JPS6360794B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a lubricious coating composition, and in particular, an energy ray-curable lubricious coating composition characterized by blending a lubricant into a cationic polymerization-based energy ray-curable resin composition. Regarding. More specifically, metals such as cold-rolled and hot-rolled steel sheets, pickled steel sheets, stainless steel sheets, surface-treated steel sheets,
The present invention relates to an energy ray-curable lubricating film-forming composition that has excellent workability for plastic working such as press working of aluminum plates and provides rust prevention before and after working. Traditionally, after metal steel sheets such as cold-rolled steel sheets and stainless steel sheets are produced at steel manufacturers, they are stored for quite a long time before being used at processing companies for stamping, metal plating, anti-corrosion painting, welding, etc. In order to prevent rusting during this period, some sort of anti-rust treatment is generally performed. The usual way to prevent rust on the surface of these metal steel sheets is to apply mineral oil-based anti-rust oil, but the anti-rust coating used for anti-corrosion treatment has both anti-corrosion properties and processes such as press working. Excellent workability during plastic working is required. Conventionally used anti-rust oils have some lubricity during press processing, but this alone is not sufficient, so a high viscosity press oil based on mineral oil is used during press processing. Currently, press molding is performed after further applying a wax-based lubricant. However, solid lubricants such as press oil, wax-based lubricants, and metal soaps alone cannot be used when pressing conditions are severe, such as pressing or deep drawing of high-strength steel sheets such as hot-rolled steel sheets and high-strength steel sheets. When the surface pressure is high, linear scratches or seizures (hereinafter referred to as mold galling) are unavoidable due to direct contact between the workpiece steel plate and the processing tool, which not only reduces the value of the molded product but also causes press cracks. There are problems such as this occurring. On the other hand, when using these anti-corrosion oils and press oils, it is inevitable that the surface of the steel plate becomes sticky, which is not only inconvenient to handle, but also
Press oil used during press processing may adhere to or scatter around the work area, resulting in problems such as deterioration of the work environment. As a method to solve these problems during press processing, the metal surface is coated with an organic polymer compound, so that the surface is dry or semi-fluid and has both rust prevention properties and lubricity during pressing. A method has been proposed for forming a film having a metal surface on a metal surface. According to this method, the steel plate manufactured by the steel manufacturer can be pressed as is without using press oil etc. during processing, so it is not only effective in terms of production efficiency and cost, but also improves the working environment. Very advantageous. Specific methods include a two-layer coating method, in which an organic polymer compound is applied to the metal surface, and then a resin softener that forms a semi-fluid resin layer with excellent lubricity is applied; There is a more solid coating type in which a lubricant such as solid oil, fatty acid, or metal soap is mixed and applied to the steel plate. However, lubricating compositions using these polymer compounds are diluted with a large amount of organic solvent and applied by solvent evaporation, so the drying process takes a long time and there is a risk of fire caused by the solvent. It has the disadvantage of deteriorating the working environment. Furthermore, in order to coat and dry various coiled steel plates at high speed, a large drying device is required, which not only increases the equipment cost but also requires a large amount of thermal energy. Recently, water-based resin compositions have been developed from the viewpoint of safety and health, such as working environment with organic solvents, fire protection, and resource saving.
In order for steel manufacturers to process steel sheets using high-speed continuous steel plate processing equipment that operates at speeds of 100 m/min or more, a line length of approximately 50 m is required, which poses a difficult problem in terms of equipment.
On the other hand, the two-layer coating type requires two coating steps to form a lubricating coating after the resin coating is formed, and is not an advantageous method in terms of workability, cost, and equipment. Also, very recently, from the perspective of continuous high-speed processing using small-scale equipment, it has been proposed to form a cured resin film by polymerizing and crosslinking through a radical polymerization reaction using active energy rays such as ultraviolet rays and electron beams. Methods have also been proposed, but these radical polymerization resin compositions suffer from curing inhibition due to the influence of oxygen in the air during curing due to the radical polymerization reaction, making them unsuitable for practical use in high-speed continuous processing lines for steel plates. It is necessary to irradiate energy rays in an active gas atmosphere, and it is difficult to say that this method is industrially satisfactory in terms of equipment and cost. Furthermore, cured coatings made from these radically polymerized lubricating coating compositions do not necessarily provide satisfactory adhesion and press workability to various steel plates. The present invention was developed as a result of intensive studies to eliminate various drawbacks of such conventional lubricious coating compositions.
It is complete. The purpose of the present invention is to utilize the fast curing characteristics of a cationic polymerization energy beam curable resin composition in a normal atmosphere to enable high speed processing and to provide energy beam curing that has excellent press workability and temporary rust prevention properties. An object of the present invention is to provide a lubricating coating composition. Another object of the present invention is to utilize the fast-curing characteristics of the cationic polymerization-based energy beam-curable resin composition to produce an energy beam-curable resin composition that can be processed at high speed and has excellent press workability and anti-blocking properties. An object of the present invention is to provide a method for forming a lubricious coating film. That is, the lubricity coating composition according to the present invention comprises an epoxy resin composition containing 10 to 90% by weight of an epoxy resin having an epoxy group on an alicyclic ring as essential components, an energy ray sensitivity sensitizer, and Cationic polymerization energy ray curable resin composition 100 consisting of
This is an energy ray-curable lubricious coating composition comprising 1 part by weight and 0.5 to 20 parts by weight of at least one type of lubricant. The lubricating coating composition of the present invention can be applied to the surface of various metal materials such as steel plates, and then cured and dried in a very short time by irradiating it with energy rays in a normal atmosphere, saving resources and energy. This is a solvent-free composition that improves the working environment. In particular, unlike radical polymerization-based coating compositions, the lubricious coating composition of the present invention does not require curing in an inert gas atmosphere during irradiation, and almost no drying oven is required, so equipment space is also reduced. It has great economic and industrial value, as it can save a lot of money, reduce the risk of fire due to solvent scattering, and also greatly reduce operating energy. First, the cationic polymerizable energy ray curable resin composition used in the present invention is a conventionally known energy ray sensitive sensitizer (photopolymerization initiator) that is polymerized or crosslinked to form a coating film by irradiation with energy rays. ) containing cationic polymerizable resin compositions, such as epoxy resin compositions that are polymerized by cationic ring-opening polymerization of epoxy rings, and cationically polymerizable compositions containing cyclic ethers, lactones, vinyl compounds, etc. The catalyst described in Publication No. 49-17040 and several other catalysts such as photosensitive onium salts described in Japanese Patent Publication No. 52-14278 are known, but none of them are sensitive to energy rays such as ultraviolet rays. Among them, epoxy resin compositions that are polymerized by cationic ring-opening polymerization of epoxy rings are preferred. Epoxy resins used in such epoxy resin compositions include conventionally known aromatic epoxy resins, alicyclic epoxy resins, and aliphatic epoxy resins. Particularly preferred aromatic epoxy resins are polyglycidyl ethers of polyhydric phenols or alkylene oxide adducts thereof having at least one aromatic nucleus, and
Examples include glycidyl ether and epoxy novolak resin produced by the reaction of bisphenol A or its alkylene oxide adduct with epichlorohydrin. Particularly preferable alicyclic epoxy resins include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or compounds containing cyclohexene or cyclopentene rings, which are epoxidized with a suitable oxidizing agent such as hydrogen peroxide or peracid. There are cyclohexene oxide- or cyclopentene oxide-containing compounds obtained by. Typical examples of polyglycidyl ethers include glycidyl ethers produced by reacting hydrogenated bisphenol A or its alkylene oxide adduct with epichlorohydrin. Further, representative examples of cyclohexene oxide or cyclopentene oxide-containing compounds include those represented by the following formula.

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Particularly preferable aliphatic epoxy resins include polyglycidyl ethers of aliphatic polyhydric alcohols or their alkylene oxide adducts, and polyglycidyl esters of aliphatic long-chain polybasic acids, representative examples of which include 1,4-butane. Diglycidyl ether of diol, diglycidyl ether of 1,6-hexanediol, triglycidyl ether of glycerin, triglycidyl ether of trimethylolpropane, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol , polyglycidyl ether of polyether polyol obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to aliphatic polyhydric alcohol such as glycerin, diglycidyl ester of aliphatic long-chain dibasic acid can be mentioned. Furthermore, monoglycidyl ethers of aliphatic higher alcohols, phenol, cresol, butylphenol, monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to these, glycidyl esters of higher fatty acids, etc. can be added as diluents. can. In the epoxy resin composition of the present invention, these aromatic epoxy resins, alicyclic epoxy resins, or aliphatic epoxy resins can be used alone or appropriately blended according to desired performance, but particularly preferred epoxy resin compositions include The product contains an alicyclic epoxy resin, preferably 10 to 90% by weight of an epoxy resin having an epoxy group on the alicyclic ring, such as a compound containing a cyclohexene oxide group and/or a cyclopentene oxide group. teeth
It contains 35 to 85% by weight. In addition, aliphatic long chain polybasic acids (8 to 8 carbon atoms) are aliphatic epoxy resins.
A composition containing 5 to 25% by weight of the polyglycidyl ester (50) is particularly preferred in terms of adhesion, processability, etc. On the other hand, the energy rays contained in the cationic polymerizable energy ray curable resin composition used in the present invention decompose under energy ray irradiation and release a catalyst that has the effect of causing polymerization or crosslinking of the cationic polymerizable resin. The sensitizer (photopolymerization initiator) is not particularly limited, but particularly preferred are those in the group of double salts, which are onium salts that release Lewis acids capable of initiating polymerization upon irradiation. Such compounds basically have the general formula [R ¹ _a R ² _b R ³ _c R ⁴ _d Z] ^+m
[MX _o+n ] ^-m [In the formula, the cation is onium,
Z is N≡N, S, Se, Te, P, As, Sb, Bi,
O, halogen (e.g. I, Br, Cl), R ¹ ,
R ² , R ³ and R ⁴ are organic groups which may be the same or different. a, b, c, and d are each integers of 0 to 3, and a+b+c+d is equal to the valence of Z. M is a metal or metalloid that is the central atom of the halide complex, and B, P,
As, Sb, Fe, Sn, Bi, Al, Ca, In, Ti, Zn,
Sc, V, Cr, Mn, Co, etc. X is a halogen atom, m is the net charge of the halide complex ion, and n is the number of halogen atoms in the halide complex ion. ]. Such catalyst precursors are known per se,
For example, a compound where Z is N≡N is disclosed in U.S. Patent No.
It is described in No. 3708296, No. 3949143, No. 3794576, etc. Other onium catalyst precursors are described in Belgian Patent No. 828841, Belgian Patent No. 828669, French Patent No. 2270269, US Patent No. 4,139,655, etc. The above diazonium compounds are described in the above US patents.
It can be obtained by the method described in No. 3708296, No. 3949143, etc. Compounds where Z is S, Se, Te are described in J. Knapozyk et al., JACS, 91 , 145,
(1969), AL Maycock et al. J. Organic
Chemistry, 35 , No. 8, 2532 (1970), Goethals et al., Bul.Soc.Chim.Belg., 73 , 546 (1964), HM
It can be produced by the method described in Laicestar et al., JACS, 51 , 3587 (1929). Z is P, N, As,
Representative onium salts such as Sb and Bi are J. Goerdeler
Methoden der Organishen Chimie, 11/12 ,
591-640 (1958), K. Sasse's 12/1, 79-112
(1963). A typical onium salt where Z is halogen is OAPtitsyna
Dokl.Adad.Nauk., SSSR, 163 , 383
(1965), M. Drexler et al. JACS, 75 , 2705
(1953) and others. Also, the onium salt mentioned here has a US patent
Also included are pyrylium salts such as thiopyrylium described in No. 4139655 and oxonium salts such as aryloxysulfoxonium salts described in JP-A-56-8428. Other compounds that can be used to initiate the polymerization of cationically polymerizable resins include iodoform, α,α-dibromoparaxylene, bromoform, carbon tetrabromide, hexachloroparaxylene, and U.S. Pat. No. 3,895,954. Other catalysts mentioned,
Bis(perfluoroalkylsulfonyl)methane salts, and US Pat. No. 3,586,616, German Patent No.
It is an organic halogen compound such as a diazonium salt of sulfonylmethane as described in No. 2419274. In addition, the above-mentioned cations may be added to the cationically polymerized resin compositions such as epoxy resins, cyclic ethers, lactones, and vinyl compounds, which are constituent elements of the present invention, as necessary, as long as they do not impair the effects of the present invention. Olefin resins other than polymerizable substances, acrylic resins, ester resins, petroleum resins, alkyd resins, polyether resins, polyvinyl chloride resins, butyral resins, polyvinyl alcohol resins, polyvinyl acetate resins, Acid anhydride-based epoxy resin curing agents and various paint additives can be blended. Furthermore, after press working, the coat of coated steel sheets is often removed using a weak alkaline cleaning agent. Therefore, in such cases, it is preferable to incorporate compounds or resins having groups such as hydroxyl groups, fatty acid groups, and fatty acid bases in the energy ray curable resin composition. Furthermore, as proposed in U.S. Pat. No. 4,156,035, acrylate or methacrylate compounds and carbonyl photosensitizers are added to the cationically polymerized resin composition that is a component of the present invention to form a coating film. It is also possible to improve physical properties and curability. The lubricants that are important components of the lubricious coating composition of the present invention include stearic acid linoleic acid,
Fatty acids such as oleic acid, linolenic acid, and palmitic acid; organic acids such as stearic acid, lauric acid, octenoic acid, ricinoleic acid, naphthenic acid, rosin, and tar oil fatty acids; and calcium, aluminum, barium, magnesium, zinc, copper, and iron. Metal soaps obtained from metals such as , lead, and tin; Fatty acid soaps obtained from fatty acids and sodium, potassium, and ammonia; Paraffin hydrocarbons such as paraffin wax, beeswax, vegetable wax, and chlorinated paraffin; Lanolin, palm Fats and oils such as oils; higher alcohols such as lauryl alcohol and stearyl alcohol; aliphatic amides obtained from fatty acids and amines;
Examples include organic lubricants such as sorbitol fatty acid esters, pentaerythritol fatty acid esters, particularly fatty acid esters, and derivatives of the above compounds, and inorganic lubricants such as graphite, molybdenum disulfide, talc, and boron compounds. Each of the above lubricants can be used alone, but it is also possible to use a combination of two or more to exhibit their respective characteristics. Among these lubricants, preferred in combination with the cationically polymerized resin composition are fatty acid metal soaps that are solid or semi-solid at room temperature, fatty acid esters, and fatty acids, or a combination of two or more thereof. It is something that The amount of these lubricants added to the lubricious coating composition of the present invention can vary widely depending on the type of lubricant to be added, the type of cationically polymerizable resin composition, and the required lubricating performance. Generally, the amount of the lubricant is suitably in the range of 0.5 to 20 parts by weight, preferably 1.0 to 10 parts by weight, per 100 parts by weight of the cationic polymerizable energy beam curable resin composition. In the above formulation, if the amount of lubricant is less than 0.5 parts by weight, no lubrication effect will be obtained, and conversely, if the amount of lubricant is more than 20 parts by weight, the inherent performance of the energy beam cured coating tends to deteriorate, resulting in a decrease in adhesion. , problems arise in the press workability of the coated steel sheet, such as the coating becoming brittle. In addition to the essential components described above, the lubricious coating composition of the present invention includes a rust preventive agent, a plasticizer, an antioxidant, an antifoaming agent,
Appropriate amounts of surfactants, extreme pressure additives, pigments, dyes, preservatives, etc. can also be incorporated within the range that does not impair the objectives and effects of the present invention. For example, rust preventives include red lead, zinc powder, zinc oxide, zinc oxide, lead cyanamide, basic chromate, zinc chromate, barium potassium chromate, barium zinc chromate, calcium lead acid, condensed phosphate, benzoate. Examples include acid soda, alkyl acid amides, and chelate compounds. The lubricious coating composition of the present invention can be applied to the surface of a substrate by conventional methods such as roll coater, gravure coater, gravure offset, spray, squeeze and dipping methods. The thickness of the cured film is determined depending on the required performance for various substrates, but is suitably in the range of about 0.5 to 15 microns, preferably in the range of about 2 to 6 microns.
Energy rays used to apply the coating composition of the present invention to various substrates to form a cured film include ultraviolet rays, electron beams, and radiation. Among these, methods using ultraviolet irradiation are practical. This is the most preferable method. Furthermore, coating formation with the coating composition is performed after heat-treating the base material.
Alternatively, the coating can be carried out while being heated, or the coating composition may be coated on the substrate and then heat treatment and energy ray irradiation may be used in combination to promote the coating more effectively. In addition, when coating the coating composition, it is also possible to use a solvent such as an organic solvent or water to adjust the viscosity within a range that does not cause any adverse effects such as deterioration of the performance of the lubricant coating composition. . The lubricating coating composition of the present invention is solvent-free and can form a lubricating coating film on the surfaces of various metal materials in a high-speed processing line using energy ray irradiation.
It is extremely advantageous in terms of workability, cost, equipment, work environment, etc. Further, steel sheets coated with the coating composition have extremely high press workability, deep drawing workability, and blocking resistance as well as blocking resistance and temporary rust prevention properties. The lubricious coating composition of the present invention is particularly useful for metal materials that require processing such as punching, pressing, and forming, such as automobile bodies, automobile parts, and home appliances, such as cold-rolled and hot-rolled steel sheets, pickled steel sheets, etc. It exhibits excellent effects when coated on stainless steel plates, surface-treated steel plates, aluminum plates, etc. Hereinafter, typical examples of the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to the following Examples. In the examples, "parts" means parts by weight. Example 1 3,4-epoxycyclohexylmethyl-3,
80 parts of 4-epoxycyclohexylcarboxylate (epoxy equivalent: 131-143), 20 parts of diglycidyl ester of aliphatic long-chain dibasic acid (manufactured by Okamura Oil Co., Ltd., trade name: OS Resin-101), 0.2 parts of silicone surfactant, and Photopolymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd.,
A composition of the present invention was obtained by mixing 2 parts of calcium stearate as a lubricant with a cationic polymerization type energy ray curable resin composition consisting of 3 parts (trade name: PP-33). Example 2 3,4-epoxycyclohexylmethyl 3,4
-60 parts of epoxycyclohexyl carboxylate (epoxy equivalent: 131-143), bis(3,4-epoxycyclohexyl) adipate (epoxy equivalent:
180-200) 20 parts, diglycidyl ester of aliphatic long-chain dibasic acid (manufactured by Okamura Oil Co., Ltd., trade name OS Resin-102) 15 parts, polyester resin (molecular weight 20,000~
25,000) 5 parts, silicone surfactant 0.5 part, photopolymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33)
A composition of the present invention was obtained by mixing 3 parts of zinc stearate as a lubricant with a cationic polymerization type energy beam curable composition consisting of 3 parts. Example 3 3,4-epoxycyclohexylmethyl-3,
30 parts of 4-epoxycyclohexane carboxylate (epoxy equivalent: 131-143), bisphenol A diglycidyl ether (epoxy equivalent: 180-143)
200) 50 parts, 1,4-butanediol diglycidyl ether (epoxy equivalent: 125-143) 20 parts, silicone surfactant 2 parts, photopolymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33) 3 A composition of the present invention was obtained by mixing 2 parts of calcium stearate as a lubricant and 5 parts of 130% paraffin wax into a cationically polymerized energy beam curable composition consisting of 1. Example 4 3,4-epoxycyclohexylmethyl-3,
75 parts of 4-epoxycyclohexane carboxylate (epoxy equivalent: 131-143), polyethylene glycol glycidyl ether (epoxy equivalent: 185
~215), 15 parts of cresyl glycidyl ether (epoxy equivalent: 167-200), 1 part of a silicone surfactant, and 3 parts of a photopolymerization initiator (manufactured by Asahi Denka Kogyo Co., Ltd., trade name PP-33). A composition of the present invention was obtained by mixing 3 parts of calcium stearate and 2 parts of a rust preventive pigment with a polymeric energy ray curable resin composition. Example 5 In Example 1, a composition of the present invention was obtained by using 3 parts of diphenyliodonium tetrafluoroborate instead of the photopolymerization initiator PP-33. Example 6 In Example 1, a composition of the present invention was obtained by using 3 parts of triphenylsulfonium hexafluoroantimonate instead of the photopolymerization initiator PP-33. Comparative Example 1 5 parts of stearic acid as a lubricant was mixed with a radical polymerization type energy ray curable composition consisting of 60 parts of polymethyl methacrylate, 40 parts of triethylene glycol diacrylate, and 3 parts of benzoin methyl ether as a photopolymerization initiator. A comparative example composition was obtained. Completely degreased cold-rolled steel sheets (material JIS.G.3141, SPCC-
SD, 0.8 mm thick) was coated using a roll coater to a film thickness of 4 to 5 μm. Then immediately 10
Under high pressure mercury lamp (8KW x 2) installed at a height of cm
A cured film was obtained by irradiating ultraviolet rays by passing at a speed of 80 m/min. The physical properties of the coating film were investigated using the coated steel plate coated and cured in this way.
It was as described in 1. Furthermore, since the composition of Comparative Example 1 did not form a cured film sufficiently under the above curing conditions, the physical properties of the coating film were measured after irradiating it with ultraviolet rays at a curing speed of 30 m/min.

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Claims (1)

[Scope of Claims] 1. A cationic polymerization energy system consisting of an epoxy resin composition containing 10 to 90% by weight of an epoxy resin having an epoxy group on an alicyclic ring as an essential component and an energy ray sensitivity sensitizer. 100 parts by weight of a linear curable resin composition and 0.5 to 0.5 parts by weight of at least one lubricant
An energy beam-curable lubricating coating composition comprising 20 parts by weight. 2 The lubricant is one or two selected from paraffinic hydrocarbons, fatty acids, or metal salts thereof.
The energy beam-curable lubricious coating composition according to claim 1, which is a mixture of more than one kind.