KR19990061309A - UV Curing Coating Composition - Google Patents

Abstract

The present invention relates to a UV-curable coating composition, which is a coating composition comprising an acid-modified rosin ester resin, a reactive monomer, a photoinitiator, a leveling agent and an additive having excellent adhesion and curability, which are ABS, polycarbonate, acrylic, fine bag, In the UV-curable coating composition made of plastic such as polyvinyl chloride, polyethylene, polystyrene or polypropylene, the polypropylene is made up to compensate for the problems of poor wettability of paint and very poor adhesion to materials such as polypropylene or polyethylene. Or it can be used without any surface pretreatment even on the base of polyethylene, etc., and also has excellent adhesion to polypropylene or polyethylene material, and excellent flexibility and water resistance.

Description

UV Curing Coating Composition

The present invention relates to an ultraviolet curable coating film composition, and more particularly, to an ultraviolet curable resin composition having excellent adhesion and curability, and having excellent wettability to substrates such as polypropylene or polyethylene, and excellent adhesion and ultraviolet curability. It relates to a coating film composition.

In general, many plastic products that benefit our surroundings are indispensable as a resource to make life easier.

Plastics have unique properties depending on the type.They are light, inexpensive, and easy to process compared to materials such as glass and metal, and they can be used in automobile parts, electronic parts, construction materials, aircraft parts, cosmetic cases and telephones. It is applied in various fields that can be easily encountered in daily life.

However, to protect the surface of such a plastic product or to have a better appearance, the coating is applied.

At this time, various paints can be applied. Among them, UV-curable paints have excellent productivity compared to other paints, and due to the green advantage of emitting very little VOCs to the atmosphere, Has been applied across the field.

Plastics used for UV coating are variously used for acrylonitrile-butadiene-styrene (hereinafter referred to as ABS), polypropylene, polycarbonate, polyethylene, acrylic, fine bags, polyvinyl chloride, etc. Applies to ABS material.

This is because cosmetic cases, telephones, home appliances, etc. use ABS materials, and almost all of the plastic UV curable paints are for ABS coatings.

However, in recent years, polypropylene material is used for highway cards, safety sign sheets, etc., and UV coating is applied to it, and it is expected to emerge as a new market for ultraviolet curing paint.

This overcomes the conventional technical limitation that polypropylene cannot be painted due to its low surface tension. Polypropylene is not only lightweight, excellent in formability and chemical properties but also much cheaper than ABS in terms of price, and thus, it is a new alternative. This is because it is likely to lead the market.

However, even if UV curable paint is applied to highway card or safety sign sheet, the application of polypropylene is still difficult due to technical limitations.

On the other hand, the basic types and properties of polypropylene, difficulties in adhesion, and pretreatment methods are as follows.

Polymerization of naphtha and propylene from natural gas is used as a raw material to polymerize in a n-hexane solvent using a Ziegler-Natta catalyst to form isotactic polymers.

Polypropylene is the lightest and most transparent among the general purpose plastics with a density of 0.09 to 0.92. It is excellent in heat resistance, electrical insulation, chemical resistance and bending resistance and nontoxic, but has a low cold shock resistance.

In recent years, the product which superposed | polymerized ethylene and other olefinic monomers in order to improve the cold shock resistance of polypropylene is marketed as a molding material.

Polypropylene is mainly used in films, stools, various containers, automobile parts, fishing nets, ropes and fibers, and the like is classified according to the presence and structure of the copolymer.

In addition, polypropylene is a polymerized product of propylene with a catalyst, and its type is classified according to the stereoregularity of the methyl group as a substituent and the composition and structure of the copolymer.

Since polypropylene and copolymers thereof are composed entirely of hydrocarbon units, the surface of the polypropylene and the copolymer thereof is nonpolar, and thus hardly adheres.

On the other hand, one of the absolute standards for the maximum binding energy between paint and plastic body is wettability, which is determined by making a series of droplets on the solid surface and measuring the contact angle θ.

However, in the case of polypropylene, even traces of microscopic contamination in the surface of the ohm-strong unit make the contact angle large and adversely affect the adhesion due to the inherent low surface energy.

Therefore, in order to achieve maximum adhesion, the pretreatment must be carried out before applying the surface coating to polypropylene or polyethylene.

In order to apply basic plastic coatings, various methods of pretreatment of polypropylene surfaces have been developed to achieve better wetting properties: flame, plasma discharge, benzophenone / UV, corona Chemical pretreatment methods such as corona discharge or chromic sulfuric acid treatment.

However, among these methods, plasma or corona discharge methods require a vacuum chamber, and when the flame method is applied in a place where a high concentration of solvent such as a paint booth exists, there is a serious fire risk. The benzophenone / UV method is expensive and takes a long time.

In addition, the chemical pretreatment method has a problem of strong corrosion.

An object of the present invention is to solve the problem that the conventional polypropylene or polyethylene has a poor adhesion, such as pre-treatment during painting, UV curing type having excellent adhesion and curability prepared using rosin or rosin modified oligomer By containing a resin, when applied to an ultraviolet curable coating film composition, it is excellent in wettability on the surface of polypropylene or polyethylene resin, and provides an ultraviolet curable coating film composition having good chemical resistance, boiling resistance, moisture resistance, ultraviolet curability, and other cured product properties. There is.

UV-curable coating composition of the present invention for achieving the above object is 10 to 70 parts by weight of acid-modified rosin ester resin, 10 to 60 parts by weight of reactive monomer, 0.1 to 20 parts by weight of photoinitiator represented by the following formula (1), (2) or (3) It is characterized by containing 0-10 weight part of leveling agents and a small amount of additives.

Formula 1

Where

ego,

R ₃ is a hydrogen atom or a methyl group.

Formula 2

Wherein R is a hydrogen atom or a methyl group.

Formula 3

Wherein R is a hydrogen atom or a methyl group.

The present invention will be described in more detail as follows.

The ultraviolet curable resin used in the present invention may be prepared by the following method.

First, the compound represented by Chemical Formula 1 is esterified in the presence of a catalyst having a rosin represented by the following Chemical Formula 4 and an acrylate monomer having a double bond and an epoxy ring represented by the following Chemical Formula 5 at the same time in a 10: 1 to 10: 9.5 molar ratio. It is obtained by reaction.

Formula 4

Formula 5

In the above formula, R ₁ is a hydrogen atom or a methyl group.

In this case, the rosin may be selected from one or more of wood rosin (wood rosin), tall rosin (tall rosin), gum rosin (gum rosin) and polyethylene terephthalate rosin (PET rosin).

In addition, glycidyl methacrylate or glycidyl acrylate may be used as an acrylate monomer having a double bond and an epoxy ring represented by the formula (5).

As a method for producing an ultraviolet curable resin using a rosin alone, a mixture of polybisphenol phthalate or polybisphenol maleate is mixed with rosin, heated to 220-230 ° C. and dissolved therein, followed by a bifunctional or higher glycol or polyester polyol. To prepare a rosin copolyester having a final acid value of 20 to 50 by raising the reaction temperature to 260 ℃, and then to the rosin copolyester 10 having a monomer having a double bond and the epoxy ring represented by the formula (2): It is prepared by adding in a molar ratio of 1 to 10: 8 and reacting in the presence of a known catalyst.

The ultraviolet curable resin thus produced is particularly excellent in scratch resistance and flexibility.

Examples of the glycol having two or more functional groups include ethylene glycol, propylene glycol, neopentyl glycol, di-ethylene glycol, glycerin, trimethylol propane, pentaerythritol, dipentaerythritol, and polyester polyols represented by the following Chemical Formulas 6 or 7. One or more kinds can be selected and used.

Formula 6

(CH _{n + 2} OH) _n

Wherein n is an integer of 1-3.

Formula 7

(C _{n + 1} H _2n OH) _n

Wherein n is an integer of 4-5.

A UV curable resin prepared by mixing polybisphenol phthalate with rosin, glycerin, and then adding glycidyl methacrylate is represented by the following formula (9), and an ultraviolet curable resin prepared by mixing polybisphenol maleate with rosin Is represented by the following formula (10).

Formula 9

Wherein R and R ₁ are as defined above.

Formula 10

Wherein R and R ₁ are as defined above.

The polyester polyol is represented by the formula (8), and is prepared through the condensation reaction of an acid having two carboxyl groups and an alcohol having two hydroxy groups.

Formula 8

Wherein R ₄ and R ₅ are aliphatic or aromatic compounds having 2 to 10 carbon atoms,

n is an integer of 1-20.

In addition, the polyester polyol preferably has a hydroxyl value of 200 to 250 and a molecular weight of 450 to 560 in consideration of hardness and the like.

As the acid having two carboxyl groups used in the production of the polyester polyol, one or more selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, maleic acid and terephthalic acid may be used. As the alcohol, one or more selected from ethylene glycol, propylene glycol, neopentyl glycol and di-ethylene glycol can be used.

In another ultraviolet curable coating composition of the present invention, the resin added is a compound represented by Chemical Formula 2 or 3, and the fumaric acid is added to Levopimaric acid in the isomer of rosin represented by Chemical Formula 4. After addition of maleic anhydride to the adduct through Diels-Alder Reaction, the acid value is 150-C using a glycol represented by Formula 6 or 7 or a polyester polyol represented by Formula 8 After the acid-modified rosin ester of 20 was prepared, an acrylate monomer having a double bond and an epoxy ring represented by Chemical Formula 5 was added thereto.

Specifically, the UV-curable resin prepared by using acid-modified rosin is a levopimaric acid (Levopimaric), which is one of the isomers by first using the property of isomerization of the rosin represented by Chemical Formula 4 at a high temperature of 180 ° C. or higher. acid) and fumaric acid or maleic anhydride are added to the mixture by Diels-Alder Reaction, followed by reacting the glycol represented by Formula 6 or 7, or the polyester polyol represented by Formula 8. It is prepared by reacting an acrylate monomer having a double bond and an epoxy ring represented by the formula (5).

The ultraviolet curable resin represented by Chemical Formula 2 or 3 is a case of preparing fumaropimaric acid using fumaric acid, and the ultraviolet curable resin represented by Chemical Formula 2 is a case of using (CH ₄ OH) ₂ as glycol, The ultraviolet curable resin represented by Chemical Formula 3 is prepared by using (C ₅ H ₈ OH) ₄ as a glycol and reacting with a monomer having a double bond and an epoxy ring represented by Chemical Formula 5.

In addition, maleic anhydride may be prepared using maleic anhydride to react with a monomer having a double bond with a glycol and an epoxy ring. The structure thereof is also the same as shown in Chemical Formulas 2 and 3 above.

Examples of the acid which can be reacted with the above levopimaric acid include at least one of maleic anhydride, maleic acid, fumaric acid, citraconic acid (Citraconic Acid), and dimer acid (dimeric acid-unsaturated fatty acid polymerized by two molecules). Can be selected and used.

At this time, maleic anhydride exhibits an exothermic reaction with rosin at 90 ° C. or higher, and gradually increases the temperature to 180 ° C., and then the adduct reaction is completed. The required time at this time is about 1 to 2 hours depending on the reaction molar ratio.

On the other hand, fumaric acid is slow in reactivity and generates less heat due to structural steric hindrance. Therefore, starting at 185 ° C to increase the temperature to 220 ° C 4 hours to complete the addition reaction.

At this time, the reaction state was confirmed by IR, and the reaction molar ratio of rosin: fumaric acid or maleic anhydride was 1: 0.8 to 1: 0.1 to improve the adhesion by adjusting the acid value near the end of the reaction. desirable.

When this step is completed, the glycol represented by Chemical Formula 6 or 7 or the polyester polyol represented by Chemical Formula 8 is reacted, wherein the molar ratio of fumaropymic acid: glycol or polyester polyol is 3: 0.5 to 3: It is preferable to set it as 2.6, and it is preferable to make it react with 3: 0.6-3: 2.4 in the case of maleopimaric acid.

In addition, the reaction temperature and the reaction time was carried out for 4 hours at 270 ℃ for fumaropimaric acid, the final acid value was adjusted to 150 ~ 20, 2 to 4 hours at 240 ℃ in the case of maleopymic acid Final acid value was adjusted to 100-20.

At this time, it is preferable to perform the reaction while injecting nitrogen to facilitate the outflow of water and to prevent oxidation of the reactants.

The glycols that can be used here are ethylene glycol, propylene glycol, diethylene glycol, 1,6-hexanediol, 1,3-butylene glycol, 1,4-butylene glycol, glycerin, trimethylolpropane, pentaerythritol and dipenta One or more types can be selected and used out of erythritol.

On the other hand, the polyester polyol is produced by the condensation reaction of an acid having two carboxyl groups and an alcohol having two hydroxyl groups, and using a polyester polyol having a hydroxyl value of 200 to 250 and a molecular weight of 450 to 560 in consideration of the hardness of the cured coating film. It is good.

The acid having two carboxyl groups and the alcohol having two hydroxy groups used in the preparation of the polyester polyol are as described above.

It is preferable to use two or three kinds of such glycols, or a combination of polyester polyols and a constant molar ratio. In this case, the reaction temperature should be changed while changing the reaction temperature to 100-200 ° C. To minimize this.

Into the maleic modified rosin ester or fumaric modified rosin ester prepared above, an acrylate monomer having a double bond and an epoxy ring represented by Chemical Formula 5 was added thereto, followed by a reaction at 115 ° C. for 6 hours to give a final acid value of 5 or less. Curable resins can be produced in the presence of a known catalyst.

The maleic modified rosin ester and the acrylate monomer may be prepared in a 1: 0.1 to 1: 0.5 molar ratio, and the fumaric modified rosin ester and the acrylate monomer may be prepared in a 1: 0.2 to 1: 0.6 molar ratio. have.

However, in order to have excellent adhesion to polypropylene or polyethylene substrates and finally good adhesion to vapor deposition films when applied to UV-curable coating compositions, the type of glycol and the reaction molar ratio are selected and the final acid value. The control of, and the proportion of acrylate monomers is very important.

Therefore, in order to achieve the object of the present invention, it is preferable to react rosin and maleic anhydride or fumaric acid in a molar ratio of 1: 0.1 to 1: 0.8 when producing an ultraviolet curable resin, wherein 0.8 mole of maleic anhydride or fumaric acid is used for rosin. If it exceeds, the coating film becomes too hard, and if it is less than 0.1 mole, the coating film may become weak.

In addition, when reacting with a glycol or polyester polyol, maleophymaric acid or fumaropymic acid: glycol or polyester polyol is preferably in a molar ratio of 3: 0.5 to 3: 2.6. When the coating composition is applied, adhesion is poor with time and less than 0.5 moles causes wrinkles on the surface during curing.

Finally, when the maleic modified rosin ester or fumaric modified rosin ester is reacted with the acrylate monomer, the molar ratio is preferably 1: 0.1 to 1: 0.6. This may become poor, and if it is less than 0.1 mol, the scratch resistance of the cured coating film is inferior.

Finally, the ultraviolet curable resin added in the present invention is a bifunctional or higher glycol, polybisphenol phthalate or polybisphenol maleate to the adduct obtained by adding fumaric acid and maleic anhydride to the levocimaric acid through Diels-Alder reaction. After applying each of the rosin copolyester to prepare, it is also possible to use those obtained by reacting with glycidyl methacrylate and glycidyl acrylate represented by the formula (5).

The ultraviolet curable resin obtained by the above method contains 10 to 70 parts by weight of the total coating composition, if the content is less than 10 parts by weight, the heat resistance, water resistance and chemical resistance is lowered, if the coating film exceeds 70 parts by weight The appearance and adhesion of the film becomes poor.

More preferably, the content of the ultraviolet curable resin is 25 to 60 parts by weight.

On the other hand, in the ultraviolet curable coating film composition of the present invention, the reactive monomer is at least one compound selected from monofunctional monomers, bifunctional monomers, and polyfunctional monomers.

Here, the monofunctional monomer is 2-ethylhexyl acrylate, octadecyl acrylate, stearyl acrylate, behenyl acrylate, tridecyl methacrylate, nonyl phenol ethoxylate monoacrylate, β-carboxyethyl acrylate, Isobornyl acrylate, tetrahydrofurfuryl acrylate, tetrahydroperfuryl methacrylate, 4-butylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate, ethoxyethoxyethyl acrylate At least one selected from the group consisting of latex and ethoxylated monoacrylate.

And, the bifunctional monomer is 1,6-hexanediol diacrylate, triphenyl glycol diacrylate, butanediol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate , Neopentyl glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate At least one selected from polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, and ethoxylated neopentyl glycol diacrylate.

The polyfunctional monomer is one or more selected from pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate and alkoxylated tetraacrylate.

Among the above monofunctional monomers, bifunctional monomers, and polyfunctional monomers, in particular, polyfunctional monomers are used to improve scratch resistance of the paint surface. The content of the polyfunctional monomers is preferably 10 to 30 parts by weight, If the content is less than 10 parts by weight, scratch resistance is significantly lowered, and if it is more than 30 parts by weight, the adhesion is poor.

Therefore, it is preferable to use a combination of a bifunctional monomer and a monofunctional monomer, and considering the scratch resistance and adhesion, the polyfunctional monomer, the bifunctional monomer and the monofunctional monomer are added by mixing in a 3: 2: 1 weight ratio. It is desirable to.

Such a reactive monomer is contained in 10 to 60 parts by weight of the ultraviolet curable coating composition, if the content is less than 10 parts by weight, there is a problem that the scratch resistance is significantly lowered, if more than 60 parts by weight of the surface scratches due to the increase in the instantaneous curing rate There is a problem that arises.

On the other hand, photoinitiators are conventional polymerization initiators exhibiting activity by ultraviolet rays, and in particular, benzophenone series, benzyldimethyl ketal series, acetophenone series, adraquinone series, thioxanthone series, acylphosphine oxide series, aminoalkylphenone series, As a hydroxyalkyl phenone type, a dialkoxy acetophenone type, and the benzyl ketal type, 2-hydroxy-1, 2- diperphenyl ethanone, 2-ethoxy-1, 2- diphenyl ethanone, 2- Isopropyl-1,2-phenyl ethanone, 2-butoxy-1,2-diphenyl ethanone, 2-isobutoxy-1,2-diphenyl ethanone, 2,2-dimethoxy-1,2- Diphenyl ethanone, 2,2-dibutoxy-1-phenyl ethanone, 1-hydroxycyclohexylphenyl ketone, dimethoxyhydroxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2 -Methyl propanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propanoone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -buta Non or 3,6-bis [2-methyl-2-morpholino (propa) Nonyl)]-butylcarbazole, and bis (2,4,6-trimethyl benzoyl) -phenylphosphine oxide alone or in a mixture thereof.

In particular, it is preferable to mainly use a benzophenone-based, acetophenone-based, benzyl ketal-based or phosphine oxide-based photoinitiator, which is to improve the lack of curing due to the internal unsaturated group in the structure, two or three of these photoinitiators It can mix and use 1: 1: 1: 3 by weight ratio.

In the coating composition of the present invention, the leveling agent is a compound of silicone diacrylate or silicone polyacrylate, and its content is 0 to 10 parts by weight of the total coating composition.

If semi-gloss or matte is required for the coating composition, 0 to 10 parts by weight of the matting agent may be added in the overall coating composition according to the required gloss.

In addition, as the additive, chlorinated polypropylene or chlorinated polyethylene may be used, and the content thereof is 0.5 to 1 parts by weight, which is a very important factor for time-lapse adhesion after coating film curing.

If the content is less than 0.5 parts by weight, adhesion with time is poor, and if more than 1 part by weight, compatibility with the paint is poor and the coating film becomes cloudy.

Painting of plastic moldings is accomplished by spraying, depositing, or roller coating, which may be advantageous depending on the material of the plastic, the shape of the molding and the thickness of the coating.

Different viscosity is required depending on the coating method, which can be used by adjusting the viscosity by adding an appropriate amount of volatile solvent.

In addition, the volatile solvent serves to facilitate the painting work and smooth the appearance.

At this time, the solvent which can be used is ketone, acetate, an aromatic compound, a high boiling point aliphatic hydrocarbon compound, etc., It can select from these and can use individually or in mixture.

It is preferable that the usage-amount makes a varnish: solvent 4: 1-1: 4 weight ratio.

In addition, as other additives, an antifoaming agent or the like can be used in accordance with known compound properties.

The UV curable coating composition thus prepared may be used by coating it on a metal vacuum deposition molded article made of polypropylene or polyethylene of cosmetics, household goods and industrial products.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited by the Examples.

Preparation Example 1

714.1 parts by weight of rosin was placed in a four-necked round flask, and the temperature was raised to 180 ° C after attaching a condenser, a stirrer, a thermometer, and an H tube. After lowering the reaction temperature to 90 ℃ 50 parts by weight of maleic anhydride was added and slowly heated to maintain the reaction for 2 hours at 180 ℃. At this time, the nitrogen injection was started.

Thereafter, 0.2 parts by weight of zinc acetate, which was a catalyst, was added, and 50 parts by weight of glycerin was added dropwise into a panel to be slowly injected.

When the input is completed, the reaction temperature is raised to 220 ° C. and the reaction is maintained for 2 hours. At this time, the water flowing out through the H tube is removed from time to time, and the acid value is measured. When the acid value reaches 100, the reaction temperature is lowered to 115 ° C. and the catalyst 0.1 parts by weight of triphenylphosphine was added thereto, and 185.6 parts by weight of glycidyl acrylate was added dropwise to carry out a maintenance reaction for 6 hours to prepare an ultraviolet curable resin having a final acid value of 5.

Preparation Example 2

656.4 parts by weight of rosin was placed in a four-necked round flask, and the temperature was raised to 180 ° C after attaching a condenser, a stirrer, a thermometer, and an H tube. Thereafter, the reaction temperature was lowered to 90 ° C., and then 50 parts by weight of fumaric acid was added thereto, and the temperature was gradually raised to maintain the reaction at 220 ° C. for 2 hours. At this time, the nitrogen injection was started.

Then, 0.2 parts by weight of zinc acetate as a catalyst was added, and 105 parts of pentaerythritol was slowly added. When the addition is completed, the reaction temperature is raised to 240 ° C. and the reaction is maintained for 2 hours. At this time, the water flowing out through the H tube is often removed, and the acid value is measured. When the acid value reaches 100, the reaction temperature is lowered to 115 ° C. and the catalyst 0.1 parts by weight of triphenylphosphine was added thereto, and 185.8 parts by weight of glycidyl acrylate was added dropwise to carry out a maintenance reaction for 6 hours to prepare an ultraviolet curable resin having a final acid value of 5.

Preparation Example 3

648.0 parts by weight of rosin was placed in a four-necked round flask, and a condenser, a stirrer, a thermometer, and an H tube were mounted, and the temperature was raised to 220 ° C.

After lowering the reaction temperature to 90 ℃ 50 parts by weight of fumaric acid was added slowly and the temperature was slowly maintained at 220 ℃ for 2 hours. At this time, the nitrogen injection was started.

Thereafter, 0.2 parts by weight of zinc acetate, a catalyst, and 116.6 parts by weight of glycerin were slowly added. When the input is completed, the reaction temperature is raised to 240 ° C. and the reaction is maintained for 2 hours. At this time, the water flowing out through the H tube is removed from time to time, and the acid value is measured. 0.1 parts by weight of triphenylphosphine was added thereto, and 183.3 parts by weight of glycidyl acrylate was added dropwise to carry out a maintenance reaction for 6 hours to prepare an ultraviolet curable resin having a final acid value of 5.

Example 1

500 parts by weight of the ultraviolet curable resin prepared according to Preparation Example 1, 114.2 parts by weight of pentaerythritol triacrylate, UCB company 114.2 parts by weight of trimethylolpropane triacrylate, 152.3 parts by weight of 1,6-hexanediol diacrylate, 76.3 parts by weight of hydroxypropyl acrylate, 10 parts by weight of benzophenone, 23 parts by weight of benzyldimethylketan (hereinafter referred to as BDK, manufactured by Longchem), 10 parts by weight of UCB Ebecryl 350, and a viscosity of 300 cps at 25 ° C. An ultraviolet curable coating film composition was prepared.

Example 2

500 parts by weight of ultraviolet curable resin prepared according to Example 2, 114.2 parts by weight of pentaerythritol triacrylate, UCB's 114.2 parts by weight of trimethylolpropane triacrylate, 152.3 parts by weight of 1,6-hexanediol diacrylate, 76.3 parts by weight of ethylhexyl acrylate, 20 parts by weight of benzophenone, 13 parts by weight of BDK and 10 parts by weight of Ebecryl 350 manufactured by UCB were stirred to prepare an ultraviolet curable coating composition having a viscosity of 320 cps at 25 ° C.

Example 3

584.3 parts by weight of the ultraviolet curable resin prepared according to Preparation Example 3, 228.4 parts by weight of trimethylolpropane triacrylate, 152.3 parts by weight of 1,6-hexanediol diacrylate, 10 parts by weight of BDK, 15 parts by weight of benzophenone, UCB 10 parts by weight of Ebecryl 350, Inc. was prepared to prepare an ultraviolet curable coating composition having a viscosity of 330 cps at 25 ° C.

Comparative Example 1

444 parts by weight of Ebecryl 3700 of epoxy acrylate UCB, 200 parts by weight of pentaerythritol triacrylate, 200 parts by weight of trimethylolpropanetriacrylate, 106 parts by weight of 1,6-hexanediol diacrylate, 40 parts of Darocure 1173 and 10 parts by weight of UCB Ebecryl 350 were stirred to prepare an ultraviolet curable coating composition having a viscosity of 400 cps at 25 ° C.

Experimental Example

UV-curable coating composition according to Examples 1 to 3 and Comparative Example 1 was applied to the metal vacuum deposition degree of the cosmetic case was tested for physical properties.

At this time, in order to spray coating, methyl ethyl ketone and toluene, which are mixed solvents, were mixed in a 1: 1 weight ratio to the UV curable coating composition, and diluted to 50% by weight. was applied, radiation-curing in two minutes to evaporate the solvent at 50 ℃ dried curing energy 800mJ / ㎠: after (UV irradiator US American Ultra Violet company), aluminum was vacuum vapor deposited in a vacuum of ^10-4 Torr. At this time, Haniljin Co., Ltd. product was used as the vacuum evaporator.

At this time, the cured coating film thickness was 15 micrometers.

The heat resistance was measured after 96 hours in a 180 ℃ oven, the adhesion was measured by JIS 0202 using a cross cut, the hot water resistance was the adhesion after 240 hours in 40 ℃ hot water Measured.

Acid resistance among chemical resistance was measured after immersion in 1% sulfuric acid solution for 10 minutes at acid temperature, and alkali resistance was measured after immersion for 10 minutes in 1% sodium hydroxide solution at room temperature, and 3% sodium chloride at room temperature. It was measured after immersion in the solution for 10 minutes.

Example 1 Example 2 Example 3 Comparative Example 1 Heat resistance Good Good Good Bad Adhesion 100/100 100/100 100/100 0/100 Hot water resistance 100/100 100/100 100/100 0/100 Chemical resistance Acid resistance Good Good Good Bad Alkali resistance Good Good Good Bad Saline resistance Good Good Good Bad

From the results in Table 1 above, in the case of the ultraviolet curable coating film composition containing the ultraviolet curable resin using the acid-modified rosin ester as in the present invention, adhesion to the base material such as polypropylene, heat resistance, It can be seen that the water resistance and chemical resistance is excellent.

As described in detail above, a coating film composition containing an ultraviolet curable resin having excellent adhesion and curability prepared through rosin or modified rosin according to the present invention, and adding a reactive monomer, a photoinitiator, a leveling agent, etc. Polypropylene or polyethylene, such as cosmetics, household goods, and industrial goods, which require vacuum deposition or other adhesion promotion, can be usefully used for holding the material because of its excellent resistance to heat, water, and chemicals.

Claims (21)

10 to 70 parts by weight of the acid-modified rosin ester resin represented by the following Chemical Formulas 1, 2 or 3, 10 to 60 parts by weight of reactive monomer, 0.1 to 20 parts by weight of photoinitiator, 0 to 10 parts by weight of leveling agent and a small amount of additives UV curable coating composition. Formula 1 Where ego, R ₃ is a hydrogen atom or a methyl group. Formula 2 Wherein R is a hydrogen atom or a methyl group. Formula 3 Wherein R is a hydrogen atom or a methyl group. According to claim 1, wherein the acid-modified rosin ester resin represented by the formula (1) is a rosin represented by the following formula (4) and an acrylate monomer having a double bond and a double bond at the same time 10: 1 to 10: 9.5 An ultraviolet curable coating film composition obtained by esterification in the presence of a catalyst at a molar ratio. Formula 4 Formula 5 In the above formula, R ₁ is a hydrogen atom or a methyl group. According to claim 2, wherein the rosin represented by the formula (4) is at least one selected from wood rosin (Tall rosin), Tall rosin (Gall rosin), gum rosin (Gum rosin) and polyethylene terephthalate rosin (PET rosin) UV curable coating composition, characterized in that the compound. According to claim 1 or 2, wherein the acid-modified rosin ester is a final acid value of 50 to 20 by reacting a polybisphenol phthalate or polybisphenol maleate with a glycol or polyester polyol of at least two functional groups to a rosin represented by the formula (4) After preparing a phosphorus rosin copolyester, UV curable coating composition, characterized in that it is prepared by adding an acrylate monomer having a double bond and an epoxy ring represented by the formula (5). The method of claim 1 or 3, wherein the acrylate monomer having a double bond and an epoxy ring represented by the formula (2) is glycidyl methacrylate or glycidyl acrylate. The acid-modified rosin ester resin of claim 1, wherein the acid-modified rosin ester resin represented by Formula 2 or 3 is added to fumaric acid or maleic anhydride to levopimaric acid among isomers of the rosin represented by Formula 4. After the addition (Adduct) through the reaction (Diels-Alder Reaction), acid-modified rosin ester having an acid value of 150 to 20 by using a glycol represented by the following formula (6) or (7) or a polyester polyol represented by the following formula (8) And an ultraviolet curable coating composition prepared by reacting an acrylate monomer having a double bond and an epoxy ring represented by Formula 5 at the same time. Formula 6 (CH _{n + 2} OH) _n Wherein n is an integer of 1-3. Formula 7 (C _{n + 1} H _2n OH) _n Wherein n is an integer of 4-5. Formula 8 Wherein R ₄ and R ₅ are aliphatic or aromatic compounds having 2 to 10 carbon atoms, n is an integer of 1-20. According to claim 1 or 6, wherein the acid-modified rosin ester resin represented by the formula (2) or 3 is reacted with levopimaric acid (Levopimaric acid), and fumaric acid or maleic anhydride in a 1: 0.1 to 1: 0.8 molar ratio UV curable coating film composition, characterized in that obtained. 7. The ultraviolet light according to claim 6, wherein the acid capable of addition reaction with levopimaric acid is at least one compound selected from maleic anhydride, maleic acid, fumaric acid, citraconic acid, and dimeric acid. Curable coating composition. 7. The UV curable coating composition according to claim 6, wherein the content ratio of acid-modified rosin and glycol or polyester polyol added using an acid capable of the addition reaction is 3: 0.5 to 3: 2.6 molar ratio. According to claim 6, wherein the glycol represented by the formula (6) or 7 is characterized in that at least one selected from ethylene glycol, propylene glycol, neopentyl glycol, di-ethylene glycol, glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol An ultraviolet curable coating film composition. The method according to claim 6, wherein the polyester polyol represented by Formula 8 is prepared by the condensation reaction of an acid having two carboxyl groups and an alcohol having two hydroxy groups, having a hydroxyl value of 200 to 250 and a molecular weight of 450 to 560. An ultraviolet curable coating film composition. The acid having two carboxyl groups is at least one compound selected from oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, phthalic acid, maleic acid and terephthalic acid, and the alcohol having two hydroxy groups is ethylene glycol and propylene. UV curable coating composition, characterized in that at least one selected from glycol, neopentyl glycol and di-ethylene glycol. The acid-modified rosin ester having an acid value of 150 to 20 and glycidyl methacrylate or glycidyl acrylate, which are acrylate monomers represented by the formula (4), are reacted at a molar ratio of 1: 0.1 to 1: 0.6. Ultraviolet curable coating composition, characterized in that. According to claim 1, wherein the acid-modified rosin ester resin is a bifunctional or higher glycol and polybisphenol phthalate or polybisphenol to the adduct obtained by adding fumaric acid or maleic anhydride to the levocimaric acid of claim 6 through Diels-Alder reaction After the rosin copolyester is prepared by applying malate, UV curable coating composition characterized in that it is prepared by reacting with glycidyl methacrylate or glycidyl acrylate represented by the formula (2). The UV curable coating composition according to claim 1, wherein the reactive monomer is at least one compound selected from a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer. 16. The monofunctional monomer according to claim 15, wherein the monofunctional monomer is 2-ethylhexyl acrylate, octadecyl acrylate, stearyl acrylate, behenyl acrylate, tridecyl methacrylate, nonyl phenol ethoxylate monoacrylate, β- Carboxyethyl acrylate, isobornyl acrylate, tetrahydroperfuryl acrylate, tetrahydrofurfuryl methacrylate, 4-butylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate An ultraviolet curable coating film composition, characterized in that at least one selected from oxyethoxyethyl acrylate and ethoxylated monoacrylate. The method of claim 15, wherein the bifunctional monomer is 1,6-hexanediol diacrylate, triphenylglycol diacrylate, butanediol diacrylate, 1,3-butylene glycol dimethacrylate, 1,6-hexane Diol dimethacrylate, neopentyl glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, triethylene glycol dimethacrylate, An ultraviolet curable coating composition comprising at least one selected from polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, dipropylene glycol diacrylate, and ethoxylated neopentyl glycol diacrylate. The ultraviolet curable coating film according to claim 15, wherein the polyfunctional monomer is at least one selected from pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, ditrimethylolpropane tetraacrylate, and alkoxylated tetraacrylate. Composition. 16. The UV curable coating composition according to claim 1 or 15, wherein the reactive monomer is a mixture of a monofunctional monomer, a bifunctional monomer, and a polyfunctional monomer in a 1: 2: 3 weight ratio. The method of claim 1, wherein the photoinitiator is 2-hydroxy-1,2-diperphenyl ethanone, 2-ethoxy-1,2-diphenyl ethanone, 2-isopropyl-1,2-phenyl ethanone, 2-butoxy-1,2-diphenyl ethanone, 2-isobutoxy-1,2-diphenyl ethanone, 2,2-dimethoxy-1,2-diphenyl ethanone, 2,2-dibutoxy -1-phenyl ethanone, 1-hydroxycyclohexylphenyl ketone, dimethoxyhydroxy acetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methyl propanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino propane, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 3,6-bis [2-methyl An ultraviolet curable coating composition, characterized in that it is a single or a mixture thereof selected from 2-morpholino (propanoyl) -butylcarbazole and bis (2,4,6-trimethyl benzoyl) -phenylphosphine oxide. Metal vacuum deposition molded article of polypropylene or polyethylene coated with the ultraviolet curable coating composition of claim 1.