JPH0711089A - Composition capable of forming a lubricious film and metal plate excellent in lubricity using the same - Google Patents

Abstract

(57) [Summary] [Object] To provide a composition capable of forming a lubricating film excellent in workability, corrosion resistance, and suitability for topcoating, and a lubricating metal plate coated with the composition. [Composition] A water-dispersible or water-soluble resin (A) 1 comprising a polyurethane resin (a) and an acrylic resin (b)
A composition containing 5 to 50 parts by weight of silica particles (B) and 0.5 to 30 parts by weight of a lubricating function-imparting agent (C) per 100 parts by weight, and a dry film obtained from the composition. Of the elastic modulus E ₁ at 100 ° C. of 1.0 × 10 ⁹ dyn / cm ²
A composition capable of forming a lubricating film, which is characterized by the above, and a metal plate having excellent lubricity obtained by forming a film on the metal plate with this composition.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention is applied to a composition capable of forming a lubricating film excellent in workability, corrosion resistance and suitability for top coating, and applied to the field of household appliances, building materials, automobile products, etc. Lubricated metal plate.

[0002]

2. Description of the Related Art When a metal plate is subjected to processing such as press molding, it is possible to apply a press oil or the like to the metal plate for the purpose of preventing damage to the metal plate due to lack of slippage. Has been done. In this case, Freon, 1,1,1-trichloroethane, and other unfavorable solvents for the protection of the global environment are often used in the washing step after press molding.

In recent years, various lubricious metal plates have been studied for the purpose of further improving moldability and not using a solvent which is not preferable in a particular global environment. The prior art relating to a lubricious metal plate is as follows: (1) A lubricating treatment method for imparting a high degree of corrosion resistance, characterized by forming both layers of an oil-based lubricant and a rust preventive oil (Japanese Patent Publication No. 57-31471). (2) A chromate film treatment is applied to a zinc-based plated steel sheet, and an acrylic resin-based water-based organic composite silicate containing a water-dispersible lubricant is applied thereon to form a film. Anti-corrosion lubricated steel plate (JP-A-61-6088)
No. 6), (3) Solvent-based coating containing a zinc-plated steel sheet, a chromate film treatment, and then a urethane-containing epoxy ester resin, silica powder, hydrophilic polyamide resin, and polyethylene wax as a lubricant. An organic composite steel sheet coated with the composition in an amount of 0.3 to 5 μm and having excellent cationic electrodeposition coatability (see JP-A-63-35798), (4) A chromate film is formed on a zinc alloy-plated steel sheet, and the chromate is formed. Urethane resin and Si on the film
A coating layer containing a composite substance or a mixed substance of O ₂ as a main component is formed, and 1 to 50% of silica particles are further formed on the coating layer.
Lubricated steel sheets obtained by forming a contained wax film (see Japanese Patent Application Laid-Open No. 2-124997) are disclosed.

However, the lubricating steel sheets obtained by the above (1) to (3) are all effective for low speed working such as Erichsen deep drawing at room temperature, but for example, high speed of about 500 mm / sec. Press processing or 80-1
When heated at 00 ° C, the coating layer easily peels off, and the peeling powder adheres to the work material or processing tool, which scrapes the work material and damages the surface appearance of the work material. There was a problem that Further, in (3), it is necessary to sufficiently disperse the silica powder, and in (4), there is a problem that the number of lubricating film layers is two and the number of coating steps increases.

[0005]

Means for Solving the Problems The present inventors have solved the above-mentioned drawbacks of the prior art, and have excellent continuous moldability and corrosion resistance without applying a liquid lubricant even during high-speed press working, and have a fingerprint etc. during handling. As a result of earnest research to obtain a composition capable of forming a lubricating film excellent in adhesion when a general thermosetting alkyd-based paint or thermosetting acrylic-based paint is overcoated A composition in which silica particles and a lubricating function-imparting agent are blended in a specific amount in an aqueous resin containing a resin and an acrylic resin as main components, and a dry film of the composition exhibits specific viscoelastic properties is described above. The inventors have found that the object can be achieved and arrived at the present invention.

That is, according to the present invention, silica particles (B) in solid content are added to 100 parts by weight of water-dispersible or water-soluble resin (A) consisting of polyurethane resin (a) and acrylic resin (b). A composition containing 5 to 50 parts by weight and a lubricant function-imparting agent (C) in a solid content of 0.5 to 30 parts by weight, wherein 100 is a dry film obtained from the composition.
The present invention provides a composition capable of forming a lubricating film, which has a modulus of elasticity E ₁ at 1.0 ° C. of 1.0 × 10 ⁹ dyn / cm ² or more.

Further, the present invention provides a composition capable of forming the above-mentioned lubricating film on a metal plate in a dry film weight of 0.5 to 5.
The present invention provides a metal plate having excellent lubricity, which is formed by applying 0 g / m ² and forming a film.

The water-dispersible or water-soluble resin which is the component (A) in the present invention comprises a water-dispersible or water-soluble polyurethane resin (a) and a water-dispersible or water-soluble acrylic resin (b). Hereinafter, "water-dispersible or water-soluble" may be abbreviated as "aqueous".

The polyurethane resin (a) used as the component (A) of the composition of the present invention is a polyurethane composed of a polyol such as polyester polyol and polyether polyol and diisocyanate, and if necessary, 2 such as diol and diamine. A chain extender, which is a low molecular weight compound having one or more active hydrogens, is chain-extended and stably dispersed or dissolved in water, and known compounds can be widely used (for example, JP-B-42-24192). Japanese Patent Publication, Japanese Patent Publication No. 42-24194, Japanese Patent Publication No. 42-5118, Japanese Patent Publication No. 49-986, Japanese Patent Publication No. 49-331.
04, Japanese Patent Publication No. 50-15027, Japanese Patent Publication No. 5
3-29175 gazette). As a method for stably dispersing or dissolving the polyurethane resin in water, for example, the following method can be used.

(1) A method of imparting hydrophilicity by introducing an ionic group such as a hydroxyl group, an amino group or a carboxyl group into a side chain or a terminal of a polyurethane polymer and dispersing or dissolving it in water by self-emulsification. (2) The polymer of which the reaction is completed or the terminal isocyanate group is blocked with a blocking agent such as oxime, alcohol, phenol, mercaptan, amine and sodium bisulfite is forcibly dispersed in water by using an emulsifier and mechanical shearing force. how to. Furthermore, a method in which a urethane prepolymer having a terminal isocyanate group is mixed with water / emulsifier / chain extender and the mechanical shearing force is used to simultaneously disperse and increase the molecular weight. (3) A method in which a water-soluble polyol such as polyethylene glycol is used as the polyol which is the main raw material of polyurethane, and is made into a water-soluble polyurethane to disperse or dissolve in water.

The above-mentioned polyurethane resin (a) is not limited to a single method for the above-mentioned dispersion or dissolution method, and a mixture obtained by each method can be used.

Examples of the diisocyanate that can be used in the synthesis of the polyurethane resin (a) include aromatic, alicyclic and aliphatic diisocyanates.
Hexamethylene diisocyanate, tetramethylene diisocyanate, 3,3'-dimethoxy-4,4'-biphenylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, 1,3-
(Diisocyanatomethyl) cyclohexanone, 1,4-
(Diisocyanatomethyl) cyclohexanone, 4,4 '
-Diisocyanatocyclohexanone, 4,4'-methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-phenylene diisocyanate, diphenylmethane diisocyanate, m-phenylene diisocyanate, 2 , 4-naphthalene diisocyanate, 3,3'-dimethyl-4,4 '
-Biphenylene diisocyanate, 4,4'- diphenylene diisocyanate, etc. are mentioned. Of these, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate,
Isophorone diisocyanate is particularly preferred.

A preferred polyol that can be used for the synthesis of the polyurethane resin (a) has a molecular weight of 50.
Polyhydroxy compounds such as 0 to 8,000 polyethers, polyacetals, polyesters, polyamides, polyesteramides.

Examples of the polyether include polymerization products of ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, and copolymerization products or graft polymerization products thereof, and copolymerization products thereof, and polyhydric alcohols or Included are polyethers obtained by condensation of mixtures, as well as polyhydric alcohols and polyethers obtained by alkoxylation of amino alcohols. Examples of the polyacetal include those synthesized from hexanediol and formaldehyde.

Polyesters, polyesteramides, and polyamides as polybasic saturated and unsaturated carboxylic acids and polyhydric saturated and unsaturated alcohols, aminoalcohols, diamines, polyamines and predominantly linear groups obtained from them. A condensate is applied.

The chain extender having at least two active hydrogens, which can be optionally used for the synthesis of the polyurethane resin (a), includes the following.

(1) Saturated and unsaturated glycols such as ethylene glycol or a condensate of ethylene glycol, butanediol, propanediol-1,3, propanediol-1,2, neopentyl glycol and mono- and bis-alkoxylated products. Aliphatic, cycloaliphatic, aromatic and heterocyclic primary amines such as N-methyldiethanolamine, N-butyldiethanolamine, N
-Oleyldiethanolamine, N-cyclohexyldiisopropanolamine. (2) Isomers of aliphatic, alicyclic and aromatic diamines such as ethylenediamine, hexamethylenediamine, 1,4-cyclohexylenediamine and phenylenediamine. (3) Amino alcohols such as ethanolamine, propanolamine, butanolamine. (4) Aliphatic, alicyclic and aromatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid and maleic acid.

The polyurethane resin (a) used in the present invention preferably has a glass transition point of 80 ° C. or higher (according to a dynamic viscoelasticity measuring device) from the viewpoint of the elastic modulus E ₁ of the final coating. Commercially available products of the above polyurethane resin (a) include Hydran HW-330, HW-340, and H
W-350 [All are Dainippon Ink and Chemicals, Inc.
Manufactured by Daiichi Kogyo Seiyaku Co., Ltd., and the like.

The acrylic resin (b) used as the component (A) of the composition of the present invention is obtained by emulsion polymerization, suspension polymerization, or emulsion polymerization of a vinyl monomer mixture containing at least one of acrylic acid ester and methacrylic acid ester. It is a resin that has been solution-polymerized and, if necessary, is neutralized and hydrated, or a resin obtained by modifying the resin, and typical examples thereof include the following.

(1) An emulsion obtained by emulsion polymerization of a vinyl monomer mixture in water in the presence of an emulsifier or a high molecular weight resin dispersion stabilizer. (2) A solution obtained by solution-polymerizing a vinyl-based monomer mixture containing a carboxyl group-containing monomer or an amino group-containing monomer in an organic solvent, neutralizing it with a neutralizing agent that is a base or an acid, and making it aqueous. Among these, the acrylic resin (b) includes (1)
It is preferably an emulsion type resin.

The above acrylic resin (b) may be crosslinkable at room temperature. For example, a method in which a carbonyl group is added to an acrylic resin emulsion and a polyhydrazide compound is added to crosslink (USP 3,345, USP 3,345). No. 336, JP-A No. 63-179910) and the like can be used.

The monomer components of the vinyl monomer mixture used for preparing the acrylic resin (b) used in the composition of the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, Butyl acrylate (n-, i-, t-), hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, decyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, Ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, butyl methacrylate (n-, i-, t-), hexyl methacrylate, 2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, Methacrylic acid Teariru, carbon atoms of acrylic acid or methacrylic acid cyclohexyl methacrylate 1-18
(1 to 24) alkyl ester or cycloalkyl ester: of acrylic acid or methacrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, ethoxybutyl methacrylate. Alkoxyalkyl ester having 2 to 18 carbon atoms: Acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid and the like carboxyl group-containing unsaturated monomers: 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3-hydroxypropyl methacrylate, hydroxybutyl acrylate, C ₂ -C ₈ arsenate of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate B alkoxyalkyl esters: N, N
-Dimethylaminoethyl (meth) acrylate, N, N
-Nitrogen-containing alkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate: acrylamide, methacrylamide, N-butoxymethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethylaminoethyl Polymerizable amides such as (meth) acrylamide: glycidyl (meth)
Epoxy group-containing unsaturated monomers such as acrylate and allyl glycidyl ether: vinyl acetate, styrene, α-methylstyrene, vinyltoluene, α-chlorostyrene,
Acrylonitrile etc. can be mentioned.

The acrylic resin (b) has a glass transition point of 4
It is preferably 0 ° C. or higher (by a dynamic viscoelasticity measuring device) from the viewpoint of the elastic modulus E ₁ of the final coating.

In the aqueous resin (A) used in the composition of the present invention, the mixing ratio of the polyurethane resin (a) and the acrylic resin (b) is not particularly limited, but the solid content weight is The ratio is usually (a) / (b)
Is 80/20 to 20/80, and further 70/30 to 3
When it is in the range of 0/70, it does not show tackiness at room temperature and high temperature as a resin component of the lubricating film-forming composition, it has excellent deep drawing workability, and it has good water resistance and topcoat adhesion. It is preferable from the viewpoint that the resin composition can be blended in a well-balanced manner so as to form the film shown.

The silica particles which are the component (B) in the composition of the present invention contribute to the improvement of adhesion and corrosion resistance and have a particle size of 5 nm to 100 μm, preferably 5 nm to 50 nm.
μm silica particles, vapor phase silica, ground silica,
Any silica particles such as water-dispersible colloidal silica may be used. Examples of commercially available water-dispersible colloidal silica include Snowtex N, Snowtex C,
Snowtex O (both manufactured by Nissan Kagaku Co., Ltd.) and the like can be mentioned. Examples of commercially available other silica particles include AEROSIL 200V and R-811 (manufactured by Nippon Aerosil Co., Ltd.).

The lubricating function-imparting agent which is the component (C) in the composition of the present invention may be any one as long as it imparts lubricity to the resulting film, and particularly, it is composed of a polyolefin wax and / or a fluororesin fine powder. Is preferred. As a polyolefin wax, the average particle size is 3.0 μm
In the following, the range of 0.6 to 1.1 μm is more preferable,
It is more suitable that the particle size distribution width is small, and the melting point is 11
Those made of polymers of olefinic hydrocarbons such as polyethylene and polypropylene at 0 ° C. or higher are preferable, and these can be used alone or in combination of two or more kinds.

By using a fluorine-based resin powder together with the above-mentioned polyolefin-based wax, or by using only the fluorine-based resin powder, the lubricity can be further improved as compared with the polyolefin-based wax alone. Examples of the fluorinated resin fine powder include fine powders of polytetrafluoroethylene resin, polyvinylidene fluoride resin, polyfluoroethylene resin, etc. Among them, the polytetrafluoroethylene resin powder having a maximum particle size of 15 μm or less is preferable. .

When a metal plate having a lubricious film is pressed or otherwise processed, the surface temperature rises due to frictional heat during continuous high-speed processing accompanied by heat generation, so that the lubricating function imparting agent having a low melting point becomes liquid, and It is not preferable because it is not fixed to the film and adheres to and accumulates on the mold to damage the surface of the workpiece. Melting point 110 in high-speed machining with heat generation
It is suitable to use a polyolefin wax having a temperature of ℃ or more, preferably 130 to 150 ℃, and the wax is fixed uniformly on the lubricating film even at a considerably high temperature, and the lubricating function is effectively provided without damaging the surface of the workpiece. Can be demonstrated. Further, as the lubricating function-imparting agent, a combination of the above-mentioned polyolefin wax and a fluorine-based resin fine powder, or a fluorine-based resin fine powder alone shows generally superior performance. The reason for this is considered to be that the surface energy of the fluororesin powder is extremely low and a low friction coefficient is given.

(B) and (C) in the composition of the present invention
The mixing ratio of the components is as follows based on 100 parts by weight of the component (A) in terms of solid content ratio. Component (B): 5 to 50 parts by weight, preferably 10 to 30 parts by weight (C) Component: 0.5 to 30 parts by weight, preferably 5 to 20 parts by weight
Parts by weight. Silica, which is the component (B), contributes to the improvement of adhesion and corrosion resistance. However, if the amount of silica is less than 5 parts by weight, sufficient adhesion cannot be obtained, and the resulting lubricous film may be used. The effect of dispersing corrosion current is small and the effect of improving corrosion resistance is small. On the other hand, if it exceeds 50 parts by weight, the gloss value of the film is lowered and the smoothness of the surface is lost, and the elongation rate of the film is drastically reduced, the film is easily peeled off by processing, and press workability is deteriorated. However, it is not preferable because it tends to cause galling.

The lubricating function-imparting agent, which is the component (C), is for imparting lubricity to the material to be processed and performing processing such as pressing without problems, but the amount of the lubricating function-imparting agent is 0.5 parts by weight. When it is less than the above, the effect of improving the lubricity is small. On the other hand, if the amount of the lubricating function-imparting agent exceeds 20 parts by weight, the gloss value of the film decreases and the surface smoothness is lost, the elongation rate and adhesive force of the film decrease sharply, and the film easily peels off. Not only the effect of imparting the function cannot be fully utilized, but the press workability is deteriorated and mold galling is likely to occur, and when the top coat paint is applied onto this film, the adhesion of the top coat film is lowered.

In the composition of the present invention, (A), (B),
Although the three components (C) may be simply mixed,
The aqueous acrylic resin (b) and the silica particles (B) in the component (A) may be reacted with each other to form an organic composite silicate. When the organic composite silicate is used, it is necessary that the aqueous acrylic resin (b) has at least one group of a hydroxyl group and a carboxyl group, and the acrylic resin (b) and the component (B) are combined. It can be obtained by mixing a water-dispersed colloidal silica in an aqueous medium in the presence of a di- or trialkoxysilane compound, and heating the mixture as necessary to react the mixture (JP-A-61-60886). (See the official gazette).

The composition of the present invention is required to exhibit viscoelastic properties such that the dry film obtained from the composition has an elastic modulus E ₁ value at 100 ° C. of 1.0 × 10 ⁹ dyne / cm ² or more. is there. Here, the elastic modulus E ₁ is a vertical type dynamic viscoelasticity measuring apparatus DVE-V4 type FT Rheospectler (manufactured by Rheology) by forced vibration non-resonance, using a frequency of 110 Hz and a temperature rising rate of 4. It is a value measured under the conditions of 0 ° C./minute and a constant static load of 10 g.

When the elastic modulus E ₁ value at 100 ° C. of the dry film is less than 1.0 × 10 ⁹ , the film softens due to the temperature increase on the surface of the material to be processed during high-speed pressing, and the film strength is reduced. At the same time, it becomes easy to peel itself off, and at the same time, the lubricant function-imparting agent cannot be fixed uniformly. For this reason, continuous moldability is remarkably reduced, which is not preferable.

The composition of the present invention comprises (A), (B) and (C)
In addition to the components and water, a neutralizing agent, a reaction accelerator, a thickener, a defoaming agent, an organic solvent and the like may be appropriately contained.

The composition of the present invention exerts its function sufficiently by applying it to a metal plate to form a lubricous film. Examples of the metal plate include cold rolled steel plate, zinc plated steel plate, iron-zinc alloy plated steel plate, nickel-zinc alloy plated steel plate, zinc-aluminum alloy plated steel plate, aluminum plated steel plate, tin plate and aluminum plate. The metal plate may be subjected to a known chemical conversion treatment such as chromate treatment, zinc phosphate treatment, iron phosphate treatment, phosphoric acid-chromium treatment. From the viewpoint of corrosion resistance, those subjected to chemical conversion treatment are preferable.

The amount of chromate coating in the above chromate treatment is 10 to 100 mg / m ² as the amount of chromium element, and the amount of treated coating in the iron phosphate treatment or zinc phosphate treatment is 0.2 to 0.5 g / m 2. ² is the corrosion resistance,
It is preferable in terms of workability.

The composition of the present invention has a dry coating weight of 0.5 to 5.0 g / m ² , more preferably 1.5 to 3.0 on the above metal plate.
It is desirable that the coating is applied so as to be g / m ² and dried to form a film. If the dry film weight is less than 0.5 g / m ² , the effect of improving the corrosion resistance is small and a sufficient lubricating function cannot be obtained. ^{On the other hand} , if it exceeds 5 g / m ² , corrosion resistance is improved, but press workability is deteriorated, and cost is high, which is not economical.

Further, in order to impart welding suitability to a steel sheet coated with a lubricating coating of the composition of the present invention, the coating weight should be 2.2 g / m ² or less, more preferably 1.8 g / m ² or less. Is desirable. If the coating weight exceeds 2.2 g / m ² , dust is likely to occur during spot welding, and the welding strength becomes insufficient, resulting in a rapid drop in continuous spot aptitude.

When the composition of the present invention is applied onto a metal plate to form a film, the viscosity of the composition is adjusted appropriately with a diluent such as water to a range of 5 to 20 centipoise depending on the application amount, and the like. After being coated by a generally known method such as roll coater coating, spray coating, dipping coating, and brush coating so as to have a predetermined coating weight, it is usually dried at an ambient temperature of 100 to 300 ° C. for 10 to 120 seconds. The maximum plate temperature (PMT) of the material at this time is 80-150
It is preferably in the range of ° C. By coating and drying the coating composition having a lubricating function in this manner, a metal plate having excellent lubricity and excellent in press working is manufactured.

[0040]

The lubricating film obtained from the composition of the present invention uses a polyurethane resin and an acrylic resin as resin components, and has no tackiness even in a high temperature region (100 ° C.), so that the metal film can be used even in a high temperature region. Adhesion to the plate is good, and even if the temperature of the coating rises during continuous high-speed processing such as press working, the strength of the coating does not easily decrease. Further, since it contains silica particles, it is possible to improve the adhesiveness, disperse the corrosion current, and greatly improve the corrosion resistance.

Since the lubricating function-imparting agent is uniformly present in the film and has a good lubricating function, it can be pressed as it is without applying a liquid lubricant or the like. Therefore, application and degreasing of the liquid lubricant at the time of processing are possible. The process can be omitted, not only the working environment can be improved, but also the cost can be reduced, and the use of wax having a melting point of 110 ° C or higher causes the lubricant function-imparting agent to become liquid even in continuous high-speed processing, and the mold can be used. The lubricating function can be effectively exhibited without adhering to and accumulating on the work piece and damaging the work piece. At the same time, dirt such as fingerprints is hard to get on during handling. Furthermore, it is possible to provide a lubricating film having excellent adhesiveness even when a general thermosetting acrylic paint or thermosetting aminoalkyd paint is applied onto this film.

[0042]

EXAMPLES Hereinafter, the composition of the present invention will be described more specifically by way of examples. In the following description, [parts] and [%] mean [parts by weight] and [% by weight], respectively, unless otherwise specified.

Synthesis Example 1 Synthesis of Acrylic Emulsion 1,2-Polybutadiene (molecular weight 3,000, manufactured by Nippon Soda Co., Ltd.) was added to butyl cellosolve with maleic polybutadiene having an acid value of about 100 to give a solid content of 7.
Ammonia water was added to 13 parts of the resin solution adjusted to 5% for neutralization (1.0 equivalent), and further 60 parts of deionized water was added to uniformly dissolve the resin solution. Styrene 11 in this solution
Part, 2-hydroxyethyl methacrylate 3 parts, 2-ethylhexyl acrylate 9 parts, and 2-ethylhexyl methacrylate 2 parts were added and stirred to give 5% as a reaction initiator.
After adding 1 part of ammonium persulfate aqueous solution, 80-85 ° C
And reacted for 2 hours to obtain an emulsion having a solid content of 35%.

Synthesis Example 2 Synthesis of Organic Composite Silicate 228.6 parts of the acrylic emulsion obtained in Synthesis Example 1 above, 126 parts of water, pH 8.4, particle size 10 to 20 μm.
Aqueous colloidal silica aqueous dispersion 10 with m and solid content of 20%
0 parts was added, and then 2.4 parts of γ-methacryloxypropyltrimethoxysilane was added dropwise with stirring, and then 8
The mixture was reacted at 5 ° C for 2 hours to obtain a milky white organic composite silicate aqueous dispersion. The solid content of the obtained dispersion was 22%.

Preparation of coating composition Example 1 (solid content) HW-350 (Note 1) 166.7 parts (50 parts) 35% acrylic emulsion obtained in Synthesis Example 1 142.9 parts (50 parts) Colloidal silica (Note 4) 125.0 parts (25 parts) Wax a (Note 5) 12.5 parts (12.5 parts) After uniformly mixing with the above composition mixture, the viscosity is 10 cps with deionized water ( The viscosity was adjusted to be a B-type viscometer, 20 ° C.) to prepare a coating composition.

Examples 2 to 12 and Comparative Examples 1 to 11 The same as Example 1 except that the solid content composition (parts by weight) of the coating composition is as shown in Table 1 below. Then, each coating composition was obtained. In Table 1, when the organic composite silicate is used, the acrylic resin content and the silica particle content in the organic composite silicate are also shown.

Coating Film Performance Test Using the composition liquids obtained in the above Examples and Comparative Examples, a coating test was performed on an object to be coated. As the objects to be coated, those obtained by subjecting the following metal plates to the following chemical conversion treatment and those not treated were used. (1) Kind of metal plate ・ Electrogalvanized steel plate (EG) plate thickness 0.6mm Zinc coating amount 20g / m ²・ Cold rolled steel plate (CRS) JIS G-3141 (SPCC-SD) plate thickness 0.6mm ・electrolytic zinc - nickel-plated steel plate (Ni-Zn) thickness 0.6mm zinc - nickel coating weight 20 g / m ² nickel content 12%-galvanized steel (HDG) thickness 0.6mm zinc coating weight 120 g / m ²

(2) Chemical conversion treatment / Chromate treatment A coating type chromate treatment liquid (Cosmer # 300 manufactured by Kansai Paint Co., Ltd.) consisting of chromium hydrate having a ratio of Cr ⁺⁶ : Cr ⁺³ of 0.65: 0.35. Was coated on a galvanized steel sheet, a cold rolled steel sheet, a galvanized galvanized steel sheet and a galvanized steel sheet with a rubber roll, and then dried in a hot air drying oven. The amount of chromate film deposited is 5 in terms of elemental chromium.
It was set to 0 mg / m ² . -Iron phosphate treatment The cold-rolled steel sheet was spray-treated with Parphos 1077, which is an iron phosphate treating agent manufactured by Nippon Parkerizing Co., Ltd. The coating weight was 500 mg / m ² .

(3) Method of applying the composition for coating onto the article to be coated With the combinations shown in Table 1 below, each coating composition onto the article to be coated was dried with a bar coater to give a dry film weight of 2.0 g / m ^2. And was dried at 150 ° C. for 30 seconds (PMT 100 ° C.) to form a film. Various tests were performed using the obtained coated object having a film as a test piece. Further, the elastic modulus E ₁ of the coating film of the coating composition was also measured. The test results are shown in Table 1 below.

(4) Test method Measurement of elastic modulus E ₁ of the film: The coating composition was applied repeatedly so that the dry film thickness was 50 μm, and finally 150 ° C.
And dried for 30 seconds to obtain a free coating film having a thickness of 50 μm. About this free coating film, dynamic viscoelasticity measuring device DV
Using an E-V4 type FT Rheospectr (manufactured by Rheology), frequency 110 Hz, temperature rising rate 4.0 ° C./min,
The elastic modulus E ₁ was measured under the condition of a constant static load of 10 g. The elastic modulus E ₁ is the value at 20 ° C. and 100 ° C.

Deep drawing workability: The test piece was tested by using a metal thin plate deep drawing tester 142 type manufactured by Erichsen. a. Conditions for processing test at 20 ° C ・ Sheet holder pressure 1,500kg ・ Punch diameter 50mm ・ Blank diameter 110mm ・ Drawing speed 10mm / sec b. Conditions of processing test at 100 ° C ・ Sheet holder pressure 1,500kg ・ Punch diameter 50mm ・ Blank diameter 110mm ・ Drawing speed 10mm / sec c. Evaluation Criteria A cup deep drawing test was used to evaluate the presence or absence of a coating composition adhering to the die and the surface condition of the workpiece. ⊚: No adhesion to the die, no scratches on the surface of the work piece. ◯: There is a slight amount of adhesion on the die, and minute scratches are recognized on the surface of the work piece. Δ: The die has a little adhesion, and many scratches are recognized on the surface of the work piece. X: A large amount of die is attached, and scratches are observed on the entire surface of the workpiece.

Corrosion resistance: Salt spray test (JIS-Z23
71) was performed and the time (hr) until the occurrence of red rust was evaluated. Two types of tests were performed on a flat plate before processing and on a material subjected to deep drawing at 20 ° C.

Topcoat Adhesion: Amylac # 1000, a thermosetting alkyd-type paint, and Magicron # 1000, a thermosetting acrylic paint, on the dry film of the test piece.
(Both manufactured by Kansai Paint Co., Ltd., color is white) was applied to a dry film thickness of 25 μm and baked under the following conditions. Amylak # 1000: baked at 130 ° C. for 20 minutes, Magiclon # 1000: baked at 150 ° C. for 20 minutes, Evaluation Criteria The above coated plate was subjected to a gooseneck tape test to evaluate the adhesiveness from the state of peeling of the coating film. ⊚: No peeling of the top coating film is observed in the scotch tape test. ◯: Peeling of 1 to 2 top-coat coating films was observed in the scoring tape test. (Triangle | delta): Peeling of 3-10 pieces of top-coat coating film is recognized by the scoring tape test. X: Peeling of 10 or more top-coat coating films was observed in the scoring tape test.

[0054]

[Table 1]

[0055]

[Table 2]

(Note) in Table 1 is as follows. (Note 1) HW-350: manufactured by Dainippon Ink and Chemicals, Inc., tolylene diisocyanate type hard type aromatic polyester polyurethane emulsion, solid content 30
%. (Note 2) AP-60: manufactured by Dainippon Ink and Chemicals, Inc.
Isophorone diisocyanate type soft type polyester polyurethane emulsion. (Note 3) GD-900: manufactured by Kanebo NSC Co., Ltd.,
Acrylic emulsion, resin glass transition temperature 15 ° C.

(Note 4) Colloidal silica: particle size 10 to 2
0 μm, pH 8.6 colloidal silica aqueous dispersion, heating residue 20%. (Note 5) Wax a: molecular weight 4,000, softening point 116
Medium density polyethylene wax with a particle size of 1.1 μm at ℃. (Note 6) Wax b: molecular weight 3,000, softening point 132
High-density polyethylene wax with a particle size of 1.1 μm at ℃. (Note 7) PTFE: Polytetrafluoroethylene resin powder having a particle size of 2 to 3 μm.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C09D 133/06 PGH (C08L 33/06 23:00 27:12) (C10M 173/02 107 : 44 107: 28 125: 26 159: 06 147: 02) C10N 20:00 AZ 20:06 Z 30:12 50:02

Claims (3)

[Claims] 1. A water-dispersible or water-soluble resin (A) comprising a polyurethane resin (a) and an acrylic resin (b).
A composition containing 5 to 50 parts by weight of silica particles (B) in a solid content and 0.5 to 30 parts by weight of a lubricating function-imparting agent (C) in a solid content relative to 100 parts by weight, A composition capable of forming a lubricating film, wherein the dry film obtained from the composition has a modulus of elasticity E ₁ at 100 ° C. of 1.0 × 10 ⁹ dyn / cm ² or more. 2. The composition according to claim 1, wherein the lubricating function-imparting agent (C) comprises a polyolefin wax and / or a fluororesin fine powder having a melting point of 110 ° C. or higher. 3. A metal plate having excellent lubricity, which is formed by coating the composition according to claim 1 or 2 on a metal plate in a dry film weight of 0.5 to 5.0 g / m ² .