JP3355777B2 - Lubricity imparting agent and paint for outer surface of can containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful lubricating agent . The lubricity imparting agent of the present invention can be widely used as a base agent and an additive for paints, inks, coating agents, and the like.

[0002]

2. Description of the Related Art Conventionally, in order to obtain a lubricating coating film, a silicone compound has been used as a lubricating component in a coating composition. However, these silicone compounds have the disadvantage that they are detached from the coating film after the formation of the coating film, and the lubricity of the coating film decreases over time. The decrease in lubricity of the coating film is particularly noticeable after immersion treatment with boiling water or the like.
Attempts have been made to use a silicone compound having a reactive functional group in order to prevent such a silicone compound from detaching from the coating surface. In this method, a reactive silicone compound is reacted with a resin component having a reactive functional group in a coating composition at the time of forming a coating film, and is fixed to a coating film surface. However, in general, a coating film forming process such as drying and heat curing is performed in a very short time, and it has been difficult for the reactive silicone compound and the resin component to sufficiently react with each other.

[0003] In recent years, paints have been made water-soluble from the viewpoint of environmental protection. However, conventionally used silicone compounds have poor solubility in water-based paints. Has been attempted. However, the water-soluble silicone compound has poor water resistance, and the lubricity after the immersion treatment with boiling water or the like is significantly reduced.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lubricity imparting agent in which a coating film containing the same has excellent lubricity and furthermore, a decrease in lubricity of the coating film is suppressed. .

[0005]

Means for Solving the Problems That is, the present invention provides anti
Provided is a lubricity imparting agent characterized in that an amino compound having a triazine ring is methylolated and, if necessary, etherified in the presence of a silicone compound having a reactive functional group .

The lubricating resin imparting agent of the present invention comprises a reactive functional
It is obtained by methylolating an amino compound having a triazine ring in the presence of a silicone compound having a group ,
Partial etherification of the methylol-modified amino compound and the silicone compound, physical entanglement between the generated amino resin and the silicone compound, and the like occur. Therefore, a silicone compound having no compatibility with the paint resin alone can be used as the paint component,
A decrease in the lubricity of the coating film due to detachment of the silicone compound from the coating film is also suppressed.

[0007] The silicone compound preferably has at least one reactive functional group selected from a hydroxyl group, a carboxyl group and a glycidyl group at the terminal or side chain. Since these silicone compounds condense with an amino compound having a triazine ring or a methylol group, storage stability and compatibility with the coating resin can be improved.

It is also preferable to use a silicone compound having a group represented by the following general formula [I]. Due to the hydrophobicity, anchor effect, and the like of the group represented by the general formula [I], it is possible to improve the water resistance of the lubricity imparting agent and prevent a decrease in lubricity due to desorption of the silicone compound after boiling water treatment or the like. it can.

[0009]

Embedded image (Wherein n1 and n3 are 0 or 1, n2 is an integer of 0 to 150, and n1, n2 and n3 are not all 0. R1 is an alkylene group having 30 or less carbon atoms, and R2 is a carbon number. An alkylene group of 34 or less, R3 is an alkylene group of 18 or less carbon atoms, X represents hydrogen or a hydroxyl group.) Specifically, it is obtained by ring-opening polymerization of an alkyl group, an alkoxyl group, a fatty acid ester group, or a lactone. Silicone oil having a polyester group or the like, fatty acid-modified silicone oil, oxyacid-modified silicone oil, and the like can be given.

The amino compound having a triazine ring is not particularly limited, and examples thereof include melamine, benzoguanamine, acetoguanamine, and spiro guanamine. Lubricity imparting agent of the present invention, in the presence of the silicone compound, by reacting the amino compound having a triazine ring and aldehydes to form methylol, and further formed, if necessary, a methylol group and a hydroxyl group of an alcohol. Can be obtained by dehydration-condensation and etherification. The silicone compound is contained in the resin composition
It is preferably used in the range of 0.1 to 90% by weight. If the amount is less than 0.1% by weight, it becomes difficult to obtain good lubricity. If the amount is more than 90% by weight, it becomes difficult to obtain compatibility with the amino compound.

Methylolation of an amino compound having a triazine ring can be carried out with formaldehyde.
Formaldehyde sources include formalin, paraformaldehyde and the like. The methylolation of the amino compound is carried out in an acidic or alkaline reaction atmosphere under the conditions of 40 to 150.
The reaction can be carried out by adding an appropriate amount of an aldehyde to the amino compound and reacting the mixture at a temperature of ° C. In this case, the amino compounds can be used alone or as a mixture of two or more. The amount of the aldehyde added is appropriately adjusted depending on the desired degree of methylolation of the amino compound. The appropriate degree of methylolation cannot be unconditionally determined depending on the type of amino compound used, but it is considered preferable to react aldehydes in an amount of 0.5 equivalent or more per equivalent of active hydrogen contained in the amino compound. If the degree of methylolation is too low, the resulting amino resin may not exhibit thermosetting properties, which is not preferable.

The methylol-containing amino compound having a triazine ring is optionally condensed with alcohols while being dehydrated and etherified. At the time of etherification, an acid catalyst such as formic acid or acetic acid may be added. The alcohol is preferably used in an amount of 0.5 equivalent or more based on 1 equivalent of the methylol group introduced into the amino compound, and can be used as a solvent during the reaction. If the amount is less than 0.5 equivalent, the condensation between the methylolated amino compounds remarkably progresses, the molecular weight increases, and it may be insoluble, which is not preferable.

Examples of the alcohols include methanol, ethanol, propanol, butanol, ethylene glycol nomomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol, diethylene glycol, triethylene glycol, and propylene. Glycol, butanediol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, and the like.

The lubricity- imparting agent of the present invention is used as a main component of paints, inks and the like, but can also be used as an additive in combination with other resins. Other resins are not particularly limited as long as they are generally used for paints, inks, etc., and include acrylic resins, alkyd resins, polyester resins, urethane resins, vinyl resins, polyamide resins, epoxy resins, and amino resins. And phenolic resins. The mixing ratio of the lubricating agent to the other resin is preferably 0.1 to 10 parts by weight of the silicone compound in the lubricating agent with respect to 100 parts by weight of the other resin. Further, the lubricity imparting agent of the present invention, if necessary, dyes and pigments for coloring and the like, various additives for improving the properties of the cured product, such as fillers, leveling agents, curing agents, flame retardants , A thickener and the like.

[0015]

[Production Example 1]

Attach a regulator for temperature control, a condenser, and a stirrer to the separable four-necked flask.
61 parts, 288 parts of paraformaldehyde, hydroxyl-modified silicone oil ("Silaprene FM4421" manufactured by Chisso) 212
Parts, n-butanol (1060 parts), pH was adjusted to about 9 with triethylamine, and about 3
The reaction was carried out for an hour, 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration to obtain a grant agent A-1 having a nonvolatile content of about 70%.

Production Example 2 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Part, formaldehyde-containing isopropyl alcohol 40%
900 parts of solution (“Hormit IP” manufactured by Koei Chemical Co., Ltd.) and carboxyl group-modified silicone oil (“X-22 manufactured by Shin-Etsu Chemical Co., Ltd.”
-3701E "), and 430 parts of isopropyl alcohol were charged, and the temperature was gradually increased while stirring, and the mixture was heated at the reflux temperature for 30 minutes. After 1 part of formic acid was charged, the reaction was continued for 8 hours while heating and refluxing dehydration, followed by cooling and adjusting with butyl cellosolve to obtain grant agent A-2 having a nonvolatile content of about 70%.

Production Example 3 In the same reactor as in Production Example 1, 265 parts of melamine, 168 parts of benzoguanamine, 486 parts of paraformaldehyde, 102 parts of a glycidyl group-modified silicone oil (“Silaprene FM5521” manufactured by Chisso), 102 parts of butyl cellosolve 1020 parts were charged, the pH was adjusted to about 10 with a 10% aqueous sodium hydroxide solution, and the reaction was carried out for about 3 hours while maintaining the liquid temperature at 90 ° C.
Thereafter, 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropically dehydrating to obtain a grant agent A-3 having a nonvolatile content of about 70%.

[Production Example 4] In the same reactor as in Production Example 1, spirologamine 651 was added.
Parts, 900 parts of a formaldehyde-containing methanol 40% solution (“Hormit MH” manufactured by Koei Chemical Co., Ltd.) and 112 parts of stearic acid-modified silicone oil (“PS053” manufactured by Chisso) were charged.
Adjust the pH to about 8 with sodium methylate and at 60 ° C
Heated for 60 minutes. Charge 2 parts of nitric acid and continue heating to 60
After reacting at 10 ° C. for 10 hours, neutralized amount of sodium hydroxide was added, and the aqueous layer was separated and removed. Then, methanol and water were removed under reduced pressure, and further adjusted with butyl cellosolve.
Was obtained.

Production Example 5 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Parts, 288 parts of paraformaldehyde, 17 parts of alkyl-modified silicone oil (“KF-412” manufactured by Shin-Etsu Chemical Co., Ltd.) and 870 parts of n-butanol, the pH was adjusted to about 9 with dimethylethanolamine, and the liquid temperature was adjusted to 90. About 3
A time reaction was performed. Thereafter, 100 parts of xylene was added and the reaction was carried out for about 3 hours while azeotropically dehydrating to obtain a grant agent A-5 having a nonvolatile content of about 70%.

[Production Example 6] In the same reactor as in Production Example 1, 113 parts of melamine, 393 parts of benzoguanamine, 331 parts of paraformaldehyde, and a higher alkoxy group-modified silicone oil (“X-22-801B” manufactured by Shin-Etsu Chemical Co., Ltd.) 209 parts) and 1050 parts of n-butanol were added, the pH was adjusted to about 9 with triethylamine, and the reaction was carried out for about 3 hours while maintaining the liquid temperature at 90 ° C. Then xylene 1
The reaction was carried out for about 3 hours while azeotropic dehydration was carried out to obtain imparting agent A-6 having a nonvolatile content of about 70%.

Production Example 7 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Part, 288 parts of paraformaldehyde, higher aliphatic ester modified silicone oil (“KF-910” manufactured by Shin-Etsu Chemical Co., Ltd.)
Add 94 parts and 1010 parts of butyl cellosolve, adjust the pH to about 9 with triethylamine, carry out the reaction for about 3 hours while maintaining the liquid temperature at 90 ° C., add 100 parts of xylene, and react for about 3 hours while azeotropically dehydrating. And apply about 70% non-volatile content .
Additive A-7 was obtained.

[Production Example 8] In a reaction apparatus similar to that of Production Example 1, 378 parts of melamine, 540 parts of paraformaldehyde, an alkyl group and a hydroxyl-modified silicone oil (polydimethyl-methyldecylsiloxane modified with a hydroxyl group at a terminal, 60 Si, methyl (Decyl siloxane unit 48-52 mol%) 102 parts, n-butanol 1020 parts
The pH was adjusted to about 10 with a 10% aqueous sodium hydroxide solution, and the reaction was carried out for about 3 hours while maintaining the liquid temperature at 90 ° C. afterwards,
100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration to obtain a grant agent A-8 having a nonvolatile content of about 70%.

[Production Example 9] In the same reactor as in Production Example 1, benzoguanamine 374 was added.
Parts, 192 parts of paraformaldehyde, 377 parts of caprolactone-modified silicone oil (polydimethylsiloxane with 60 Si and 40 lactone chains) and 940 parts of n-butanol, adjust the pH to about 9 with triethylamine, and adjust the liquid temperature. 90
The reaction was carried out for about 3 hours while maintaining the temperature. Thereafter, 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration to obtain a grant agent A-9 having a nonvolatile content of about 70%.

Production Example 10 Benzoguanamine 561 was placed in the same reactor as in Production Example 1.
Parts, 288 parts of formaldehyde and 1272 parts of hydroxyl-modified silicone oil ("KF6003" manufactured by Shin-Etsu Chemical Co., Ltd.)
The pH was adjusted to about 9 with triethylamine, and the liquid temperature was adjusted to 90.
The reaction was carried out for about 3 hours while the temperature was maintained at 0 ° C., and 100 parts of xylene was added, and the reaction was carried out for about 3 hours while azeotropic dehydration was carried out to obtain grant agent A-10 having a nonvolatile content of about 70%.

[Production Example 11] 240 parts of butyl cellosolve was charged into the same reactor as in Production Example 1, the temperature was raised to about 90 ° C, and the inside of the reaction vessel was purged with nitrogen.
Parts, ethyl acrylate 112 parts, 2-ethylhexyl acrylate 84 parts, 2-hydroxyethyl methacrylate 112
Parts, N-methoxymethylacrylamide 56 parts, acrylic acid
28 parts, organic peroxide ("Perbutyl O" manufactured by NOF Corporation)
28 parts were added dropwise over 3 hours. One hour after the completion of the dropwise addition, 2.8 parts of an organic peroxide "perbutyl O" was added, and the reaction was continued for another hour. A resin solution B-1 having a nonvolatile content of about 70% was obtained.

Examples 1 to 10 and Comparative Examples 1 to 3 Compositions (solid content ratio) shown in Table 1 using the imparting agents obtained in Production Examples 1 to 10 and the resin solution obtained in Production Example 11 After mixing the components according to Example 1, 5, 6, 7, 9, 1
0, Comparative Example 1 was adjusted to a solid content of 35% with butyl cellosolve, and Examples 2, 3, 4, 8, and Comparative Examples 2 and 3 were added with butyl cellosolve and water to reduce the organic solvent amount to 15% and a solid content of 35%.
%. Add 0.3% of paratoluenesulfonic acid to these
% To obtain an aqueous coating composition. This paint was applied on a TFS plate (chrome-treated steel plate) using a natural roll coater, and baked and cured at 180 ° C. for 10 minutes. Film thickness 6 ~
An 8 μm coating film was obtained.

[0027]

[Table 1]

* 1 Ethyl etherified benzoguanamine resin, manufactured by Mitsui Cyanamid Inc. * 2 Partially butyl etherified benzoguanamine resin, manufactured by Mitsui Cyanamid Inc. * 3 Methyl etherified melamine resin, manufactured by Mitsui Cyanamid Inc. * 4 Butyl etherified melamine resin, manufactured by Mitsui Cyanamid Inc. * 5 Thyraplane FM4421

Table 2 shows the results of examining the stability of the paints prepared in Examples and Comparative Examples and the slipperiness of the cured coating film before and after the boiling water treatment. Each test method is as follows. Paint stability: After the paint was stored at 50 ° C. for one week, the state of gelation and separation of the resin in the paint was observed. Coating film sliding property; Surface property measuring device (“HEIDON-14” manufactured by Shinto Kagaku
The dynamic friction coefficient was measured at 25 ° C. and 50% RH under the conditions of a load of 200 g, a ball indenter φ of 10 mm, and a moving speed of 100 mm / min. The same test was performed on the cured coating film after the boiling water treatment for 30 minutes. ◎-Dynamic friction coefficient less than 0.1 ○-Dynamic friction coefficient 0.1 or more and less than 0.2 ×-Dynamic friction coefficient 0.2 or more

[0030]

[Table 2]

[0031]

The lubricity imparting agent of the present invention is excellent in storage stability and compatibility with resins used for paints and the like.
Further, the coating film containing the lubricity imparting agent of the present invention has lubricity.
A decrease in the lubricity of the coating film due to detachment of the silicone compound in the imparting agent is suppressed, and no decrease in the lubricity of the coating film is observed even when a boiling water treatment or the like is performed. Therefore, the lubricity imparting agent of the present invention can be used for a wide range of applications as a binder for paints, inks, coating agents, and the like, and is industrially extremely useful.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 7/12 C09D 7/12 C10M 169/04 C10M 169/04 // (C10M 169/04 107: 50 107: 50 133: 42 133: 42) C10N 30:06 C10N 30:06 50:08 50:08 (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 83/00-83/16

Claims (5)

(57) [Claims] 1. A hydroxyl group, a carboxyl group and glycidyl.
A lubricity imparting agent obtained by converting an amino compound having a triazine ring into methylol in the presence of a silicone compound having at least one reactive functional group selected from the group consisting of: 2. A hydroxyl group, a carboxyl group and glycidyl.
A lubricating agent characterized in that an amino compound having a triazine ring is methylolated and then etherified in the presence of a silicone compound having at least one reactive functional group selected from the groups . 3. A silicone compound according to claim 1 or 2 characterized by having a group represented by the following general formula [I]
The lubricity imparting agent as described in the above. Embedded image (Wherein n1 and n3 are 0 or 1, n2 is an integer of 0 to 150, and n1, n2 and n3 are not all 0. R1 is an alkylene group having 30 or less carbon atoms, and R2 is a carbon number. An alkylene group of 34 or less, R3 represents an alkylene group having 18 or less carbon atoms, and X represents hydrogen or a hydroxyl group.) During wherein imparting agent, a hydroxyl group, a carboxyl group and
At least one reactive function selected from glycidyl groups
Claims 1, characterized by using 0.1 to 90 wt% of a silicone compound having a group 3 lubricity according to any one
Granting agent . 5. A claims 1 to with Lubrication of 4 according any
A paint for the outer surface of a can, characterized by containing an additive .