JP3399078B2 - Lubricating resin composition and paint for outer surface of can containing the same - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful lubricating resin composition. INDUSTRIAL APPLICABILITY The lubricating resin composition of the present invention can be widely used as a main 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 coating film having lubricity, a silicone compound has been used as a lubricity imparting component in a coating composition. However, these silicone compounds have a drawback that they are detached from the coating film after the coating film is formed, and the lubricity of the coating film decreases with time. The decrease in the lubricity of the coating film is particularly remarkable after the immersion treatment with boiling water or the like.
It has been attempted to use a silicone compound having a reactive functional group in order to prevent the silicone compound from being detached from the coating surface. The reactive silicone compound is allowed to react with the resin component having a reactive functional group in the coating composition at the time of forming the coating film to fix it on the surface of the coating film. However, generally, coating film formation by drying, thermosetting, etc. is carried out 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.

In recent years, paints have been made water-based from the viewpoint of environmental protection, but conventionally used silicone compounds have poor solubility in water-based paints, and the water-based properties of silicone compounds due to introduction of ethylene oxide chains or the like. Attempts are being made. However, the silicone compound hydrophilized in this way has poor water resistance, and the lubricity after 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 lubricating resin composition in which a coating film containing the same has excellent lubricity and in which deterioration of the lubricity of the coating film is suppressed. is there.

[0005]

[Means for Solving the Problems] That is, the present invention relates to 1 to 70% by weight of an amino resin and 0.1 to 70% of a silicone compound.
Provided is a lubricating resin composition characterized by being obtained by polymerizing 10 to 98.9% by weight of an α, β-unsaturated monomer in the presence of% by weight.

The lubricating resin composition of the present invention is obtained by polymerizing an α, β-unsaturated monomer in the presence of an amino resin and a silicone compound. Condensation reaction, graft reaction, entanglement of molecular chains, etc. occur between the α, β-unsaturated monomer. Therefore, a silicone compound which is not compatible with the paint resin by itself can be used as a paint component, and deterioration of the lubricity of the paint film due to desorption of the silicone compound from the paint film is also suppressed.

The silicone compound is not particularly limited, and examples thereof include compounds having a main chain skeleton of dimethylsiloxane, methylhydrosiloxane, methylalkylsiloxane, diphenylsiloxane, methylphenylsiloxane and the like, and mixtures thereof. The silicone compound may have a reactive functional group at the terminal or side chain, and particularly preferably has at least one reactive functional group selected from a hydroxyl group, a carboxyl group and a glycidyl group. Since these silicone compounds condense with the amino resin, the storage stability and the 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]. Improving the water resistance of the lubricating resin composition due to the hydrophobicity, anchoring effect, etc. of the group represented by the general formula [I], and preventing deterioration of the lubricity of the coating film due to desorption after boiling water treatment etc. You can

[0009]

[Chemical 2] (In the formula, 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. 34 or less alkylene group, R3 is an alkylene group having 18 or less carbon atoms, X is hydrogen or hydroxyl group.) Specifically, it is obtained by ring-opening polymerization of alkyl group, alkoxyl group, fatty acid ester group, or lactone. Examples thereof include silicone oil having a polyester group, fatty acid-modified silicone oil, oxyacid-modified silicone oil, and the like.

As the amino resin, urea resin, melamine resin, benzoguanamine resin, spiroguanamine resin,
Glycoluril resins and the like can be mentioned, and these can be used alone or in admixture of two or more. The structure of the amino resin preferably has a methylol group and / or an alkoxyl group.

The α, β-unsaturated monomer is not particularly limited, and examples thereof include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid,
Alkyl (meth) acrylate having an alkyl group having 18 or less carbon atoms, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyamyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate , Styrene, α-methylstyrene, vinyltoluene, alkyl vinyl esters and alkyl vinyl ethers having an alkyl group having 1 to 18 carbon atoms, N-methylol (meth) acrylamide, 4 carbon atoms
The following alkyl-containing N-alkoxymethyl (meth) acrylamides, (meth) acrylonitriles and the like can be mentioned, and they can be used alone or as a mixture. When the lubricating resin composition of the present invention is used in water-based paints, water-based inks, etc., it is preferable to use monomers having a carboxyl group such as acrylic acid and methacrylic acid.

The lubricating resin composition of the present invention is an amino resin
It is obtained by polymerizing 10 to 98.9% by weight of an α, β-unsaturated monomer in the presence of 1 to 70% by weight and a silicone compound of 0.1 to 70% by weight. The storage stability of the lubricating resin composition and the compatibility with the coating resin and the like are improved. The types and composition ratios of the amino resin, the silicone compound, and the α, β-unsaturated monomer can be appropriately selected depending on the compatibility with the resin system in which the lubricating resin composition is used and the required physical properties.

The amino resin and the silicone compound may be mixed in advance while being melted by heating, and at this time, an acid catalyst may be added if necessary. Α, β in these mixtures
The polymerization of the unsaturated monomer is carried out by a usual polymerization method, under an inert gas stream at 50 to 150 ° C. for 2 to 6 hours,
You may use a solvent together. As the polymerization initiator, an organic azo compound, an organic peroxide or the like is used in an amount of 1 to 20% by weight based on the α, β-unsaturated monomer. In particular, it is preferable to use an organic peroxide, and since a graft reaction easily occurs, a lubricating resin composition having good storage stability and compatibility with a coating resin can be obtained. Representative examples of organic peroxides include benzoyl peroxide, cumene hydroperoxide, t-butyl hydroperoxide, diisopropyl peroxycarbonate, di t-butyl peroxide, t-butyl peroxybenzoate and the like. .

The lubricating resin composition of the present invention is used as a main ingredient of paints, inks and the like, but it may be used as an additive in combination with other resins. The other resin is not particularly limited as long as it is a resin generally used in paints, inks, etc., and acrylic resins, alkyd resins,
Examples thereof include polyester resin, urethane resin, vinyl resin, polyamide resin, epoxy resin, amino resin and phenol resin. The compounding ratio of the other resin and the lubricating resin composition is preferably 0.1 to 10 parts by weight of the silicone compound in the lubricating resin composition with respect to 100 parts by weight of the other resin.
Further, the lubricating resin composition of the present invention, if necessary,
Dyes and pigments for coloring and the like, various additives for improving the physical properties of the cured product, such as fillers, leveling agents, curing agents, flame retardants, thickeners and the like can be contained.

[0015]

The present invention will be described in more detail with reference to the following examples. In the examples, "parts" means "parts by weight" and "%" means "% by weight". [Production Example 1] A separable four-necked flask was equipped with a temperature control regulator, a cooling tube, and a stirrer. Partially butyl etherified benzoguanamine resin ("Cimel 1128" manufactured by Mitsui Cyanamid Co., Ltd., solid content 70%) 229 parts, hydroxyl group-modified silicone Oil ("Cilaplane FM44 manufactured by Chisso"
21 ") 80 parts and 171 parts of butyl cellosolve are charged, and the temperature is about 90 ° C.
After the temperature was raised to and the inside of the reaction vessel was replaced with nitrogen, 16 parts of acrylic acid and 24 parts of 2-hydroxyethyl methacrylate were added from a dropping pipe.
64 parts of styrene, 24 parts of ethyl acrylate, 16 parts of 2-ethylhexyl acrylate, 16 parts of N-methoxymethyl methacrylate, 16 parts of organic peroxide (“Perbutyl O” manufactured by NOF CORPORATION), 142 parts of butyl cellosolve were added dropwise over 3 hours. did. One hour after the completion of dropping, 1.6 parts of the organic peroxide "Perbutyl O" was added, and the reaction was continued for another hour.
Resin composition A-1 having a solid content of 50.3% was obtained.

[Manufacturing Example 2] A methyl, ethyl etherified benzoguanamine resin (“Cymel 1123” manufactured by Mitsui Cyanamid Co., solid content 1) was placed in the same reactor as in Manufacturing Example 1.
00%) 140 parts, carboxyl group-modified silicone oil (“X-22-3701E” manufactured by Shin-Etsu Chemical Co., Ltd.) 60 parts, butyl cellosolve 200 parts, and 1.4 parts formic acid were charged, and the mixture was heated to about 90 ° C. and mixed for 2 hours. After replacing the inside of the reaction vessel with nitrogen, add 30 parts of acrylic acid and 30 parts of 2-hydroxyethyl methacrylate from the dropping pipe.
Parts, styrene 60 parts, ethyl acrylate 40 parts, 2-ethylhexyl acrylate 20 parts, N-methoxymethyl methacrylate 20 parts, organic peroxide "perbutyl O" 20 parts, and butyl cellosolve 178 parts were added dropwise over 3 hours. One hour after the completion of the dropping, 2.0 parts of the organic peroxide "Perbutyl O" was added, and the reaction was continued for another hour. A resin composition A-2 having a solid content of 49.9% was obtained.

[Production Example 3] 196 parts of methyl etherified melamine resin ("Cymel 303" manufactured by Mitsui Cyanamid Co., Ltd., solid content 100%), glycidyl group-modified silicone oil (produced by Chisso Co.) in the same reactor as in Production Example 1 (Cyraplane FM5521)) 4 parts, n-butanol 200 parts, about 90
After the temperature was raised to ℃ and the inside of the reaction vessel was replaced with nitrogen, 30 parts of acrylic acid and 2-hydroxyethyl methacrylate
Parts, styrene 60 parts, ethyl acrylate 40 parts, 2-ethylhexyl acrylate 20 parts, N-methoxymethyl methacrylate 20 parts, organic peroxide "perbutyl O" 20 parts, and n-butanol 178 parts were added dropwise over 3 hours. One hour after the completion of the dropping, 2.0 parts of the organic peroxide "Perbutyl O" was added, and the reaction was continued for another hour. After the reaction was completed, 40.8 parts of N, N-dimethylaminoethanol and 1000 parts of water were added to n-
The butanol was distilled off. A resin composition A-3 having a solid content of 39.7% was obtained.

[Production Example 4] 80 parts of a methyl etherified melamine resin ("Cymel 303" manufactured by Mitsui Cyanamid Co., Ltd., solid content 100%), stearic acid-modified silicone oil (produced by Chisso Co.) were placed in the same reactor as in Production Example 1. "PS053")
40 parts, butyl cellosolve 120 parts were charged, the temperature was raised to about 90 ° C and the inside of the reaction vessel was replaced with nitrogen, and then acrylic acid was added from the dropping pipe
42 parts, 2-hydroxyethyl methacrylate 42 parts, styrene 84 parts, ethyl acrylate 56 parts, 2-ethylhexyl acrylate 28 parts, N-methoxymethyl methacrylate 28
Parts, 28 parts of organic peroxide "Perbutyl O" and 249 parts of butyl cellosolve were added dropwise over 3 hours. One hour after the completion of the dropping, 2.8 parts of organic peroxide "Perbutyl O" was added, and the reaction was continued for another hour. A resin composition A-4 having a solid content of 50.0% was obtained.

[Production Example 5] In a reactor similar to that of Production Example 1, 196 parts of butyl etherified melamine resin ("Mycoat 506" manufactured by Mitsui Cyanamid Co., Ltd., solid content 100%), alkyl-modified silicone oil (Shin-Etsu Chemical Co., Ltd.) Made `` KF-41
2 '') 4 parts, butyl cellosolve 200 parts were charged, the temperature was raised to about 90 ° C and the inside of the reaction vessel was replaced with nitrogen, and then 20 parts of acrylic acid, 30 parts of 2-hydroxyethyl methacrylate, 80 parts of styrene, ethyl acrylate were added from a dropping pipe. 30 parts, 2-ethylhexyl acrylate 20 parts, N-methoxymethyl methacrylate
20 parts, 20 parts of organic peroxide "Perbutyl O", and 178 parts of butyl cellosolve were added dropwise over 3 hours. 1 hour after the end of the dropping, 2.0 parts of the organic peroxide "Perbutyl O" was added,
The reaction was continued for another hour. Resin composition A-5 having a solid content of 50.2% was obtained.

[Production Example 6] 200 parts of a butyl etherified melamine resin ("Mycoat 506" manufactured by Mitsui Cyanamid Co., Ltd., solid content 100%), a higher alkoxy group-modified silicone oil (Shin-Etsu Chemical Co., Ltd.) were used in the same reactor as in Production Example 1. (X-22-801B manufactured by Kogyo Co., Ltd.) 120 parts, butyl cellosolve 320 parts were charged, the temperature was raised to about 90 ° C., and the inside of the reaction vessel was replaced with nitrogen. Part, styrene 24 parts, ethyl acrylate 12 parts, 2-
Ethylhexyl acrylate 12 parts, N-methoxymethyl methacrylate 8 parts, organic peroxide "Perbutyl O" 8
And 71 parts of butyl cellosolve were added dropwise over 3 hours. One hour after the completion of dropping, the organic peroxide "Perbutyl O" 0.8
Parts were added and the reaction was continued for another hour. Solid content 49.9
% Resin composition A-6 was obtained.

[Production Example 7] Partially butyl etherified benzoguanamine resin (“Cymel 1128” manufactured by Mitsui Cyanamid Co., Ltd., solid content 70%) 286 was placed in the same reactor as in Production Example 1.
, 120 parts of higher aliphatic ester-modified silicone oil (“KF-910” manufactured by Shin-Etsu Chemical Co., Ltd.), and 200 parts of butyl cellosolve were charged, the temperature was raised to about 90 ° C., and the atmosphere in the reaction vessel was replaced with nitrogen. Acid 12 parts, 2-hydroxyethyl methacrylate 12 parts, styrene 24 parts, ethyl acrylate
12 parts, 2-ethylhexyl acrylate 12 parts, N-methoxymethyl methacrylate 8 parts, organic peroxide "Perbutyl O" 8 parts, and butyl cellosolve 71 parts were added dropwise over 3 hours. One hour after the completion of dropping, 0.8 part of the organic peroxide "Perbutyl O" was added, and the reaction was continued for another hour. A resin composition A-7 having a solid content of 50.1% was obtained.

[Production Example 8] A methyl, ethyl etherified benzoguanamine resin ("Cymel 1123" manufactured by Mitsui Cyanamid Co., solid content 1) was placed in the same reactor as in Production Example 1.
00%) 166 parts, alkyl group, hydroxyl group-modified silicone oil (terminal hydroxyl group-modified polydimethyl-methyldecylsiloxane, Si number 60, methyldecylsiloxane unit 48 to 52 mol%) 4 parts, n-butanol 200 parts After the temperature was raised to 90 ° C and the inside of the reaction vessel was replaced with nitrogen, acrylic acid was added through the dropping pipe.
42 parts, 2-hydroxyethyl methacrylate 42 parts, styrene 84 parts, ethyl acrylate 42 parts, 2-ethylhexyl acrylate 42 parts, N-methoxymethyl methacrylate 28
Part, organic peroxide "Perbutyl O" 28 parts, n-butanol
249 parts was added dropwise over 3 hours. 1 hour after the end of dropping,
2.8 parts of organic peroxide "Perbutyl O" was added, and the reaction was continued for another 1 hour. After completion of the reaction, 40.8 parts of N, N-dimethylaminoethanol and 800 parts of water were added to distill off n-butanol. A resin composition A-8 having a solid content of 40.5% was obtained.

[Production Example 9] A methyl, ethyl etherified benzoguanamine resin ("Cymel 1123" manufactured by Mitsui Cyanamid Co., Ltd., solid content 1) was placed in the same reactor as in Production Example 1.
00%) 120 parts, terminal caprolactone-modified silicone oil (polydimethylsiloxane with 60 Si and 40 caprolactone chain) 80 parts, and 234 parts butyl cellosolve were charged, and the temperature was raised to about 90 ° C and nitrogen was purged inside the reaction vessel before dropping. From the tube acrylic acid 30 parts, 2-hydroxyethyl methacrylate 30 parts, styrene 60 parts, ethyl acrylate 30 parts, 2-ethylhexyl acrylate 30 parts, N-methoxymethyl methacrylate
20 parts, 20 parts of organic peroxide "Perbutyl O", and 178 parts of butyl cellosolve were added dropwise over 3 hours. 1 hour after the end of the dropping, 2.0 parts of the organic peroxide "Perbutyl O" was added,
The reaction was continued for another hour. A resin composition A-8 having a solid content of 50.0% was obtained.

[Manufacturing Example 10] 240 parts of butyl cellosolve were charged in the same reactor as in Manufacturing Example 1, heated to about 90 ° C., and the atmosphere in the reaction vessel was replaced with nitrogen.
Parts, ethyl acrylate 112 parts, 2-ethylhexyl acrylate 84 parts, 2-hydroxyethyl methacrylate 112
Part, N-methoxymethylacrylamide 56 parts, acrylic acid 28
And 28 parts of organic peroxide "Perbutyl O" were added dropwise over 3 hours. One hour after the completion of dropping, 2.8 parts of organic peroxide "Perbutyl O" was added, and the reaction was continued for another hour.
A resin solution B-1 having a solid content of 70.2% was obtained.

[Examples 1 to 9 and Comparative Examples 1 to 3] Production Example 1
After mixing each component according to the composition (solid content ratio) shown in Table 1 using the resin composition obtained in Example 9 to the resin solution obtained in Production Example 10, Examples 1, 5, 6, 7 Comparative Example 1 was adjusted to a solid content of 35% with butyl cellosolve, and Example 2,
Examples 4 and 9 and Comparative Examples 2 and 3 were neutralized with N, N-dimethylaminoethanol in an equal amount, and then butyl cellosolve and water were added to adjust the amount of the organic solvent to 15% and the solid content to 35%. 8 added butyl cellosolve and water to reduce the amount of organic solvent to 15
% And solid content 35%. 0.3% of paratoluenesulfonic acid was added to these to obtain an aqueous coating composition. This paint was applied on a TFS plate (chrome-treated steel plate) with a natural roll coater and baked and cured at 180 ° C for 10 minutes. A coating film having a film thickness of 6 to 8 μm was obtained.

[0026]

[Table 1] * 1 Sila plane FM4421

Table 2 shows the results of an examination of 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 1 week, the state of gelation and separation of the resin in the paint was observed. Sliding property of coating film: Surface property measuring device ("HEIDON-14" manufactured by Shinto Scientific Co., Ltd.)
)), The dynamic friction coefficient was measured at 25 ° C. and 50% RH under the conditions of a load of 200 g, a ball indenter φ10 mm, and a moving speed of 100 mm / min. The same measurement was performed on the cured coating film after the treatment with boiling water 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

[0028]

[Table 2]

[0029]

The lubricating resin composition of the present invention has excellent storage stability and compatibility with resins used for paints and the like. Further, the coating film containing the lubricating resin composition of the present invention, the deterioration of the lubricity of the coating film due to the desorption of the silicone compound in the lubricating resin composition is suppressed, even after boiling water treatment or the like. No decrease in lubricity of the coating film is observed. Therefore, the lubricating resin composition of the present invention can be used in a wide range of applications as a binder for paints, inks, coating agents and the like, and is extremely useful industrially.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-6-33015 (JP, A) JP-A-5-202320 (JP, A) JP-A-5-132647 (JP, A) JP-A-5- 93171 (JP, A) JP-A-51-4221 (JP, A) JP-B-47-13185 (JP, B1) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 2/00-2 / 60 C08L 1/00-101/16 C09D 1/00-201/10

Claims (5)

(57) [Claims] 1. Lubrication characterized by polymerizing 10 to 98.9% by weight of an α, β-unsaturated monomer in the presence of 1 to 70% by weight of an amino resin and 0.1 to 70% by weight of a silicone compound. Resin composition. 2. The lubricating resin composition according to claim 1, wherein the silicone compound has at least one reactive functional group selected from a hydroxyl group, a carboxyl group and a glycidyl group. 3. The silicone compound has a group represented by the following general formula [I], wherein:
The lubricating resin composition described. [Chemical 1] (In the formula, 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. 34 or less alkylene group, R3 represents C18 or less alkylene group, and X represents hydrogen or hydroxyl group.) 4. An organic peroxide is used when polymerizing an α, β-unsaturated monomer.
The lubricating resin composition according to any one of the above. 5. A paint for an outer surface of a can, comprising the lubricating resin composition according to any one of claims 1 to 4.