JP5467715B2 - Hydrophilic lubricating paint for aluminum and article to be coated using the same - Google Patents

Description

  In order to enable a workpiece made of an aluminum plate or a precoated aluminum plate to be pressed without supplying a press lubricant, the present invention provides a lubricant coating on the outermost surface of the workpiece in advance. The present invention relates to a hydrophilic lubricating paint for forming and an article to be coated using the same.

  2. Description of the Related Art Conventionally, heat exchangers that operate as an evaporator or a condenser have been used in air conditioners such as home air conditioners, automobile air conditioners, packaged air conditioners, and refrigerators. And most commonly used in domestic indoor air conditioners and commercial packaged air conditioners are cross fin tube heat exchangers (plate fin tube heat exchangers). The cross fin tube which comprises this cross fin tube heat exchanger is comprised from the air side aluminum plate fin and the refrigerant | coolant side heat exchanger tube (copper pipe).

The aluminum plate fin may form various functional films such as hydrophilicity or water repellency by coating with resin, silica fine powder, water glass or the like.
The above-mentioned aluminum plate fin is a fin for passing a heat transfer tube by a process in which punching, overhanging, drawing, squeezing, shearing, etc. are combined after immersing or spraying processing oil on the surface of the aluminum plate fin material. It can be obtained by applying surface treatment to improve the color and surface heat transfer coefficient.

  The aluminum plate fin material causes adhesion of aluminum on the surface of the punching punch, overhanging punch, or ironing punch if no processing oil is used during the press working. For this reason, the aluminum fin does not have a predetermined shape, or due to molding defects such as flare cracking, the adhesion between the aluminum plate fin and the heat transfer tube is reduced, resulting in a decrease in the performance of the heat exchanger. Fatal problems such as damage to the mold itself occur.

  As the processing oil, degreasing with a chlorinated solvent is unnecessary, and it is common to use a low-viscosity press oil having a kinematic viscosity of about 1 to 3 cSt having self-volatility. In the case of using such processing oil, after pressing, heat transfer tubes are passed through the aluminum plate fins, the heat transfer tubes are expanded, and the aluminum plate fins and the heat transfer tubes are fixed to form a heat exchanger. The processing oil is evaporated by exposing it to an atmosphere of 200 ° C. for about 10 minutes.

  However, various kinds of substances such as an oily agent that inhibits hydrophilicity are added to the processing oil to be used, which may cause a decrease in hydrophilic performance necessary for the aluminum fin material. In addition, there are some which swell and deteriorate the coating resin itself applied to the aluminum fin material. When a heat exchanger is produced using such an aluminum fin material, the flow and discharge of condensed water are hindered, and the heat exchanger performance is degraded.

In addition, the above-mentioned processing oil is poor in lubricity due to low viscosity, and often causes material breakage when processing fin collars, and also tends to cause aluminum adhesion to the tool. Has also increased.
Furthermore, it is necessary to pass through a drying furnace in order to heat and heat the heat exchanger to dissipate the processed oil, increasing CO ₂ emissions related to the operation of the drying furnace, releasing volatilized oil into the atmosphere, etc. There is a problem of adversely affecting the global environment.
Thus, in the aluminum fin material used conventionally, even if it uses a low-viscosity processing oil in the case of press work, the above-mentioned problem occurs.

  Moreover, the same problem may arise when not only a fin material but the press work of other aluminum plates.

JP-A-6-39347 JP 7-43093 A JP-A-9-145281 Japanese Patent Laid-Open No. 10-103858 Japanese Patent Laid-Open No. 10-306997 JP 2003-287394 A JP 2005-344144 A

  The present invention has been made in view of such conventional problems, and it is possible to press a workpiece made of an aluminum plate or a pre-coated aluminum plate without supplying press lubricant. , Hydrophilic lubrication for aluminum for forming a lubricating coating film on the outermost surface of the workpiece in advance, which is excellent in lubricity and water removability and does not impair the function given to the coating film of the precoated aluminum plate An object of the present invention is to provide a paint and an article to be coated using the paint.

According to a first aspect of the present invention, in order to allow a workpiece made of an aluminum plate or a precoated aluminum plate to be pressed without supplying a press lubricant, a lubricant coating is previously applied to the outermost surface of the workpiece. A hydrophilic lubricating paint for forming a film,
The hydrophilic lubricating paint comprises a water-soluble polyether having a number average molecular weight (hereinafter simply referred to as “molecular weight”) of 4000 to 400,000 and a lubricating additive,
The lubricating additive is H.264. L. B. Is an alkylene oxide adduct of a monohydric or higher alcohol in the range of 3 to 20, a hydrocarbyl ether of an alkylene oxide adduct of a monohydric or higher alcohol (provided that the hydrocarbyl group is a hydrocarbon having 1 to 24 carbon atoms) And the hydrocarbon group is an alkyl group, an alkenyl group, a cycloalkyl group, or an alkylcycloalkyl group) , a fatty acid ester of an alkylene oxide adduct of a mono- or higher valent alcohol, a carboxylate, an alkylsulfonic acid A salt, an alkyl sulfate ester salt, an alkyl phosphate salt, or one or more fatty acid alkanolamides,
The content of the lubricating additive is 1.0 to 50%, assuming that the entire solid content of the hydrophilic lubricating coating is 100% (mass%, hereinafter the same),
The work material on which the lubricating coating film is formed is a hydrophilic lubricating paint for aluminum characterized in that it is used for a fin material for a heat exchanger (claim 1).

The hydrophilic lubricating paint for aluminum contains a water-soluble polyether having a molecular weight of 4000 to 400,000 and a specific lubricating additive. Therefore, when a lubricating coating film is formed on the surface of the workpiece using this hydrophilic lubricating paint for aluminum, lubricity can be imparted to the workpiece, without using press oil, Press molding can be performed satisfactorily.
For this reason, the purchase cost and drying cost of press oil can be reduced, the discharge | emission of the organic substance to air | atmosphere can be reduced, and the influence on an environment can be reduced.

  In addition, since it consists of a water-soluble polyether having a molecular weight of 4000 to 400,000 and a specific lubricating additive, it can be easily removed by water, and functions such as hydrophilic performance and water repellency performance of the substrate surface after the removal can be obtained. There is no hindrance.

  The hydrophilic lubricating paint for aluminum is 100% due to the water-soluble polyether and the lubricating additive, but in actual use, in order to stably operate the above-described excellent effects, In addition to the water-soluble polyether and the above-mentioned lubricating additive, one kind of water-soluble resin, second additive, colloidal silica, antioxidant, rust inhibitor, corrosion inhibitor, antifoaming agent, etc., as described later, as necessary. Of course, two or more kinds may be further added.

  As described above, according to the present invention, in order to allow a workpiece made of an aluminum plate or a pre-coated aluminum plate to be pressed without supplying a press lubricant, the above-mentioned workpiece is preliminarily processed. It is possible to provide a hydrophilic lubricating paint for aluminum for forming a lubricating coating film on the surface that is excellent in lubricity and water-removability and does not impair the function imparted to the coating film of the precoated aluminum plate.

According to a second aspect of the present invention, there is provided a workpiece made of an aluminum plate or a pre-coated aluminum plate, and lubrication comprising the aluminum hydrophilic lubricating paint according to any one of claims 1 to 6 formed on the surface of the workpiece. Consisting of a coating film,
The film thickness of the lubricating coating, Ri 10~10000mg / m ² der,
An object to be coated is used for a fin material for a heat exchanger .

  The object to be coated is formed by forming a lubricating coating film on a workpiece using the hydrophilic lubricating paint for aluminum of the first invention. Thereby, the workpiece can have lubricity excellent in press workability, and can be processed without using press oil. For this reason, the purchase cost and drying cost of press oil can be reduced, the discharge | emission of the organic substance to air | atmosphere can be reduced, and the influence on an environment can be reduced.

  Moreover, since the said lubricating coating uses the said hydrophilic lubricating paint for aluminum which consists of a water-soluble polyether with a molecular weight of 4000-400000 and a specific lubricating additive, it can be easily removed with water, and the work material is In the case of a pre-coated aluminum plate provided with a coating film having functions such as hydrophilic performance and water repellency, the function of the workpiece surface is not hindered after removal.

  As described above, according to the present invention, in order to be able to perform press working on a workpiece made of an aluminum plate or a pre-coated aluminum plate without supplying press lubricant, the outermost surface of the workpiece. Furthermore, it is possible to provide a coated article having a lubricating coating film that is excellent in lubricity and removability by water and that does not impair the function imparted to the coating film of the precoated aluminum plate.

As described above, the hydrophilic lubricating paint for aluminum according to the first aspect of the invention contains a water-soluble polyether having a molecular weight of 4000 to 400,000 and a lubricating additive.
When the molecular weight of the water-soluble polyether is less than 4000, there is a problem that the coating powder accumulates on the mold surface during pressing, and the lubricating coating of the lubricating coating is lowered so There is a problem that the film is easily fused, and the materials after coating are stuck to each other and workability is lowered. On the other hand, when the molecular weight of the water-soluble polyether exceeds 400,000, there is a problem that the cost increases.

  The water-soluble polyether constituting the hydrophilic lubricating paint for aluminum is polyalkylene glycol, polyalkylene glycol alkyl ether, polyalkylene glycol aryl ether, aliphatic polyalkylene glycol ester, aliphatic polyalkylene glycol sorbitan ester. It is preferable that it consists of 1 type, or 2 or more types chosen from the polyether which consists of 1 type, or 2 or more types, and the polymer by 1 type, or 2 or more types of urethane bond among the said polyethers (Claim 2).

  That is, the water-soluble polyether includes polyalkylene glycol, polyalkylene glycol alkyl ether, polyalkylene glycol aryl ether, aliphatic polyalkylene glycol ester, aliphatic polyalkylene glycol sorbitan ester, and one or more of these urethanes. One kind selected from polymers obtained by bonding may be used alone, or a plurality of kinds of mixtures may be used.

The polyether can be obtained, for example, by polymerizing alkylene oxide and replacing the hydroxyl group with an alkyl group, alkenyl group, alkynyl group or the like. Specific examples of the alkylene oxide constituting the polyether include ethylene oxide, propylene oxide, 1,2-epoxybutane (α-butylene oxide), 2,3-epoxybutane (β-butylene oxide), Examples include 1,2-epoxy-1-methylpropane and 1,2-epoxyheptane.
The polymerization form of the alkylene oxide or the like is not particularly limited, and may be homopolymerization of one kind of alkylene oxide, random copolymerization of two or more kinds of alkylene oxide, block copolymerization, random / block copolymerization, or the like.

  Moreover, the polymer by the urethane bond of the said polyether is 1 type or 2 types in polyalkylene glycol, polyalkylene glycol alkyl ether, polyalkylene glycol aryl ether, aliphatic polyalkylene glycol ester, aliphatic polyalkylene glycol sorbitan ester. The above can be obtained by reacting with isocyanate.

  The lubricating additive is H.264. L. B. Is an alkylene oxide adduct of a monohydric or higher alcohol in the range of 3 to 20, a hydrocarbyl ether of an alkylene oxide adduct of a monohydric or higher alcohol, a fatty acid ester of an alkylene oxide adduct of a monohydric or higher alcohol, or a carboxylic acid It consists of 1 type (s) or 2 or more types of a salt, alkyl sulfonate, alkyl sulfate ester salt, alkyl phosphate, and fatty acid alkanolamide. That is, as the lubricating additive, one selected from the listed materials may be used alone, or a mixture of two or more having different structures may be used.

H. of the above lubricating additive. L. B. Is less than 3, there is a problem that the lubricating additive is easily separated and separated.
H. L. B. (Hydrophile-Lipophile Balance) is a value representing the degree of affinity of a surfactant with water and oil (an organic compound insoluble in water).

  Alcohol oxide adduct of monohydric or higher alcohol, hydrocarbyl ether of alkylene oxide adduct of monohydric or higher alcohol, alcohol constituting fatty acid ester of alkylene oxide adduct of monohydric or higher alcohol, Have six.

Examples of such alcohols include monovalent alcohols having 8 to 23 carbon atoms, and may have a molecular chain, an unsaturated bond, or a cyclic structure in the molecule. Specific examples include octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, ethylphenol, nonylphenol, and the like. These may be used alone or as a mixture thereof. Further, if it is divalent or more, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol, 2-butyl-2-ethyl-1,3-propanediol, 2 -Methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol and the like.
Further, from the viewpoint of lubricity and water removability, the alcohol preferably has 12 to 18 carbon atoms.

The alkylene oxide adduct of the above-mentioned monohydric or higher alcohol alkylene oxide adduct, the hydrocarbyl ether of the monohydric or higher alcohol alkylene oxide adduct, the alkylene oxide adduct constituting the fatty acid ester of the monohydric or higher alcohol alkylene oxide adduct is carbon. It is preferable to obtain by addition polymerization of alkylene oxides having 2 to 6 carbon atoms, and it is more preferable to carry out addition polymerization of alkylene oxides having 2 to 4 carbon atoms.
Specific examples of the alkylene oxide having 2 to 6 carbon atoms include ethylene oxide, propylene oxide, 1,2-epoxybutane (α-butylene oxide), 2,3-epoxybutane (β-butylene oxide), Examples include 1,2-epoxy-1-methylpropane and 1,2-epoxyheptane.

The polymerization form of alkylene oxide or the like is not particularly limited, and may be homopolymerization of one type of alkylene oxide, random copolymerization of two or more types of alkylene oxide, block copolymerization, random / block copolymerization, or the like.
Moreover, when adding an alkylene oxide to the polyhydric alcohol which has 2-6 hydroxyl groups, you may add to all the hydroxyl groups, and you may add only to a part of hydroxyl groups.

  Alkylene oxide adduct of monohydric or higher alcohol, hydrocarbyl ether of alkylene oxide adduct of monohydric or higher alcohol, terminal hydroxyl group of alkylene oxide adduct constituting fatty acid ester of alkylene oxide adduct of monohydric or higher alcohol A part or all of the above can be hydrocarbyl etherified.

Here, the hydrocarbyl group is a hydrocarbon group having 1 to 24 carbon atoms.
Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, and an alkylcycloalkyl group .

  Examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, straight chain or branched Pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, straight Chain or branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched Hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, linear or branched heicosyl group, linear Or a branched docosyl group, linear or branched There tricosyl group, and Tetoraikoshiru group of straight or branched is.

  Examples of the alkenyl group having 2 to 24 carbon atoms include a vinyl group, a linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group, and a linear or branched hexenyl group. Group, linear or branched heptenyl group, linear or branched octenyl group, linear or branched nonenyl group, linear or branched decenyl group, linear or branched undecenyl group, linear or Branched dodecenyl group, linear or branched tridecenyl group, linear or branched tetradecenyl group, linear or branched pentadecenyl group, linear or branched hexadecenyl group, linear or branched heptadecenyl group A linear or branched octadecenyl group, a linear or branched nonadecenyl group, a linear or branched icosenyl group, a linear or branched henicosyl group, a linear or branched dococenyl group, a linear or branched group Branch tricocenyl , And there is a tetracosenyl group of straight or branched.

  Examples of the cycloalkyl group having 5 to 7 carbon atoms include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

  Examples of the alkylcycloalkyl group having 6 to 11 carbon atoms include a methylcyclopentyl group, a dimethylcyclopentyl group (including all structural isomers), a methylethylcyclopentyl group (including all structural isomers), a diethylcyclopentyl group ( Including all structural isomers), methylcyclohexyl group, dimethylcyclohexyl group (including all structural isomers), methylethylcyclohexyl group (including all structural isomers), diethylcyclohexyl group (including all structural isomers) Including), methylcycloheptyl group, dimethylcycloheptyl group (including all structural isomers), methylethylcycloheptyl group (including all structural isomers), and diethylcycloheptyl group (including all structural isomers) ) Etc.

  As the fatty acid ester of the above alkylene oxide adduct of monohydric or higher alcohol and the fatty acid constituting the hydrocarbyl ether, any of linear saturated fatty acid, branched saturated fatty acid, linear unsaturated fatty acid, branched unsaturated fatty acid is used. May be. In terms of carbon number, those having 7 to 22 carbon atoms are preferred. Specifically, for example, caprylic acid, pelargonic acid, capric acid, methyl laurate, myristic acid, palmitic acid, stearic acid, oleic acid, eicosane An acid etc. are mentioned.

  Examples of the carboxylate include polyoxyethylene / alkyl ether / carboxylate, N-acyl sarcosine, N-acyl glutamate, and the like. Examples of the cationic counter ion forming the salt include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.

  Examples of the alkyl sulfonate include dialkyl sulfo-succinate, alkane sulfonate, alpha olefin sulfonate, linear alkyl benzene sulfonate, molecular chain alkyl benzene sulfonate, naphthalene sulfonate- Examples include formaldehyde condensates, alkyl naphthalene sulfonates, N-methyl-N-acyl taurines, and the like. Examples of the cationic counter ion forming the salt include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.

  Examples of the alkyl sulfate include polyoxyethylene / alkyl ether / sulfate, oil and fat sulfate ester salt, and the like. Examples of the cationic counter ion forming the salt include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.

  Examples of the phosphate include alkyl phosphate, polyoxyethylene / alkyl ether / phosphate, polyoxyethylene / alkyl phenyl ether / phosphate, and the like. Examples of the cationic counter ion forming the salt include metal ions such as alkali metal (sodium, potassium, lithium, etc.) ions, alkaline earth metal (magnesium, calcium, barium, etc.) ions, ammonium ions, and the like.

The content of the lubricating additive is 1.0 to 50% with the entire solid content of the hydrophilic lubricating coating as 100%.
When the content of the lubricating additive is less than 1.0% with the total solid content of the hydrophilic lubricating coating as 100%, the lubricity is insufficient, the press die is broken, and the shape of the processed material is poor. Such problems arise. On the other hand, when the content of the lubricating additive exceeds 50%, there is a problem that the removability of the lubricating coating with water decreases, or the surface of the workpiece made of the precoated aluminum plate is made of a hydrophilic lubricating paint. After forming the lubricating coating film and then removing the lubricating coating film with water, the function imparted to the coating film of the precoated aluminum plate may be impaired.

Furthermore, it is preferable that the water-soluble resin is contained in an amount of 1.0 to 50% based on 100% of the entire solid content of the hydrophilic lubricating coating (Claim 3).
In this case, it is possible to suppress the transfer and deposition of the lubricating coating film onto the transport roll of the base material, the processing mold, and the like after forming the lubricating coating film.

  When content of the said water-soluble resin is less than 1.0%, there exists a possibility that the above-mentioned effect may not fully be acquired. On the other hand, when the content of the water-soluble resin exceeds 50%, the lubricating coating film may be difficult to remove with water.

  The water-soluble resin is not particularly limited as long as it is a resin that dissolves in water. For example, a water-soluble alkyd resin, a water-soluble acrylic-modified alkyd resin, a water-soluble epoxy ester resin, and a water-soluble acrylic resin. , Water-soluble polyvinyl alcohol, polyurethane, melamine resin and the like.

Further, as the second additive, further, as an additive, an amine derivative, an alkylene oxide adduct of a polyhydric alcohol having a number average molecular weight of 200 or more and less than 1000 and having 3 to 6 hydroxyl groups, its hydrocarbyl ether, number average One or two or more kinds selected from hydrocarbyl ethers of polyalkylene glycols having a molecular weight of 120 or more and less than 1000 and dihydric alcohols having 2 to 10 carbon atoms, with the total solid content of the hydrophilic lubricating paint as 100%. It is preferable to contain 01 to 2.0% (Claim 4).
In this case, an effect of suppressing adhesion of the metal powder to the press tool can be obtained.

Furthermore, the amine derivatives, alkanolamines, aliphatic polyamines, aromatic amines, cycloaliphatic amines, heterocyclic amines, and it is their alkylene oxide adducts preferably (claim 5).
The amine derivative may contain a hydroxyl group or an ether group.

  Specific examples of the aliphatic amine include methylamine, ethylamine, butylamine, caprylamine, laurylamine, stearylamine, oleylamine, tallowamine dimethylamine, diethylamine, dioctylamine, butyloctylamine, distearylamine, Dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylmyristylamine, dimethylpalmitylamine, dimethylstearylamine, dimethylbehenylamine, dilaurylmonomethylamine, trioctylamine and the like can be used.

  Examples of the alkanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N, N-dimethylethanolamine, N-ethylethanolamine, N, N-diethylethanolamine, and N-isopropylethanol. Amine, N, N-diisopropylethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-methylisopropanolamine, N, N-dimethylisopropanolamine, N-ethylisopropanolamine, N, N-diethylisopropanolamine, N-isopropylisopropanolamine, N, N-diisopropylisopropanolamine, mono-n-propanolamine, di-n-propanol , Tri-n-propanolamine, N-methyln-propanolamine, N, N-dimethyln-propanolamine, N-ethyln-propanolamine, N, N-diethyln-propanolamine, N-isopropyln-propanol Amine, N, N-diisopropyl n-propanolamine, monobutanolamine, dibutanolamine, tributanolamine, N-methylbutanolamine, N, N-dimethylbutanolamine, N-ethylbutanolamine, N, N-diethylbutanol Amine, N-isopropylbutanolamine, N, N-diisopropylbutanolamine and the like can be used.

Examples of the aliphatic polyamine include ethylene diamine, diethylene triamine, triethylene tetraamine, hexamethylene diamine, and cured beef tallow propylene diamine.
As the aromatic amine, for example, aniline, dimethylaniline, diethylaniline and the like can be used.

  Examples of the alicyclic amine include N-cyclohexylamine, N, N-dicyclohexylamine, N, N-dimethyl-cyclohexylamine, N, N-diethyl-cyclohexylamine, N, N-di (3-methyl- (Cyclohexyl) amine, N, N-di (2-methoxy-cyclohexyl) amine, N, N-di (4-bromo-cyclohexyl) amine and the like can be used.

  Examples of the heterocyclic amine include pyrrolidine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, piperazine, homopiperazine, N- Methylpiperazine, N-ethylpiperazine, N-propylpiperazine, N-methylhomopiperazine, N-acetylpiperazine, N-acetylhomopiperazine, 1- (chlorophenyl) piperazine, N-aminoethylpiperidine, N-aminopropylpiperidine, N -Aminoethylpiperazine, N-aminopropylpiperazine, N-aminoethylmorpholine, N-aminopropylmorpholine, N-aminopropyl-2-pipecoline, N-aminopropyl-4-pipecoline, 1,4-bis (aminopropyl) Use piperazine Rukoto can.

  The alkylene oxide adduct can be obtained, for example, by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, α-olefin oxide, and styrene oxide. The polymerization form of the added alkylene oxide is not particularly limited, and may be homopolymerization of one type of alkylene oxide, random copolymerization of two or more types of alkylene oxide, block copolymerization, random / block copolymerization, or the like.

  The number average molecular weight is 200 or more and less than 1000, and the polyhydric alcohol alkylene oxide adduct having 3 to 6 hydroxyl groups has a number average molecular weight of 200 or more and less than 1000 and has 3 to 6 hydroxyl groups. Specific examples of the alcohol include glycerin, polyglycerin (a dimer to tetramer of glycerin, such as diglycerin, triglycerin, and tetraglycerin), and a trimethylol alkane (such as trimethylolethane and trimethylolpropane). , Trimethylolbutane, etc.) and this 2-tetramer, pentaerythritol, dipentaerythritol, 1,2,4-butanetriol, 1,3,5-butanetriol, 1,2,6-hexanetriol, 1, 2,3,4-butanetetraol, sorbitol, sol Tan, sorbitol glycerin condensate, anidol, arabitol, xylitol mannitol, idylitol, taritol, dulcitol, allitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sh Claus etc. are mentioned.

Moreover, the said alkylene oxide adduct can be obtained by addition-polymerizing the same alkylene oxide etc. as what was enumerated as the alkylene oxide which comprises the above-mentioned polyether. The polymerization form of the added alkylene oxide is not particularly limited, and may be homopolymerization of one type of alkylene oxide, random copolymerization of two or more types of alkylene oxide, block copolymerization, random / block copolymerization, or the like.
Moreover, when adding an alkylene oxide to the polyhydric alcohol which has 3-6 hydroxyl groups, the hydroxyl groups to be added may be all hydroxyl groups or some hydroxyl groups.

Moreover, what made some or all of the terminal hydroxyl groups of the alkylene oxide adduct which comprises the alkylene oxide adduct of the said polyhydric alcohol into hydrocarbyl ether can also be used.
As the hydrocarbyl group, the above-mentioned alkylene oxide adduct of monohydric or higher alcohols, hydrocarbyl ether of alkylene oxide adducts of monohydric or higher alcohols, fatty acid esters of alkylene oxide adducts of monohydric or higher alcohols are constituted. There are the same as those listed as hydrocarbyl groups constituting a part of or all of the terminal hydroxyl groups of the alkylene oxide adduct to be hydrocarbyl etherified.

  In addition, as the hydrocarbyl ether of polyalkylene glycol having a number average molecular weight of 120 or more and less than 1000, those obtained by converting a part or all of the terminal hydroxyl groups of polyalkylene glycol into hydrocarbyl ether can be used.

The alkylene oxide constituting the hydrocarbyl ether of polyalkylene glycol having a number average molecular weight of 120 or more and less than 1000 preferably has 2 to 6 carbon atoms.
Examples of such alkylene oxides include those listed as alkylene oxides constituting the above-mentioned polyether.
Examples of the hydrocarbyl group include each group listed as the hydrocarbyl group constituting the alkylene oxide adduct of the above-mentioned polyhydric alcohol and the hydrocarbyl ether thereof.

  The dihydric alcohol having 2 to 10 carbon atoms does not have an ether bond in the molecule and has 2 to 10 carbon atoms. For example, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl -1,3-propanediol, 2-methyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3 -Propanediol, 1,8-octanediol, 1,9-nonanediol, 2-butyl-2-ethyl-1,3-propanediol, and 1,10 Decanediol, and the like.

  When the content of the second additive is less than 0.01% with the total solid content of the hydrophilic lubricating paint for aluminum being 100%, the above effects may not be sufficiently obtained. On the other hand, when the content of the second additive exceeds 2.0%, the hydrophilicity may be lowered after the lubricating coating is removed.

Further, the colloidal silica composed of a colloidal solution of silica fine particles having a particle diameter of 50 μm or less of an alkali-soluble type is preferably contained in an amount of 1 to 30% based on 100% of the total solid content of the hydrophilic lubricating paint. 6).
In this case, it is possible to obtain an effect of preventing adhesion and accumulation of the resin component on the transport roll and the processing mold after forming the lubricating coating film.

When the particle diameter of the silica fine particles exceeds 50 μm, the particles may fall off the lubricating coating film, and the effect may not be obtained.
Moreover, when content of the said colloidal silica is less than 1%, there exists a possibility that the above-mentioned effect may not fully be acquired. On the other hand, when the content of the colloidal silica exceeds 30%, the lubricity may be lowered.

As described above, the article to be coated of the second invention comprises a workpiece made of an aluminum plate or a pre-coated aluminum plate, and the aluminum hydrophilic lubricating paint according to claim 1 formed on the surface of the workpiece. The film thickness of the lubricating coating is 10 to 10,000 mg / m ² .

When the film thickness of the lubricating coating is less than 10 mg / m ² , there is a problem that sufficient lubricity cannot be obtained. On the other hand, when the film thickness of the lubricating coating exceeds 10,000 mg / m ^2. Has a problem that the lubricating coating is brittle and easily peels off, and is deposited on the mold, thus obstructing press working.

In addition, when the workpiece is a precoated aluminum plate having various functional coatings such as hydrophilicity and water repellency according to the application by coating resin, silica fine powder, water glass, etc., an aluminum plate and a coating film Between these, it is preferable to form a chemical conversion film.
In addition, as the chemical conversion film, chemical treatment such as chromate treatment such as phosphate chromate and chromate chromate, non-chromate treatment with titanium phosphate other than chromium compounds, zirconium phosphate, molybdenum phosphate, zinc phosphate, zirconium oxide, etc. A film obtained by film treatment, so-called chemical conversion treatment, is employed.

The presence of the base treatment layer made of this chemical conversion film can effectively improve the adhesion between the aluminum plate and the precoat coating film. In addition, excellent corrosion resistance has been realized, and corrosion under the coating caused when corrosive substances such as water and chlorine compounds have permeated the surface of the aluminum plate is suppressed. Can be planned.
The chemical conversion treatment methods such as chromate treatment and non-chromate treatment include a reaction type and a coating type, but any method may be adopted in the present invention.

The precoated aluminum plate has a precoat layer formed on the surface of the aluminum plate, and the outermost layer of the precoat layer is preferably made of a hydrophilic film.
The precoat layer may be a precoat layer consisting only of a hydrophilic film in which a hydrophilic film is directly formed on the surface of the aluminum plate, or a layer consisting of a chemical conversion film or the like between the aluminum plate and the hydrophilic film. It may be a precoat layer comprising a plurality of types of formed layers.

The precoat layer may comprise a base layer made of any one of a chromate film, a zirconium film, and a corrosion-resistant resin film formed on the surface of the aluminum plate, and a hydrophilic film further formed on the base layer. Preferred (claim 9).
In this case, as described above, the adhesion between the aluminum plate and the hydrophilic film can be effectively improved. In addition, excellent corrosion resistance has been realized, and corrosion under the coating caused when corrosive substances such as water and chlorine compounds have permeated the surface of the aluminum plate is suppressed. Can be planned.

Further, the precoat layer further comprises an underlayer made of a chromate film or a zirconium film formed on the surface of the aluminum plate, an intermediate layer made of a corrosion-resistant resin film further formed on the underlayer, and an intermediate layer. It is preferable to consist of the formed hydrophilic resin film (claim 10).
Also in this case, the precoat layer can be formed with excellent adhesion to the aluminum plate, and a precoated aluminum plate excellent in corrosion resistance can be obtained.

Moreover, it is preferable that the said hydrophilic film | membrane contains the organic resin containing 1 type, or 2 or more types among a hydroxyl group, a carboxyl group, an ester group, and an ether group (Claim 11).
The hydrophilic film may be composed of only an organic resin containing one or more of the hydroxyl group, carboxyl group, ester group and ether group, or a surfactant added to the organic resin. It may be composed of

The hydrophilic film may further contain silicate and / or colloidal silica (claim 12).
In this case, excellent hydrophilicity can be further imparted to the hydrophilic film.

Moreover, it is preferable that the said to-be-coated article is used for the fin material for heat exchangers .
In this case, the lubricating film formed on the outermost surface is excellent in lubricity and water removability and does not impair the function imparted to the coating film of the precoated aluminum plate. Exchanger fins can be obtained.

Example 1
In this example, as examples according to the present invention, the objects to be coated (samples E1 to E23) shown in Table 1 and Table 2, and as a comparative example according to the present invention, the objects to be coated (samples C1 to C1) shown in Table 3. Sample C5) was prepared.
As shown in FIG. 1, a workpiece 1 produced in this example is composed of a workpiece 2 and a lubricating coating 3 formed on the surface of the workpiece 2.
This will be described in detail below.

First, as the aluminum plate 21, an aluminum plate having A1050-H26 and a thickness of 0.100 mm was prepared.
Then, the aluminum plate 21 is degreased with a commercially available weak alkaline degreasing agent as necessary, and then phosphoric acid, hydrofluoric acid or hydrofluoric acid is used in a liquid comprising chromic acid, phosphoric acid, and hydrofluoric acid. A chemical conversion film 22 mainly composed of phosphoric acid chromate was formed with a liquid composed of hydrofluoric acid. The chromium content in the chemical conversion film at this time was 20 mg / m ² . Next, if necessary, a hydrophilic coating composition is applied to the aluminum plate subjected to the chemical conversion treatment using a roll coater, and then heat-treated at 200 ° C. for 20 seconds to obtain a predetermined content. The hydrophilic film 23 was baked and cured. In this way, a precoated aluminum plate (work material) 2 was produced.

As the hydrophilic coating composition, the following six types of hydrophilic coating compositions were prepared.
A1: Water glass hydrophilic paint,
10 parts by weight of alkali silicate (SiO ₂ : Na ₂ O = 3: 5), ₂ parts by weight of hydroxyethyl acrylate-acrylic acid copolymer, 0.5 part by weight of ammonium carbonate zirconium salt. A2: Resin-based hydrophilic paint + silica-based hydrophilic paint,
70 parts by weight of acrylic resin, 15 parts by weight of melamine resin, 10 parts by weight of polyoxyethylene alkylphenyl ether (surfactant), 5 parts by weight of colloidal silica.
A3: Resin-based hydrophilic paint
10 parts by weight of hydroxyethyl cellulose (water-soluble cellulose resin), 10 parts by weight of an acrylic acid-acrylamide copolymer (water-soluble acrylic resin).
A4: Resin-based hydrophilic paint
2-acrylamido-2-methylpropanesulfonic acid 20 parts by weight, methacrylic acid 60 parts by weight, methyl methacrylate 15 parts by weight, dimethylaminoethyl methacrylate 5 parts by weight.
A5: Resin-based hydrophilic paint
25 parts by weight of sodium salt of carboxymethylcellulose, 50 parts by weight of ammonium salt of carboxymethylcellulose, 25 parts by weight of N-methylolacrylamide, 5 parts by weight of sodium alkyldiphenyl ether disulfonate (surfactant).
A6: Resin-based hydrophilic paint
Polyvinyl alcohol 50 parts by weight, carboxymethylcellulose 50 parts by weight, zirconium chelate compound 5 parts by weight, dialkylsulfosuccinic acid ester salt (surfactant) 5 parts by weight.

  And the hydrophilic coating material for aluminum of the composition shown to Table 1-Table 3 is apply | coated to the surface of the workpiece 2 which consists of the said aluminum plate or the said precoat aluminum plate by the roll coater method, and is 120 degreeC x 30 second after that. The lubricating film 3 having the film thickness shown in Tables 1 to 3 was formed by heat treatment. In this way, objects to be coated 1 (sample E1 to sample E23 and sample C1 to sample C5) were produced. In Tables 1 to 3, the contents of the lubricating additive, the water-soluble resin, the additive, and the silica are the contents when the entire solid content of the hydrophilic lubricating coating is 100% by mass.

Here, symbols in Tables 1 to 3 will be described.
A1-A6: The above-mentioned hydrophilic coating composition B1: Polyethylene glycol B2: Polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (ethylene glycol 80%)
B3: Polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer (70% ethylene glycol)
D1: Trimethylolpropane trimyristate ethylene oxide 5-mol adduct (HLB: 3)
D2: 2-butyl-2-ethyl-β-1,3-hydroxyethoxy-ethoxy-cypropane (HLB: 13)
D3: Hexaethylene glycol monooleate (HLB: 9)
D4: Decaethylene glycol monolauryl ether (HLB: 12)
D5: Petroleum sulfonate (Na salt) (HLB: 11)
D6: Sodium oleate (HLB: 20)
D7: Carnauba wax (HLB: 1)
D8: Trimethylolpropane trimyristate ethylene oxide 3 mol adduct (HLB: 2)
F1: Polymethyl acrylate G1: N, N-cyclohexylamine ethylene oxide 2-mol adduct

  As is known from Tables 1 and 2, Samples E1 to E23 as examples include water-soluble polyethers having a molecular weight of 4000 to 400,000, L. B. Is an alkylene oxide adduct of a monohydric or higher alcohol in the range of 3 to 20, a hydrocarbyl ether of an alkylene oxide adduct of a monohydric or higher alcohol, a fatty acid ester of an alkylene oxide adduct of a monohydric or higher alcohol, or a carboxylic acid A lubricant additive comprising one or more of a salt, an alkyl sulfonate, an alkyl sulfate ester salt, an alkyl phosphate, and a fatty acid alkanolamide, and the content of the lubricant additive is the hydrophilic lubricant paint. It turns out that it is 1.0-50 mass% by making the whole solid content of 100 mass%.

Next, the obtained coated objects (samples E1 to E23 and samples C1 to C5) were evaluated for aluminum adhesion, coating film deposition, and removal of the lubricating coating film with water.
First, press work was applied to the object to be coated using a 9.52 mmφ drawless mold (manufactured by Hidaka Seiki Co., Ltd.). Table 4 shows the press working conditions. The processing speed was 250 spm, and the number of evaluation shots was 20000.

評価点が１０〜９点の場合を評価○とし、評価点が８〜６点の場合を評価△とし、評価点が５〜０点の場合を評価×とし、評価が○及び△の場合を合格、評価が×の場合を不合格とした。 <Aluminum adhesion>
The aluminum adhesion was evaluated using the following formula from the aluminum adhesion area on the piercing punch surface and the second ironing punch surface after performing 20000 shots of pressing. The results are shown in Table 5.

When the evaluation score is 10 to 9 points, the evaluation is ◯, when the evaluation point is 8 to 6 points, the evaluation is △, when the evaluation point is 5 to 0 points, the evaluation is ×, and when the evaluation is ○ and △ The case where it passed and evaluation was x was made unsuccessful.

<Coating deposition>
For coating film deposition, the surface of the mold was visually observed after performing 20000 shots of press working, and the case where deposition of coating film powder was not confirmed was accepted (evaluation ○), and deposition of coating film powder was observed. The case was determined to be rejected (evaluation x). The results are also shown in Table 5.

<Removability of lubricating coating with water>
The removability of the lubrication coating film with water is as follows. First, the objects to be coated (sample E1 to sample E22 and sample C1 to sample C5) using pre-coated aluminum plates as work materials are immersed in water at room temperature for 2 minutes, and then The combination of drying with cold air for 6 minutes was defined as one cycle, and 500 cycles were performed. Then, the removability by the water of a lubricating coating was evaluated by measuring the contact angle with the water of the workpiece surface.
Since Sample E1 to Sample E22 and Sample C1 to Sample C5 have a hydrophilic coating film formed under the lubricating coating, if the contact angle with water is 30 ° or less after 500 cycles, It can be said that hydrophilicity was developed by removing the membrane. Therefore, the case where the contact angle was 30 ° or less was regarded as acceptable (evaluation ○), and the case where the contact angle exceeded 30 ° was regarded as unacceptable (evaluation x). The results are also shown in Table 5.

As is known from Table 5, Sample E1 to Sample E22 as examples showed good results in all the items of aluminum adhesion, coating film deposition, and lubrication coating removal by water.
In addition, since the sample E23 as an example forms the same lubricating coating as the lubricating coating of the sample E1, it is considered that the sample E23 has the same performance. It can be said that there is.

  Thus, according to the present invention, in order to enable the workpiece to be pressed without supplying the press lubricant, the outermost surface of the workpiece is previously provided with lubricity and water removal. It can be seen that it is possible to provide an excellent hydrophilic lubricating paint for aluminum for forming a lubricating coating film that is excellent and does not impair the function imparted to the coating film of the precoated aluminum plate, and an object to be coated using the same.

Further, as is known from Table 5, the sample C1 as a comparative example is composed of a hydrophilic paint for aluminum made of a water-soluble polyether having a molecular weight lower than the lower limit of the present invention. The coating powder was deposited on the mold surface and the coating deposition was unacceptable.
Further, in Sample C2 as a comparative example, since the lubricating coating film was made of a hydrophilic lubricating paint for aluminum containing carnauba wax as a lubricating additive, the removability of the lubricating coating film with water was unacceptable.

Sample C3 as a comparative example is that the lubricating coating is made of a hydrophilic lubricating coating for aluminum in which the content of the lubricating additive exceeds the upper limit of the present invention. there were.
Sample C4 as a comparative example has a lubricating coating film made of a hydrophilic lubricating paint for aluminum that does not contain a lubricating additive. Therefore, lubricity cannot be obtained, and aluminum adhesion has failed. It was.
Sample C5 as a comparative example has a lubricating coating film with H.P. L. B. Is made of a hydrophilic lubricating paint for aluminum containing an adduct of 3 moles of trimethylolpropane trimyristate ethylene oxide below the lower limit of the present invention. The removability was unacceptable.

FIG. 3 is an explanatory diagram showing an object to be coated in Example 1.

Explanation of symbols

1 Workpiece 2 Work material 3 Lubricating coating

Claims (12)

In order to allow a workpiece made of an aluminum plate or a pre-coated aluminum plate to be pressed without supplying a press lubricant, a lubricant coating is previously formed on the outermost surface of the workpiece. A hydrophilic lubricating paint,
The hydrophilic lubricating paint comprises a water-soluble polyether having a number average molecular weight of 4000 to 400,000 and a lubricating additive,
The lubricating additive is H.264. L. B. Is an alkylene oxide adduct of a monohydric or higher alcohol in the range of 3 to 20, a hydrocarbyl ether of an alkylene oxide adduct of a monohydric or higher alcohol (provided that the hydrocarbyl group is a hydrocarbon having 1 to 24 carbon atoms) And the hydrocarbon group is an alkyl group, an alkenyl group, a cycloalkyl group, or an alkylcycloalkyl group) , a fatty acid ester of an alkylene oxide adduct of a mono- or higher valent alcohol, a carboxylate, an alkylsulfonic acid A salt, an alkyl sulfate ester salt, an alkyl phosphate salt, or one or more fatty acid alkanolamides,
The content of the lubricating additive is 1.0 to 50%, assuming that the entire solid content of the hydrophilic lubricating coating is 100% (mass%, hereinafter the same),
The hydrophilic lubricating paint for aluminum, wherein the work material on which the lubricating coating film is formed is used for a fin material for a heat exchanger.   The water-soluble polyether according to claim 1, wherein the water-soluble polyether is one or more of polyalkylene glycol, polyalkylene glycol alkyl ether, polyalkylene glycol aryl ether, aliphatic polyalkylene glycol ester, and aliphatic polyalkylene glycol sorbitan ester. A hydrophilic lubricating paint for aluminum, characterized in that it comprises one or two or more selected from polyethers obtained by polymerization and polymers of one or more urethane bonds among the polyethers.   3. The hydrophilic lubricating paint for aluminum according to claim 1 or 2, further comprising a water-soluble resin in an amount of 1.0 to 50% based on 100% of the total solid content of the hydrophilic lubricating paint.   The additive according to any one of claims 1 to 3, further comprising, as an additive, an amine derivative, an alkylene oxide adduct of a polyhydric alcohol having a number average molecular weight of 200 or more and less than 1000 and having 3 to 6 hydroxyl groups, and hydrocarbyl thereof. 1 type or 2 types or more selected from a ruether, a hydrocarbyl ether of a polyalkylene glycol having a number average molecular weight of 120 or more and less than 1000, and a dihydric alcohol having 2 to 10 carbon atoms, and the total solid content of the hydrophilic lubricating paint is 100 A hydrophilic lubricating paint for aluminum, characterized by containing 0.01 to 2.0% as a percentage. In claim 4, the amine derivative, alkanolamines, aliphatic polyamines, aromatic amines, cycloaliphatic amines, heterocyclic amines, and aluminum for the hydrophilic lubricating coating which is a their alkylene oxide adducts .   In any 1 item | term of Claims 1-5, the colloidal silica which consists of a colloidal solution of the silica fine particle of 50 micrometer or less of an alkali-soluble type | mold particle size is further set to 1 to 1 as the whole solid content of the said hydrophilic lubricating paint is 100%. A hydrophilic lubricating paint for aluminum, containing 30%. It consists of a workpiece made of an aluminum plate or a pre-coated aluminum plate, and a lubricating coating film made of the aluminum hydrophilic lubricating paint according to any one of claims 1 to 6, formed on the surface of the workpiece,
The film thickness of the lubricating coating is 10 to 10,000 mg / m ² ,
An object to be coated, which is used as a fin material for a heat exchanger.   8. The article to be coated according to claim 7, wherein the precoat aluminum plate has a precoat layer formed on the surface of the aluminum plate, and the outermost layer of the precoat layer is made of a hydrophilic film.   9. The precoat layer according to claim 8, wherein the precoat layer comprises a base layer made of any one of a chromate film, a zirconium film, and a corrosion-resistant resin film formed on the surface of an aluminum plate; and a hydrophilic film further formed on the base layer. An article to be coated characterized by comprising:   9. The precoat layer according to claim 8, wherein the precoat layer comprises an underlayer made of a chromate film or a zirconium film formed on the surface of an aluminum plate, an intermediate layer made of a corrosion-resistant resin film further formed on the underlayer, and the intermediate layer An article to be coated comprising a hydrophilic resin film further formed on the layer.   11. The article to be coated according to any one of claims 8 to 10, wherein the hydrophilic film contains an organic resin containing one or more of hydroxyl group, carboxyl group, ester group and ether group. .   12. The article to be coated according to claim 11, wherein the hydrophilic film further contains silicate and / or colloidal silica.

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