodiment
Explain the present invention below.
Crosslinkable microparticles of the present invention is the resin particle that is formed by multipolymer, and the monomer component of this multipolymer is made up of the monomer (a) of described formula (1) expression, monomer (b) and other polymerizable monomer (c) with polyoxyalkylene chain and the two keys of polymerizability.In the described crosslinkable microparticles, functional group reactions such as the carboxyl of the methylol of described (a), hydroxyethyl and described (b), hydroxyl; Condensation reaction between methylol, the hydroxyethyl; The carboxyl of described (c) and hydroxyl reaction are so it when using as composition of hydrophilic finishing agent, can form the firm hydrophilic coating film of water-insoluble.In addition, the wetting ability of described crosslinkable microparticles is strong, has more unreacted functional group, so when using as the composition of hydrophilic finishing agent, the hydrophilic resin reaction with other does not damage wetting ability, can improve the hydrophilic persistence after the pollution significantly.Further, because described crosslinkable microparticles is less to the swelling ratio of water, in water, dissolve so also can suppress established hydrophilic coating film.
The monomer (a) of described formula (1) expression is N hydroxymethyl acrylamide, N-methylol methacrylamide, N-hydroxyethyl acrylamide or N-hydroxyethyl methacrylamide.If hydrophilic finishing agent contains the crosslinkable microparticles that obtains under the situation of the monomer (a) that uses described formula (1) expression, just can form the tunicle of hydrophilic persistence and adaptation excellence.These materials can use separately, also can more than 2 kinds or 2 kinds and use.
Described crosslinkable microparticles obtains the monomer component copolymerization, the monomer (a) of described formula (1) that described monomer component contains expression following be limited to 30 quality %, on be limited to 95 quality %.Because the proportional quantity of the monomer (a) of described formula (1) expression in described scope, so it not only has the function as crosslinked composition, also has the function as principal constituent in the composition that forms hydrophilic coating film.Promptly, mix when using as just the function of crosslinked composition, general its proportional quantity is with less than described scope, and for crosslinkable microparticles of the present invention, use the monomer (a) of described formula (1) expression with the proportional quantity of described scope, even so after the copolymerization, still residual in crosslinkable microparticles have methylol, a hydroxyethyl.Therefore, when using the hydrophilic finishing agent that contains described crosslinkable microparticles to form hydrophilic coating film, can obtain firm adaptation and hydrophilic persistence with other hydrophilic resin reaction.Thereby, even adhered on the hydrophilic coating film of formation plastics such as Palmiticacid, stearic acid, paraffinic acid with lubricator, after the pollution substance such as phthalic acid di-isooctyl, the still sustainable adequate time of the wetting ability of described hydrophilic coating film.
In addition, for obtaining crosslinkable microparticles, be cause by its proportional quantity by the monomer (a) that mixes described formula (1) expression, degree of crosslinking also increases.Therefore, the hydrophilic coating film that can suppress to form can form the excellent tunicle of adaptation (adaptation when tunicle exposes) because of moisture causes dissolving in moisture.
With respect to the monomer component of 100 quality %, the proportional quantity of the monomer (a) of preferred described formula (1) expression following be limited to 30 quality %, on be limited to 90 quality %.Proportional quantity is during less than 30 quality %, and after hydrophilic coating film was contaminated, hydrophilic persistence may descend.Proportional quantity then might be made difficulty greater than 90 quality %.Described lower limit more preferably is 40 quality %, and the described upper limit more preferably is 80 quality %.
Described monomer (b) just be not particularly limited, but preferred its is the compound of described formula (2) and/or described formula (3) expression so long as have polyoxyalkylene chain and the monomer of the two keys of polymerizability.Can obtain water-dispersion crosslinkable microparticles stable, the wetting ability excellence thus.
In described formula (2), described R 3With described R 4Identical or different, expression hydrogen or methyl.Described R 5Expression hydrogen, methyl, SO 4H, SO 4Na or SO 4NH 4
In described formula (2), n represents to be limited to down 6, on be limited to 300 integer.N is less than 6 o'clock, dispersion stabilization, wetting ability deficiency, and n is greater than 300 manufacturings difficulty that becomes.Described lower limit more preferably is 30, and the described upper limit more preferably is 200.
In described formula (3), described R 6And R 8Identical or different, expression hydrogen or methyl.Described R 9Expression hydrogen, methyl, SO 4H, SO 4Na or SO 4NH 4Described R 7Expression CH 2Perhaps phenyl ring (coming out with chemical formulation).
In described formula (3), m represents to be limited to down 6, on be limited to 300 integer.M is less than 6 o'clock, dispersion stabilization, wetting ability deficiency, and m is greater than 300 manufacturings difficulty that becomes.Described lower limit more preferably is 30, and the described upper limit more preferably is 200.
As described monomer (b), have no particular limits, except that the compound of described formula (2), described formula (3) expression, can list for example methoxy poly (ethylene glycol) monomethacrylates, methoxy poly (ethylene glycol) mono acrylic ester, octyloxy polyethylene glycol-propylene glycol mono acrylic ester etc.These can use separately, also can more than 2 kinds or 2 kinds and use.
Preferred described monomer (b) is the compound of polyoxyalkylene chain content more than or equal to 50 quality %.Wherein, so-called more than or equal to 50 quality %, when the quality of all solids composition that is meant the monomer (b) of use was counted 100 quality %, all solids composition quality of polyoxyalkylene chain portion was more than or equal to 50 quality %.Less than 50 quality %, the wetting ability of hydrophilic coating film has the danger of decline.The polyoxyalkylene chain that more preferably described monomer (b) contains following be limited to 80 quality %, on be limited to 99 quality %.
With monomer component is 100 quality %, the following 5 quality % that are limited to of the proportional quantity of described monomer (b), on be limited to 60 quality %.Its proportional quantity less than 5 quality %, the dispersiveness of crosslinkable microparticles descends in hydrophilic finishing agent, has again, and the wetting ability of hydrophilic coating film has the danger of decline.Its proportional quantity surpasses 60 quality %, and then the adaptation of hydrophilic coating film is insufficient, the danger that the film after the pollution has hydrophilic persistence to descend.Described lower limit more preferably is 10 quality %, and the described upper limit more preferably is 40 quality %.
Described other polymerizable monomer (c) is as long as have the polymerizability unsaturated link(age) in its 1 molecule, can with the monomer (a) of described formula (1) expression and the compound of described monomer (b) copolymerization, just specific restriction can be do not done, for example vinylformic acid can be enumerated, methacrylic acid, methylene-succinic acid, toxilic acid etc., vinyl-acetic ester, vinylformic acid 2-hydroxyl ethyl ester, Propylene glycol monoacrylate etc., the N-vinyl acetamide, the N-vinyl formamide, the N-vinyl pyrrolidone, the N-vinyl imidazole, vinyl cyanide, methyl acrylate, methyl methacrylate, vinylbenzene, the tensio-active agent that contains unsaturated double-bond, acrylamide, Methacrylamide, N methacrylamide, the N-vinyl sulfonic acid, the N-allyl sulphonic acid, Sodium styrene sulfonate, the 2-acrylamide, 2-methyl propane sulfonic acid etc.Moreover, can be the unsaturated monomer that can be used for radical polymerization usually also with the acrylate beyond methyl acrylate, the methyl methacrylate, methacrylic ester etc.Wherein, from improving the wetting ability angle of the crosslinkable microparticles that obtains, preferably use vinylformic acid, methacrylic acid.These monomers can use separately, also can more than 2 kinds or 2 kinds and use.
With monomer component is 100 quality %, described other proportional quantity following of polymer monomer (c) be limited to 0 quality %, on be limited to 50 quality %.When described proportional quantity surpassed 50 quality %, the wetting ability of the crosslinkable microparticles that obtains, bridging property had the danger of decline, and the hydrophilic persistence in the contaminated back of hydrophilic coating film also has the danger of decline.The described upper limit more preferably is 30 quality %.
The water swelling ratio of preferred crosslinkable microparticles of the present invention is smaller or equal to 1.5.Thus, under the situation that forms hydrophilic coating film, even be exposed in the moisture, the adaptation that also can suppress tunicle descends.For acquisition smaller or equal to 1.5 water swelling ratio, can be by the monomer (a) of described formula (1) expression, described monomer (b) and described other the proportioning of polymerizable monomer (c) be set at described proportioning, suitably set reaction conditions and obtain water swelling ratio smaller or equal to 1.5.Described water swelling ratio more preferably is limited to 1.0 down, on be limited to 1.3.Moreover the water swelling ratio of this specification sheets is the value of calculating with " particle diameter in the particle diameter/solvent in water swelling ratio=aqueous solution ".Particle diameter is the value of measuring with electrophoresis light-scattering photometer photal ELS-800 (big mound electronics corporation produces).
The manufacturing of crosslinkable microparticles of the present invention can be by for example under the condition that does not have dispersion stabilizer, described N-methylol (methyl) acrylamide with 30 quality %～95 quality %, the monomer (b) of 5 quality %～60 quality % and described other polymerizable monomer (c) of 0～50 quality % with the two keys of described polyoxyalkylene chain and polymerizability, in water Combination organic solvent, or copolymerization is incompatible in the mixed solvent that forms of water Combination organic solvent and water carries out the monomer solubilized of wherein said solvent for using, but the undissolved in fact solvent of multipolymer that generates.
Make polymerization process in the described crosslinkable microparticles, can and use dispersion agent.As described dispersion agent, for example can list polyvinylpyrrolidone, polyvinyl alcohol, poly carboxylic acid etc. and disperse resins, or negatively charged ion, positively charged ion, the various tensio-active agents of nonionic etc.
In the manufacturing of crosslinkable microparticles of the present invention, the copolymerization of the monomer component of being made up of described (a), described (b) and described (c) can be carried out in following solvents, for example mixed solvent of ether solvent, methoxypropanol, these solvents and water such as alkylene glycol monoalkyl ethers (for example ethylene glycol monobutyl ether etc.) etc.
By described (a), the copolymerization of the monomer component that described (b) and described (c) forms is carried out in the presence of radical polymerization initiator usually.As described radical polymerization initiator, there is no particular limitation, and common employed radical polymerization initiator can use.Can enumerate for example superoxide such as benzoyl peroxide, dodecanoyl superoxide, ditertiary butyl peroxide, cumene hydroperoxide, the sad tert-butyl ester of mistake, tert-butyl hydroperoxide-2-ethylhexanoate; 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two (4-methoxyl group-2,4-methyl pentane nitrile), dimethyl-2,2 '-azo-bis-iso-butyl, 4,4 '-azo two azo-compounds such as (4-cyanopentanoic acids); 2,2 '-azo two (2-amidine propane) dihydrochloride, 2,2 '-azo two (N, N '-dimethylene isobutyl amidine), 2, amidine compounds such as 2 '-azo two (N, N '-dimethylene isobutyl amidine) dihydrochloride; Persulfide such as Potassium Persulphate, ammonium persulphate class initiator or therein and with a class initiator of Sulfothiorine, amine etc.They can use separately, also can more than 2 kinds or 2 kinds and use.With respect to monomeric total amount, generally the usage quantity with initiator is set in the scope of 0.2 quality %～5 quality %.
The polymerization temperature of described copolymerization can change according to the kind of the polymerization starter that uses etc., usually, 70 ℃ within the range having a lower limit of of temperature that are fit to, on be limited in 140 ℃ the scope.Polymerization temperature is during less than 70 ℃, and bridging property is insufficient, and polymerization temperature surpasses 140 ℃, then is difficult to the control reaction.Described lower limit more preferably is 90 ℃, and the described upper limit more preferably is 120 ℃.Reaction times generally is 0.2～5 hour.Reaction times less than 0.2 hour, then bridging property is insufficient, even the reaction times surpasses 5 hours, reacts constant, is disadvantageous economically.Be not less than 90 ℃ by polymerization temperature is set at, and can make in the particle take place crosslinked.Crosslinking reaction in the particle generally takes place during less than 70 ℃ in polymerization temperature hardly in the polymerization process, thus generally after polyreaction, be not less than 90 ℃ temperature with the polymkeric substance heating that generates 0.2～5 hour, make take place in the particle crosslinked.
In order to make the polymer beads in the polyreaction or after the polyreaction that crosslinking reaction in the particle take place quickly, can in polymerization reaction system, add catalyst for cross-linking reaction as required.As the catalyzer of described crosslinking reaction, can list for example strong acid catalyst such as Witco 1298 Soft Acid, tosic acid; Methacrylic acid sulfo-ethyl ester etc. contains the strong acid catalyst of the two keys of polymerizability etc.
As the particle diameter of the above-mentioned crosslinkable microparticles that obtains like that, there is no particular limitation, but from the stability of crosslinkable microparticles, its particle diameter is generally at 0.03～1 μ m, and preferred range is 0.05～0.6 μ m.
The hydrophilic finishing agent that contains described crosslinkable microparticles and hydrophilic resin can form the hydrophilic tunicle of hydrophilic persistence and adaptation excellence.Such hydrophilic finishing agent also is one of the present invention.Described hydrophilic finishing agent is used for metal, especially when aluminium and alloy thereof, can form the hydrophilic tunicle of hydrophilic persistence and adaptation excellence.
For described hydrophilic resin, if the resin of possess hydrophilic property just is not particularly limited, can list the unsaturated polymerization monomer that for example contains carboxyl and/or hydroxyl or unsaturated polymerization aqueous high molecular compound, the natural sex macromolecular compound or derivatives thereof that contains carboxyl and/or hydroxyl, aqueous alkide resin, aqueous polyester resin, water-based polybutadiene, aqueous polyamide resin, aqueous epoxy resins, waterborne polyurethane resin, aqueous phenolic aldehyde resin, water-compatible amino resin etc.
As unsaturated polymerization monomer that contains described carboxyl and/or hydroxyl or unsaturated polymerization aqueous high molecular compound, can list for example poly-(methyl) vinylformic acid, (methyl) vinylformic acid-(methyl) acrylate copolymer, vinylbenzene-(methyl) acrylic copolymer, the polyvinyl acetate resin is carried out the partly-hydrolysed polyvinyl alcohol that obtains, polyvinylpyrrolidone etc.Wherein, the multipolymer of poly-(methyl) vinylformic acid, (methyl) vinylformic acid-(methyl) acrylate can improve alkali resistance and corrosion resistant feeding habits.Polyvinyl alcohol after the polyvinyl acetate resin is partly-hydrolysed has the deodorization of giving and hydrophilic effect.Polyvinylpyrrolidone has the effect that part improves hydrophilic persistence.In addition, in the scope of not damaging effect of the present invention, can add the polymkeric substance of polyester vinyl acetate resin, polyvinyl chloride (PVC) RESINS, vinyl chloride-vinyl acetate copolymer, (methyl) acrylamide etc.
As the natural sex macromolecular compound or derivatives thereof that contains described carboxyl and/or hydroxyl, can list for example carboxymethyl cellulose (CMC), Natvosol (HEC), hydroxypropylcellulose (HPC), methylcellulose gum (MC), ethyl cellulose (EC), Type 3U derivatived celluloses such as (EHEC) and methylcellulose gum derivative etc.Certainly, cellulosic derivative is not limited only to this, can be cellulosic carboxymethylether, carboxyethyl ester, hydroxymethyl ether, hydroxyethyl ether, also can be starch acetates, starch phosphates.The derivative of methylcellulose gum is not limited only to this, can be the affixture that forms behind addition hydroxyethyl, hydroxypropyl on the methylcellulose gum.In addition, can also use contain carboxyl or addition oxyethane (EO) or the glue class of propylene oxide (PO), the derivative of polyose, also can use tannic acid, lignin sulfonic acid, alginic acid, hyaluronic acid etc.In addition, also can use polyglutamic acid (PGA), when using poly-paddy chloric acid, can improve hydrophilic persistence significantly, polyglutamic acid has the branch of r-PGA and α-PGA, with any can.
As described aqueous alkide resin, for example can list the material that diprotic acid condensation such as polyvalent alcohols such as glycerine, tetramethylolmethane, ethylene glycol, trimethylolethane and the higher fatty acid that obtains from grease such as Palmiticacid, Tetra hydro Phthalic anhydride, maleic anhydride is obtained.
As described aqueous polyester resin, the acid anhydrides that for example can list hydroxyl in the vibrin and trimellitic acid carries out the half ester reaction, with the residual carboxyls of neutralization such as amine, the product that obtains after the Water-borne modification.In addition, make the reaction of polyoxyethylene glycol and polyprotonic acid in addition, with the product of polyester resin aqueousization.
As described water-based polybutadiene, for example can list with catalyzer 1 after polymerizing butadiene, 2-type, 1, the product of 4-type, they can use together.These materials can utilize heat, and superoxide, Sulfur etc. make its film forming.
As described aqueous polyamide resin, can list water-soluble substances that changes into by following product etc., described product is (1) product, (2) 1 by the ε-Ji Neixianan ring-opening polymerization, polycondensation product, the ring-opening polymerization of (5) ω-dodecanoic lactam (ω-ラ ウ system ラ Network system) or the polycondensation product of 12 amino dodecanoic acid of the polycondensation product of the polycondensation product of 6-hexanediamine and hexanodioic acid, (3) 1,6-hexanediamines and sebacic acid, the amino undecanoic acid of (4) 11-.
As described aqueous epoxy resins, can list two of aliphatic polyol for example-or poly--glycidyl ether, dicarboxylic acid 2-glycidyl ester, nitrogenous heterocyclic epoxy compounds, they belong to water-soluble epoxy resin.In addition, can also list the suitable emulsifying agent of adding in the mixed solution of water or water and organic solvent, make the product of Resins, epoxy dispersion and emulsion; By making epoxy resin modification, and it is dissolved in the water or the product of dispersion and emulsion, they belong to aqueous acidic Resins, epoxy, specifically, it is to introduce hydrophilic radical in Resins, epoxy, perhaps introduce cation groups such as anionic group such as carboxyl or amino, neutralize, form the polymer electrolyte of water-based with hydroxyl or acid.
As described urethane resin, can list and for example in molecule, introduce anionic group or cation group, the aqueous product that is transformed into.In addition, can also list endways and to be addition hydrosulphite on the urethane prepolymer of isocyanate group, to the isocyanate group protection, the aqueous product that is transformed into because of the wetting ability of sulfonate simultaneously.In addition, can also list with end-capping reagent with urethane prepolymer end-blocking after, forcibly carry out emulsification dispersive product.
As described aqueous phenolic aldehyde resin, for example can list aldehydes such as formaldehyde, furfurals at phenol, xylenol, to alkylphenol, p-phenyl phenol, chlorophenol, dihydroxyphenyl propane, sulfocarbolic acid, Resorcinols etc. have addition on the material of phenol hydroxyl, condensation, the aqueous product that resulting polymer substance is transformed into.These materials are divided into classes such as phenol-formaldehyde resin, cresol-formaldehyde resin, phenol-furfural resin, resorcinol resin usually.For described aqueous phenolic aldehyde resin, form crosslinkedly at interlaminar resin, the effect that improves film-forming properties is arranged.
As described water-compatible amino resin, can list for example normal-butyl melamine resin, melamine resin such as isobutyl melamine resin and the water-soluble substances that is transformed into by urea resin etc.These resins generally are with on the aminocompounds such as aldehyde such as formaldehyde, Paraformaldehyde 96 and trimeric cyanamide, benzo guanamine, carry out addition reaction or addition-condensation reaction, are that 1～4 monohydroxy-alcohol carries out etherificate and obtains with the product carbonatoms that obtains.For described water-compatible amino resin, form crosslinkedly at interlaminar resin, the effect that improves film-forming properties is arranged.As described melamine resin, can list for example alkoxy methyl melamine resin, wherein alkoxyl group is methoxyl group, oxyethyl group, n-butoxy, isobutoxy etc.
Preferred described hydrophilic resin is at least a material that is selected from the group of being made up of more than or equal to acrylic resin, polyvinyl alcohol, carboxymethyl cellulose and their modified resin of 200mgKOH/g more than or equal to 200mgKOH/g or hydroxyl value acid number.Can further improve the hydrophilic persistence and the adaptation of formed hydrophilic coating film thus.
For the acrylic resin of described acid number, when acid number deficiency 200mgKOH/g, the hydrophilic persistence of hydrophilic coating film and the danger that adaptation reduces are arranged more than or equal to 200mgKOH/g.Described acid number more preferably lower limit is that 200mgKOH/g, the upper limit are 800mgKOH/g.
For the acrylic resin of described hydroxyl value, when hydroxyl value deficiency 200mgKOH/g, the hydrophilic persistence of hydrophilic tunicle and the danger that adaptation reduces are arranged more than or equal to 200mgKOH/g.Described hydroxyl value more preferably be limited to down 200mgKOH/g, on be limited to 1500mgKOH/g.
In the described hydrophilic finishing agent, the proportioning of described crosslinkable microparticles and described hydrophilic resin more preferably is 1/99 to 80/20, and during described proportioning less than 1/99, the hydrophilic persistence of hydrophilic coating film has the danger of reduction, described proportioning surpasses at 80/20 o'clock, the danger that then has processibility to descend.Described proportioning more preferably is 5/95 to 50/50.
To form colored hydrophilic coating film is purpose, can add pigment in described hydrophilic finishing agent.Coloured hydrophilic coating film has the market requirement, be in hydrophilic finishing agent, to add pigment and form colored hydrophilic tunicle in the past, but the hydrophilic tunicle that obtains by in the past hydrophilic finishing agent, along with hydrophilic resin is dissolved in water, pigment also dissolves, so tunicle can fade.In addition, pigment generally is hydrophobic, so pigment adds in the hydrophilic finishing agent, hydrophilic finishing agent just produces the problem that wetting ability worsens.Relative with it, for the coloured hydrophilic finishing agent that in containing the hydrophilic finishing agent of described crosslinkable microparticles, is added with pigment, because hydrophilic coating film is bonding with securely, so pigment indissoluble extremely fades hardly.In addition, the wetting ability height of hydrophilic coating film is not so almost cause that because of adding pigment wetting ability hinders.Therefore, use the hydrophilic finishing agent that contains described crosslinkable microparticles and pigment, coloured hydrophilic coating film of the tunicle decolouring that can be fully suppressed.As the pigment that adds, there is no particular limitation, can use normally used tinting pigments such as mineral dye, pigment dyestuff.Wherein preferably use through organic water dispersions of dispersion agent dispersive such as resin or tensio-active agents.
Described hydrophilic finishing agent can add other composition of necessary amount therein according to additional function, can list for example hydrophilic additives such as tensio-active agent, silica gel, titanium oxide, carbohydrate; Rust-inhibiting additives such as tannic acid, imidazoles, triazines, triazole species, guanine class, hydrazine class, resol, zirconium compounds, silane coupling agent; Linking agents such as melamine resin, Resins, epoxy, blocked isocyanate, amine, resol, silicon-dioxide, aluminium, zirconium; Antiseptic-germicide, dispersion agent, lubricant, deodovization agent, solvent etc.
The coating method that comprises the hydrophilic coating film of the operation that is coated with described hydrophilic finishing agent also is one of the present invention.Use the coating method of described hydrophilic coating film, the wetting ability of the hydrophilic coating film of formation, especially pollution substance adhere to later hydrophilic persistence excellence and adaptation is also excellent.This method is especially applicable to aluminium or its alloy.
In the coating method of hydrophilic coating film of the present invention, at first want metal sheets such as skimming treatment aluminum or aluminum alloy usually, secondly, carry out as required as the chemical treatment of non-corrosibility pre-treatment or the priming paint of coating corrosion-resisting resin.
As described skimming treatment, can adopt solvent degreasing, for example trieline, tetrachloroethylene, gasoline, the degreasing of normal hexane equal solvent, or employing alkali degreasing, for example use alkaline solutions such as sodium hydroxide, yellow soda ash, water glass, sodium phosphate, can adopt wherein any method as described skimming treatment.In addition, as described chemical treatment, can enumerate the phosphoric acid chromate treating; The application type chromate treating; Vinylformic acid, Resins, epoxy, the resinoid priming paint of phenol or urethane is handled; Chromate-free processing etc.For described phosphoric acid chromate treating, can utilize the treatment solution that is added with additive in chromic trioxide and the phosphoric acid to carry out.Can be by impregnated in the treatment solution or inject process liquid carries out described phosphoric acid chromate treating.
Preferred its chromium (Cr) amount of the antirust tunicle that obtains behind the described phosphoric acid chromate treating is 3～50mg/m 2Described chromium amount is less than 3mg/m 2The time, the rust-preventing characteristic deficiency surpasses 50mg/m 2Then can react, wetting ability is descended with hydrophilic coating film.The metals such as aluminum or aluminum alloy that formed antirust tunicle will be washed usually.At this moment washing was preferably carried out 10～30 seconds.
The agent of described application type chromate treating is to be used for the chromate treating agent that the coating of roller coating machine etc. is handled.In this case, the chromium amount in the tunicle is preferably 5～30mg/m 2
Described chromate-free treatment agent is the treatment agent that does not contain chromium, can list zirconium class treatment agent.As described zirconium class treatment agent, can list the mixture of polyacrylic acid and Zirconium tetrafluoride etc.
In the tunicle that described zirconium class treatment agent obtains, preferred Zr amount is 0.1～40mg/m 2Zr quantity not sufficient 0.1mg/m 2The time, erosion resistance is insufficient, and the Zr amount surpasses 40mg/m 2Then uneconomical.Behind chromate treating, remake the zirconium class and handle better effects if.
After the coating resin priming paint, carry out 10 seconds～1 minute baking 180～280 ℃ temperature.Film preferably at 0.5～2g/m 2Scope.Not enough 0.5g/m films 2The time, the rust-preventing characteristic deficiency surpasses 2g/m 2The danger that then has cost to uprise.
As the pre-treatment of the coating method of hydrophilic coating film of the present invention, described skimming treatment of arbitrary combination and necessary described chemical treatment usually.
The coating method of hydrophilic coating film of the present invention carries out the painting process of described hydrophilic finishing agent on the metallic surfaces such as aluminum or aluminum alloy of implementing described pre-treatment.As coating process, can list rolling method, bar is coated with method (barcoat), pickling process, gunite, spread coating etc., and can be used for precoating.Preferably after coating, by 120～300 ℃ temperature, drying, the baking carried out 3 seconds～60 minutes obtain hydrophilic coating film.During 120 ℃ of storing temperature less thaies, can not obtain sufficient film-forming properties, the danger of tunicle dissolved is arranged behind the water retting.When storing temperature surpasses 300 ℃, resin dissolves, the impaired danger of wetting ability are arranged then.
From the above mentioned, the hydrophilic coating film that coating method by described hydrophilic coating film forms be the present invention at metal, the tunicle that forms on aluminium and the alloy surface thereof especially, its wetting ability, especially pollutent adheres to later hydrophilic persistence excellence, and adaptation is also excellent.Hydrophilic tunicle so also is one of the present invention.
The thickness of described hydrophilic coating film is preferably greater than and equals 0.05g/m 2, more preferably be 0.1～2g/m 2The not enough 0.05g/m of thickness 2The time, the hydrophilic persistence of film and processibility deficiency.
Crosslinkable microparticles of the present invention is the multipolymer that is obtained by the monomer component copolymerization, and described monomer component is made up of the monomer (a) of described formula (1) expression of 30 quality %～95 quality %, the contain polyoxyalkylene chain and the monomer (b) of the two keys of polymerizability and other polymerizable monomers (c) of 0～50 quality % of 5 quality %～60 quality %.That is, the monomer (a) of described formula (1) expression is not only to use fewer amount as crosslinked composition, and its main component as the crosslinkable microparticles moiety is used, so the wetting ability height of described crosslinkable microparticles contains many unreacted functional groups.Therefore, use contains the hydrophilic finishing agent of described crosslinkable microparticles, when on metallic surfaces such as aluminium or its alloy, forming hydrophilic coating film, formed tunicle possess hydrophilic property, after even contaminated material pollutes, especially by plastics such as Palmiticacid, stearic acid, paraffinic acid with lubricator, after pollution substance such as phthalic acid Diisooctyl pollutes, it still can bring into play excellent hydrophilic persistence and adaptation.In addition, described crosslinkable microparticles is the smaller material of water swelling ratio, thereby has also suppressed established hydrophilic coating film and dissolve in water.Therefore, described crosslinkable microparticles is suitable for as the composition of hydrophilic finishing agent and uses.
Embodiment
Below enumerate embodiment, illustrate in greater detail the present invention, but the present invention is not limited only to these embodiment.
The preparation of Production Example 1 crosslinkable microparticles
The azo-initiator that will be dissolved in the monomer solution that forms in the methoxypropanol of 200 mass parts and produce by the N hydroxymethyl acrylamide of 70 mass parts and the methoxy poly (ethylene glycol) monomethacrylates of 30 mass parts (number of repeating unit is 100 Polyethylene Chain)) is dissolved in the solution that forms in the methoxypropanol of 50 mass parts by " ACVA " (Da mound chemical company of 1 mass parts, respectively from different mouths, under nitrogen atmosphere gas, in 105 ℃ of methoxypropanol that are added drop-wise to 150 mass parts, dropping time flavor 3 hours, reheat stir and made it polymerization in 1 hour.In the dispersion liquid that obtains, the median size of crosslinkable microparticles is that the water swelling ratio of 250nm, crosslinkable microparticles is 1.10, was determined as 17 seconds with No. 4 viscosity Ford cup, and the concentration of solids component is 20 quality %.The electrophoretic light scattering photometer that the median size of crosslinkable microparticles is produced with photal ELS-800 (Da mound electronics corporation) measures (following mensuration similarly).
The preparation of Production Example 2 crosslinkable microparticles
Use the N hydroxymethyl acrylamide of 60 mass parts, the methoxy poly (ethylene glycol) monomethacrylates of 20 mass parts (number of repeating unit is 100 Polyethylene Chain), the vinylformic acid of 10 mass parts and the acrylamide of 10 mass parts as monomer component, other and Production Example 1 are prepared equally.In the dispersion liquid that obtains, the median size of crosslinkable microparticles is that the water swelling ratio of 350nm, crosslinkable microparticles is 1.15, is determined as 18 seconds, the concentration of solids component with No. 4 viscosity Ford cup to be 20 quality %.
The preparation of Production Example 3 crosslinkable microparticles
Will be by the N hydroxymethyl acrylamide of 50 mass parts, the azo-initiator that the N-hydroxyethyl acrylamide of 20 mass parts and the methoxy poly (ethylene glycol) monomethacrylates of 20 mass parts (number of repeating unit is 100 Polyethylene Chain) are dissolved in the monomer solution that forms in the methoxypropanol of 200 mass parts and are produced by " ACVA " (Da mound chemical company of 1 mass parts) is dissolved in the solution that forms in the methoxypropanol of 50 mass parts, respectively from different mouths, under nitrogen atmosphere gas, in the mixture that 95 ℃ of 50 quality % Polyvinylpyrolidone (PVP) aqueous solution (weight-average molecular weight is 20000) that are added drop-wise to by pure and mild 10 mass parts of methoxy propyl of 140 mass parts form, the dropping time is 3 hours, and reheat stirs and made it polymerization in 1 hour.In the dispersion liquid that obtains, the median size of crosslinkable microparticles is that the water swelling ratio of 310nm, crosslinkable microparticles is 1.13, is determined as 16 seconds, the concentration of solids component with No. 4 viscosity Ford cup to be 21 quality %.The electrophoretic light scattering photometer that the median size of crosslinkable microparticles is produced with photalELS-800 (Da mound electronics corporation) measures.
The preparation of Production Example 4 crosslinkable microparticles
In the dispersion liquid that Production Example 1 obtains, add ion exchanged water, solvent is sloughed in decompression under 60 ℃, 70mmHg, obtains the crosslinkable microparticles that solids component is 10 quality %.
Compare Production Example 5
To be the mixture that forms of 5 methacrylic acid macrogol ester (MA50 that Japanese emulsifying agent company produces) and be dissolved in the solution that forms in 20 parts of ion exchanged waters by 21 parts of N-V-Pyrol RCs, 4 parts of N hydroxymethyl acrylamides, 5 parts of repeating unit numbers by the water miscible azo-initiator of dimethylethanolamine neutralization becoming (ACVA of big mound chemical company production) of 0.5 part of 1 part of usefulness, respectively from different mouths, under nitrogen atmosphere gas, be added drop-wise in 50 parts the ion exchanged water in 80 ℃, the dropping time is 3 hours, and reheat stirs and made it polymerization in 2 hours.Add 500 parts of ion exchanged waters therein and dilute, regulate the concentration of solids component.
Compare Production Example 6
As monomer component, use Block レ Application マ one PME-4000 (the methoxy poly (ethylene glycol) monomethacrylates that Nof Corp. produces of 20 mass parts, the number of repeating unit is 98 Polyethylene Chain), the propylene glycol monomethyl ether of the vinylformic acid of the N hydroxymethyl acrylamide of the acrylamide of 50 mass parts, 20 mass parts, 10 mass parts, 200 mass parts, 1.5 mass parts 2,2 '-azo two (2-methylbutyronitrile), other and Production Example 1 are prepared equally.In the dispersion liquid that obtains, the median size of crosslinkable microparticles is that the water swelling ratio of 270nm, crosslinkable microparticles is 1.41, and being determined as 16 seconds, the concentration of solids component with No. 4 Ford cup of viscosity is 20 quality %.
Production Example 7
To be dissolved in the monomer solution that forms in the pure water of 300 mass parts by the vinylformic acid 2-hydroxyl ethyl ester of the vinylformic acid of 80 mass parts and 20 mass parts and be dissolved in the solution that forms in the pure water of 50 mass parts by the ammonium persulphate of 1 mass parts, respectively from different mouths, under nitrogen atmosphere gas, in 70 ℃, be added drop-wise in the ion exchanged water of 300 mass parts, the dropping time is 90 minutes, and reheat stirs and made it polymerization in 1 hour, add ion exchanged water, be prepared into the acrylic resin that solids component is 10 quality %.In the acrylic resin that obtains, the acid number of solids component is 620, the hydroxyl value of solids component is 110.
Production Example 8
To be dissolved in the solution that forms in the pure water of 300 mass parts by the Sodium styrene sulfonate of the vinylformic acid of 60 mass parts and 40 mass parts and be dissolved in the solution that forms in the 50 mass parts pure water by the ammonium persulphate of 1 mass parts, respectively from different mouths, under nitrogen atmosphere gas, in 80 ℃, be added drop-wise in the ion exchanged water of 300 mass parts, the dropping time is 90 minutes, and reheat stirs and made it polymerization in 1 hour, add ion exchanged water, be prepared into solids component and be 10% acrylic resin.In the acrylic resin that obtains, the acid number of solids component is 470.
Embodiment 1～12 and comparative example 1～7
Composition with Production Example, comparison Production Example obtain mixes with the proportioning shown in the table 1, the preparation hydrophilic finishing agent.
Table 1
Embodiment Comparative example
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7
Crosslinkable microparticles (1) Production Example 1 2 2 3 2 2
Production Example 2 2 2 2
Production Example 3 2 2 2 2
Production Example 4 2
Compare Production Example 5 3.5
Compare Production Example 6 2
Hydrophilic resin (2) Production Example 7 2 1 2 1.5
Production Example 8 2 2 3
PAA 3 1 2 1 2 2 4 2.5 2
PVA 3 2 2 2
CMC 2 2
Hydrophilic resin (3) PEO 1 1 2 2 1 1 1 4.5 2.5
PAAm 2 1
PNaSS 1
Resol 0.1
Urea resin 0.1
PVP 1
Additive Ethylene acrylic 3
H 2ZrF 6 0.1
Pigment 0.2 0.2
N-MAM 3
Annotate: the percentage composition PNaSS sodium polystyrene sulfonate (weight-average molecular weight 50000) of numeral solids component
PAA polyacrylic acid (weight-average molecular weight 20000, acid number 780) resol weight-average molecular weight 600, cresols type
PVA polyvinyl alcohol (weight-average molecular weight 20000) urea resin UFR65 (production of Mitsui Chemicals company)
CMC carboxymethyl cellulose (weight-average molecular weight 20000) PVP polyvinylpyrrolidone (weight-average molecular weight 20000)
PEO polyethylene oxide (weight-average molecular weight 20000) ethylene acrylic weight-average molecular weight 20000
PAAm polyacrylamide (weight-average molecular weight 20000) pigmentary copper phthalocyanine water dispersion
The N-MAM N hydroxymethyl acrylamide
The making of test plate (panel)
The 1000 serial aluminiums of 150mm * 200mm * 0.13mm are immersed in surface cleaner (SURFCLEANER) the EC370 solution that 1% Japanese paint company produces, 70 ℃ of 5 seconds of degreasing, the SURF4130 solution of Japanese paint company production with 10%, in 60 ℃, carry out the zirconium in 5 seconds and handle.Then, solids component in the hydrophilic finishing agent is adjusted to 5%,,, heated for 20 seconds, make it dry solidification, make test plate (panel) at 220 ℃ with #4 bar coating machine.
With the hydrophilic persistence after the test plate (panel) pollution of following method evaluation making, wet adaptation, processibility, fading property.The result is as shown in table 2.
The evaluation of the hydrophilic persistence after the pollution
The test plate (panel) of making was being soaked 30 minutes taking-up, drying from the beginning in the current (flow is 15 kilograms/hour).Add 3 mass parts stearic acid, 3 mass parts 1-Stearyl alcohols, 3 mass parts Palmiticacid, 3 mass parts phthalic acids two (2-ethylhexyl) ester in container, at 150 ℃ of heating evaporations, 20 roasting test plate (panel)s of circulation are estimated its water contact angle and wettability in 8 hours.Use automatic contact angle meter (the CA-Z type of FACE; Condition: room temperature, measure after dripping 30 seconds) measures water contact angle.Wettability is that test plate (panel) is cooled to 5 ℃, and after 15 minutes, the wetting regime of range estimation dew is estimated (wetting area is represented with %).
Wet adaptation
Purge with pure water spraying on the test plate (panel), increasing the weight of under the situation of about 500g, with the paper tunicle that rubs.With 1 back and forth as once, the number of times till estimating substrate and exposing.
Processibility
On test plate (panel), be the hard sphere of 5mm with diameter, increase the weight of 50g, measure kinetic friction coefficient with 300 mm/min.
Fading property
On test plate (panel), purge with the pure water spraying, increasing the weight of under the situation of about 500g, with paper tunicle is rubbed 1 time to and fro, with the color on the following standard judgement paper and the face of friction.
◎: no color is adhered to
Zero: coloured a little on the paper
△: coloured on the paper, do not expose background color on the palette
*: coloured on the paper, expose background color on the plate
Table 2
Embodiment Comparative example
1 2 3 4 5 6 7 8 9 10 11 12 1 2 3 4 5 6 7
Pollute wetting ability (contact angle) 35 32 27 33 37 29 42 37 30 39 33 25 109 88 103 112 105 115 131
Pollute wetting ability (estimating wettability (%)) ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 ＞95 80 ＞95 20 40 40 45 20 15 5
Wet close property (inferior) ＞30 ＞30 20～30 20～30 20～30 20～30 ＞30 ＞30 ＞30 20～30 ＞30 ＞30 5～20 5～20 5～20 5～20 ＜5 5～20 ＞30
Processibility (kinetic friction coefficient) 0.12 0.12 0.04 - 0.06 0.05 0.11 0.12 0.14 0.07 0.12 0.12 0.05 0.16 0.07 0.06 0.05 0.13 0.04
Fade - - - - - - - - - - ○ - - - - - - × -
As seen from Table 2, by the hydrophilic tunicle that embodiment obtains, all respects such as the wetting ability after pollution, wet adaptation, processibility, fading property are all excellent.On the other hand, the tunicle that obtains of comparative example is all poor.
Crosslinkable microparticles of the present invention is owing to have described formation, so the hydrophilic tunicle that uses the hydrophilic finishing agent contain described crosslinkable microparticles to form is even after being polluted by the pollution substance of Palmiticacid etc., still keeping hydrophilic persistence, and, also be excellent aspect adaptation.Therefore, crosslinkable microparticles of the present invention goes for the radiator element of the aluminum-made heat exchanger that conditioner for example etc. uses etc.

Claims (8)

1, crosslinkable microparticles, it is characterized by, it is obtained by the monomer component copolymerization, and described monomer component is made up of the contain polyoxyalkylene chain and the monomer b of the two keys of polymerizability and other polymerizable monomer c of 0～50 quality % of monomer a, 5～60 quality % of following formula (1) expression of 30～95 quality %;
Figure C2004100479670002C1
In the formula, R 1The expression methyl; R 2Expression CH 2Or C 2H 4
2, crosslinkable microparticles as claimed in claim 1, wherein, described monomer b is the compound with following formula (2) and/or following formula 3 expressions;
Figure C2004100479670002C2
In the formula, R 3And R 4Identical or different, expression hydrogen or methyl; R 5Expression hydrogen, methyl, SO 4H, SO 4Na or SO 4NH 4N represents 6～300 integer;
Figure C2004100479670002C3
In the formula, R 6And R 8Identical or different, expression hydrogen or methyl; R 9Expression hydrogen, methyl, SO 4H, SO 4Na or SO 4NH 4R 7Expression CH 2Or
Figure C2004100479670002C4
M represents 6～300 integer.
3, crosslinkable microparticles as claimed in claim 1 or 2, wherein, described other polymerizable monomer c contains (methyl) acrylic acid compound.
4, hydrophilic finishing agent is characterized by, and it contains just like claim 1,2 or 3 described crosslinkable microparticles and hydrophilic resins.
5, hydrophilic finishing agent as claimed in claim 4, wherein, described hydrophilic resin be selected from by acid number more than or equal to 200 or the group formed more than or equal to 200 acrylic resin, polyvinyl alcohol, carboxymethyl cellulose and their modified resin of hydroxyl value at least a material.
6, as claim 4 or 5 described hydrophilic finishing agents, wherein, the proportioning of described crosslinkable microparticles and hydrophilic resin is 1/99 to 80/20.
7, the coating method of hydrophilic coating film is characterized by, and it comprises the operation of coating as claim 4,5 or 6 described hydrophilic finishing agents.
8, hydrophilic coating film is characterized by, and it is that coating method by hydrophilic coating film as claimed in claim 7 forms.
CNB2004100479671A 2003-06-09 2004-06-09 Crosslinked microparticle, hydrophilic treatment agent, method for coating hydrophilic capsule and hydrophilic capsule Expired - Lifetime CN100348632C (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP164276/2003 2003-06-09
JP2003164276A JP4464076B2 (en) 2003-06-09 2003-06-09 Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film

Publications (2)

Publication Number Publication Date
CN1572804A CN1572804A (en) 2005-02-02
CN100348632C true CN100348632C (en) 2007-11-14

Family

ID=34091114

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB2004100479671A Expired - Lifetime CN100348632C (en) 2003-06-09 2004-06-09 Crosslinked microparticle, hydrophilic treatment agent, method for coating hydrophilic capsule and hydrophilic capsule

Country Status (3)

Country Link
JP (1) JP4464076B2 (en)
KR (1) KR101081136B1 (en)
CN (1) CN100348632C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104884177A (en) * 2012-06-19 2015-09-02 日本油漆株式会社 Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger
CN106867346A (en) * 2015-10-08 2017-06-20 日本帕卡濑精株式会社 Surface conditioning agent, overlay film and surface treatment method

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009149715A (en) * 2007-12-19 2009-07-09 Kansai Paint Co Ltd Composition for hydrophilization treatment
JP5180145B2 (en) * 2009-05-20 2013-04-10 日本ペイント株式会社 Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film
CN101914338A (en) * 2010-08-31 2010-12-15 天长市稼菱涂料有限公司 Method for preparing stain-proof hydrophilic coating from self-crosslinking hydrophilic particles
JP2012206031A (en) * 2011-03-30 2012-10-25 Mitsubishi Chemicals Corp Emulsifier and resin dispersion body
CN104395416B (en) * 2013-05-08 2018-05-22 关西涂料株式会社 For the primer coating compositions of aluminium wheels
WO2016002484A1 (en) * 2014-06-30 2016-01-07 日本ペイント・サーフケミカルズ株式会社 Method for coating aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger
JP6654814B2 (en) * 2015-06-03 2020-02-26 日本ペイント・サーフケミカルズ株式会社 Hydrophilizing agent, hydrophilic film forming method and hydrophilic film
JP2018023932A (en) * 2016-08-10 2018-02-15 日本ペイント・サーフケミカルズ株式会社 Hydrophilic film coating method of aluminum fin material, aluminum fin material, and heat-exchanger made of aluminum
JP6857996B2 (en) * 2016-10-25 2021-04-14 日本パーカライジング株式会社 Surface treatment agent, film and surface treatment method
JP6941465B2 (en) * 2017-04-07 2021-09-29 日本ペイント・サーフケミカルズ株式会社 Hydrophilization treatment agent and method for forming a hydrophilic film
JP7194587B2 (en) 2018-12-28 2022-12-22 日本ペイント・サーフケミカルズ株式会社 Hydrophilic treatment agent, method for forming hydrophilic film, and hydrophilic film
KR20230054880A (en) * 2020-08-27 2023-04-25 도오꾜오까고오교 가부시끼가이샤 Surface treatment liquid and hydrophilic treatment method
CN112108009B (en) * 2020-10-13 2022-04-22 上海希沃环境科技有限公司 Polytetrafluoroethylene membrane and hydrophilic treatment method and application thereof
KR102662618B1 (en) 2022-06-17 2024-05-02 전남대학교산학협력단 Hydrophilic treatment agent for metal material, hydrophilic treatment liquid containing the same, method for producing the same, and method for

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08120003A (en) * 1994-10-24 1996-05-14 Kansai Paint Co Ltd Hydrophilic crosslinked polymer microparticle and its production
CN1342732A (en) * 2001-10-18 2002-04-03 东南大学 Nm-class hydrophilic coating material for aluminium foil and its preparing process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08120003A (en) * 1994-10-24 1996-05-14 Kansai Paint Co Ltd Hydrophilic crosslinked polymer microparticle and its production
CN1342732A (en) * 2001-10-18 2002-04-03 东南大学 Nm-class hydrophilic coating material for aluminium foil and its preparing process

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104884177A (en) * 2012-06-19 2015-09-02 日本油漆株式会社 Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger
CN106867346A (en) * 2015-10-08 2017-06-20 日本帕卡濑精株式会社 Surface conditioning agent, overlay film and surface treatment method

Also Published As

Publication number Publication date
KR20040105619A (en) 2004-12-16
CN1572804A (en) 2005-02-02
JP2005002151A (en) 2005-01-06
JP4464076B2 (en) 2010-05-19
KR101081136B1 (en) 2011-11-07

Similar Documents

Publication Publication Date Title
CN100348632C (en) Crosslinked microparticle, hydrophilic treatment agent, method for coating hydrophilic capsule and hydrophilic capsule
CN100467502C (en) Water-based emulsion for vibration damper
EP2862634B1 (en) Method for covering aluminum fin material with hydrophilic film, aluminum fin material, and aluminum heat exchanger
CN101277979B (en) Waterborne curable resin composition
CN101333408B (en) Aqueous primer composition and coating method using the composition
US7910649B2 (en) Maleimide-containing latex dispersions
CN106479295B (en) A kind of aqueous bicycle coating of high-performance environment protection type and preparation method thereof
CN106660071B (en) Method for coating aluminum fin material with hydrophilic coating film, aluminum fin material, and aluminum heat exchanger
EP0709409B1 (en) Hydrophilic crosslinked polymer fine particles and process for production thereof
KR19980057362A (en) Water-based antirust coating composition using acrylic emulsion resin
KR20180015155A (en) A hydrophilic treatment agent, a method for forming a hydrophilic film, and a hydrophilic film
EP0654514B1 (en) Hydrophilic surface-treating aqueous solution and hydrophilic surface-treating method
JP5180145B2 (en) Crosslinkable fine particles, hydrophilic treatment agent, hydrophilic film coating method and hydrophilic film
JP2009179811A5 (en)
CN113993637B (en) Hydrophilizing agent and method for forming hydrophilic coating film
JP2000328038A (en) Composition and method for improving hydrophilicity
EP2782968B1 (en) Aqueous coating compositions
KR20210047273A (en) Primer composition
CN113226571B (en) Hydrophilizing agent, method for forming hydrophilic coating film, and hydrophilic coating film
EP0070498B1 (en) Aqueous dispersions of synthetic materials, process for their preparation and their use
JP2000248225A (en) Composition for hydrophilic treatment, and hydrophilic treatment
JP2001164175A (en) Hydrophilifying agent for heat-exchanger fin material
KR100725876B1 (en) Corrosion-resistant composition for treating the surface of aluminum material and coating composition containing the same
JPH11293150A (en) Surface treatment agent and surface treatment membrane
JPH0718206A (en) Highly hydrophilic coating material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
C41 Transfer of patent application or patent right or utility model
C56 Change in the name or address of the patentee
CP03 Change of name, title or address

Address after: Osaka Japan

Patentee after: NIPPON PAINT HOLDINGS CO.,LTD.

Address before: Osaka

Patentee before: NIPPON PAINT Co.,Ltd.

TR01 Transfer of patent right

Effective date of registration: 20160114

Address after: Tokyo, Japan

Patentee after: NIPPON PAINT SURF CHEMICALS CO.,LTD.

Address before: Osaka Japan

Patentee before: NIPPON PAINT HOLDINGS CO.,LTD.

CX01 Expiry of patent term

Granted publication date: 20071114