JPH0521960B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention improves the lubricity during processing of low-carbon steel sheets such as hot-rolled steel sheets, cold-rolled steel sheets, and electrogalvanized steel sheets, as well as metal materials such as stainless steel, aluminum, copper, and titanium. The present invention relates to temporary coating compositions used for the purpose of improving. [Prior Art] In general, metal materials used in automobiles, weak electrical appliances, and other metal products are manufactured by material manufacturers for rust prevention before being processed and painted at processing companies. A mineral oil-based rust preventive agent is applied.
Will be shipped. Further, when pressing metal materials, press oil is generally applied to improve the workability. However, these anti-rust oils and press oils are non-drying, so the surface of the material becomes sticky.
In addition to being inconvenient to handle, press oil scatters around the work area during pressing, resulting in problems such as deterioration of the work environment. In addition, when the press conditions are severe, such as when press working or deep drawing of high-strength steel sheets, that is, when the surface pressure of the die is high,
The occurrence of linear scratches or seizures (hereinafter referred to as die galling) due to direct contact between the steel plate and the processing tool is unavoidable, and may lead to press cracks. In order to solve these problems, studies are progressing on lubricating materials in which a solid coating such as wax having lubricating properties is formed on the surface of the material, and some of them have been implemented. However, these also have many problems when applied and dried by material manufacturers. In other words, when coating these materials on metal materials,
It is used dispersed or dissolved in a solvent, but
When the solvent is an organic solvent, there are problems such as deterioration of the working environment due to its volatilization, installation of solvent treatment equipment, and the risk of fire, so water is often used as the solvent. However, even when water is used,
As described in Japanese Patent Application No. 51-70175, when processing is performed using continuous processing equipment at a material manufacturer or the like, the material is preheated or hot air is blown onto it after coating to speed up the evaporation of water. Even if these methods are used, for example, if the material is heated to 50℃ before coating and then blown with hot air at 80℃ after coating, the drying time will be 10% for a coating amount of 4g/ ^m2 . It takes ~15 seconds. Recent continuous processing equipment for metal materials is
It has a processing speed of 100m/min.
If coating is to be carried out using continuous processing equipment with a processing speed of 10 to 15 minutes, a line length of 17 to 25 meters is required to ensure a drying time of 10 to 15 seconds. It is difficult in terms of equipment to process the material over this length without coming into contact with feed rolls, pinch rolls, etc. In this regard, we focused on the fact that radically polymerizable compositions are cured in a very short time by irradiation with ionizing radiation or electromagnetic waves, especially ultraviolet rays,
The use of energy rays such as electron beams and ultraviolet rays for coating metal materials has become publicly known, including the above-mentioned Japanese Patent Laid-Open No. 70175/1983. The present inventors have already proposed a temporary coating composition for an energy ray curing agent containing a specific monomer mixture, a lubricant, and, if necessary, a sensitizer (Japanese Patent Application Laid-Open No. 59-1979-1).
Publication No. 204668). This composition has higher lubricity and rust prevention than press oil, and can be removed with a weak alkaline solution. However, this composition generally has a high viscosity and has difficulty in coating workability. For this reason, acrylic esters and/or methacrylic esters are used to adjust their viscosity, but when monofunctional (meth)acrylates are used, there is generally a decrease in curability or a weak alkaline solution depending on the amount added. There is a decrease in performance such as a decrease in film removability or a decrease in rust prevention. In order to maintain film removability with weakly alkaline solutions, it is desirable to use (meth)acrylates with hydroxyl groups, such as hydroxyethyl (meth)acrylate and hydroxypropyl (meth)acrylate, but these are highly irritating to the skin and difficult to handle. Caution is required. Furthermore, when a polyfunctional (meth)acrylate is used, the film removability with a weakly alkaline solution generally decreases as the amount of the polyfunctional (meth)acrylate added increases. [Means for solving the problems] As a result of further studies to solve these problems, (meth)acryloylmorpholine was used instead of the (meth)acrylic acid ester disclosed in JP-A No. 59-204668. They found what they needed to do and completed the present invention. That is, the present invention provides an energy beam-curable temporary coating comprising 1 to 30 parts by weight of a lubricant () and, if necessary, 0.5 to 20 parts by weight of a sensitizer () to 100 parts by weight of a monomer mixture (). In the composition, the monomer mixture (A) reacts 1 mole of a compound having one oxirane ring with 0.8 to 1.1 mole of an α,β-ethylenically unsaturated carboxylic acid having one carboxyl group, and then reacts with a polybase. Product (a) obtained by reacting 0.5 to 1 mol of acid and/or its anhydride, 1 mol of acrylic ester or methacrylic ester having a hydroxyl group at the terminal and 0.8 to 1.1 mol of polybasic acid and/or its anhydride. product obtained by reacting moles
(b), or a mixture of the above product (a) and product (b); and (B) formula: [In the formula, R represents hydrogen or a methyl group. ] An energy beam-curable temporary coating composition for lubricating metal materials, which contains (meth)acryloylmorpholine represented by 5 to 100 parts by weight of component (B) per 100 parts by weight of component (A). provide. (Meth)acryloylmorpholine is a low viscosity liquid and functions satisfactorily as a viscosity reducing agent in place of (meth)acrylic acid ester. In addition, the primary skin irritation value of acryloylmorpholine is 0.5 as measured by the Huntingdon Research Institute in the UK, which is extremely low compared to low molecular weight acrylic esters (for example, 6.2 for 2-hydroxypropyl acrylate). It can be judged that the irritation to the skin is low.
Furthermore, compared to the use of other monofunctional (meth)acrylates, the curability decreases less, and film removability with weak alkaline solutions and rust prevention properties are also good. Examples of compounds having one oxirane ring for obtaining the product (a) used in the present invention include monoglycidyl ethers, monoglycidyl esters, and alicyclic monoepoxides. Examples of the monoglycidyl ethers include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 2-methyloctyl glycidyl ether, lauryl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, nonyl phenyl glycidyl ether, and phenyl (2-methyl glycidyl ether). ) ether, 2,4-
dibromophenyl glycidyl ether, 2,4,
Examples include 6-tribromophenyl glycidyl ether. The monoglycidyl esters mentioned above include n-hexanoic acid glycidyl ester, 2-ethylhexanoic acid glycidyl ester, isononanoic acid glycidyl ester, benzoic acid glycidyl ester, phenyl acetic acid glycidyl ester, Cardiula E (manufactured by Ciel Chemical Co., Ltd., versatate glycidyl ester, epoxy equivalent weight 240-250), etc. Examples of the alicyclic monoepoxides include cyclohexene oxide, cyclopentene oxide, bicycloheptene oxide, dipentene monoxide, 2-pinene oxide, octylene oxide,
Examples include styrene oxide. These compounds having one oxirane ring can be used alone or in combination of two or more.
In the composition of the present invention, when rust prevention and curability are particularly important, aromatic monoglycidyl ethers such as phenylglycidyl ether are preferably used as the compound having one oxirane ring. Further, as the α,β-ethylenically unsaturated carboxylic acid having one carboxyl group to obtain the product (a), acrylic acid, methacrylic acid, crotonic acid, cinnamic acid, itaconic acid monoalkyl ester (for example, methyl ester, ethyl ester, n-
propyl ester, isopropyl ester), etc., and these may be used alone or in combination of two or more. From the viewpoint of curability of the composition of the present invention, it is preferable to use acrylic acid. In addition, polybasic acids and their anhydrides for obtaining the product (a) include phthalic acid, isophthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, hemicic acid, methyl hymic acid,
Trimellitic acid, pyromellitic acid, succinic acid, adipic acid, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, hymic anhydride, methyl hymic anhydride, trimellitic anhydride Examples include acids, pyromellitic anhydride, succinic anhydride, etc., and these may be used alone or in combination of two or more. In terms of curability and rust prevention properties of the composition of the present invention, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, hymic acid, methyl hymic acid,
It is desirable to use cyclic polybasic acids such as trimellitic acid and pyromellitic acid and their anhydrides. The product (a) used in the present invention is obtained by first reacting a compound having one oxirane ring with an α,β-ethylenically unsaturated carboxylic acid having one carboxyl group, and adding a polybasic acid and a polybasic acid to the reaction product. It can be obtained by reacting its anhydride. The reaction between a compound having one oxirane ring and an α,β-ethylenically unsaturated carboxylic acid having one carboxyl group can be carried out without a catalyst; In order to avoid polymerization, it is desirable to carry out the reaction at the lowest possible temperature and in the shortest possible time, and for this purpose it is convenient to use a catalyst. As this catalyst, tertiary amines such as N,N-dimethylaniline, triethylamine, benzyldimethylamine, N,N-dimethylaminoethyl methacrylate, and ammonium salts such as trimethylbenzylammonium chloride give good effects. In addition, in order to prevent thermal polymerization of α,β-ethylenically unsaturated groups during the reaction, common thermal polymerization inhibitors (e.g. hydroquinone, t-
Phenols such as butylhydroquinone, hydroquinone monomethyl ether, catechol, t-butylcatechol, quinones such as benzoquinone and diphenylbenzoquinone) are combined with a compound having one oxirane ring and α having one carboxyl group,
Based on the total amount of β-ethylenically unsaturated carboxylic acids
It is desirable to use it in a range of 0.01 to 0.5% by weight. The reaction may be carried out at a temperature of 100-130°C for 1-15 hours. If it is difficult to carry out the reaction without a solvent, the reaction may be carried out using a solvent that does not have a carboxyl group or a hydroxyl group (for example, toluene, xylene, butyl acetate). The reaction product thus obtained is not isolated, but is reacted with a polybasic acid and its anhydride at a temperature of 100 to 130°C to obtain the desired product (a). It will be done. If the reaction is delayed or the reaction system has problems with thermal stability due to the use of acid anhydrides of polybasic acids, add the above-mentioned catalyst or thermal polymerization inhibitor to proceed with the reaction. Good too. Further, when the reaction system has a high viscosity and is difficult to stir, the above catalyst may be used. When using a polybasic acid, a conventional esterification method may be employed. That is, the reaction may be allowed to proceed while using an acid catalyst such as para-toluenesulfonic acid and removing water produced as the reaction proceeds from the system by azeotropy with the catalyst. When the obtained product (a) is synthesized using a solvent, the solvent is distilled off under reduced pressure. If necessary, the solvent may be added after adding (meth)acryloylmorpholine, which is a component of the composition of the present invention, and, in some cases, acrylic ester and/or methacrylic ester (2) within a range that does not impair curability. may be distilled off under reduced pressure. Since a compound having one oxirane ring does not have a polymerizable double bond, it is not cured by active energy rays. Therefore, it is necessary to react with an α,β-ethylenically unsaturated carboxylic acid having one carboxyl group as efficiently as possible. Furthermore, since α,β-ethylenically unsaturated carboxylic acid having one carboxyl group has weak acidity, it is desirable to leave it as little as possible from the viewpoint of rust prevention. Based on these facts, the molar ratio of the compound having one oxirane ring and the α,β-ethylenically unsaturated carboxylic acid having one carboxyl group is 1:0.8~
1.1, preferably 1:0.9 to 1.0.
It is desirable to use the polybasic acid and its anhydride in an amount of 0.5 to 1.0 mole per mole of the compound having one oxirane ring. If it is less than 0.5 mol, the amount of carboxyl groups introduced into the curable component will decrease, resulting in poor film removability, while if it exceeds 1.0 mol, an excess amount of polybasic acid and its anhydride will remain, resulting in poor rust prevention. Decreases sex. Examples of acrylic acid or methacrylic acid having a hydroxyl group at the terminal (hereinafter referred to as hydroxyl group-containing (meth)acrylic acid) for obtaining the product (b) used in the present invention include 2-hydroxyethyl (meth)acrylate, 2-hydroxy Examples include propyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and the like. These may be used singly or as a mixture of two or more, if necessary. Further, the polybasic acid and its anhydride for obtaining the product (b) are the same as those mentioned above. From the viewpoint of curability and rust prevention properties of the composition of the present invention, cyclic polybasic acids and anhydrides such as phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hymic acid, methyl hymic acid, trimellitic acid, and pyromellitic acid are preferred. Use is recommended. The reaction between hydroxyl group-containing (meth)acrylic acid, polybasic acid, and its anhydride is the reaction between the aforementioned compound having one oxirane ring and α, having one carboxyl group.
The reaction may be carried out in the same manner as in the case where the reaction product of the β-ethylunsaturated carboxylic acid is reacted with a polybasic acid and its anhydride. The molar ratio of the hydroxyl group-containing (meth)acrylic acid to the polybasic acid and its anhydride is preferably in the range of 1:0.8 to 1.1, preferably 1:0.9 to 1.0. If it is less than 0.8, the amount of carboxyl groups introduced into the curing component will decrease, while if it exceeds 1.0 mol, an excess amount of polybasic acid and its anhydride will remain, reducing the rust prevention property. (Meth)acryloylmorpholine, which is an essential component of the present invention, can be synthesized by reacting (meth)acryloyl chloride with morpholine, but there are problems such as the lachrymatory properties of (meth)acryloyl chloride remaining indefinitely. . In order to solve this problem, it is desirable to adopt the method described in Japanese Patent Publication No. 54-9170. That is, cyclopentadiene and a (meth)acryloyl group-containing compound (for example, (meth)acrylic acid and its ester, acrylonitrile, etc.) are subjected to a Diels-Alder addition reaction, this Diels-Alder adduct is amidated with morpholine, and then thermally decomposed. By doing this, (meth)acryloylmorpholine can be obtained. By blending (meth)acryloylmorpholine with the above-mentioned product (a) alone, product (b) alone, or a mixture of product (a) and product (b), the film removability with weak alkali is reduced. The viscosity can be adjusted to the desired value without having to do so. However, the product (a), product (b) or mixture 100
If (meth)acryloylmorpholine is blended in an amount exceeding 100 parts by weight, curability may deteriorate, so it is desirable to limit the blending amount to 100 parts by weight. The lubricant used in the present invention includes organic and inorganic lubricants. The former organic lubricants include fatty acids (e.g. oleic acid, linoleic acid, palmitic acid, stearic acid, etc.), metal soaps (e.g. lauric acid, stearic acid, ricinoleic acid, rosin, naphthenic acid, etc.) and aluminum. , barium, calcium, iron, magnesium, lead, tin, zinc, etc.), aliphatic soaps (e.g., those obtained by reacting the above fatty acids with sodium, potassium, ammonia), paraffin hydrocarbons (e.g. paraffin wax, beeswax, vegetable wax, chlorinated paraffin, etc.), higher alcohols (e.g. lauryl alcohol, stearyl alcohol, palmityl alcohol, etc.), fatty acid amides (e.g. those obtained from the above fatty acids and amines) , fluororesin powder,
Examples include polyethylene wax, polyethylene powder, polypropylene powder and derivatives thereof. As the latter inorganic lubricant, graphite,
Examples include molybdenum disulfide and boron nitride.
These can be used alone or in combination of two or more. In the present invention, it is preferable to use the above-mentioned fluororesin powder, particularly tetrafluoroethylene resin powder, in order to impart good press workability without impairing the curability and adhesion of the target composition. . As a commercially available tetrafluoroethylene resin, “Hostaflon”
TF9202'', ``Hostaflon TF9205'' (manufactured by Hoechst Japan), ``Rubloon L-2'', ``Rubloon L-5''
(manufactured by Daikin Industries), etc. The above lubricant is blended in an amount of 1 to 30 parts by weight per 100 parts by weight of the monomer mixture (). If the amount is less than the specified amount, the lubricating effect of the composition of the present invention will be poor, while if it is in excess, the strength of the cured coating will decrease, causing problems such as coating pieces adhering to the die during press processing. will occur. The sensitizer () used in the present invention may be incorporated when the composition of the present invention is cured by ultraviolet rays, as is conventionally known, and does not necessarily need to be incorporated in the case of electron beam curing. Specific examples thereof may also be known in the art. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoin butyl ether, benzophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4,4'-dimethylbenzoin, benzyldimethyl Ketal, 1,1,1-trichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-
(4-isopropylphenyl)-2-hydroxy-
2-methylpropan-1-one, 2-methyl-1
-[4-(methylthio)phenyl]-2-morpholinopropane-1 and the like. These can be used alone or in combination of two or more. This sensitizer () is blended in an amount of 0.5 to 20 polymerized parts per 100 polymerized parts of the monomer mixture (). If the amount is less than the specified amount, the curing of the composition of the present invention will be slow during UV curing, while if it is in excess, the curability will not improve, which is economically disadvantageous. In addition to the above-mentioned components () to (), the composition of the present invention may contain (meth)acrylic acid ester for viscosity adjustment within the range that does not impair curability or film removability with a weak alkaline solution. In general, low molecular weight (meth)acrylic esters are highly irritating to mucous membranes and skin, and it is desirable to avoid their use as much as possible. These (meth)acrylic acid esters include:
It may be one that has been conventionally used in the relevant field,
For example, methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, ) acrylate, 2-
Hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, cellosolve (meth)acrylate, 2-butoxyethyl (meth)acrylate, carbitol (meth)acrylate, dipropylene glycol monomethyl Examples include ether monoacrylate, triethylene glycol monomethyl ether monoacrylate, and tetrahydrofurfuryl (meth)acrylate. These may be used alone or in combination of two or more. Furthermore, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, 1,6-hexanediol di( Polyfunctional (meth)acrylates such as meth)acrylate and tritylolpropane triacrylate can also be used;
Although acrylate accelerates the curing of the composition of the present invention, it reduces adhesion to steel materials and also reduces film removability with a weak alkaline solution, so care must be taken in the amount used. Further, it is known that a phosphate ester type (meth)acrylic ester shown in the following formula is used in active energy ray-curable paints to impart adhesion to metal materials such as iron and aluminum. [However, R ₁ is a hydrogen terminal or a methyl group, R ₂ is a substituted or unsubstituted alkylene group (which may contain an oxygen atom), m is an integer from 1 to 3, and n is 0.1 or 2. , m+n=3] Also in the present invention, the above-mentioned compounds can be used within a range that does not cause any problems. Furthermore, if necessary, materials used in normal paint compositions, such as antifoaming agents, anti-sagging agents, surface conditioners, rust preventive agents, plasticizers, colorants, and solvents, may be added to the paints to adversely affect rust prevention and film removability. It may be blended within the range that does not affect. The composition of the present invention can be obtained by mixing the above-mentioned components using a conventional dispersing machine (for example, a ball mill, three-roll mill, sand mill, high-speed mixer, etc.). Next, conventionally known techniques may be employed to coat a metal material with the composition of the present invention. That is,
For its application, ordinary methods such as a roll coater, spray, curtain flow coater, etc. can be used. The composition applied to the metal material may then be cured using ultraviolet rays or electron beams in accordance with conventional methods. As sources of ultraviolet rays, ordinary high-pressure mercury lamps, ultra-high-pressure mercury lamps, and
Metal halide lamps etc. can be used. In the electron beam irradiation process, an electron beam accelerator that generates an electron beam with an energy of 10 KeV to 3 MeV can be used.
The lubricated material thus obtained is coated with a solid film that is excellent in rust prevention, press workability, and removability with a weak alkaline solution. Next, the present invention will be specifically explained with reference to Reference Examples, Examples, and Comparative Examples. In addition, in these examples, parts mean parts by weight. Reference Example 1 150 parts (1 mol) of phenyl glycidyl ether and 1.1 parts of N,N-dimethylaminoethyl methacrylate were placed in a flask equipped with a stirrer, and the temperature was raised to 110°C. Thereafter, while maintaining the same temperature and stirring, a mixture of 72 parts (1 mole) of acrylic acid and 0.2 part of hydroquinone monomethyl ether was added dropwise over about 1 hour. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. After the reaction product was allowed to cool to room temperature, 41.6 parts of toluene, 0.8 parts of N,N-dimethylaminoethyl methacrylate, 0.2 parts of hydroquinone monomethyl ether, and 152 parts (1 mol) of tetrahydrophthalic anhydride were added thereto, and the mixture was stirred. The reaction was carried out at 115°C for 3 hours to obtain a solution of reaction product (a). The acid value of this reaction product solution was 145. Next, toluene was distilled out of the system under reduced pressure to obtain a reaction product (a). The general formula of the reaction product (a) is as follows. Reference Example 2 150 parts (1 mol) of phenyl glycidyl ether and 1.1 parts of N,N-dimethylaminoethyl methacrylate were placed in a flask equipped with a stirrer, and the temperature was raised to 110°C. Thereafter, while maintaining the same temperature and stirring, a mixture of 72 parts (1 mole) of acrylic acid and 0.2 part of hydroquinone monomethyl ether was added dropwise over about 1 hour. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. After the reaction product was allowed to cool to room temperature, 41.1 parts of toluene, 0.7 parts of N,N-dimethylaminoethyl methacrylate, 0.1 part of hydroquinone monomethyl ether, and 148 parts (1 mol) of phthalic anhydride were added thereto, and the mixture was stirred for 115 parts. React at ℃ for 3 hours,
A solution of reaction product (a) was obtained. The acid value of this reaction product solution was 149. The general formula of the reaction product (a) is as follows. Thereafter, the reaction product solution was allowed to cool to 50°C, and 158.6 parts of acrylylmorpholine was added thereto, and stirring was continued to form a uniform solution. Next, toluene was distilled off from this solution under reduced pressure to obtain a solution consisting of 70 parts of reaction product (a) and 30 parts of acryloylforin. Reference Example 3 150 parts (1 mole) of phenyl glycidyl ether and 1.1 parts of N,N-dimethylaminoethyl methacrylate were placed in a flask equipped with a stirrer, and the temperature was raised to 110°C. Thereafter, while maintaining the same temperature and stirring, a mixture of 72 parts (1 mole) of acrylic acid and 0.2 part of hydroquinone monomethyl ether was added dropwise over about 1 hour. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. After the reaction product was allowed to cool to room temperature, 35.8 parts of toluene, 0.5 part of N,N-dimethylaminoethyl methacrylate, 0.1 part of hydroquinone monomethyl ether, and 100 parts (1 mol) of succinic anhydride were added thereto, and the mixture was stirred for 120 minutes. React at ℃ for 3 hours,
A solution of reaction product (a) was obtained. The acid value of this reaction product solution was 170. The general formula of the reaction product (a) is as follows. Thereafter, the reaction product solution was allowed to cool to 50°C, and 138 parts of acryloylmorpholine was added thereto, and stirring was continued to form a uniform solution. Next, toluene was distilled off from this solution under reduced pressure to obtain a solution consisting of 70 parts of reaction product (a) and 30 parts of acryloylmorpholine. Reference Example 4 Put 186 parts (1 mol) of 2-ethylhexyl glycidyl ether and 1.3 parts of N,N-dimethylaminoethyl methacrylate into a flask with a stirrer, and add 110 parts of N,N-dimethylaminoethyl methacrylate.
The temperature was raised to ℃. Thereafter, while maintaining the same temperature and stirring, a mixture of 72 parts (1 mol) of acrylic acid and 0.3 part of hydroquinone monomethyl ether was added dropwise over about 1 hour. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. After the reaction product was allowed to cool to room temperature, 45.6 parts of toluene, 0.8 parts of N,N-dimethylaminoethyl methacrylate, 0.2 parts of hydroquinone monomethyl ether, and 152 parts (1 mol) of tetrahydrophthalic anhydride were added thereto, and the mixture was stirred. The reaction was carried out at 115°C for 6 hours to obtain a solution of the reaction product (a). The acid value of this reaction product solution was 136. The general formula of the reaction product (a) is as follows. Thereafter, the reaction product solution was allowed to cool to 50°C, and 176 parts of acryloylmorpholine was added thereto, and stirring was continued to form a uniform solution. Next, toluene was distilled off from this solution under reduced pressure to obtain a solution consisting of 70 parts of reaction product (a) and 30 parts of acryloylmorpholine. Reference Example 5 29 parts of toluene, 148 parts (1 mol) of phthalic anhydride, 116 parts (1 mol) of 2-hydroxyethyleacrylate, 1.1 parts of N,N-dimethylaminoethyl methacrylate, and 0.2 parts of hydroquinone monomethyl ether were placed in a flask with a stirrer. and reacted at 100°C for 5 hours to obtain a solution of the reaction product (b). The acid value of this reaction product solution was 195. The general formula of the reaction product (b) is as follows. Then, toluene was distilled off under reduced pressure to obtain the reaction product.
I got (b). Examples 1-4 Each component shown in Table 1 was mixed in the indicated amount and uniformly dispersed using a three-roll mill. In addition, the fluororesin powder in the table: "Luburon L-2" manufactured by Daikin Industries, Ltd., and the acryloylmorpholine: a product of Kojin Co., Ltd. were used. The obtained composition was applied to a cold rolled steel plate having a thickness of 0.8 mm using a natural roll coater to a film thickness of 2 to 4 μm. Thereafter, the coated steel plate was passed under two ozone-type concentrating ultraviolet irradiation lamps with an input of 80 W/cm at a speed of 30 m/min to obtain a lubricated steel plate. A sample piece was cut from this steel plate and a performance investigation was conducted. The results are shown in Table 1. The details of the adopted testing method are as follows. (1) Press workability: 50φ cylindrical deep drawing test, critical drawing ratio measurement at BHF = 0.5 tons (2) Film removability: Using "Fine Cleaner-4349" 20g/manufactured by Nippon Parkerizing Co., Ltd. at 60℃ Measure the film removal rate at each spray time under the conditions of spray pressure 1.0Kg/cm ³ . (3) Rust prevention: Wet/dry cycle test (1 cycle: 60℃98
%RH, 2 hours + 60℃ drying) Measurement of rusted area in each cycle.

[Table] Examples 5 to 7, Comparative Examples 1 to 2 In the same manner as Examples 1 to 4, each component shown in Table 2 was mixed in the indicated amounts to obtain a composition. The composition was coated on a steel plate in the same manner as in Example 1 and subjected to performance investigation. The results are shown in Table 2. Surface tackiness was evaluated by touching the coated surface with a finger immediately after irradiation with ultraviolet rays and determining whether there was a feeling of tackiness. Acryloylmorpholine has a low viscosity (approximately 10
centipoise), and as its proportion in the formulation increases, the viscosity of the formulation decreases, making the paint easier to handle. Further, even if the amount of acryloylmorpholine added is increased, no decrease in curability is observed. On the other hand, when 2-hydroxypropyl acrylate is used as a viscosity modifier instead of acryloylmorpholine,
Rust prevention properties are reduced, and when phenoxyethyl acrylate is used, curability and film removability are reduced. Comparative Example 3 A cold-rolled steel sheet coated with a commercially available press oil (“Press Oil #620” manufactured by Nippon Craft Oil Co., Ltd.) was subjected to a performance investigation.
The results are shown in Table 2.

【table】

[Table] Examples 8 to 12 In the same manner as Examples 5 to 7, each component shown in Table 3 was mixed in the indicated amount to obtain a composition. The composition was coated on a hot rolled steel plate, stainless steel plate, aluminum plate, copper plate, and titanium plate in the same manner as in Example 1,
The pressability and film removability were investigated. The results are shown in Table 3. Surface tackiness was evaluated by touching the painted surface with a finger immediately after irradiation with ultraviolet rays and judging whether there was a feeling of tackiness. Comparative Examples 4 to 8 A commercially available press oil ("Press Oil #620" manufactured by Nippon Kosakusha) was applied to the materials used in Examples 8 to 12, and pressability and unveiling properties were investigated. The results are shown in Table 3.

【table】

[Table] [Effects of the Invention] As shown in the Examples section, the present invention improved the critical drawing ratio during pressing by about 0.2 compared to the comparative material using press oil. Furthermore, it was possible to prevent mold galling due to contact between the press mold and the metal material.

Claims (1)

[Scope of Claims] 1 Energy ray-curable type comprising 1 to 30 parts by weight of a lubricant () and, if necessary, 0.5 to 20 parts by weight of a sensitizer () to 100 parts by weight of a monomer mixture (). In the temporary coating composition, the monomer mixture (A) reacts 1 mol of a compound having one oxirane ring with 0.8 to 1.1 mol of an α,β-ethylenically unsaturated carboxylic acid having one carboxyl group, and then Product (a) obtained by reacting 0.5 to 1 mol of polybasic acid and/or its anhydride, 1 mol of acrylic ester or methacrylic ester having a hydroxyl group at the end and 0.8 mol of polybasic acid and/or its anhydride. A product (b) obtained by reacting ~1.1 mol, or a mixture of the above product (a) and product (b); and (B)
formula: [In the formula, R represents hydrogen or a methyl group. An energy beam-curable temporary coating composition for lubricating metal materials, which contains (meth)acryloylmorpholine represented by: 5 to 100 parts by weight of component (B) per 100 parts by weight of component (A). 2. The coating composition according to claim 1, wherein the lubricant () is a fluororesin powder.