JP3170994B2 - Lubricating resin composition 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 resin composition. INDUSTRIAL APPLICABILITY The lubricating resin composition 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, silicone compounds have been used as lubricity-imparting components in coating compositions in order to obtain lubricating coating films. However, these silicone compounds have a disadvantage that they are detached from the coating film after the formation of the coating film, and the lubricity of the coating film decreases with time. In order to suppress the decrease in lubricity of the coating film due to detachment of the silicone compound after forming the coating film, and to further improve the compatibility with the coating resin, a silicone compound having a polymerizable functional group is copolymerized with another silicone compound. Investigations have been made on possible copolymers with unsaturated monomers.

[0003] However, under severe conditions such as boiling water treatment, even if these silicone copolymers are used, it is not possible to sufficiently suppress the decrease in the lubricity of the coating film. The decrease in lubricity was particularly remarkable when a silicone-based copolymer obtained by copolymerizing an α, β-unsaturated carboxylic acid, a polymerizable group-containing ethylene oxide, or the like was used for aqueous conversion.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a lubricating resin composition in which a coating containing them has excellent lubricity, and furthermore, a decrease in the lubricity of the coating due to boiling water treatment or the like is suppressed. In providing things.

[0005]

That is, the present invention relates to an α, β-unsaturated monomer containing a silicon compound having a (meth) acryloyl group in the presence of 1 to 80% by weight of an amino resin.
To 20% by weight of a lubricating resin composition.

The lubricating resin composition of the present invention is obtained by polymerizing an α, β-unsaturated monomer containing a silicon compound having a (meth) acryloyl group in the presence of an amino resin.
Between the amino resin and the silicon compound having a (meth) acryloyl group and the α, β-unsaturated monomer, a condensation reaction, a graft reaction, entanglement of molecular chains, and the like occur partially. Therefore, the silicon compound having a (meth) acryloyl group and the α, β-unsaturated monomer are incorporated into the thermosetting system of the amino resin, and a decrease in lubricity of the coating film due to boiling water treatment or the like is suppressed.

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

[0008] The silicon compound having a (meth) acryloyl group is not particularly limited, and dimethylsiloxane, methylhydrosiloxane, methylalkylsiloxane, diphenylsiloxane, methylphenylsiloxane or the like having a main chain skeleton of (meth) acryloyl. Compounds having groups and mixtures thereof. Among them, from the viewpoint of polymerizability with other α, β-unsaturated monomers,
A silicon compound having a (meth) acryloyl group at one end is suitably used. The silicon compound having a (meth) acryloyl group is preferably used in an amount of 0.1 to 70% by weight in the α, β-unsaturated monomer.

The α, β-unsaturated monomer is not particularly restricted but includes, for example, 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) acrylamide, (meth) acrylonitrile and the like are used, and they are used alone or as a mixture.

In particular, when an α, β-unsaturated monomer having a hydroxyl group is used, a condensation reaction with an amino resin is easily caused, so that a decrease in lubricity due to boiling water treatment or the like is further suppressed, which is preferable. The α, β-unsaturated monomer having a hydroxyl group is
It is preferable to use 1 to 50% by weight of the α, β-unsaturated monomer. If it exceeds 50% by weight, the viscosity of the system increases due to the increase in the molecular weight, and the compatibility with the coating resin and the coating property deteriorate. When the lubricating resin composition of the present invention is used for an aqueous paint, an aqueous ink or the like, it is preferable to use a monomer having a carboxyl group such as acrylic acid and methacrylic acid.

The lubricating resin composition of the present invention comprises an amino resin
It is obtained by polymerizing 99 to 20% by weight of an α, β-unsaturated monomer containing a silicon compound having a (meth) acryloyl group in the presence of 1 to 80% by weight. When the polymerization is performed, the storage stability of the lubricating resin composition and the compatibility with the coating resin and the like are improved. The type and composition ratio of the amino resin, the silicon compound having a (meth) acryloyl group, and the α, β-unsaturated monomer are appropriately determined according to the compatibility with the resin system in which the lubricating resin composition is used and the required physical properties. You can choose.

The polymerization of an α, β-unsaturated monomer containing a silicon compound having a (meth) acryloyl group in the presence of an amino resin is carried out by a usual polymerization method in an inert gas stream under a flow of 50 to 15 times.
The reaction is performed at 0 ° C. for 2 to 6 hours, and in this case, a solvent may be used in combination. 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 the graft reaction is likely to occur, the suppression of a decrease in the lubricity of the coating film due to the treatment with boiling water is further enhanced. Representative 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 can 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,
Examples include polyester resin, urethane resin, vinyl resin, polyamide resin, epoxy resin, amino resin, and phenol resin. The compounding ratio of the lubricating resin composition to the other resin is such that the silicon compound having a (meth) acryloyl group in the lubricating resin composition is 100 parts by weight of the other resin.
0.1 to 10 parts by weight is preferred. Further, the lubricating resin composition of the present invention may contain, as necessary, a dye or pigment for coloring or the like, and various additives for improving the properties of the cured product, for example, fillers, leveling agents, curing agents, and the like. A flame retardant, a thickener, and the like can be contained.

[0014]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” represents “parts by weight”, and “%” represents “% by weight”. [Production Example 1] A separable four-necked flask was equipped with a regulator for temperature control, a condenser, and a stirrer, and 143 parts of partially butyl etherified benzoguanamine resin (“Symel 1128” manufactured by Mitsui Cyanamid Co., 70% solids), 57 parts of butyl cellosolve After the temperature was raised to about 90 ° C. and the inside of the reaction vessel was replaced with nitrogen, 120 parts of a methacryloyl group-containing silicone (“X-22-174D” manufactured by Shin-Etsu Chemical Co., Ltd.), 30 parts of acrylic acid, 30 parts of hydroxyethyl methacrylate, 30 parts of styrene, 30 parts of ethyl acrylate, 30 parts of 2-ethylhexyl acrylate, N-methoxymethyl methacrylate
30 parts, organic peroxide ("Perbutyl O" manufactured by NOF Corporation)
15 parts and 284 parts of butyl cellosolve were added dropwise over 3 hours. One hour after the completion of the dropwise addition, 1.5 parts of an organic peroxide "perbutyl O" was added, and the reaction was continued for another hour. A resin composition A-1 having a solid content of 50.1% was obtained.

[Production Example 2] A methyl and ethyl etherified benzoguanamine resin (“Cymel 1123” manufactured by Mitsui Cyanamid Co., Ltd.
20%), 20 parts of butyl cellosolve were charged, the temperature was raised to about 90 ° C., and the inside of the reaction vessel was replaced with nitrogen. Then, 76 parts of a methacryloyl group-containing silicone “X-22-174D”, 57 parts of acrylic acid, 57 parts of 2-hydroxyethyl methacrylate, 57 parts of styrene, 57 parts of ethyl acrylate, 38 parts of 2-ethylhexyl acrylate, N-methoxymethyl methacrylate
38 parts, 19 parts of organic peroxide "perbutyl O" and 359 parts of butyl cellosolve were added dropwise over 3 hours. One hour after the completion of the dropwise addition, 1.9 parts of an organic peroxide “perbutyl O” was added,
The reaction was continued for another hour. A resin composition A-2 having a solid content of 50.0% was obtained.

Production Example 3 A partially butyl etherified benzoguanamine resin (“Cymel 1128” manufactured by Mitsui Cyanamid Co., solid content 70%) was placed in the same reactor as in Production Example 1.
Parts, butyl cellosolve 91 parts, the temperature was raised to about 90 ° C., and the inside of the reaction vessel was purged with nitrogen. Then, 2.4 parts of methacryloyl group-containing silicone “X-22-174D” and acrylic acid 24 were added through a dropping tube.
Parts, 2-hydroxyethyl methacrylate 36 parts, styrene
72 parts, ethyl acrylate 40.8 parts, 2-ethylhexyl acrylate 43.2 parts, N-methoxymethyl methacrylate 24
Parts, 12 parts of an organic peroxide "perbutyl O" and 227 parts of butyl cellosolve were added dropwise over 3 hours. One hour after completion of the dropwise addition, 1.2 parts of an organic peroxide "perbutyl O" was added, and the reaction was continued for another hour. As a result, a resin composition A-3 having a solid content of 49.9% was obtained.

[Production Example 4] In a reaction apparatus similar to that of Production Example 1, 40 parts of a methyl etherified melamine resin (“Cymel 303” manufactured by Mitsui Cyanamid Co., solid content 100%) and 40 parts of butyl cellosolve were charged. And the inside of the reaction vessel was purged with nitrogen, and 36 parts of a methacryloyl group-containing silicone `` X-22-174D '', 36 parts of acrylic acid, 54 parts of 2-hydroxyethyl methacrylate, 90 parts of styrene, and 90 parts of ethyl acrylate were added through a dropping tube. Parts, 2-ethylhexyl acrylate 54
Parts, N-methoxymethyl methacrylate 36 parts, organic peroxide "Perbutyl O" 18 parts, butyl cellosolve 340 parts 3 parts
It was dropped over time. One hour after the completion of the dropwise addition, 1.8 parts of an organic peroxide "perbutyl O" was added, and the reaction was continued for another hour. A resin composition A-4 having a solid content of 50.1% was obtained.

[Preparation Example 5] A reaction apparatus similar to Preparation Example 1 was charged with 120 parts of butyl cellosolve, heated to about 90 ° C., and the inside of the reaction vessel was purged with nitrogen, and then a methacryloyl group-containing silicone “X- 22-174D '' 160 parts, acrylic acid
40 parts, 2-hydroxyethyl methacrylate 40 parts, styrene 40 parts, ethyl acrylate 40 parts, 2-ethylhexyl acrylate 40 parts, N-methoxymethyl methacrylate 40
, 20 parts of organic peroxide "perbutyl O" and 258 parts of butyl cellosolve were added dropwise over 3 hours. One hour after the completion of the dropwise addition, 2.0 parts of an organic peroxide “perbutyl O” was added, and the reaction was continued for another hour. As a result, a resin composition A-5 having a solid content of 50.2% was obtained.

[Production Example 6] Into the same reactor as in Production Example 1, 120 parts of butyl cellosolve was charged, the temperature was raised to about 90 ° C, and the inside of the reaction vessel was purged with nitrogen. 22-174D '' 80 parts, acrylic acid 60
Parts, 2-hydroxyethyl methacrylate 60 parts, styrene
60 parts, ethyl acrylate 60 parts, 2-ethylhexyl acrylate 40 parts, N-methoxymethyl methacrylate 40 parts,
Organic peroxide "Perbutyl O" 20 parts, butyl cellosolve
258 parts were added dropwise over 3 hours. One hour after the end of dropping,
2.0 parts of an organic peroxide “perbutyl O” was added, and the reaction was continued for another hour. Resin composition A having a solid content of 49.9%
6 was obtained.

[Production Example 7] 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
And 28 parts of an organic peroxide "perbutyl O" 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 solid content of 70.2% was obtained.

[Examples 1-4, Comparative Examples 1-2] Production Example 1
After mixing the components according to the compositions (solid content ratios) shown in Table 1 using the resin compositions obtained in Preparation Examples 6 to 6 and the resin solution obtained in Production Example 7, Examples 1 and 3 and Comparative Example 1 were performed. Was adjusted to a solid content of 35% with butyl cellosolve, and in Examples 2, 4 and Comparative Example 2, after neutralization with N, N-dimethylaminoethanol in an equal amount, butyl cellosolve and water were added to reduce the organic solvent amount to 15%, and Minute adjusted to 35%. To these were added 0.3% of paratoluenesulfonic acid 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. A coating film having a thickness of 6 to 8 μm was obtained.

[0022]

[Table 1]

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 films 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 instrument (“HEIDON-14” manufactured by Shinto Kagaku 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 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

[0024]

[Table 2]

[0025]

According to the lubricating resin composition of the present invention, since a chemical bond and / or a physical entanglement occur between the silicone copolymer and the amino resin, the lubricating resin composition has good storage stability and paint. Excellent compatibility with the resin used. Further, the coating film containing the lubricating resin composition of the present invention has excellent lubricity, and a decrease in lubricity due to boiling water treatment or the like is suppressed. Therefore, the lubricating resin composition of the present invention can be used for a wide range of applications as a binder for paints, inks, coating agents, and the like,
It is extremely useful industrially.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-7-258312 (JP, A) JP-A-63-162704 (JP, A) JP-A-55-12101 (JP, A) JP-A-53-123 19394 (JP, A) JP-A-51-131539 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 283/00 C08F 2/44

Claims (5)

(57) [Claims] An α, β-containing silicon compound having a (meth) acryloyl group in the presence of 1 to 80% by weight of an amino resin.
A lubricating resin composition obtained by polymerizing 99 to 20% by weight of an unsaturated monomer. 2. The lubricating resin composition according to claim 1, wherein the α, β-unsaturated monomer contains 0.1 to 70% by weight of a silicon compound having a (meth) acryloyl group. 3. The lubricating resin composition according to claim 1, wherein the α, β-unsaturated monomer contains 1 to 50% by weight of an α, β-unsaturated monomer having a hydroxyl group. object. 4. The method according to claim 1, wherein an organic peroxide is used when polymerizing the α, β-unsaturated monomer.
The lubricating resin composition according to any one of the above. 5. A paint for the outer surface of a can, comprising the lubricating resin composition according to claim 1.