JP2014058654A - Lubrication treatment agent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubrication treatment agent composition capable of forming a coating film excellent in scratch resistance, blocking resistance and conductivity.SOLUTION: A lubrication treatment agent composition contains an aqueous urethane resin (A), a polyalkylene oxide compound (B), a colloidal silica (C) and a lubricity imparting agent (D), and the glass transformation temperature of the aqueous urethane resin (A) is 25 to 70°C, the solid content of the aqueous urethane resin (A) is 60 to 90 mass%, the solid content of the polyalkylene oxide compound (B) is 10 to 40 mass%, the solid content of the colloidal silica (C) is 5 to 30 mass%, and the solid content of the lubricity imparting agent (D) is 5 to 30 mass% based on the total mass of the solid content of the aqueous urethane resin (A) and the polyalkylene oxide compound (B).

Description

  The present invention relates to a lubricant composition capable of forming a coating film excellent in scratch resistance, blocking resistance and conductivity, and a coating film forming method thereof.

Conventionally, in order to improve moldability, precoated aluminum alloy plates whose surfaces are coated with a lubricant treatment composition have been widely used as materials for home appliances and electrical equipment casings. In such applications, the coating film obtained from the lubricant composition is required to have both excellent scratch resistance and excellent conductivity for antistatic. Furthermore, since the alloy plate may be left for a long time in a stacked state, the coating film covering the surface is also required to have blocking resistance.
Patent Document 1 discloses a water-based lubricating coating composition containing an ether / ester type urethane resin having a bisphenol type skeleton, an epoxy resin, a polyolefin wax, and silica. Patent Document 2 discloses a composition containing a solid lubricant containing a hydroxyl group-containing urethane prepolymer, a block polyisocyanate prepolymer as a curing agent, and an amino resin, and a fluororesin. However, the coating film obtained by the composition described in Patent Documents 1 and 2 may have reduced scratch resistance when the film thickness is reduced in order to ensure conductivity necessary for antistatic, When the coating film was softened in order to ensure conductivity without reducing the film thickness, the blocking resistance was sometimes inferior.
Patent Document 3 includes a substrate made of an aluminum alloy plate, a chemical conversion film formed on one or both surfaces of the substrate, and a precoat layer formed on the chemical conversion film. A pre-coated aluminum alloy plate excellent in scratch resistance, characterized by having an overcoat layer containing a substance and an inner wax, is disclosed. However, in the top coat layer, the degree of conductivity may vary depending on how the resin beads are distributed.

  Patent Document 4 includes a chemical conversion film formed on one or both surfaces of the substrate, and a conductive layer formed on the chemical conversion film. The conductive layer includes urethane resin, ionomer resin, polyethylene resin, epoxy resin, fluorine resin. It consists of a resin composed of one or more of resins and polyester resins, and has a film thickness of 0.05 to 1.0 μm. A conductive pre-coated aluminum alloy plate excellent in blocking properties is disclosed. However, in patent document 4, although electroconductivity can be provided in the range of the said film thickness, the damage resistance of the electroconductive layer may be inadequate. In particular, an electronic device housing for a CD-ROM drive or the like has a heavy load because the drive is inserted and removed many times, and a film having sufficient scratch resistance in such an application cannot be obtained.

JP-A-6-145559 Japanese Patent Laid-Open No. 7-163940 JP 2004-98624 A JP 2009-34973 A

  An object of the present invention is to provide a lubricating treatment composition that can form a coating film excellent in scratch resistance, blocking resistance and conductivity.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. That is, the present invention comprises the following items.
Item 1. A lubricating treatment composition comprising an aqueous urethane resin (A), a polyalkylene oxide compound (B), colloidal silica (C) and a lubricating function-imparting agent (D), wherein the glass transition temperature of the aqueous urethane resin (A) Is 25 to 70 ° C., and the solid content of the aqueous urethane resin (A) is 60 to 90% by mass based on the total solid mass of the aqueous urethane resin (A) and the polyalkylene oxide compound (B). The solid content of the oxide compound (B) is 10 to 40% by mass, the solid content of the colloidal silica (C) is 5 to 30% by mass, and the solid content of the lubricating function-imparting agent (D) is 5 to 30% by mass. Lubricant composition characterized by the above.
Item 2. Item 2. The lubricating treatment composition according to Item 1, wherein the raw material polyol of the aqueous urethane resin (A) contains a compound having at least one chemical bond selected from the group consisting of an ether bond, an ester bond and a carbonate bond in the molecule.
Item 3. A film forming method comprising coating the lubricant composition according to Item 1 or 2 on a metal plate so that the dry film thickness is in the range of 0.3 to 0.6 μm.

  By using the lubricant composition of the present invention, a coating film excellent in scratch resistance, blocking resistance and electrical conductivity can be formed on an object to be coated.

  The lubricant composition of the present invention is a lubricant composition containing an aqueous urethane resin (A), a polyalkylene oxide compound (B), colloidal silica (C), and a lubricant function-imparting agent (D), The glass transition temperature of the aqueous urethane resin (A) is 25 to 70 ° C., and the solid content of the aqueous urethane resin (A) is based on the total solid mass of the aqueous urethane resin (A) and the polyalkylene oxide compound (B). The solid content of the polyalkylene oxide compound (B) is 10 to 40% by mass, the solid content of the colloidal silica (C) is 5 to 30% by mass, and the solid content of the lubricating function-imparting agent (D). Is 5 to 30% by mass.

Aqueous urethane resin (A)
The aqueous urethane resin (A) in the present invention has a glass transition temperature of 25 to 70 ° C., is produced from a raw material mainly composed of polyisocyanate and polyol, and two or more active hydrogens in the molecule as necessary. It may be one obtained by chain extension reaction in the presence of a chain extender, which is a compound having the above, or it is dispersed or dissolved in water, and known ones can be widely used.
The aqueous urethane resin (A) may have at least one hydrophilic group selected from the group consisting of an anionic group, a nonionic group and a cationic group. Moreover, the water-based urethane resin (A) can use what was disperse | distributed or dissolved in water using the dispersing agent which has this hydrophilic group as needed. In the present specification, the anionic group is not particularly limited as long as it is an anionic group. For example, a carboxyl group, a sulfonic acid group, a phosphonic acid group, and neutralization of these groups with a basic compound. Mention may be made of the groups obtained. In addition, the cationic group is not particularly limited as long as it is a group having a cationic property or a group that exhibits a cationic property by addition of a cationic species such as a proton or a carbocation. For example, an amino group, a sulfide group, and these groups Examples include groups obtained by neutralization with acidic compounds, aprotic quaternary ammonium bases, tertiary sulfonium bases, and the like.

The aqueous urethane resin (A) having an anionic group can be obtained, for example, by reacting a polyisocyanate, a polyol, and an anionic group-containing polyol.
Examples of the polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, dimer acid diisocyanate, and lysine diisocyanate; burette type adducts, isocyanurate ring adducts of these diisocyanate compounds; isophorone diisocyanate, 4, 4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4- (or-2,6-) diisocyanate, 1,3- (or 1,4-) di (isocyanatomethyl) cyclohexane, 1,4-cyclohexane Alicyclic diisocyanate compounds such as diisocyanate, 1,3-cyclopentane diisocyanate, 1,2-cyclohexane diisocyanate; these diisocyanates Burette type adducts of compounds, isocyanurate cycloadducts; xylylene diisocyanate, metaxylylene diisocyanate, tetramethyl xylylene diisocyanate, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 1, 4-naphthalene diisocyanate, 4,4'-toluidine diisocyanate, 4,4'-diphenyl ether isocyanate, (m- or p-) phenylene diisocyanate, 4,4'-biphenylene diisocyanate, 3,3'-dimethyl-4,4 ' -Aromatic diisocyanate compounds such as biphenylene diisocyanate, bis (4-isocyanatophenyl) sulfone, isopropylidenebis (4-phenylisocyanate); Burette type adduct of isocyanate compound, isocyanurate cycloadduct; triphenylmethane-4,4 ′, 4 ″ -triisocyanate, 1,3,5-triisocyanatobenzene, 2,4,6- Polyisocyanate compounds having three or more isocyanate groups in one molecule such as triisocyanatotoluene, 4,4′-dimethyldiphenylmethane-2,2 ′, 5,5′-tetraisocyanate; view of these polyisocyanate compounds Let type adducts, isocyanurate ring adducts; ethylene glycol, propylene glycol, 1,4-butylene glycol, dimethylolpropionic acid, polyalkylene glycol, trimethylolpropane, hexanetriol and other isocyanate groups in excess of hydroxyl groups Ratio Urethane adduct obtained by reacting a polyisocyanate compound; these urethane adducts of views - let type adducts can include an isocyanurate ring adducts.

  As the polyol, those having a number average molecular weight in the range of 62 to 100,000 can be used. Specifically, for example, polyethylene glycol, polypropylene glycol, polyethylene-propylene (block or random) glycol, polytetramethylene ether glycol, Polyether polyols such as polyhexamethylene ether glycol and polyoctamethylene ether glycol; dicarboxylic acids (adipic acid, succinic acid, sebacic acid, glutaric acid, maleic acid, fumaric acid, phthalic acid, etc.) and glycols (ethylene glycol, propylene glycol) 1,4-butanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, bishydroxymethylcyclohexane, etc.) Polyols such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyester polyols such as polyethylene / butylene adipate, polyneopentyl / hexyl adipate; polycaprolactone polyol, poly- 3-methylvalerolactone polyol; polycarbonate polyol; ethylene oxide or propylene oxide adduct of bisphenol A, ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,4-butanediol, tetramethylene glycol, hexamethylene Glycol, decamethylene glycol, octanediol, tricyclodecane dimethylo Le, hydrogenated bisphenol A, cyclohexane dimethanol, low molecular weight glycols such as 1,6-hexanediol; and the like. These may be used alone or in combination.

Examples of the anionic group-containing polyol include dimethylolacetic acid, dimethylolpropionic acid, and dimethylolbutyric acid.
The aqueous urethane resin (A) having an anionic group has an acid value of 5 to 100 mgKOH / g, preferably 10 to 70 mgKOH / g, from the viewpoint of storage stability and water resistance of the formed coating film. It is preferable to be within the range.
When the aqueous urethane resin (A) has an anionic group, the anionic group may be neutralized with a basic compound. The basic compound is not particularly limited, and examples thereof include monoethanolamine, ethylamine, dimethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, butylamine, dibutylamine, and 2-ethylhexyl. Amino, ethylenediamine, propylenediamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, 2-amino-2-methylpropanol, diethanolamine, amino compounds such as morpholine, ammonia, alkali metal compounds, alkaline earth metal compounds, etc. be able to. The basic compound can be used in a proportion of usually 0.2 to 2.0 equivalents, preferably 0.5 to 1.3 equivalents, relative to 1 equivalent of a carboxyl group in the aqueous urethane resin. These basic compounds may be mixed with the aqueous urethane resin (A) to neutralize the anionic group, and then the aqueous urethane resin (A) may be dispersed in water, or the aqueous urethane resin (A) may be dispersed in water. You may add and neutralize simultaneously.
The aqueous urethane resin (A) may have a cationic group obtained by reacting, for example, a polyisocyanate, a polyol, and a polyol having a cationic group. The said polyisocyanate and polyol can use the same thing as the description in the urethane prepolymer which has the said anionic group.

  Examples of the polyol having a cationic group include diol compounds having a tertiary amino group such as N-methyldiethanolamine, N-ethyldiethanolamine, and N-isobutyldiethanolamine, and diol compounds having a thioether group such as thiodiglycol, Examples include triols having a tertiary amino group such as triethanolamine and triisopropanolamine. When the aqueous urethane resin (A) in the present invention has a tertiary amino group, the amine value of the solid content of the resin is in the range of 5 to 50 mg-KOH / g. From the viewpoint of stability, it is preferably in the range of 10 to 35 mg-KOH / g. In addition, the amine value in this specification means the measured value by the titration method prescribed | regulated to JISK7237.

  The aqueous urethane resin (A) having a tertiary amino group is used by neutralizing the tertiary amino group with an acid compound and ammonium chloride, or by aprotic quaternary ammonium chloride by a known method. May be. Examples of the acid compound used for neutralization include formic acid, acetic acid, lactic acid, and phosphoric acid. These acid compounds may be mixed with the aqueous urethane resin (A) to neutralize the tertiary amino group, and then the aqueous urethane resin (A) may be dispersed in water. It may be added at the same time as dispersion and neutralized.

The aqueous urethane resin (A) having a nonionic group can be obtained, for example, by reacting a polyisocyanate and a mixture of polyol compounds including a polyol compound having a hydrophilic nonionic group. Examples of the polyol compound having a hydrophilic nonionic group include a polyol having hydroxyl groups at both ends of a hydrophilic polyoxyalkylene chain such as polyethylene glycol, a copolymer of ethylene glycol and propylene glycol, or a side chain. Examples include polyols having a polyethylene glycol chain.
When the polyol compound having a hydrophilic nonionic group is used, from the viewpoint of the stability of the lubricant composition of the present invention, the compound is 1 to 25% by mass in the solid content of the aqueous urethane resin (A). Furthermore, it is more preferable to use within the range of 3 to 15% by mass.

  The aqueous urethane resin (A) can be dispersed or dissolved in water by a known method. For example, (1) A method of dispersing or dissolving in water by self-emulsification of an aqueous urethane resin having a hydrophilic group; (2) Dispersing or dissolving the aqueous urethane resin in water by a mechanical shear force using a dispersant. The method etc. are mentioned. Even when the water-based urethane resin has an isocyanate group, it may be dispersed or dissolved in water by the method (1) or (2) as it is. High molecular weight (chain extension reaction) may be carried out simultaneously with the dispersion into the polymer. Examples of the chain extender include known compounds such as polyamines such as ethylenediamine, isophoronediamine, and piperazine, adipic acid dihydrazide, and water. Also, when the aqueous urethane resin has an isocyanate group, the isocyanate group is blocked with a blocking agent such as oxime, alcohol, phenol, mercaptan, amine, sodium bisulfite, and then dispersed or dissolved in water. Also good. The molecular weight of the aqueous urethane resin (A) is not particularly limited, but is preferably 10,000 or more in terms of weight average molecular weight. In the aqueous dispersion of the aqueous urethane resin (A), depending on the aqueous urethane resin (A) The formed particles may be crosslinked particles.

Examples of commercially available aqueous dispersions of the aqueous urethane resin (A) include, for example, Hydran HW-330, Hydran HW-340, Hydran HW-350 (all manufactured by Dainippon Ink & Chemicals, Inc.), Superflex 100, Superflex. 110, Superflex 150, Superflex F-8438D, Superflex 420 (all manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Adeka Bon Tider HUX-232, Adeka Bon Tider HUX-260, Adeka Bon Tider HUX-320, Adeka Bon Tider HUX-350, Adeka Bon Tider HUX-380, Adeka Bon Tider HUX-540, Adeka Bon Tider UX-206 (all manufactured by Adeka) and the like can be mentioned.
In this invention, it is suitable that the glass transition temperature of water-based urethane resin (A) is 25-70 degreeC, Preferably it is 30-65 degreeC, Furthermore, 40-60 degreeC. When the glass transition temperature is lower than 25 ° C., the scratch resistance of the coating film obtained from the lubricating treatment composition of the present invention may be inferior. When the glass transition temperature is higher than 70 ° C., the conductivity of the coating film obtained is inferior. It may be insufficient.
In this specification, the glass transition temperature Tg is a glass transition temperature Tg measured using a differential scanning calorimeter “DSC-220U” (manufactured by Seiko Instruments Inc.). The measurement is performed by taking a dried solid measurement sample in a measuring cup and obtaining a caloric change curve (caloric curve) in the range of −20 ° C. to + 200 ° C. at a temperature rising rate of 10 ° C./min. As the solid measurement sample, for example, in the case of an aqueous dispersion of an aqueous urethane resin, a dispersion obtained by heating and drying the dispersion at 105 ° C. for 3 hours is used. And the temperature of the secondary transition point (onset) which appears in the caloric curve at the time of measurement is the glass transition temperature Tg.

Polyalkylene oxide compound (B)
The polyalkylene oxide compound (B) is used to achieve both scratch resistance and conductivity of the coating film obtained from the treatment composition of the present invention, and has a polyalkylene oxide unit in the molecule. Thus, for example, a compound represented by the following formula can be used.
R ¹ O— (R ² O) _n —R ³
[Wherein, R ¹ and R ³ are a hydrogen atom or an alkyl group having 2 or less carbon atoms, and may be the same or different. R ² is an alkylene group having 2 to 4 carbon atoms which may be branched, and different alkylene groups may be contained in any ratio. n is an average degree of polymerization, and is an integer of 3 to 700, preferably 40 to 650, and more preferably 80 to 500. ].
Examples of the polyalkylene oxide compound (B) include polyalkylene oxides such as polyethylene oxide, polypropylene oxide, and polytetramethylene oxide; alkoxy polyalkylene oxides such as methoxypolyethylene oxide, ethoxypolyethylene oxide, ethoxypolypropylene oxide, and ethoxypolybutylene oxide. In particular, polyethylene oxide, a copolymer of ethylene oxide and propylene oxide, or a block copolymer is preferable in terms of scratch resistance.

Colloidal silica (C)
The colloidal silica (C) in the present invention is so-called silica sol or finely divided silica, and usually has a particle size of about 5 nm to 200 nm, preferably about 8 nm to 100 nm, and is usually dispersed in water or an organic solvent. The supplied one can be used as it is, or finely divided silica can be used by dispersing it in water or an organic solvent. Colloidal silica (C) is used to improve the scratch resistance of the coating film obtained from the treatment composition of the present invention. The colloidal silica may be neutralized with a basic compound such as ammonia, an amine compound, or an alkali metal as necessary, or may have a surface chemically modified with an organic substance.

  Examples of commercially available colloidal silica include “Snowtex” series (manufactured by Nissan Chemical Industries, Ltd.) such as “Snowtex NXS” and “Snowtex C”, “Oscar” series (manufactured by Catalytic Chemical Industries), "Silica Doll" series (Nippon Kagaku Kogyo Co., Ltd.), "AEROSIL" series (Nippon Aerosil Co., Ltd.), "Sildex" series (Asahi Glass Co., Ltd.), "E220A", "E220" (all manufactured by Nippon Silica Kogyo Co., Ltd.) “SYLYSIA 470” (manufactured by Fuji Silysia Chemical Co., Ltd.) “organosol” (manufactured by Nissan Chemical Co., Ltd.)

Lubricating agent (D)
The lubrication function-imparting agent only needs to impart lubricity to the resulting film. Specifically, for example, fluororesin fine powder (for example, tetrafluoroethylene resin, tetrafluoroethylene-hexafluoropropylene copolymer resin, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer resin, tetrafluoroethylene- Fine particles of ethylene copolymer resin, ethylene trifluoride chloride resin, vinylidene fluoride resin, etc.), polyolefin wax (eg, polyethylene wax, polypropylene wax, etc.), polyolefin and fluororesin are mixed in one particle Lubricants, graphite, boron nitride, carbon fluoride and the like. Among these, polyethylene wax is particularly preferable, and this is usually used as an aqueous dispersion, and those having an average particle diameter of 0.05 to 7.5 μm are preferably used. The average particle size is preferably in the range of 1.0 μm to 5.0 μm because it is particularly excellent in scratch resistance. The average particle diameter is a value measured using LA-500 (manufactured by Horiba, Ltd., laser diffraction particle size distribution analyzer).

  Examples of such commercially available polyethylene wax include HI-DISPER A-375, HI-DISPER AB-50, HI-DISPER AF-41, HI-DISPER AG-73, HI-DISPER A-512, and HI-DISPER A. -332, HI-DISPER AE-04, HI-DISPER A-514 (manufactured by Gifu Shellac Co., Ltd.), Chemipearl W100, Chemipearl W300, Chemipearl W401, Chemipearl W500, Chemipearl W640, Chemipearl W700, Chemipearl W900, Chemipearl W950 (above , Manufactured by Mitsui Chemicals, Inc.).

  In the treatment agent composition of the present invention, the solid content of the aqueous urethane resin (A) is 60 to 90% by mass based on the total solid content of the aqueous urethane resin (A) and the polyalkylene oxide compound (B). Preferably it is 65-88 mass%, Furthermore, it is preferable that it is 75-85 mass%. When the solid content of the aqueous urethane resin (A) is less than 60% by mass, the resulting coating film of the treating agent may have poor blocking resistance and scratch resistance, and when it is more than 90% by mass, the resulting treatment is obtained. The conductivity of the agent coating film may be inferior.

  The solid content of the colloidal silica (C) is preferably 5 to 30% by mass, more preferably 7 to 20% by mass, based on the total mass of the solid content of the aqueous urethane resin (A) and the polyalkylene oxide compound (B). When the solid content of the colloidal silica (C) is less than 5% by mass, the scratch resistance of the obtained treatment agent coating film may be inferior, and when it is more than 30% by mass, the conductivity of the obtained treatment agent coating film is inferior. May be inferior.

  The solid content of the lubricating function-imparting agent (D) is preferably 5 to 30% by mass, more preferably 7 to 20% by mass, based on the total solid content of the aqueous urethane resin (A) and the polyalkylene oxide compound (B). . When the solid content of the lubricating function-imparting agent (D) is less than 5% by mass, the obtained scratch-resistant coating film may be inferior. When the solid content is more than 30% by mass, the resulting coating film is obtained. May have poor blocking resistance.

  The lubricating treatment composition of the present invention comprises an aqueous modifying resin such as an acrylic resin, epoxy ester resin, polyester resin, alkyd resin; polyisocyanate compound, blocked polyisocyanate compound, amino resin, phenol resin, if necessary. Curing agents such as: Colored pigments, extenders, anticorrosive pigments, glittering materials, resin particles, dispersants, antifoaming agents, antiseptics, leveling agents, anti-waxing agents, flash last inhibitors, pigment dispersants, antirust agents Normal paint additives such as thickeners, film-forming aids, curing catalyst antioxidants, UV absorbers, water, organic solvents, etc. are appropriately blended, and water-based urethane resin (A), polyalkylene oxide compound (B ), Colloidal silica (C), and lubricating function-imparting agent (D), and may be mixed and dispersed together.

Coating plate formation method The metal plate to which the lubricant composition of the present invention is applied includes an aluminum alloy plate, a zinc-based plated steel plate, etc., and those subjected to a known chemical conversion treatment such as phosphate chromate or zinc phosphate. desirable. In particular, the lubricating treatment composition of the present invention is suitably applied to an aluminum alloy plate in order to provide the strength and workability required to insert and remove the drive many times in an electronic device casing for a CD-ROM drive. The

  The lubricant composition of the present invention can form a coating film by coating the composition on the metal plate and drying it. Examples of the coating method include dip coating, shower coating, spray coating, roll coating, and electrodeposition coating.

  As for the drying conditions of the said coating film, it is suitable to make it dry normally for 2 second-30 minutes on the conditions from which a raw material highest temperature becomes 60-250 degreeC. When the dry film thickness is particularly in the range of 0.3 to 0.6 μm, the lubricant composition of the present invention exhibits excellent performance in scratch resistance, blocking resistance and conductivity. When the dry film thickness is thinner than 0.3 μm, the scratch resistance may be insufficient, and when the dry film thickness is thicker than 0.6 μm, the conductivity of the coating film may be insufficient.

Next, an Example is given and this invention is demonstrated more concretely. Here, “parts” and “%” mean “parts by mass” and “% by mass”, respectively.
Manufacture of water-based urethane resin
(Production Example 1)
In a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropping device, 200 parts of a polyester polyol having a number average molecular weight of 1700 (“Teslac 2477” manufactured by Hitachi Chemical Co., Ltd.), 4 parts of trimethylolpropane, 12 parts of methylolpropionic acid, 80 parts of dicyclohexylmethane diisocyanate, and 207 parts of methyl ethyl ketone were reacted at 75 ° C. for 4 hours, and a urethane prepolymer having a free isocyanate group content of 1.5% by mass with respect to the nonvolatile content. A methyl ethyl ketone solution was obtained. The solution was cooled to 45 ° C, neutralized by adding 9.1 parts of triethylamine, and then 761 parts of deionized water was gradually added and emulsified and dispersed while maintaining the temperature at 45 ° C or lower. The obtained aqueous dispersion was kept at 50 ° C. for 2 hours to complete the chain extension reaction with water, and then methyl ethyl ketone was distilled off at 50 ° C. or less under reduced pressure to obtain an aqueous urethane resin (A An aqueous dispersion of -1) was obtained. The glass transition temperature of the obtained aqueous urethane resin solid content was about 28 ° C.
(Production Example 2)
In a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser, and a dropping device, 200 parts of polytetramethylene ether glycol having a number average molecular weight of about 1000 (“Poly THF-1000” manufactured by BASF) and 1,4 -Add 200 parts of cyclohexanedimethanol, 6 parts of trimethylolpropane, 15 parts of dimethylolpropionic acid, 133 parts of isophorone diisocyanate, and 243 parts of methyl ethyl ketone, and react at 75 ° C. for 4 hours while stirring and mixing in a nitrogen stream. Thus, a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content with respect to the nonvolatile content of 1.7% by mass was obtained. Next, the mixture was cooled to 45 ° C., neutralized by adding 11.3 parts of triethylamine with stirring, and then 962 parts of deionized water was gradually added and emulsified while maintaining the temperature at 45 ° C. or lower. The obtained aqueous dispersion was kept at 50 ° C. for 2 hours to complete the chain extension reaction with water, and then methyl ethyl ketone was distilled off at 50 ° C. or less under reduced pressure to obtain an aqueous urethane resin (A -2) was obtained. The glass transition temperature of the obtained aqueous urethane resin solid content was about 30 ° C.
(Production Example 3)
In a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropping device, 80.8 parts of polyester polyol (Nipporan 4009 manufactured by Nippon Polyurethane Industry Co., Ltd.) and propylene oxide adduct of bisphenol A (Adeka Industry) "Polyether BPX-11") 162 parts, trimethylolpropane 6.8 parts, dimethylolpropionic acid 16.2 parts, hexamethylene diisocyanate 135.8 parts, methyl ethyl ketone 321 parts, The reaction was carried out at 4 ° C. for 4 hours to obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 1.5% by mass with respect to the nonvolatile content. The solution was cooled to 45 ° C., neutralized by adding 12 parts of triethylamine, and then 1031 parts of deionized water was gradually added and emulsified and dispersed while maintaining the temperature at 45 ° C. or lower. The obtained aqueous dispersion was held at 50 ° C. for 2 hours to complete the chain extension reaction with water, and then methyl ethyl ketone was distilled off at 50 ° C. or less under reduced pressure to obtain an aqueous urethane resin (A- An aqueous dispersion 3) was obtained. The glass transition temperature of the obtained aqueous urethane resin solid content was about 50 ° C.
(Production Example 4)
In a reaction vessel equipped with a thermometer, thermostat, stirrer, reflux condenser and dropping device, 110 parts of castor oil-based polyol (“HS2G-160R” manufactured by Toyokuni Oil Co., Ltd.) and propylene oxide adduct of bisphenol A (Adeka Industries Co., Ltd.) "Polyether BPX-11") 27.5 parts, 8.8 parts of trimethylolpropane, 11 parts of dimethylolpropionic acid, 142.5 parts of dicyclohexylmethane diisocyanate, and 240 parts of methyl ethyl ketone are added, and 75 ° C. To obtain a methyl ethyl ketone solution of a urethane prepolymer having a free isocyanate group content of 3.9% by weight based on the nonvolatile content. The solution was cooled to 45 ° C. and neutralized by adding 8.3 parts of triethylamine, and then 771 parts of deionized water was gradually added and emulsified and dispersed while maintaining the temperature at 45 ° C. or lower, and then 7.5 parts by weight of ethylenediamine was added. The chain was elongated by addition, and methyl ethyl ketone was distilled off at 50 ° C. under reduced pressure to obtain an aqueous dispersion of an aqueous urethane resin (A-4) having a nonvolatile content of about 30%. The glass transition temperature of the obtained aqueous urethane resin solid content was about 60 ° C.
(Comparative Production Example 1)
In a reaction vessel equipped with a thermometer, a thermostat, a stirrer, a reflux condenser and a dropping device, 200 parts of an ethylene oxide adduct of bisphenol A (“New Pole BPE-40” manufactured by Sanyo Chemical Industries Ltd.) and trimethylolpropane 5 Part, dimethylolpropionic acid 15 parts, dicyclohexylmethane diisocyanate 195 parts, and methyl ethyl ketone 291 parts are reacted at 75 ° C. for 4 hours, and the content of free isocyanate groups with respect to the nonvolatile content is 1.7% by weight. A methyl ethyl ketone solution of urethane prepolymer was obtained. The solution was cooled to 45 ° C, neutralized by adding 11.3 parts of triethylamine, and then 1067 parts of deionized water was gradually added and emulsified while maintaining the temperature at 45 ° C or lower. The obtained aqueous dispersion was held at 50 ° C. for 2 hours to complete the chain extension reaction with water, and then methyl ethyl ketone was distilled off at 50 ° C. or less under reduced pressure to obtain an aqueous urethane resin (A- An aqueous dispersion 5) was obtained. The glass transition temperature of the obtained aqueous urethane resin solid content was about 90 ° C.

Production of Lubricant Composition (Example 1)
80 parts (solid content) of the aqueous urethane resin (A-1) obtained in Production Example 1, 20 parts of PEG6000S (Note 2), 10 parts (solid content) of silica dol 40G-80 (Note 3) and Chemipearl W- 950 (Note 4) 15 parts were mixed with stirring, and the solid content was adjusted with deionized water to obtain a lubricant composition F-1 having a solid content of 15% by mass.

(Examples 2-15, Comparative Examples 1-10)
In the same manner as in Example 1, each component was mixed with stirring according to the formulation shown in Table 1 and Table 2 below, and the solid content was adjusted by adding deionized water, and the lubricant composition having a solid content of 15% by mass. F-2 to 25 were prepared. In addition, the compounding quantity of each component in Table 1, 2 is based on solid content.

Preparation of test plate (Example 16)
Both surfaces of an aluminum alloy plate (material: JIS A5052, plate thickness: 0.6 mm) were degreased with a commercially available aluminum degreasing agent, washed with water, and then subjected to chemical conversion treatment with a commercially available phosphoric acid chromate treatment solution. Next, the lubricant composition F-1 was applied only to one of the chemical conversion treated surfaces, dried for 20 seconds at a maximum temperature (PMT) 210 ° C. of the coating object, and a test plate G having a dry film thickness of 0.4 μm. -1 was obtained.

(Examples 17 to 32, Comparative Examples 11 to 20, Reference Examples 1 and 2)
In the same manner as in Example 16, each of the lubricant treatment compositions F-2 to 25 shown in Tables 3 and 4 below was applied, dried at a maximum temperature (PMT) 210 ° C. of the article to be coated for 20 seconds, and dried. Test plate G-2 to 25 having a thickness of 0.4 μm, Test plate G-3-2 having a thickness of 0.3 μm, Test plate G-3-3 having a dry thickness of 0.6 μm, and 0.2 μm of dry thickness Test plate G-3-4 (Reference Example 1) and test plate G-3-5 (Reference Example 2) having a dry film thickness of 0.8 μm were obtained.

  Tables 3 and 4 show the results of each test plate subjected to the test according to the test method described below.

Component A (Note 1) “UW-3300”: manufactured by Ube Industries, water-based urethane resin, glass transition temperature 40 ° C.
(Note 2) “Superflex 860”: Daiichi Kogyo Seiyaku Co., Ltd., water-based urethane resin, glass transition temperature 68 ° C.
Component B (Note 3) “PEG-4000”: manufactured by Sanyo Chemical Industries, polyethylene glycol average polymerization degree 70
(Note 4) “PEG-6000S”: manufactured by Sanyo Chemical Industries, polyethylene glycol average polymerization degree 200
(Note 5) “PEG-20000”: manufactured by Sanyo Chemical Industries, polyethylene glycol Average polymerization degree 450
(Note 6) “PEG-400”: manufactured by Sanyo Chemical Industries, polyethylene glycol Average polymerization degree 8
(Note 7) "Pluronic F-68": a copolymer of polyethylene glycol and polypropylene glycol, manufactured by BASF, average polymerization degree 190
Component C (Note 8) “Silica Dole 40G-80”: Nippon Chemical Industry Co., Ltd., colloidal silica, average particle size 80 nm
(Note 9) “Snowtex CM”: Nissan Chemical Co., Ltd., colloidal silica, average particle size 20-30 nm
(Note 10) “Snowtex C”: Nissan Chemical Co., Ltd., colloidal silica Average particle size 10-20 nm
Component D (Note 11) “Chemical Pearl W-950”: Mitsui Chemicals, water-dispersed polyethylene wax, melting point 113 ° C., average particle size 0.6 μm
(Note 12) “Chemipearl W-640”: Mitsui Chemicals, water-dispersed polyethylene wax, melting point 113 ° C., average particle size 1 μm
Aqueous urethane resin (Note 13) “HUX-232”: manufactured by Adeka Corporation, aqueous urethane resin, glass transition temperature 78 ° C.
(Note 14) “HUX-350”: manufactured by Adeka, water-based urethane resin, glass transition temperature 10 ° C.
(Note 15) “HUX-232”: manufactured by Adeka, water-based urethane resin, glass transition temperature of −25 ° C.

Measurement and evaluation
(Conductivity)
The tester terminal is connected to the surface opposite to the surface of the film formed by applying the lubricant composition, the other tester terminal is connected to the surface of the film formation, and brought into contact with the brass bar with a load of 20 g weight. The electrical resistance was measured. That is, a tester terminal was brought into contact with the surface of the aluminum film on which the film was formed with a load of 20 g, and the electrical resistance value between the terminal and the aluminum material of the base material was measured.
The tester used CX270N made by Custom Co., Ltd., and zero point correction was performed with the terminals of the tester in contact with each other before measurement in order to remove the influence of the internal resistance of the tester. In addition, the most sensitive range in the tester was used for the measurement, and the resistance value when the tester display stopped was used as the measurement value. The measurement was arbitrarily performed at 10 locations, and the number of energizations and the average value thereof were adopted.
In, the number of energizations is 10, and the average value of the electrical resistance is less than 2Ω, and the conductivity is very good.

  ○ indicates that the number of energizations is 8 times or more and less than 10 times, and the average electric resistance value is less than 5Ω, and the conductivity is good.

  In x, the number of times of energization is 7 times or less, or the average electric resistance value of the number of times of energization is 5Ω or more, and the conductivity is insufficient.

(Blocking resistance)
The coated plates formed by applying the lubricant composition are cut to a size of 5 cm × 5 cm, and are superposed so that the coating surfaces are in contact with each other, and are adhered for 30 minutes under conditions of a temperature of 80 ° C. and a load of 100 kgf / cm 2. Then, the two coated plates were peeled off and evaluated according to the following criteria.

  ◎ can be easily peeled off almost without resistance, and no abnormalities are observed on the surface of the film, and the blocking resistance is very good.

  ○ shows slight resistance when the two sheets are peeled off, but no unevenness is observed on the film surface, and the blocking resistance is good.

  X indicates that the two coated plates are not peeled off or peeled while feeling resistance, and unevenness is observed on the surface of the film, resulting in insufficient blocking resistance.

(Scratch resistance)
Using a microhardness meter having a Knoop indenter with a facing angle of 136 degrees on the surface of the coating formed by applying the lubricant composition, conditions of 20 seconds for each load while changing the load to 10 g weight and 25 g weight respectively. Make an indentation. Next, the film was removed using concentrated sulfuric acid, washed with water and dried to find an indentation on the surface of the aluminum substrate, and evaluated by whether or not the indentation was observed on the surface of the aluminum substrate.

  In ◎, no indentation is observed on the surface of the aluminum base material under either load condition, and the scratch resistance is very good.

  ○ indicates that scratches are observed at a load of 25 g, but no indentation is observed on the surface of the aluminum base material, and the scratch resistance is good under the conditions of a load of 10 g.

  In x, indentation is recognized on the surface of the aluminum base material under either load condition, and the scratch resistance is insufficient.

Claims (3)

A lubricating treatment composition comprising an aqueous urethane resin (A), a polyalkylene oxide compound (B), colloidal silica (C) and a lubricating function-imparting agent (D), wherein the glass transition temperature of the aqueous urethane resin (A) Is 25 to 70 ° C., and the solid content of the aqueous urethane resin (A) is 60 to 90% by mass based on the total solid mass of the aqueous urethane resin (A) and the polyalkylene oxide compound (B). The solid content of the oxide compound (B) is 10 to 40% by mass, the solid content of the colloidal silica (C) is 5 to 30% by mass, and the solid content of the lubricating function-imparting agent (D) is 5 to 30% by mass. Lubricant composition characterized by the above. The lubricant composition according to claim 1, wherein the raw material polyol of the water-based urethane resin (A) contains a compound having at least one chemical bond selected from the group consisting of an ether bond, an ester bond and a carbonate bond in the molecule. A film forming method comprising coating the lubricant composition according to claim 1 or 2 on a metal plate so that the dry film thickness is in the range of 0.3 to 0.6 µm.