KR20040003345A - Composition for photo-curable resin with high weatherproofness for color coating, and article using the same - Google Patents

Abstract

PURPOSE: A UV curable composite resin composition for color coating and a product prepared by using the composition are provided, to improve weather resistance, screening power and curing physical properties. CONSTITUTION: The UV curable composite resin composition comprises 40-60 wt% of a prepolymer having at least two acryl groups; 20-40 wt% of a vinyl ether monomer; 3-9 wt% of free radical and cationic photoinitiators; 5-20 wt% of an organic or inorganic pigment; 0.5-1 wt% of a dispersant; and 0.5-8 wt% of a reactive urethane acrylate derivative represented by the formula 1 where both UV absorption functional group and hindered amine group are introduced, wherein Acryl is a monofunctional or polyfunctional acrylate group, R is a compound derived from a trifunctional isocyanate compound, UVA is a benzophenone group or a triazole group; and HALS is 4-amino-2,2,6,6-tetramethylpiperidine or 4-hydroxy-2,2,6,6-tetramethylpiperidine.

Description

Composition for photo-curable resin with high weatherproofness for color coating, and article using the same}

The present invention relates to an ultra-weather photocurable resin composition for color coating and a product using the same, and more specifically, it contains weather-resistant urethane acrylate derivatives into which a UV absorbing functional group and a hindered amine group are simultaneously introduced into a molecule. It relates to an excellent weather-resisting photo-curable resin composition for color coating and excellent thickening, excellent curing properties, and excellent curing properties, and a product using the same.

In recent years, photocurable coatings have a market growth rate of more than 10% every year due to the advantages of fast productivity and excellent surface properties. In particular, the range of applications from small electronic products such as mobile phones to flooring is also expanding. However, due to the curing property of the photocurable coating, it is difficult to add a color by adding a pigment (Pigment) to the coating itself. Pigment particles added to impart color cause light absorption and scattering, causing various problems in curing and final properties of the coating. For example, a pigment added coating agent is often incomplete internal curing in the case of thick film coating, but there is a problem that it is difficult to show sufficient hiding power when reducing the pigment usage. In addition, the photocurable coating agent is susceptible to ultraviolet rays and easily yellowed, causing mechanical property degradation, etc., which presents problems in long-term use.

In order to solve the above problems, a method of using a long wavelength initiator and a short wavelength initiator by mixing or adding a low molecular weight light stabilizer to the photocurable coating has been introduced. However, in the above method, it is difficult to achieve sufficient curing at the bottom of the coating layer when the UV-curable color coating including the pigment, and the low molecular weight light stabilizer is difficult to extract its performance due to the heat during processing or the surrounding environment after processing. There is a problem.

In addition, US Patent No. 4,156,035 discloses a method of curing an epoxy resin and an acrylic monomer by mixing Onium Salt and a free radical photoinitiator to solve the above problems. However, acrylic monomers are problematic because they are not only toxic to the skin but also emerging as carcinogens.

On the other hand, Japanese Patent Application Laid-Open No. 52-73886, Japanese Patent Laid-Open No. 58-122487, Japanese Patent Laid-Open No. 58-47030, Japanese Patent Laid-Open No. 58-194931, Japanese Patent Laid-Open No. 59-122487, and Japanese Patent Laid-Open No. 61-81441 Japanese Patent Application Laid-Open No. 61-176662 discloses a synurate derivative of diamine having an ether group in a molecule, but the stabilizing effect of these compounds is still insufficient. There is also a difficulty in the industrial utilization due to the compatibility issue.

Therefore, in order to solve the problems described above, research on the synthesis of the new photoinitiator and the light stabilizer, the blending, and curing process are actively conducted, but the market growth rate of the photocurable coating agent is increasing day by day. I can't follow. Therefore, there is a need for a new coating resin formulation and curing system that can solve the problems of the above-mentioned photocurable coating for color coating.

Accordingly, the present inventors have steadily researched to obtain a resin composition having excellent weather resistance and exhibiting effective photocuring properties even in a pigment-containing state, and thus, a compound having an intramolecular photocurable UV absorbing functional group and a photostable functional group is applied simultaneously. The resin composition which showed the outstanding weather resistance and showed the outstanding hardened | cured material property by the composite photocuring characteristic was obtained, and this invention was completed based on this.

Accordingly, an object of the present invention is to provide a photocurable resin composition for color coating having excellent weather resistance using a reactive acrylic derivative having a light absorbing functional group and a light stable functional group at the same time.

Another object of the present invention is to provide a photocurable resin composition for color coating having excellent cured properties in a composite photocuring system.

Still another object of the present invention is to provide a product using the photocurable resin composition for color coating.

Color-coated photocurable resin composition of the present invention for achieving the above objects and other objects is 40 to 60% by weight of a prepolymer having at least two acrylic groups, 20 to 40% by weight of vinyl ether monomer, free radical type and cationic light Reactive urethane represented by the following formula 1, wherein 3 to 9% by weight of a initiator mixture, 5 to 20% by weight of an organic or inorganic pigment, 0.5 to 1% by weight of a dispersant, and an intramolecular UV absorbing functional group and a hindered amine group were simultaneously introduced. 0.5-8% by weight of acrylate derivatives:

Wherein Acryl is a monofunctional or polyfunctional acrylate group, R is a compound derived from trifunctional isocyanate, UVA is a benzophenone group or a triazole group, and HALS is 4-amino-2,2,6, 6-tetramethyl piperidine or 4-hydroxy-2,2,6,6-tetramethyl piperidine.

Products using the color coating photocurable resin composition of the present invention for achieving the above another object is a carbonate resin, methyl methacrylate resin, vinyl chloride resin, polyethylene terephthalate resin using the photocurable resin composition for color coating Or coated with a film thickness of 20 to 120 占 퐉 on the surface of a product made of these composite materials and treated at a temperature of 30 to 90 ° C. for 1 to 20 minutes, followed by ultraviolet curing or 40 to 40 minutes after the ultraviolet curing. Prepared by treatment for 1 to 25 minutes at a temperature of 90 ℃.

Hereinafter, the present invention will be described in more detail.

As described above, in the present invention, by using a reactive acrylic derivative having a light absorbing functional group and a light stable functional group at the same time, it is excellent in weatherability and excellent hiding power, and excellent in hardened material, which can harden a thick film. There is provided a burnable resin composition and a product using the same.

The photocurable resin composition for color coating having excellent weather resistance of the present invention includes 40 to 60% by weight of a prepolymer having at least two acrylic groups, 20 to 40% by weight of a vinyl ether monomer, and a mixture of free radical and cationic photocuring initiators 3 to 9 Weight percent, 5 to 20 weight percent of organic or inorganic pigments, 0.5 to 1 weight percent of a dispersant, and 0.5 to 8 weight percent of reactive urethane acrylate derivatives simultaneously introduced with an intramolecular ultraviolet absorbing functional group and a hindered amine group.

The prepolymers used in the present invention are bifunctional to polyfunctional acrylic resins having at least two acrylic groups, for example polyester acrylates, urethane acrylates, epoxy acrylates, and partially having silicone acrylates and acrylic groups. Epoxy resins and the like. In this case, the amount of the prepolymer is preferably 40 to 60% by weight. When the amount of the prepolymer is less than 40% by weight, the physical properties of the coating film are lowered. When the amount of the prepolymer is higher than 60% by weight, the viscosity is too high. There is a problem.

The vinyl ether monomers used in the present invention include 4-cyclohexane dimethanol vinyl ether, hydroxy butyl vinyl ether, cyclohexyl vinyl ether, and the like. Currently commercially available products include RAPI-CURE of ISP Corporation (ISP). CHVE, RAPI-CURE HBVE, and RAPI-CURE CVE. In this case, the amount of the vinyl ether monomer used is preferably 20 to 40% by weight. If the amount of the vinyl ether monomer is less than 20% by weight, the viscosity is increased, so that the coating process is difficult. The physical properties of are lowered.

The initiator used in the present invention is a mixture of free radicals and cationic photocuring initiators, and the free radicals include 1-hydroxycyclohexyl-phenyl ketone, α, α-dimethoxy-α-hydroxy acetophenone, 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propane-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like. Commercially available products include Irgacure 184, Darocur 1173, Irgacure 907, and Irgacure 819 from Sivage, Switzerland. In addition, the cationic photoinitiators include triaryl sulfonium hexafluorophosphate, triaryl sulfonium hexafluoroantimonate, and iarylodonium hexafluoroantimonate, and are currently commercially available products. SarCat KI85, SarCat SR1010, SarCat SR1011, SarCat SR1012, and the like. At this time, the amount of the initiator mixture is preferably 3 to 9% by weight. If the amount of the initiator mixture is less than 3% by weight, it is difficult to sufficiently cure the coating film, thereby deteriorating the physical properties. Due to the initiator, weather resistance is lowered.

Pigments used in the present invention include organic or inorganic black, white, yellow, yellow, orange, red, green and blue pigments or these Pigments prepared from composites of these; and the like. At this time, it is preferable that the usage-amount of the said pigment is 5-20 weight%, and when the usage-amount of the said pigment is less than 5 weight%, it is difficult to provide sufficient hiding power, and when it exceeds 20 weight%, hardened | cured material property is inferior.

As a dispersant used in the present invention as a commercially available product, Disperbyk-115, Disperbyk-160, Disperbyk-161, Disperbyk-162, Disperbyk-162, Disperbyk-164, and Disperbyk- from BYK-Chemie. 182 and the like can be used. At this time, the amount of the dispersant may vary depending on the size of the pigment particles, preferably 0.5 to 1% by weight.

On the other hand, the reactive urethane acrylate derivatives used in the present invention is disclosed in the patent filed by the applicant of the Korean Patent Application No. 2002-19493 dated April 10, 2002. The contents of the method for producing a reactive urethane acrylate are all included in the present invention. According to the patent, the reactive urethane acrylate derivative is a reactive urethane acrylate in which an intramolecular ultraviolet absorber and a hindered amine group are introduced at the same time.

Formula 1

Wherein Acryl is a monofunctional or polyfunctional acrylate group, R is a compound derived from trifunctional isocyanate, UVA is a benzophenone group or a triazole group, and HALS is 4-amino-2,2,6, 6-tetramethyl piperidine or 4-hydroxy-2,2,6,6-tetramethyl piperidine.

At this time, the amount of the reactive urethane acrylate is 0.5 to 8% by weight, preferably 0.5 to 5% by weight is good, if the amount of the reactive urethane acrylate is less than 0.5% by weight can provide an effective light stability. If it exceeds 8 weight%, the cured | curing material property of a coating film will fall significantly.

Meanwhile, as the Acryl, a compound represented by the following Chemical Formula 2a, Chemical Formula 2b, Chemical Formula 2c, or Chemical Formula 2d is preferable:

Wherein R ₁ is hydrogen, methyl or OC _n H _{2n + 1} , n is an integer from 1 to 18, and R ₂ is a compound represented by the following Formula 2e, 2f, 2g:

Wherein n is an integer from 1 to 18.

In addition, the UVA is preferably a compound represented by the following general formula (3a) or (3b):

Wherein n is an integer from 1 to 18.

On the other hand, the HALS is preferably a compound represented by the following formula (4a) or (4b):

Wherein R ₁ is hydrogen, methyl or OC _n H _{2n + 1} .

In addition, R is preferably a compound represented by the following Chemical Formula 5a or the following Chemical Formula 5b:

Wherein n is an integer from 1 to 18.

On the other hand, the reactive urethane acrylate represented by the formula (1) is put 0.005 ~ 0.1 mol of trifunctional isocyanate in an organic solvent and maintained at a temperature of 25 ~ 90 ℃, in the presence of a tin-based catalyst 0.005 mol to 0.1 mol And 0.005 to 0.1 mole of the hindered amine light stabilizer was added dropwise for 30 minutes to 4 hours, and then reacted for 30 minutes to 5 hours while maintaining the temperature at 40 to 80 ° C, followed by 0.005 to 0.1 mole of acrylate containing hydroxy group. It is added dropwise and reacted for 1 to 8 hours. At this time, when the reaction molar ratio for each of the components is outside the above range, a gel is formed or coloring occurs.

On the other hand, the organic solvent is selected from the group consisting of tetrahydrofuran, anhydrous ether, diethyl ether, hexane, toluene and benzene.

In addition, the acrylate-containing acrylate is dipentaryl tritol pentaacrylate, pentaaryl tritol triaryl ether, trimethylol propane diaryl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate One selected from the group consisting of hydroxy propyl acrylate, and hydroxy propyl methacrylate.

In the present invention, by adding the reactive urethane acrylate derivative represented by the formula (1) to the photocurable resin composition to provide a photocurable resin composition for color coating excellent in weather resistance, environmentally friendly, and excellent curing properties in a composite photocuring system can do.

In addition, according to the present invention, the photocurable resin composition is applied to the surface of a product prepared as a carbonate resin, methyl methacrylate resin, vinyl chloride resin, polyethylene terephthalate resin or a composite material thereof, and the appropriate temperature There is provided a product prepared by curing at or after UV curing or by treating at an appropriate temperature after UV curing.

At this time, the thickness of the coating film is suitable 20 ~ 120㎛, if the thickness of the coating film is less than 20㎛ the hiding power is lowered, if it exceeds 120㎛ it is difficult to completely cure the coating film. In addition, the coating film is preferably treated for about 1 to 20 minutes at a temperature of 30 ~ 90 ℃, if the large deviation from the temperature and time conditions range, the surface wrinkles easily due to the difference in shrinkage between the inside and the surface of the coating film, the coating film A decrease in adhesion due to internal hardening may occur.

Hereinafter, the production method and effects of the present invention will be described in detail with reference to the following examples and comparative examples, but the scope of the present invention is not limited to the following examples.

Preparation Example 1

This was carried out in the same manner as in Example 1 of Korean Patent Application No. 2002-19493 filed by the applicant of April 10, 2002.

In a 100 ml three-necked flask equipped with an oil bath, thermometer, reflux cooler, dropping funnel, and magnetic sterling bar, 0.01 mol of trifunctional isocyanate (trade name: Tolonate HDT, Rhodia Co., Ltd.) and 30 ml of toluene were added and the temperature was raised to 50 ° C while stirring. Then, 0.03 g of dibutyl tin dilaurate, 0.009 g of Iganox 1076 (Shibagai Co., Ltd.), and 0.03 g of 4-methoxyphenol were added thereto. 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) while maintaining the reaction temperature at 50 ° C 0.02 mol of -1,3,5-triazine (Siva Specialty, Tinuvin 400-2) was added dropwise, and the reaction temperature was raised to 70 deg. C for 2 hours. To the mixture was added dropwise 0.01 mol of hydroxy propyl acrylate for 4 hours to obtain a compound having the following formula (6).

The structure of the reaction product obtained therefrom was confirmed by ¹ H-NMR:

¹ H-NMR (CDCl ₃ , 300 MHz, δ, ppm): 0.83-2.16 (-(CH ₂ ) _4- , -C ₁₁ H ₂₃ , CH ₃ , 41H of hindered amine, 2.40 (CH attached to aromatic) ₃ , 6H), 2.73 (CH ₃ , 6H attached to aromatics), 3.15 (NHCH _2- , OCH <, 7H of hindered amine), 3.42 (-OCH _2- , 2H), 3.67 (-OCH _2- , 2H ), 3.81 (-OCH _2- , OCH-, 3H), 4.21 (NCH _2- , 6H), 5.84-5.88 (Proton of Acrylic, 1H) 6.17-6.20 (Proton of Acrylic, 1H), 6.41-6.42 (Acrylic) Proton, 1H), 6.52 (aromatic proton, 2H), 7.22 (aromatic proton, 5H), 8.05 (aromatic proton, 1H), 8.48 (aromatic proton, 1H), 13.35 (proton of aromatic phenol, 1H).

Preparation Example 2

This was carried out in the same manner as in Example 2 of Korean Patent Application No. 2002-19493 filed by the applicant of April 10, 2002.

Except for using hydroxy benzophenone instead of hydroxy propyl acrylate was carried out in the same manner as in Preparation Example 1 to obtain a compound having the formula (7).

Preparation Example 3

This was carried out in the same manner as in Example 3 of Korean Patent Application No. 2002-19493 filed by the applicant of April 10, 2002.

Except for using penta erythritol triacrylate instead of hydroxy propyl acrylate was carried out in the same manner as in Preparation Example 1 to obtain a compound having the formula (8).

Preparation Example 4

This was carried out in the same manner as in Example 4 of Korean Patent Application No. 2002-19493 filed by the applicant of April 10, 2002.

Except for using hexa methylene diisocyanate, which is a bifunctional isocyanate instead of the trifunctional isocyanate, it was carried out in the same manner as in Preparation Example 1 to obtain a compound having the formula (9).

Examples 1-4

The components shown in Table 1 were stirred and mixed according to a conventional method to prepare an ultraviolet curable resin composition.

Photocurable resin composition division UV curable resin composition Oligomer (% by weight) Monomer (% by weight) Photoinitiator (% by weight) Pigment (part by weight) Dispersant (parts by weight) Light stabilizer (parts by weight) Additive (part by weight) Example 1 45 50 5 10 0.5 1 (production example 1) 0.5 Example 2 45 50 5 10 0.5 1 (production example 2) 0.5 Example 3 45 50 5 10 0.5 1 (production example 3) 0.5 Example 4 45 50 5 10 0.5 1 (production example 4) 0.5

The oligomer used Uvcure 1561 of UCB which has an acrylate group and an epoxy group. The monomer used was RAPI-CURE CHVE from ISP. The photoinitiator was used in a 1: 1 ratio of Darocur 1173 manufactured by Shiba-Gei and SarCat SR1010 manufactured by Satomer, and inorganic red was used as the pigment. BYK's Disperbyk-164 was used as a dispersant. As an additive, EFKA-2721 from Efka Chemical Co., Ltd. was used as an antifoaming agent, and Byk-333 from BYK Co., Ltd. was used as a slip agent. Here, 1 part by weight of the light stabilizer synthesized in Production Examples 1 to 4 were used, respectively. Each of the photocurable resin compositions prepared therefrom was coated on a polycarbonate sheet with a thickness of 20 μm. Curing of the coating film is first treated for 5 minutes at 80 ℃ temperature, and then UV curing to prepare the test pieces, respectively, and measured the physical properties according to the measurement method shown in Table 2 below.

Comparative Example 1

The photocurable resin base composition was carried out in the same manner as in Example 1 except that 1 part by weight of tinuvinine 400-2 and 1 part by weight of tinuvin 292, which are additives, were added as ultraviolet absorbers and light stabilizers. After preparing a photo-curable resin composition, using the same to prepare a specimen in the same manner as in Example 1, and measured the physical properties according to the measurement method shown in Table 2 below.

Comparative Example 2

After preparing a photo-curable resin composition in the same manner as in Comparative Example 1, and then directly cured ultraviolet rays without performing a temperature pretreatment step, the specimens were measured according to the following measuring method and the results are shown in Table 2 below. It was.

Comparative Example 3

Aliphatic urethane acrylate was used as the oligomer and 1,6-hexanediol diacrylate and trimethylpropane triacrylate were used in a 1: 1 ratio as the monomer. 1 part by weight of tinuine 400-2 and 1 part by weight of tinuvin 292 were added, and 1-hydroxycyclohexyl-phenyl ketone and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide were added as a photoinitiator. A photocurable resin composition was prepared using a 1: 1 ratio, and then cured by UV to prepare a specimen. And the physical properties were measured according to the following measurement method is shown in Table 2 below.

[Measurement Items and Methods]

(1) Weather resistance: In the accelerated weather resistance tester, the aging of the specimen was promoted by using a UV-B lamp which emits an ultraviolet 313 nm wavelength in a cycle of 8 hours at 50 ° C and 4 hours of water condensation at 40 ° C. The mechanical strength and surface appearance were then evaluated (ASTM D 4597).

(2) Adhesiveness: Draw 11 parallel lines of equal 1mm spacing and 11 parallel lines of equal spacing perpendicularly intersecting the parallel lines to make 100 squares. Detached:

S / 100 (S = non-falling number)

(3) Chemical resistance: After abrasion for 200 times by spraying methyl ethyl ketone on the specimen using Taber's linear abraser, chemical resistance was measured by visual observation. .

(4) Color tone: After treatment in an accelerated weather resistance tester, the surface color was expressed as a YI (Yellow Index) value using a color difference meter from Minolta.

YI = {(1.28 × X)-(1.06 × Y)} / Y

X: Red, Y: Green, Z: Blue

(5) Glossiness: The reflectance was measured when the incident angle and the received angle were 20 °, respectively, and measured by a method of expressing the percentage when the glossiness of the reference plane was 100.

(6) Pencil hardness: It measured by JIS D0202 (using UNI-PENCIL).

Evaluation of Light Stability and Coating Properties of Photocurable Resins division Adhesive Chemical resistance Pencil hardness Glossiness YI (after 1000 investigations) Before investigation After 1000 irradiation Before investigation After 1000 irradiation Example One 100 > 200 HB H 86 83 3.0 2 100 > 200 F HB 85 81 4.2 3 100 > 200 F HB 87 85 2.8 4 100 > 200 F HB 88 86 5.1 Comparative example One 100 > 200 F 2B 85 68 18.5 2 72 180 B 2B 84 66 19.6 3 90 190 B 2B 82 63 20.5

As shown in Table 2 above, the light stability and coating properties of the photocurable resin including the reactive urethane acrylate of the present invention and having a complex photocuring mechanism were compared with existing products and other curing methods. It was found that the photocurable resin using the reactive urethane acrylate according to the compound and the photocuring mechanism using the complex photocuring mechanism has superior weather resistance and coating properties compared to the existing products and curing methods.

As described above, the photocurable resin for color coating including the reactive urethane acrylate derivative according to the present invention may provide a coating film having excellent coating properties and weather resistance. In addition, the photocurable resin for color coating provides excellent coating properties through the composite photocuring process, and enables thick film curing. In addition, the photocurable resin for color coatings containing the acrylate derivatives presented in the present invention and having a complex photocuring mechanism can not only overcome the difficulty of applying a color coating including a pigment, which is a disadvantage of the conventional photocurable resins. It is expected that the weather resistance can be improved without lowering the intrinsic physical properties of the product, and thus the excellent product production and industrial utilization can be enhanced.

Claims (6)

UV-curable resin composition comprising a prepolymer, a monomer and a photoinitiator as essential components, comprising: 40 to 60% by weight of a prepolymer having at least two acrylic groups, 20 to 40% by weight of a vinyl ether monomer, a free radical type and a cationic photocuring initiator mixture 3 to 9% by weight, 5 to 20% by weight of organic or inorganic pigments, 0.5 to 1% by weight of a dispersant, a reactive urethane acrylate derivative represented by the following formula (1) in which a UV absorbing functional group and a hindered amine group are simultaneously introduced into a molecule: UV curable composite resin composition comprising ~ 8% by weight: Formula 1 Wherein Acryl is a monofunctional or polyfunctional acrylate group, R is a compound derived from trifunctional isocyanate, UVA is a benzophenone group or a triazole group, and HALS is 4-amino-2,2,6, 6-tetramethyl piperidine or 4-hydroxy-2,2,6,6-tetramethyl piperidine. The UV curable composite resin composition according to claim 1, wherein the prepolymer is one selected from the group consisting of polyester acrylate, urethane acrylate, epoxy acrylate, and an epoxy resin partially having silicone acrylate and an acrylic group. . The UV curable composite resin composition according to claim 1, wherein the vinyl ether monomer is one selected from the group consisting of 4-cyclohexane dimethanol vinyl ether, hydroxy butyl vinyl ether, and cyclohexyl vinyl ether. The method of claim 1, wherein the free radical initiator is 1-hydroxycyclohexyl-phenyl ketone, α, α-dimethoxy-α-hydroxy acetophenone, 2-methyl-1- [4- (methylthio ) Phenyl] -2-morpholino-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and a mixture thereof. . The method of claim 1, wherein the cationic photoinitiator is one selected from the group consisting of triaryl sulfonium hexafluorophosphate, triaryl sulfonium hexafluoroantimonate, and iarylodonium hexafluoroantimonate UV curable composite resin composition characterized in that. Using the resin composition according to claim 1, a coating film having a thickness of 20 to 120 µm is applied to a surface of a product made of a carbonate resin, methyl methacrylate resin, vinyl chloride resin, polyethylene terephthalate resin or a composite material thereof. A product which is produced by curing 1 to 20 minutes at a temperature of 30 to 90 ° C. and curing the ultraviolet ray or by treating it to 1 to 25 minutes at a temperature of 40 to 90 ° C. after ultraviolet curing.