KR20120060457A - UV curable Coating or Adhesion Compositions for Difficulty Adhesion Metal and a Method for Preparation of the Same - Google Patents

Abstract

PURPOSE: A photocurable coating or adhesive composition is provided to have high adhesion with aluminum, thereby capable of coating aluminum surface without specific pre-treatment, to have excellent abrasion resistance and yellowing resistance, weatherability, etc, and to be easily coated by a spray method. CONSTITUTION: A photocurable coating or adhesive composition comprises 10-100 parts by weight of methylmethacrylate monomer, 10-100 parts by weight of vinylphosphonic acid, 0.1-10 parts by weight of gamma-glycidoxypropyltrimethoxysilane, and 0.1-10 parts by weight of a photocuring agent. The equivalent of the epoxy resin is 150-250, and the viscosity is 2,000-5,000 cps. The methylmethacrylate monomer is one or more selected from a group consisting of 2-hydroxyethylacrylate and 1,6-hexanedioldiacrylate.

Description

UV curable Coating or Adhesion Compositions for Difficulty Adhesion Metal and a Method for Preparation of the Same}

The present invention relates to a photocurable coating or adhesive composition for a non-adhesive metal material and a method for manufacturing the same, and more particularly, to be coated on a hard-adhesive metal surface such as aluminum to prevent abrasion and contamination of the metal surface and to beautify aesthetics. The present invention also relates to a photocurable coating or adhesive composition for a non-adhesive metal material, which can be used as an adhesive between a hard-adhesive metal and various materials, and a method of manufacturing the same.

Aluminum is used as the main material for aircraft, ships, and vehicles because it is light, durable, resistant to low temperatures, and has excellent thermal conductivity. In addition, since oxidation does not occur well and there is no toxicity, it is used to make food industry utensils, tableware, etc., and other uses for building materials and raw materials. In addition, it is widely used for making electrical equipment, electronic components, leisure goods, and the like of communication equipment, semiconductors and computers. Compared to these advantages, it is corroded when subjected to acidic foods, and has a disadvantage in that the hardness is low, so it is easy to be scratched, and the appearance is easily damaged and deformed.

Therefore, the conventional technique for compensating for the drawbacks of aluminum was to modify the surface of aluminum through plasma treatment or heat treatment to enable painting or coating. Plasma treatment is a method of introducing the active material generated by the plasma into the functional group on the surface to strengthen the bonding strength with the coating liquid. However, the plasma treatment is an expensive treatment method that requires expensive equipment such as a vacuum chamber, a vacuum pump, and a power supply, and has a disadvantage in that a large area treatment is difficult. The heat treatment method also has the disadvantage of making the coating cost high because additional equipment and equipment must be added.

In addition, such a coating solution has a problem that its use is gradually restricted due to the problem of air pollution due to the evaporation of volatile organic compounds contained therein. At present, countries around the world are tightening the regulation of these volatile organic substances. The United States has bills related to California's Rule66, the US Environmental Protection Agency's Clean Air Act (CAA), and Reasonably Available Control 25-3 Technology (RACT), which regulate emissions and concentrations of volatile organics. Doing.

As described above, the conventional coating liquid for coating the aluminum and stainless steel surfaces with the coating liquid without separately treating the surface of the aluminum has been extremely limited in its range of use because of its low hardness and strength even if the adhesive strength does not come out or the adhesive strength comes out. In addition, it is difficult to spray due to its high viscosity, and the epoxy itself, including benzene ring, becomes prolonged by UV and turns into quinine imide, resulting in yellowing and yellowing.

Therefore, there is a need for the development of a coating composition or adhesive composition for a non-adhesive metal material having good coating and adhesion without coating the one-step and yellowing without causing pollution to the natural environment as described above.

Accordingly, the first problem to be solved by the present invention is to solve the problems of a coating agent and an adhesive made of a general epoxy resin showing a weak adhesion to a non-adhesive metal material such as aluminum, while having a high bonding strength and transparency It is to provide a photocurable coating composition or adhesive composition for a difficult-to-adhesive metal material having a low viscosity and easy operation.

A second object of the present invention is to provide a method for preparing the coating or adhesive composition.

A third object of the present invention is to provide a method for coating a metal surface by using the above coating or adhesive composition.

The fourth object of the present invention is to provide a coating agent or an adhesive for hard-adhesive metal materials prepared by the method for producing a coating or adhesive composition.

The present invention to achieve the first object,

10-100 parts by weight of methyl methacrylate monomer, 10-100 parts by weight of vinyl phosphonic acid, 0.1-10 parts by weight of gamma-glycidoxypropyltrimethoxysilane and 0.1-10 parts by weight of photocuring agent, based on 100 parts by weight of epoxy resin Disclosed is a coating or adhesive composition for a non-adhesive metal material, comprising a part.

According to one embodiment, the epoxy resin is bisphenol A epoxy resin, bisphenol F epoxy resin, novolak-type epoxy resin, flame retardant epoxy resin, cycloaliphatic epoxy resin, rubber modified epoxy resin, glycidyl At least one selected from the group consisting of an amine epoxy resin and a hydrated bisphenol A epoxy resin is used, the epoxy resin has an equivalent weight of 150-250, a viscosity of 2,000-5,000 cps,

The methyl methacrylate monomer may be used at least one selected from the group consisting of 2-hydroxyethyl acrylate and 1,6-hexanediol diacrylate, the content of the methyl methacrylate monomer is the epoxy resin 10-100 parts by weight per 100 parts by weight,

The content of the vinyl phosphonic acid is 10-100 parts by weight based on 100 parts by weight of the epoxy resin,

The gamma-glycidoxypropyltrimethoxysilane is beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, gamma- At least one selected from the group consisting of methacryloxypropyltriethoxysilane and gamma-methacrylopropylpropyltrimethoxysilane, and the gamma-glycidoxypropyltrimethocysilane is 100 parts by weight of an epoxy resin. 0.1-10 parts by weight,

The photocuring agent is at least one selected from the group consisting of hydroxy cyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl, acetofetone, benzophenone and phenyl-2-hydroxy 2-propylketone, The content of the photocuring agent may be 0.1-10 parts by weight based on 100 parts by weight of the epoxy resin.

According to another embodiment, it may further include an inorganic filler, the inorganic filler may be one or more selected from the group consisting of silica, silicon dioxide, magnesium silicate, aluminum oxide and calcium carbonate.

According to another aspect of the present invention,

(1) reacting the epoxy resin and the methyl methacrylate monomer at 23-70 ° C. for 1.5-3 hours,

(2) adding vinylphosphonic acid to the reaction product obtained in step (1) and reacting at 23-40 ° C. for 9-15 hours;

(3) adding gamma-glycidoxypropyltrimethoxysilane to the reaction product obtained in step (2) and reacting at 23-40 ° C. for 1-4 hours;

(4) adding a photocuring agent to the reaction product obtained in step (3) and reacting at 23-30 ° C. for 30 minutes to 2 hours, wherein the method for preparing a coating or adhesive composition for a non-adhesive metal material comprises It starts.

In order to achieve the third object,

(A) coating a coating or adhesive composition on a metal surface, and (B) coating the composition or coating of an adhesive composition for a non-adhesive metal material, comprising the step of curing the exposed metal by UV exposure. Or a bonding method is disclosed.

In one embodiment, the coating or bonding method may be a spray coating method, an eyedropper coating method or a thin coating method with a stick.

In another embodiment, the step of applying a coating or adhesive composition for the non-adhesive metal material on the metal surface and then exposed to UV, 1400 mJ / ㎠ And 2-4 minutes at a condition of 15 cm irradiation distance.

The photocurable coating or adhesive composition according to the present invention has a high adhesive strength with aluminum, so that the aluminum surface can be coated without a separate pretreatment, and adhesion with other substrates is possible. In addition, the coating or adhesive composition of the present invention has a low viscosity and can be easily coated by the spray method, which has the advantage of high work efficiency. In addition, the photocurable coating or adhesive composition according to the present invention can be used as a coating agent, adhesive and plastering agent because of its color transparency and compatibility with pigments, and it is very durable because it has excellent physical properties such as wear resistance, yellowing resistance, and weather resistance. Has a high effect.

1 shows an infrared spectral spectrum of Example 1. FIG.
Figure 2 shows the results of measuring the thermal stability of Example 1.

Hereinafter, the present invention will be described in detail.

In the present invention, a coating composition or an adhesive composition comprising a methyl methacrylate monomer, vinyl phosphonic acid, gamma-glycidoxypropyltrimethoxysilane and a photocuring agent in a hydrated bisphenol A epoxy resin represented by the following formula: By the preparation of these excellent properties of viscosity, hardness, coating properties, adhesion, wear resistance, yellowing resistance and weather resistance was confirmed.

The coating or adhesive composition for the hard-adhesive metal material according to the present invention is 10-100 parts by weight of methyl methacrylate monomer, 10-100 parts by weight of vinylphosphonic acid, and gamma-glycidoxypropyltrime based on 100 parts by weight of an epoxy resin. And 0.1-10 parts by weight of oxysilane and 0.1-10 parts by weight of a photocuring agent.

The epoxy resin used for this invention does not have a restriction | limiting in particular in the kind, For example, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a novolak-type epoxy resin, a flame-retardant epoxy resin, a cycloaliphatic epoxy resin , At least one selected from the group consisting of a rubber-modified epoxy resin, a glycidyl amine epoxy resin, and a hydrated bisphenol A epoxy resin, and the like, and a hydrated bisphenol A epoxy resin is most preferred. However, since it is inexpensive, excellent in physical properties and no yellowing phenomenon, it is preferable because it is industrial and suitable as a coating agent.

It is preferable that the equivalent weight of the epoxy resin is 150-250, and the viscosity is 2,000-5,000 cps. If the equivalent weight of the epoxy resin is less than 150, the hardness is too high and the flexibility may be reduced. It may not be preferable because the adhesive force may be lowered, and if the viscosity of the epoxy resin is less than 2,000 cps, the viscosity may be too low, and the adhesion and coating strength may be reduced. It is unpreferable because of number.

Hydrogenated Bisphenol A Type Epoxy Resin

Vinyl phosphonic acid

Methyl methacrylate monomer

In the above formula, n and m are molar ratios 0 <n, 0 <m and n: m is 9: 1-1: 1.

The epoxy resin used in the present invention forms a complex three-dimensional network structure by thermosetting reaction, has high mechanical strength, and exhibits excellent adhesion characteristics by having high heterogeneous intermolecular cohesive energy between substrates by epoxy groups.

However, when the base material is aluminum, the shrinkage ratio between the epoxy and the metal increases in the process of forming the three-dimensional network structure, so that it may not have a high cohesive energy between heterogeneous molecules, resulting in poor adhesion. In addition, if the deposit has a large irregularity due to the roughness surface, the coating or adhesive composition penetrates the irregularities and mechanically interlocks with the substrate, thereby increasing the adhesive strength. It is very smooth and there are few irregularities, so this effect is also hard to expect and shows lower adhesion. As a result, the adhesive force hardly appears or drops significantly, making the coating or adhesive impossible. Therefore, by adding methyl methacrylate monomer, vinyl phosphonic acid, and gamma-glycidoxy propyl trimethoxysilane to the epoxy resin as described above, it is possible to compensate for the disadvantages of using such an epoxy resin in a hard-bonding metal. Can be.

The methyl methacrylate monomer used in the present invention lowers the viscosity of the epoxy resin and acts as a monomer to improve adhesion with vinylphosphonic acid and to increase crosslinking density. Since the epoxy resin is high in viscosity and difficult to coat for spraying, it is used to lower the viscosity of the epoxy resin. In general, a volatile organic compound (VOC) is produced by using an organic solvent in a coating composition for hard-adhesive metal materials, but since a methacrylate monomer is not used, a volatile organic compound is not generated, which is very useful. .

The methyl methacrylate monomer is reacted with the epoxy resin, the alkene group breaks the epoxy group to form a bond. Some of the methyl methacrylate monomers react with vinylphosphonic acid to form a bond and increase the crosslinking density upon UV curing. The carbonyl group of the methyl methacrylate monomer is hydrophilic, thereby improving the adhesion and softening the coating agent, and the hydroxyl group is large in polarity, and reacts with the polar group on the hard-adhesive metal surface to improve adhesion.

In addition, the methyl methacrylate monomer lowers the viscosity of the composition, soaks well in the uneven portion of the surface of the adherend to mechanically fix to maximize the adhesion.

There is no restriction | limiting in particular in the kind, The said methyl methacrylate monomer can use 1 or more types chosen from the group which consists of 2-hydroxyethyl acrylate, 1, 6- hexanediol diacrylate, etc., for example. have.

The content of the methyl methacrylate monomer is preferably used 10-100 parts by weight with respect to 100 parts by weight of the epoxy resin, more preferably 20-50 parts by weight, the viscosity of the epoxy resin is less than 10 parts by weight It is not desirable to be too high to be suitable for spraying, and to have poor wettability, so that coatings and adhesives available for hard-to-adhesive metal materials do not spread completely on the metal material and can cause the compositions to stick together during curing. It is not preferable because the viscosity of the resin is too low to reduce the coating and adhesion.

The vinyl phosphonic acid used in the present invention is added to improve the adhesion, the alkene or hydroxy group and the epoxy group of the vinyl phosphonic acid reacts, on the other hand, vinyl phosphonic acid acts as an additive to improve adhesion and curing Relieves contraction Phosphorus of vinyl phosphonic acid enhances adhesion with inorganic substances, and hydroxyl group strengthens adhesion with strong polarity.

In more detail, as the vinyl phosphonic acid proceeds with UV curing, some of the vinyl phosphonic acid reacts with the hydrophobized epoxy resin, which is a hydroxyl group of vinyl phosphonic acid breaking the epoxy group of the epoxy resin, and vinyl phosphonic acid and epoxy. Becomes a bond. The other part of the vinylphosphonic acid reacts with the methylmethacrylate monomer to convert the chain into a linear structure, which increases the flexibility of the coating. Another part of the vinylphosphonic acid combines with the alkene group of the vinylphosphonic acid combined with epoxy to extend the chain linearly. This is due to the heat generated during UV curing, the double bond of the alkene group is broken and this reaction is initiated to react with other alkenes. Another part of vinylphosphonic acid causes alkenes of vinylphosphonic acid to react with each other. Another part of the vinylphosphonic acid does not react during the thermal curing but only plays a role in the position between the three-dimensional network structure. That is, by adding the vinylphosphonic acid, hydrogenated bisphenol-A epoxy resin softens the chain in the process of forming a three-dimensional network structure through UV curing and prevents over-curing, thereby shrinking the coating and composition during curing. Significantly reduces the resistance to adhesion loss due to the difference in shrinkage between the metal and the composition. In addition, when vinylphosphonic acid is added to the hydrogenated bisphenol A epoxy resin, the hydroxyl group of vinylphosphonic acid having a lot of polar groups reacts with the polar group on the hard-bonding metal surface to improve adhesion.

The content of the vinylphosphonic acid is preferably 10-100 parts by weight, and more preferably 30-80 parts by weight, based on 100 parts by weight of the epoxy resin. It is not preferable that sufficient adhesive strength as possible coatings and adhesives may not come out, and if it exceeds 100 parts by weight, the color becomes yellow during UV curing, the hardness is poor, and the wear resistance and scratch resistance may deteriorate, and thermal stability may be inferior. Not.

The gamma-glycidoxypropyltrimethoxysilane used in the present invention is used to lower the surface energy of the composition so as to penetrate better and to improve compatibility with inorganic and epoxy resins. More specifically, gamma-gly One end of the sidoxypropyl trimethoxysilane has an epoxy group, which is an organic material, to improve compatibility with the epoxy resin, and the other end has a silane group, which is an inorganic material, for compatibility with metals or inorganic materials. This improves adhesion between the hydrogenated bisphenol A epoxy resin and the metal.

The gamma-glycidoxypropyltrimethosyl silane is not particularly limited in kind, and for example, beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane (beta- (3,4-Epoxycyclohexyl) trimethoxysilane), vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, gamma-methacryloxypropyltriethoxysilane, gamma -One or more types selected from the group consisting of methacryloxypropyltrimethoxysilane and the like can be used.

The gamma-glycidoxypropyltrimethoxysilane is preferably used in an amount of 0.1-10 parts by weight, and more preferably 0.5-4.5 parts by weight, based on 100 parts by weight of an epoxy resin. It is not preferable because the compatibility between the metal and the inorganic material may be lowered and thereby the adhesive strength between the epoxy resin and the metal may be reduced, and if it exceeds 10 parts by weight, it is not preferable because of too much excess.

The photocuring agent used in the present invention is a photocuring agent is activated by UV to generate free radicals, and the radicals are used to activate the reactive oligomers, monomers to form a huge network structure.

The photocuring agent is not particularly limited in kind, and examples thereof include hydroxy cyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl, acetofetone, benzophenone and phenyl-2-hydroxy 2-propyl. One or more types selected from the group consisting of ketones and the like can be used.

The content of the photocuring agent is preferably used 0.1-10 parts by weight with respect to 100 parts by weight of epoxy resin, more preferably 0.5-5 parts by weight, if less than 0.1 parts by weight the curing rate is significantly slowed and the photopolymerization reaction is completely It is not desirable because it does not form a complete three-dimensional network structure, so it is not desirable to obtain the desired physical properties. If the content exceeds 10 parts by weight, a photocuring agent that does not participate in the reaction after photocuring remains in the material, causing poor properties and poor durability. It may be undesirable.

In addition to the above components, the coating or adhesive composition for a hard-adhesive metal material according to the present invention may further include an inorganic filler in a usual amount of the coating or adhesive composition for a hard-adhesive metal material.

There is no restriction | limiting in particular in the kind, The said inorganic filler can use 1 or more types chosen from the group which consists of a silica, a silicon dioxide, magnesium silicate, aluminum oxide, a calcium carbonate.

Method for producing a coating or adhesive composition for a non-adhesive metal material according to the present invention is characterized by consisting of the following steps.

(1) reacting the epoxy resin and the methyl methacrylate monomer at 23-70 ° C. for 1.5-3 hours,

(2) adding vinylphosphonic acid to the reaction product obtained in step (1) and reacting at 23-40 ° C. for 9-15 hours;

(3) adding gamma-glycidoxypropyltrimethoxysilane to the reaction product obtained in step (2) and reacting at 23-40 ° C. for 1-4 hours;

(4) adding a photocuring agent to the reaction product obtained in step (3) and reacting at 23-30 ° C. for 30 minutes to 2 hours.

In the present invention, the epoxy resin in step (1) is not particularly limited in kind, for example, bisphenol A-type epoxy resin, bisphenol F-type epoxy resin, novolak-type epoxy resin, flame-retardant epoxy resin, ring Cycloaliphatic epoxy resins, rubber-modified epoxy resins, glycidylamine-type epoxy resins, and hydrated bisphenol A-type epoxy resins, and the like. Type epoxy resins are most preferred, since they are inexpensive, have excellent physical properties, and have no yellowing, they are industrially suitable and suitable as coating agents.

Preferably, the epoxy resin and the methyl methacrylate monomer proceed at about 1.5-3 hours at a reaction temperature of 23-70 ° C. under a nitrogen atmosphere. If the temperature is less than 23 ° C., the reaction may not occur. If it is hardened | cured, it may harden during reaction and it is not preferable. In addition, if the reaction time is less than 1.5 hours, the reaction may not occur sufficiently, and if the reaction time is over 3 hours, the reaction may not occur properly or the curing may occur and harden.

In the present invention, in the step (2), it is preferable to add the vinyl phosphonic acid to the reactant obtained in the step (1) under a nitrogen atmosphere for 9-15 hours at 23-40 ℃, outside the above range It is not preferable because the cotton reaction may not occur properly or the reaction may occur due to overreaction.

In the present invention, in the step (3), it is preferable to add a gamma-glycidoxypropyltrimethoxysilane to the reaction obtained in the step (2) under a nitrogen atmosphere and react for 1-4 hours at 23-40 ℃. However, outside the above range, it is not preferable because the reaction may not occur properly or the reaction may occur due to overreaction.

In the present invention, in the step (4), by adding a photocuring agent to the reaction product obtained in the step (3) to 30 minutes at 23-30 ℃ The reaction is preferably performed for 2 hours, which is not preferable because the reaction does not occur properly or the reaction may be deteriorated due to overreaction.

When the reaction is carried out in the step (4), it is preferable not to enter the light, if the light proceeds to the reaction proceeds, the photocuring agent may cause a small amount of reaction to reduce the physical properties or change in viscosity, Discoloration may also occur.

The coating agent or adhesive for hard-adhesive metal materials according to the present invention

(1) reacting the epoxy resin and the methyl methacrylate monomer at 23-70 ° C. for 1.5-3 hours,

(2) adding vinylphosphonic acid to the reaction product obtained in step (1) and reacting at 23-40 ° C. for 9-15 hours;

(3) adding gamma-glycidoxypropyltrimethoxysilane to the reaction product obtained in step (2) and reacting at 23-40 ° C. for 1-4 hours;

(4) by adding a photocuring agent to the reaction product obtained in step (3) can be prepared by a manufacturing method comprising the step of reacting for 30 minutes to 2 hours at 23-30 ℃.

The method for coating a metal surface using the coating or adhesive composition for a non-adhesive metal material according to the present invention comprises the steps of (A) coating or adhering the coating or adhesive composition to the metal surface, and (B) coating or The adhesive metal is exposed to UV to cure.

In the present invention, the coating or adhesive composition for the non-adhesive metal material coating or adhesive composition in the step (A) may be made in a variety of ways, spray coating method, eyedropper coating method, a thin coating with a stick Etc., but is not limited thereto.

The spray coating method is one of the preferred methods because the viscosity of the coating or adhesive composition for the non-adhesive metal material can be adjusted low. The spray coating method is an economical method for easily coating a large area in a short time.

As another example, a dropper may be applied or a thin rod may be applied.

In the present invention, the exposure conditions in the step (B) in the step of hardening by exposing the metal coated on the metal surface of the coating or adhesive composition for the non-adhesive metal material according to the invention in the step of UV radiation with a mercury UV curing machine 1200-1600 mJ / ㎠ And photocuring by irradiating ultraviolet light for about 2-4 minutes at a condition of an irradiation distance of 10-20 cm. Outside of the above range, exposure is not sufficient, which is not preferable, and the curing condition is a metal halide (100 W / cm)-High pressure mercury (100 W / cm)-Metal halide (100 W / cm) UV curing, curing time of 2-4 minutes is preferable, less than 2 minutes is not completely cured due to poor physical properties and surface It is not preferable to have a sticky feeling, and if more than 4 minutes, yellowing may occur in the coating or adhesive composition, and side effects may occur due to overcuring, which is undesirable.

When the metal coated on the surface of the metal is exposed to UV as described above, the photocuring agent is activated by UV to generate free radicals, and the radicals continuously activate the reactive oligomer and monomer to form a huge network structure, and then stop. Through the reaction, the curing reaction is terminated. In other words, by forming a complex three-dimensional network structure by UV curing to have a high mechanical strength and adhesion.

Hereinafter, the present invention will be described in more detail with reference to preferred examples. It will be apparent to those skilled in the art, however, that these examples are provided to further illustrate the present invention, and the scope of the present invention is not limited thereto.

Example  And Comparative example

Example  1: Aluminum Metal Coating Composition Subject Synthesis

50 g of a hydrogenated bisphenol A epoxy resin having an equivalent weight of epoxy resin of 187 and 20 g of methyl methacrylate monomer were added to a Bayer bottle, and reacted at 50 ° C. for 2 hours under a nitrogen atmosphere.

25 g of vinylphosphonic acid (manufactured by BASF) was added to the reaction product obtained above, followed by reaction at 25 ° C. for 10 hours in a nitrogen atmosphere. 1 g of gamma-glycidoxypropyltrimethoxysilane was added thereto, followed by reaction at 25 ° C. for 3 hours in a nitrogen atmosphere. Finally, 0.8 g of a photocuring agent (184, manufactured by Chivacure Co.) was added thereto, and reacted to prevent light from entering at 25 ° C. for 1 hour to prepare a photocurable coating composition.

Comparative example  One

10 g of the hydrogenated bisphenol A epoxy resin and 6 g of vinyl phosphonic acid were reacted at 25 ° C. for 10 hours under a nitrogen atmosphere. Then, 0.8 g of a photocuring agent (184, manufactured by Chivacure) was added thereto, and reacted at 25 ° C. for 1 hour to prepare a photocurable coating composition.

Comparative example  2

50 g of a hydrogenated bisphenol A epoxy resin having an equivalent weight of epoxy resin of 187 and 20 g of methyl methacrylate monomer were added to a Bayer bottle, and reacted at 50 ° C. for 2 hours. 0.5 g of a thermosetting agent imidazole was added to the reaction product obtained above, and reacted at 25 ° C. for 1 hour to prepare a thermosetting coating composition.

Comparative example  3

Epoxy acrylate was synthesized by adding 100 g of hydrogenated bisphenol A epoxy resin and 20 g of acrylic acid into the flask and reacting for 3 hours at 80 ° C. under a nitrogen atmosphere. 120 g of the composition obtained above and 10 g of a photocuring agent (184, manufactured by Chivacure Co., Ltd.) were added thereto, and reacted at 25 ° C. for 60 minutes to prepare a photocurable coating composition.

Comparative example  4

100 g of a hydrogenated bisphenol A epoxy resin and 10 g of a heat curing agent imidazole were added to the flask and reacted at 25 ° C. for 1 hour to prepare a thermosetting coating composition.

Comparative example  5

50 g of a hydrogenated bisphenol A epoxy resin having a weight average molecular weight of 187 and 20 g of methyl methacrylate monomer were added to a Bayer bottle, and mixed at 50 ° C. for 2 hours. 6 g of vinylphosphonic acid (manufactured by BASF) was added to the reaction product obtained above, followed by mixing at 25 ° C. for 10 hours under a nitrogen atmosphere. Finally, 0.8 g of a photocuring agent (184, manufactured by Chivacure) was added thereto, and mixed at 25 ° C. for 1 hour to prepare a photocurable coating composition.

Experimental Example  1 (infrared spectroscopic observation)

Spectra were obtained by FT-IR measurements on the prepolymer prepared according to Example 1. 1 shows an infrared spectroscopy spectrum of a prepolymer included in the photocurable coating composition of the present invention. Referring to FIG. 1, it can be seen that a broad and strong OH characteristic peak is observed around 3400. It can be seen that OH of the vinyl phosphonic acid and the methyl methacrylate monomer came out. It can also be seen that a peak appears around 915 cm ⁻¹ , indicating the presence of an epoxy ring.

Experimental Example  2( Thermal stability  Test)

Thermogravimetric analysis (TGA) analysis was performed for Example 1 and Comparative Examples 1-5. The analysis was performed up to 600 ° C. at a heating rate of 10 ° C./min in N ₂ atmosphere. The results are shown in Table 1 below.

Figure 2 shows the results of measuring the thermal stability of the photocurable coating composition of Example 1, the weight remained at 95% at 286.4 ℃ showed high thermal stability. Therefore, it can be seen that the thermal stability of the photocurable coating composition according to the present invention is high.

Experimental Example  3 (Adhesion Test)

The coating or adhesive composition of Example 1 and Comparative Example 1-5 was applied to an aluminum substrate with a spray gun having a spray hole of 3 mm using air pressure, and a capacity of UV 1400 mJ / cm 2 using a mercury ultraviolet curing machine. And photocuring by irradiating ultraviolet light for about 120 seconds under conditions of an irradiation distance of 15 cm. Subsequently, lines were formed on the coating film cured with a cutting knife at intervals of 1 mm to make 100 Go eye shapes, and then the OPP adhesive tape was bonded and strongly pulled in the vertical direction to visually determine whether the coating surface was peeled off. As shown in Table 1, in the adhesion test results, in Example 1, all of the 100 eye shapes remained unpeeled, and in Comparative Example 1, all of the 100 shapes remained unpeeled, but the comparative example 43 for 2, 21 for Comparative Example 3, 11 for Comparative Example 4, and 90 for Comparative Example 5 were obtained.

Therefore, it can be seen that Example 1 is excellent in adhesion between the aluminum and the aluminum surface, which is a poor adhesion metal.

Experimental Example  4 (hardness test)

The coating or adhesive composition for the non-adhesive metal material of Example 1 and Comparative Example 1-5 was applied to an aluminum substrate with a spray gun having a spray hole of 3 mm using air pressure, and was 1400 mJ / cm 2 using a mercury ultraviolet curing machine. And photocuring by irradiating ultraviolet light for about 120 seconds under conditions of an irradiation distance of 15 cm. With only the wood part of the pencil (made by Mitsubishi pencil) exposed and the core exposed about 3 mm in the shape of a cylinder, the seam is placed on a flat surface at right angles and polished while drawing a circle to sharpen the end of the seam. To do so. After contacting the pencil lead at an angle of about 45 ° on the coating surface formed on the stainless substrate, the hardness tester (manufactured by Sunhayato, ASTM D5178) was set to be parallel to the coating surface. The hardness tester was moved about 10 mm forward, and each of the samples was changed five times, and the hardness of the pencil, which was scratched at least once in five times, was expressed as the hardness of the coated surface. The hardness test result evaluated that the hardness of 4H was measured. The evaluated results are shown in Table 1. Through this, the hardness of the coating film formed of the coating composition of Example 1 can be seen that the high wear resistance.

Weight 95% Decomposition Temperature (℃) Adhesive force (number of remaining eyeballs) pencil
Hardness (H) Remarks aluminum Example 1 286.4 100 3 The composition is soaked in aluminum, transparent and smooth Comparative Example 1 295.3 100 3 The composition does not spread well on aluminum but is agglomerated and slightly yellowish Comparative example
2 264.5 43 3 The composition is well immersed in aluminum and transparent Comparative Example 3 272.3 21 2 The composition is soaked in aluminum
Transparent and smooth Comparative example
4 276.7 11 3 The composition is agglomerated and yellowish without spreading well on aluminum Comparative example
5 284.2 90 3 The composition is soaked in aluminum, transparent and smooth

As shown in Table 1, Example 1 has a high decomposition temperature, high thermal stability, excellent hardness and excellent adhesion, and as a result of being coated on an aluminum substrate, having a transparent and smooth surface soaked in aluminum It will be appreciated that it is suitable for coating or adhesive compositions.

However, in the case of Comparative Example 1, the thermal stability is high, but also excellent adhesion and hardness, but the result of the coating on the aluminum substrate, the composition does not spread well in the aluminum, it is a little yellowish color due to the agglomeration, the coating for the hard-adhesive metal material Or not suitable for the adhesive composition.

Comparative Example 2-3 is a coating on an aluminum substrate, it is wet and spread well in aluminum and transparent, but compared with Example 1, the thermal stability is somewhat poor and the adhesion is very poor, it is not suitable for coating or adhesive composition for hard-adhesive metal materials. Able to know.

Comparative Example 4 is less thermally stable than Example 1, but the adhesion is very weak, and, as a result of coating on an aluminum substrate, it does not spread well on aluminum and has a yellow color, which is suitable for a coating or adhesive composition for a non-adhesive metal material. It can be seen that not.

Comparative Example 5 has excellent thermal stability and, as a result of coating on an aluminum substrate, has good wetness with aluminum and has a transparent and smooth surface. However, it is not suitable for a coating or adhesive composition for hard-adhesive metal materials due to its poor adhesion compared to Example 1. It can be seen.

Claims (14)

10-100 parts by weight of methyl methacrylate monomer, 10-100 parts by weight of vinyl phosphonic acid, 0.1-10 parts by weight of gamma-glycidoxypropyltrimethoxysilane and 0.1-10 parts by weight of photocuring agent, based on 100 parts by weight of epoxy resin Coating or adhesive composition for a non-adhesive metal material, characterized in that it comprises a part. According to claim 1, 20-50 parts by weight of the methyl methacrylate monomer, 30-80 parts by weight of the vinyl phosphonic acid, the gamma- glycidoxypropyl trimethoxysilane 0.5- with respect to 100 parts by weight of the epoxy resin Coating or adhesive composition for a hard-bonding metal material, characterized in that it comprises 4.5 parts by weight and 0.5-5 parts by weight of the photocuring agent. The epoxy resin of claim 1, wherein the epoxy resin is a bisphenol A epoxy resin, a bisphenol F epoxy resin, a novolac epoxy resin, a flame retardant epoxy resin, a cycloaliphatic epoxy resin, a rubber modified epoxy resin, or glycidylamine. Coating or adhesive composition for a non-adhesive metal material, characterized in that at least one member selected from the group consisting of epoxy resin and hydrinated bisphenol A epoxy resin. The coating or adhesive composition of claim 1, wherein the epoxy resin has an equivalent weight of 150-250 and a viscosity of 2,000-5,000 cps. The method of claim 1, wherein the methyl methacrylate monomer is one or more selected from the group consisting of 2-hydroxyethyl acrylate and 1,6-hexanediol diacrylate coating for a non-adhesive metal material, or Adhesive composition. The method of claim 1, wherein the gamma-glycidoxypropyltrimethoxysilane is beta- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldi A coating or adhesive composition for a non-adhesive metal material, characterized in that it is at least one member selected from the group consisting of methoxysilane, gamma-methacryloxypropyltriethoxysilane, and gamma-methacryloxypropyltrimethoxysilane. The method of claim 1, wherein the photocuring agent is selected from the group consisting of hydroxy cyclohexylphenyl ketone, 2,2-dimethoxy-2-phenyl, acetofetone, benzophenone and phenyl-2-hydroxy 2-propylketone Coating or adhesive composition for a non-adhesive metal material, characterized in that at least one. The coating or adhesive composition of claim 1, further comprising an inorganic filler. The coating or adhesive composition of claim 8, wherein the inorganic filler is at least one selected from the group consisting of silica, silicon dioxide, magnesium silicate, aluminum oxide, and calcium carbonate. (1) reacting the epoxy resin and the methyl methacrylate monomer at 23-70 ° C. for 1.5-3 hours,
(2) adding vinylphosphonic acid to the reaction product obtained in step (1) and reacting at 23-40 ° C. for 9-15 hours;
(3) adding gamma-glycidoxypropyltrimethoxysilane to the reaction product obtained in step (2) and reacting at 23-40 ° C. for 1-4 hours;
(4) The method of producing a coating or adhesive composition for a non-adhesive metal material, comprising adding a photocuring agent to the reaction product obtained in step (3) and reacting at 23-30 ° C. for 30 minutes to 2 hours. (1) reacting the epoxy resin and the methyl methacrylate monomer at 23-70 ° C. for 1.5-3 hours,
(2) adding vinylphosphonic acid to the reaction product obtained in step (1) and reacting at 23-40 ° C. for 9-15 hours;
(3) adding gamma-glycidoxypropyltrimethoxysilane to the reaction product obtained in step (2) and reacting at 23-40 ° C. for 1-4 hours;
(4) a coating agent for a non-adhesive metal material, characterized in that it is prepared by a manufacturing method comprising the step of reacting for 30 minutes to 2 hours at 23-30 ℃ by adding a photocuring agent to the reactant obtained in step (3) or glue. (A) coating or adhering the coating or adhesive composition according to any one of claims 1 to 9 to a metal surface, and (B) curing the metals coated or bonded with the composition by exposure to UV. Coating or bonding method of a coating or adhesive composition for a non-adhesive metal material comprising a. 13. The method of claim 12, wherein the coating or adhering to the metal surface in step (A) is performed by spray coating, eyedropper coating or thin coating with a stick. Or a bonding method. The method of claim 12, wherein in step (B), the curing of the metal coated or bonded with the composition by exposure to UV is performed using a mercury UV curing machine with a capacity of UV 1200-1600 mJ / cm 2. And coating or adhering a coating or adhesive composition for a non-adhesive metal material, which comprises photocuring by irradiating ultraviolet light for about 2-4 minutes in a condition of an irradiation distance of 10-20 cm.

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