JPS599583B2 - Active energy beam-curable coating composition for forming lubricating coatings on metal plates - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to active energy ray-curable coating compositions for forming lubricating coatings on metal plates.More specifically, the present invention relates to active energy ray-curable coating compositions for forming lubricating coatings on metal plates. An oil cleaning coating that has excellent press formability and rust prevention properties by applying it to various metal plates such as surface-treated or untreated aluminum plates, stainless steel plates, copper plates, etc. and irradiating it with active energy rays. The present invention relates to a coating composition for forming a film.

In addition, when applying a top coat to a metal sheet molded product after press forming, the present invention provides excellent adhesion to the top coat and suitability for the top coat, or, if necessary, a lubricating coating that can be formed by a simple process. The object of the present invention is to provide a coating composition for forming a lubricating coating film that also has the ability to remove the film. Furthermore, the present invention is a non-polluting and highly productive lubricating film-forming paint that does not require a large amount of energy for heating and drying, a long drying oven, or exhaust gas treatment equipment unlike conventional emulsion-type or solvent-type paints. A composition is provided. The lubricated metal plate on which the lubricant coating has been formed is subjected to press working, and at that time, the metal plate surface in contact with the die and punch is rubbed with a strong force and subjected to drawing deformation, resulting in deformation (both elongation and stiffness). Accompanied by fever.

In this way, press working is different from simple bending and forming, so the paint used to form a lubricating film on metal plates requires special performance that is different from a simple anti-rust protection paint or primary anti-rust paint. Industrial use is possible only when these various performances are balanced. 1. During press working, it reduces the working pressure, maximizes the amount of metal plate drawing, and has excellent lubrication properties that do not cause scratches or cracks on the machined surface.

2. The coating film should not come off and adhere to the press mold during press processing.

3. The rust prevention or protection effect of the metal plate is excellent before and after pressing.

4. No sticking (adhesion between paint films) when stacking painted metal plates.

5. Good adhesion with top coat paint, surface coating film, and leather.

6. If necessary, the lubricating coating film can be removed by simple treatment.

7. Metal plates have a large heat capacity, so if heating and drying is required to form a lubricating coating, it will consume a lot of energy, so this should not be necessary.

8. The process for forming a lubricating film (coating, drying process) is simple, does not require a large equipment space, does not generate solvent vapor or toxic gas, and is highly productive.

Conventionally, press oils made of mineral oil, solid lubricants such as metal soap and wax, and polymer coatings with lubricating properties added to organic polymer coatings have been used as lubricants for press processing of metal plates. However, such conventional lubricants have the following problems.

Solid lubricants such as press oil and metal soap tend to cause linear scratches and seizure phenomena on the processed surface of the metal plate when pressing conditions are severe, such as when pressing high-strength steel sheets or deep drawing. There are also problems with press forming properties, such as environmental pollution due to oil, lack of rust prevention, and detachment of the lubricating film due to contact with foreign objects during transportation. performance is insufficient.

Methods for using organic polymer coatings include simply applying and drying a solvent solution, aqueous solution, or emulsion of an organic polymer (for example, polyvinyl chloride, polyvinyl acetate, polyacrylic acid ester, etc.) onto the surface of a metal plate; A method of applying an oil that softens the surface of the molecular coating film and makes it semi-fluid during press processing. For example, Japanese Patent Publication No. 51-3702,
U.S. Pat. No. 3,568,486 describes a method of coating a metal plate with a paint prepared by adding and blending a lubricant such as polyethylene wax, solid oily fatty acid, or metal soap to an emulsion or solvent solution of an organic polymer (e.g., JP-A-Sho et al. 55-
38840), a method of coating two layers of organic coatings with different coefficients (for example, Japanese Patent Publication No. 52-475)
There are methods that use active energy ray-curable paints such as ultraviolet rays and electron beams.

Among these conventional techniques, those in which an emulsion or a solvent solution of an organic polymer is simply applied and dried are insufficient in terms of press moldability as described above.

Some methods of applying oil to the surface of the organic polymer coating film during press processing are excellent in terms of press forming performance, but they require two coats and are not conducive to contamination of the press work environment due to oil. Still not satisfied. Organic polymer emulsions or solvent solutions with lubricants added have excellent press forming performance, but they consume a lot of energy because the metal plate is also heated at the same time to dry the water and solvent. Especially in fields where the line speed is high, such as continuous production equipment for steel plates,
The drying oven also requires a very long one. Furthermore, emulsion or aqueous paints have poor rust prevention properties, and organic solvent paints have problems with the risk of ignition or contamination of the working environment, and the need for exhaust gas treatment equipment to deal with this. . The method of applying a two-layer coating requires two coats, which makes the process complicated and industrially unsatisfactory. Paints that use active energy rays such as ultraviolet rays and electron beams as curing means do not require heating, have attracted attention in recent years as energy-saving, non-polluting paints, and are being used in a variety of applications.

Active energy ray-curable paints can be classified according to the type of constituent components, including unsaturated polyester/monomer type, acrylic oligomer/monomer type, epoxy resin type, polyene/thiol type, and aminoaluminum type. Regarding acrylic oligomer/monomer systems, for example, there are multiple (meth)acryloyl groups in the molecule [in the present invention, acryloyl groups and methacryloyl groups are collectively referred to as (meth)acryloyl groups, and acrylate and methacrylate are collectively referred to as (meth)acrylates. polyhydric (meth)acrylate blended compositions having
No. 1), compositions consisting of polyvalent (meth)acrylates and mono(meth)acrylates (for example, Japanese Patent Publication No. 110-1983)
34, Japanese Patent Publication No. 52-25438), compositions consisting of polyvalent (meth)acrylate and thermoplastic resin (for example, JP-A-49-130481), polyvalent (meth)acrylate, mono(meth)acrylate and heat Compositions consisting of plastic resins (for example, JP-A-53-49027), compositions consisting of ethylenically unsaturated compounds and thermoplastic resins (JP-A-52-4539, JP-A-52-4540), α,
Various compositions such as a composition consisting of a β-ethylenically unsaturated resin and a rust preventive agent (Japanese Patent Application Laid-open No. 52-98742) are used as active energy ray-curable rust preventive coatings for metals, protective coatings, and primary rust preventive paints. Although it has been shown that it can be used as
There is no technical disclosure in these documents regarding coatings for forming lubricating coatings. On the other hand, active energy ray-curable coatings for forming lubricating coatings and steel materials using the same are those in which a two-layer coating consisting of a cured coating and an uncured fluid coating is sequentially formed on the surface of the steel (Japanese Patent Laid-Open No. 51 -70173), one in which a lubricant layer is further coated on the cured coating to form a two-layer film (JP-A-51-70174), an active energy ray-curable resin containing a lubricant is used. (Japanese Unexamined Patent Publication No. 1973)
70175), and one using a composition comprising a resin having one polymerizable double bond in the molecule and a polymerization initiator (Japanese Patent Application Laid-open No. 155172/1983).
For example, the above-mentioned lubricating film-forming paints have been used for several reasons, such as requiring two coats, and being unsatisfactory in terms of locking properties, curing speed, rust prevention, press molding properties, etc. There are still some aspects that are insufficient in terms of the balance of required properties, and it is desired to develop a coating material for forming a more excellent lubricating film.

The present inventors have conducted intensive research to improve the drawbacks of such conventional lubricants or paints and to develop a well-balanced paint that satisfies all the characteristics required of a paint for forming a lubricating film. The present invention has been completed, and the present invention consists of (a) at least one type of polyfunctional compound having a plurality of (meth)acryloyl groups in the molecule; (b) one (meth)acryloyl group in the molecule;
At least one monofunctional compound having an acryloyl group,
(c) consisting of at least one organic polymer at least partially soluble in the mixture of (a) and (b), and (d) at least one lubricant, derived from (a) (meth) The proportion of acryloyl groups is 3 based on the total amount of this and (meth)acryloyl groups derived from (b).
~60 mol%, (a), (b), (c) and (
The ratio of (d) is based on the total amount of (a) and (
An active energy ray for forming a lubricating coating film on a metal plate, characterized in that the total amount of b) is 94 to 60% by weight, (c) is 3 to 20% by weight, and (d) is 3 to 20% by weight. It is a curable coating composition.

The composition and other details of the coating composition according to the present invention are as detailed below, and this is coated on a metal plate to a thickness of 0.5 to 10μ using an appropriate coating means such as a roll coater, and activated. When irradiated with energy rays, it hardens almost instantly, creating a coating film with excellent properties such as lubricity during press processing, moldability, rust prevention, blocking properties, and adhesion to top coats and films. Form.

Furthermore, since it is a one-component solvent-free type, it is easy to handle without worrying about environmental pollution, and energy consumption is extremely low because it does not require heating.The active energy ray irradiation device is compact and compared to a heating drying oven. It has many advantages, such as requiring less installation space and being easily integrated into existing continuous production lines. The following will be explained in order.

In this specification, an acryloyl group and a methacryloyl group are collectively referred to as a (meth)acryloyl group, an acrylate and a methacrylate are collectively referred to as (meth)acrylate, and acrylic acid and methacrylic acid are collectively referred to as (meth)acrylic acid. The polyfunctional compound constituting component (a) of the present invention is a compound having multiple (meth)acryloyl groups in the molecule, and belongs to a wide range of compounds including monomers, oligomers, and prepolymers. is a compound, for example the following (
O(1) Polyol poly(meth)acrylate including those listed in 1) to (7); for example, ethylene glycol, propylene glycol, neopentyl glycol, hexanediol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol,
Polyhydric alcohols such as dipentaerythritol (
Examples include meth)acrylates.

(2) Polyether poly(meth)acrylate; for example, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, bisphenol A and alkylene oxide (such as ethylene oxide,
Polyhydric (meth)acrylates such as polyether glycols obtained by adding alkylene oxide to polyhydric alcohols such as those exemplified in (1) above, and polyether polyols obtained by adding alkylene oxide to polyhydric alcohols as exemplified in (1) above. (3) Polyester poly(meth)acrylate; for example, maleic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, terephthalic acid, isophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid A polyhydric acrylate of a polyester polyol consisting of one or more polybasic acids such as acid, trimellitic acid, pyromellitic acid, etc., and one or more polyols or polyether polyols exemplified in (1) or (2) above. Can be mentioned.

(4) Polyurethane poly(meth)acrylate; for example, organic polyhydric acid such as tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, isoborone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, etc. A reaction product between an isocyanate and a hydroxyalkyl (for example, ethyl, propyl, etc.) (meth)acrylate, or a reaction product between an organic polyvalent isocyanate and a polyol, polyether polyol or polyester polyol as exemplified in (1) to (3) above. Polyhydric (meth)acrylates having a polyurethane skeleton, such as a reaction product of a terminal isocyanate type urethane prepolymer obtained by the reaction and a hydroxyalkyl (meth)acrylate, can be mentioned.

)) Epoxy poly(meth)acrylates; for example, addition reaction products of polyvalent epoxy compounds and (meth)acrylic acid or terminal carboxy(meth)acrylates [such as phthalic acid mono(meth)acryloyloxyethyl ester, etc.] Examples include polyvalent (meth)acrylates.

Examples of the polyvalent epoxy compound include phenolic compounds having an epoxy group, such as bisphenol A1, halogenated bisphenol A1 phenol, or a novolak type polyphenol compound which is a condensation product of cresol and formalin (1) to Glycidyl ether or glycidyl ester obtained by condensing epichlorohydrin or β-methylepichlorohydrin with a polyol or polyether polyol as exemplified in (2), a dimer acid, a polybasic acid as exemplified in (3) above, etc. polyepoxy compounds of the type, cycloaliphatic polyepoxy compounds, such as vinylcyclohexene dioxide, (3,4-epoxy-6-methylcyclo-4yl)-methyl-(3,4-epoxy-6-methylcyclohexyl) Polyvalent epoxy compounds such as carboxylates or epoxy esters containing epoxy groups obtained by reacting these polyvalent epoxy compounds with polybasic acids can be used. t) Polyhydric (meth)acrylates containing phosphoric acid ester groups; for example, polyhydric (meth)acrylates obtained by reacting hydroxyalkyl (meth)acrylates with phosphorus pentoxide, or by combining this with polyhydric alcohols or, in some cases, monohydric alcohols. ) acrylate, etc.

An example thereof is shown by the following formula [1]. (However, R1 represents a hydrogen atom or a methyl group, R2 represents an alkylene group (for example, -CH2CH2- -CH2-CH-, etc.), R3 represents a residue obtained by removing the hydroxyl group from a dihydric alcohol, and R4.R , is a hydrogen atom, an alkyl group (e.g. -C
H3, C7H, 5, C, 2H25, etc.), or 1e-
R2-00C-C=CH, where n is zero or a positive integer.

) (7) Others; Polyvalent (meth)acrylate of polyamide type polyol, polyvalent (meth)acrylate of melamine initial condensate, polyvalent (meth)acrylate of organopolysiloxane type polyol, polyvalent of vinyl copolymer oligomer (meth)acrylate, multiple (meth)acrylates in the molecule
Examples include low molecular weight polymers with acryloyl groups.

(However, R1 represents a hydrogen atom or a methyl group, R2 represents a substituted or unsubstituted alkylene group (which may contain an oxygen atom), and R represents a residue obtained by removing a carboxyl group from a dibasic acid. 0) (4) Carboxyl-terminated mono(meth)acrylate One-terminated hydroxyl-type mono(meth)acrylate; for example, 2-hydroxyethyl (meth) ) acrylate, 2-hydroxypropyl (meth)acrylate, tetramethylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, etc. , monoepoxy compounds and (methacrylic acid) addition reaction products.

An example of this addition reaction product is as shown in the following formula [river]. Next, the monofunctional compound constituting component (b) of the present invention is a compound having one (meth)acryloyl group in the molecule,
Not only monomers but also oligomers can be used.

Examples include the following (1) to QV) (where Rl and R2 represent a hydrogen atom or a methyl group, and R3 represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkyl group). Aryl group, di or -CH2-0
represents R4-0-R5, and n represents zero or a positive integer.

Here, R4 represents a substituted or unsubstituted alkylene group,
R5 is the same as R3. ) Monoepoxy that can be used as a raw material for the above addition reaction. Compounds include epichlorohydrin, β-methylepichlorohydrin, monoglycidyl ether compounds (for example, monohydric phenols or monohydric alcohols such as phenol, cresol, butanol, or monohydric alcohol obtained by adding alkylene oxide to phenol or cresol). and epichlorohydrin or β-methylepichlorohydrin), styrene oxide, etc. can be used.

Furthermore, instead of (meth)acrylic acid, the terminal carboxyl type mono(meth)acrylate described in (1) below can also be used for the reaction with the monoepoxy compound. In addition, there are also polyester-type mono(meth)acrylates represented by the following formula [] obtained by the reaction of (meth)acrylic acid, dibasic acid anhydride, and alkylene oxide. tylhexahydrophthalic acid, trimellitic acid, (wherein R1 represents a hydrogen atom or a methyl group, R2 represents a substituted or unsubstituted alkylene group (which may contain an oxygen atom), and R3 represents a polybasic acid anhydride. Shows the residue of something.

) (111) Terminal phosphate ester type mono(meth)acrylate; terminal hydroxyl type mono(meth)acrylate of the above (i)
It is obtained by the reaction of acrylate and phosphorus pentoxide, and has, for example, the structure of the following formula [V].

(However, R1 represents a hydrogen atom or a methyl group, and R2 represents a substituted or unsubstituted alkylene group (which may contain an oxygen atom).

) QV) Other (meth)acrylates represented by the following formulas [] such as methyl cellosolve (meth)acrylate, carbitol (meth)acrylate, butyl cellosolve methacrylate, methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate , phenoxyethyl (meth)
acrylate, phenylcarbitol (meth)acrylate, phenoxypropyl (meth)acrylate (meth)acrylate of polyoxyalkylenated phenol, (meth)acrylate of polyoxyalkylenated alkylphenol], glycidyl (meth)acrylate, Alkyl (meth)acrylates [e.g. 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, etc.], acetoxyethyl (meth)acrylate, N-methylol acrylamide, N-di Monofunctional monomers having one (meth)acryloyl group in the molecule, such as acetone acrylamide, are used. Anhydrides such as pyromellitic acid can be used.

(However, R1 represents a hydrogen atom or a methyl group, R2 represents a substituted or unsubstituted alkylene group, R3 represents an alkyl group, a substituted or unsubstituted aryl group, and n is 1 to
Indicates an integer of 10. ) The monofunctional compound used as component (b) of the present invention is as exemplified above, but since the composition according to the present invention is generally handled as is in the coating/curing process, it has a small molecular weight, odor and irritation,
It is desirable to avoid using those with strong boiling points, preferably 200°C or higher at normal pressure, and more preferably 3
It is preferable to use a monofunctional compound having a temperature of 00°C or higher. For this reason, the compounds shown in the above formulas [...] to [] can be suitably used as monofunctional compounds in the present invention. Furthermore, among them, the terminal hydroxyl type mono(meth)acrylates exemplified in (1) above, especially those having 4 carbon atoms.
A coating composition containing the monomer represented by the formula [ ] obtained by the reaction of the above monoepoxy compound and (meth)acrylic acid as the main component of the monofunctional compound of the present invention can be cured by active energy rays. It has excellent speed, and the formed lubricating film is particularly well-balanced in terms of properties such as press forming properties, adhesion to metal plates, locking properties, rust prevention properties, and adhesion properties to surface coating films. Are better. Therefore, it can be suitably used for applications that are exposed to more severe operating conditions, such as deep drawing press working of high-strength steel. The organic polymer used for component (c) of the present invention is:
At least a part of it is soluble in the mixture of the polyfunctional compound (a) and the monofunctional compound (b), and by adding this, press moldability is improved and the amount of drawing is increased, and Detachment of the paint film and scratches on the machined surface are reduced.

The reason for this is that the cured coating film formed from a composition consisting of a polyfunctional compound and a monofunctional compound has a crosslinked structure and the polymer molecules are fixed, but due to the blending of the organic polymer, these It is thought that this is because a plasticizing effect is imparted to the molecules of the coating film by forming a micro-heterogeneous structure. Organic polymers that can be suitably used include methacrylate (co)polymers, acrylic ester (co)polymers, vinyl chloride (co)polymers, polystyrene (co)polymers, polyvinyl acetate copolymers, and carboxylic acid ester (co)polymers. , methylcellulose, polystyrene epoxy ester, polyurethane resin, polyvinyl alcohol, alkylphenol resin, rosin-modified glycerin ester,
Examples include aromatic petroleum resins, rosin-modified maleic acid resins, polyvinyl butyral resins, and polyvinyl sulfone resins.

The organic polymer preferably has a softening point of 20 to 150°C,
More preferably, the temperature is 30 to 130°C.

Even if the softening point is relatively high, the plasticizing effect is sufficiently exerted by the frictional heat generated at the contact surface between the metal plate and the metal plate during press forming and the heat generated by deformation.
Organic polymers with too high a softening point are undesirable because they tend to have poor solubility in a mixture of a polyfunctional compound and a monofunctional compound. If an organic polymer with a softening point that is too low is used, it is undesirable because a locking phenomenon (adhesion phenomenon between coating films) may occur when metal plates treated with a lubricating coating are stored in a coiled form or stacked. . The present invention (
The lubricant used in component d) has the function of reducing both the frictional force between the polymers in the coating film and the frictional force between the press-forming fittings (dies and punches) and the surface of the metal plate during press-forming. It reduces the pressing force and also shows the effect of preventing scratches on the surface of metal plates.

Suitable lubricants include, for example, hydrocarbon-based lubricants (e.g., natural paraffin, synthetic paraffin, microwax, polyethylene wax, chlorinated hydrocarbons, fluorocarbons, etc.), fatty acid-based lubricants (e.g., lauric acid, stearin, etc.). acid, palmitic acid, oxyfatty acid, etc.), fatty acid amide lubricants (e.g. stearic acid amide, 'glumitic acid amide, methylene bis stearamide, ethylene bis stearamide, oleic acid amide, ethyl acid amide, alkylene bis fatty acid) ester lubricants (e.g. lower alcohol esters of fatty acids such as butyl stearate, polyhydric alcohol esters of fatty acids such as hydrogenated castor oil, glycol esters or polyglycol esters of fatty acids such as ethylene glycol monostearate) , industrial still wax, etc.)
, alcohol-based lubricants (e.g. cetyl alcohol, stearyl alcohol, palmityl alcohol, etc.), metal soaps (e.g. calcium stearate, lead stearate, calcium laurate, calcium palmitate, etc.), metal sulfides (e.g. molybdenum disulfide). , tungsten disulfide, etc.), graphites, etc. From the viewpoint of blocking suitability, the lubricant used in the present invention is preferably solid at room temperature. These lubricants can be dispersed by suitable dispersion means (e.g. three-roll mill,
(ball mill, sand mill, high speed mixer, etc.) into the coating composition. Constituent component of the present invention (a
) polyfunctional compounds having multiple (meth)acryloyl groups in the molecule, (b) monofunctional compounds having one (meth)acryloyl group in the molecule, (c) organic polymers, and (d
) The blending ratio of each lubricant should be within the following range. That is, the blending ratio of monomers (a) and (b) is (
Based on the total amount of (meth)acryloyl groups derived from a) and (meth)acryloyl groups derived from (b), (a)
) The ratio of (meth)acryloyl groups derived from 3 to 60
It is preferably in the range of 5 to 50 mol%, more preferably in the range of 5 to 50 mol%. If the proportion of (meth)acryloyl groups derived from (a) is too high (that is, if there are too many polyfunctional compounds), the crosslinking density of the coating film will be excessive, making the coating hard or brittle, and pressing It becomes unable to follow the squeezing deformation during processing, causing surface flaws, cracks, and peeling of the paint film. On the other hand, if the proportion of (meth)acryloyl groups derived from (a) is too low, the curing speed will be reduced and other physical properties such as blocking properties, rust prevention, chemical resistance, and finger wring resistance will be affected. It also decreases, which is not desirable. Also, the proportions of (a), (b), (c) and (d) are based on the total parts by weight of these τ.
The total amount of b) is 94 to 60% by weight, more preferably 9
0 to 70% by weight, (c) is 3 to 20% by weight, more preferably 5 to 15% by weight, and (d) is 3 to 20% by weight.
% by weight, more preferably 5 to 15% by weight. If the blending ratio of the organic polymer (c) is too small, the press molding performance will decrease, which is presumed to be due to insufficient internal plasticizing effect of the coating film, and if it is too large, the viscosity of the coating composition will increase significantly. , making it difficult to paint with a solvent-free system. θ If the amount of lubricant (d) is too small, the frictional force during press molding will increase, the required pressure during press molding will become significantly high, which may cause problems such as press cracks, and may cause damage to the surface of the molded product. Scratches or peeling of the paint film are likely to occur.

Even if the lubricant is blended in an amount greater than the upper limit of the present invention, the effect of reducing the frictional force is not so significant.On the contrary, if the amount blended is too large, the viscosity of the composition may increase significantly, the strength of the coating film may decrease, Decreased adhesion to metal plates, decreased locking properties,
This causes various problems such as peeling of the paint film during press processing and decreased storage stability of the paint. The composition of the present invention is for forming a lubricating coating film on a metal plate, and the composition may have the following configurations (4) to (C), for example, in accordance with the properties required for the coating film. (4) When using a painted metal plate without peeling off the coating: For example, as in the case of applications such as automobile interior parts, electrical parts, and parts of home appliances.
For applications in which a metal plate is press-formed and then used as is without removing the lubricating coating, or in applications where the press-formed product is further coated or leather or plastic film is bonded to it, the above-mentioned method is recommended. Any of the coating compositions of the present invention can be suitably applied.) When the coating film is peeled off and a painted metal plate is used; for example, as in the case of automobile bodies and some applications of home appliances. When it is necessary to remove the lubricating coating film after press molding for electrodeposition coating or other purposes, the coating composition of the present invention and its acid value of 0.35 meq/g (milligram equivalent/g1 or less) may be used. (same) or higher, more preferably 0.70 meq/g or higher, is particularly preferably used.

By adjusting the acid value within the above range, commonly available weak alkaline degreasers (for example, "Fine Clear FC-4349" by Nippon Parkerizing Co., Ltd., and "Ridrin 75TX-51" by Nippon Paint Co., Ltd.) can be used. The lubricating coating can be removed in a short time by simple operations such as dipping or spraying under mild conditions using an aqueous solution of (e.g.). When the acid value is low, harsher conditions are required, such as requiring long-term contact with a strong alkali at high temperature for film removal. Additionally, when rust prevention is important, it is undesirable for the coating composition to have an excessive acid value, and the acid value is preferably 2.7 meq/g or less, more preferably 2.1 meq/g or less. . The acid value in the coating composition can be adjusted by blending one or more of polyfunctional compounds, monofunctional compounds, and organic polymers having acidic groups so that the acid value of the coating composition falls within the above range. It is carried out at the same time.

Examples of monofunctional compounds having an acidic group include the above (!I
) and (110), and as a polyfunctional compound having an acidic group, for example, it is a type of polyester poly(meth)acrylate of the above (3) and has the following formula [
] Carboxyl group-containing polyester poly(meth)acrylates and the like are mentioned. (However, the above compound [] is the terminal hydroxyl type mono(
meth)acrylate.

) Also, examples of organic polymers with acidic groups include (meth)
Examples include organic polymers such as (meth)acrylic acid ester copolymers, polystyrene copolymers, and polyvinyl acetate copolymers that contain acidic monomers such as acrylic acid, crotonic acid, and maleic acid as a copolymerization component. j) When attaching importance to the rust prevention and blocking resistance of the coating film;
The above (1) as meth)acrylate and monofunctional compound
When a compound having a phosphate ester group such as the terminal phosphate mono(meth)acrylate shown in 10 is used as part or all of the polymerizable compound components in the present invention, the rust prevention properties of the coating film are significantly improved. be done.

When emphasis is placed on rust prevention and blocking resistance, the blending ratio of the phosphate ester group-containing compound does not necessarily have to be all from the point of view of economic efficiency.
Preferably 2% by weight based on the total amount of and (b)
By blending the above, more preferably 10% by weight or more, a remarkable effect of improving rust prevention properties is exhibited. For this purpose, when a compound having a phosphate ester group is used as part or all of the polymerizable compound components in the present invention, a hydrocarbon lubricant (e.g. natural paraffin, synthetic paraffin, microwax, polyethylene wax) is used as the lubricant. Tsukusu,
The use of chlorinated hydrocarbons, fluorocarbons, etc.) is preferred. The coating composition of the present invention is cured by irradiation with active energy rays. Active energy rays here mean ultraviolet rays and ionizing radiation such as accelerated electron beams,
Wavelengths of 200~ emitted from metal halide lamps, etc.
Examples include ultraviolet rays of 400 nm (nanometers) and accelerated electron beams having an energy of 10 KeV (kiloelectron volts) to 3 MeV (million electron volts) accelerated by an electron accelerator. Various types of ultraviolet irradiation devices and electron beam accelerators are commercially available. In the case of curing with ionizing radiation, it is not necessary to add any initiator, but in the case of curing with ultraviolet radiation, a photoinitiator and optionally a photopolymerization accelerator are usually used. Photoinitiators that are often used industrially include, for example, carbonyl compounds [e.g., penso, benzoin alkyl ether, benzophenone, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, Phenone, 4'-isopropyl-2-hydroxy-2-methyl-propiophenone, 2'-hydroxy-2-methyl-propiophenone, methyl-(θ-benzoyl)-benzoate, 1-phenyl-1,2 -Propanedione-2-(θ-ethoxycarbonyl)-oxusim, 1-phenyl-1,2-propanedione-2-(θ-benzoyl)-oxime, chlorinated acetophenone derivative, benzyl, diacetyl, 4,
4'-bisdiethylaminobenzophenone, 4-(meth)acryloyloxybenzophenone, etc.], anthraquinone or xanthone derivatives (e.g., methylanthraquinone, chloroanthraquinone, chlorothioxanthone, 2-methyloxanthone, 2-isopropylthioxanthone, etc.) , sulfur compounds (eg, diphenyl sulfide, diphenyl disulfide, dithiocarbamate, etc.), α-chloromethylnaphthalene, anthracene, and the like. Examples of photopolymerization accelerators used as desired include amine compounds having primary, secondary, or primary and tertiary amino groups in the molecule [for example, tri(
mono-, di)ethanolamine, ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, diethylenetriamine, reaction products of epoxy compounds or acryloyl group-containing compounds with primary or secondary amines, etc.], phosphine and sulfides are used. The proportion of the photoinitiator and photopolymerization accelerator used is usually 0.1 to 15% by weight based on the composition, respectively.
Preferably it is in the range of 1 to 10% by weight. The atmosphere during curing is in an inert gas when using ionizing radiation;
Further, in the case of using ultraviolet rays, either in an inert gas or air may be used. If desired, the coating composition of the present invention may be added with a thermal polymerization inhibitor as a storage stabilizer, a chelating agent (for example, hydroquinone monomethyl ether, phenothiazine, oxalic acid, μm nitrosophenyl hydroxylamine aluminum salt, etc.), and coating suitability. Leveling and surfactants (e.g. silicone compounds,
(futsuso-based compounds, etc.), coupling agents (e.g., silane-based coupling agents, titanate-based coupling agents, etc.)
Various additives such as extender pigments (for example, silica, calcium carbonate, barium carbonate, etc.), antioxidants, ultraviolet absorbers, rust preventives, and optionally a small amount of solvent can be mixed and used depending on the purpose. The amounts of these various additives may be in accordance with those normally employed in this type of technical field. The thickness of the lubricating coating formed from the coating composition of the present invention is preferably in the range of 0.5 to 10 microns, more preferably in the range of 1 to 5 microns. If the coating film is too thin, it will not only be difficult to apply the coating, but also the physical properties of the coating film, such as rust prevention and press formability, will be insufficient. In addition, if the coating film is too thick, the cost will be high, which is disadvantageous from an economic point of view, and the coating may be peeled off during press forming because the amount of lubricating coating is too large, which may actually reduce press formability. It may decrease. The coating composition of the present invention is applied to a metal plate using a suitable coating means such as a roll coater, and is cured in a very short time by irradiation with active energy rays.

Therefore, the curing equipment becomes very compact and the equipment cost can be reduced. Furthermore, since no heating is required for curing, it has the advantage of extremely low energy consumption. Furthermore, the formed lubricating coating film has the above-mentioned lubrication effect and press forming processing properties required for the press-forming coating film, rust-preventing protection effect for metal plates, locking properties, adhesion properties with surface coating paints and leather, metal It has an excellent balance of various properties such as adhesion to the board and film removal properties as required.
Therefore, the coating composition of the present invention can be applied to, for example, hot-rolled steel plates, cold-rolled steel plates, various surface-treated steel plates (e.g., pickled, phosphate-treated, chromate-treated, tin-treated steel plates, etc.), aluminum plates (e.g., alumite-treated, chromate-treated steel plates, etc.). It can be suitably used as a coating for forming a lubricating film for press forming of various metal plate materials such as stainless steel plates and copper plates. The present invention will be explained in more detail below using Examples and Comparative Examples.

Table 1 shows the polymerizable compounds (4) and (b) used in these Examples and Comparative Examples. Table 2 shows the test methods and evaluation criteria used in Examples and Comparative Examples.

In addition, all the blending ratios of each component in each example and comparative example are indicated by the polymerization part. Example 1 and Comparative Example 1 The ultraviolet curable coating composition shown in Table 3 was applied to a degreased cold rolled steel plate (thickness 0.811) using a natural roll coater to the predetermined thickness shown in Table 4. Then, 10cm (focal point) below two ozone type concentrating high pressure mercury lamps with 80w/CTrL input at 60m/m! A UV-cured coated plate was obtained by passing the UV light at a speed of n.

Regarding this, the tests shown in Table 2 above were conducted, and the results shown in Table 4 were obtained. Example 2 and Comparative Example 2 The ultraviolet curable coating compositions shown in Table 5 were coated and tested in the same manner as in Example 1.

The results are shown in Table 6. Example 4 The ultraviolet curable paints shown in Table 9 were coated and tested on metal plates shown in Table 10 in the same manner as in Example 1.

The results are shown in Table 10. Example 5 The ultraviolet curable coating composition shown in Table 11 was coated and cured on a cold rolled steel plate (thickness 0.81B) in the same manner as in Example 1.
A film removal test and the tests shown in Table 2 above were conducted under the conditions shown below.

The results are also shown in Table 11. Film removal method o Film removal agent Fin Clear FC-4349 (manufactured by Nippon Parkerizing Co., Ltd.) 309 was dissolved in distilled water to prepare 12.

0 treatment conditions 1 kg of film remover heated to 60°C is placed on a vertically erected coating plate.
The coating was sprayed at a pressure of /Cd, and the time required for the coating to separate was measured.

Example 6 The electron beam curable coating composition shown in Table 12 was applied to a degreased cold-rolled steel plate (thickness 0.8 u) to a thickness of 29 mm using a Natieral roll coater. ) 150Ke10M using an electron beam irradiation device manufactured by
An electron beam cured coated plate was obtained by irradiation under R (megalat) conditions.

Claims (1)

[Claims] 1 (a) at least one type of polyfunctional compound having multiple (meth)acryloyl groups in the molecule, (b) 1 type in the molecule
(c) at least one organic polymer at least partially soluble in the mixture of (a) and (b), and (d) Consists of at least one type of lubricant, (
The proportion of the (meth)acryloyl group derived from a) is 3 to 60 mol% based on the total amount of this and the (meth)acryloyl group derived from (b), and (a), (b), (
The ratio of c) and (d) is based on the total amount of these, the total amount of (a) and (b) is 94 to 60% by weight, (c)
An active energy ray-curable coating composition for forming a lubricating coating film on a metal plate, characterized in that (d) is 3 to 20% by weight and 3 to 20% by weight.