KR100972625B1

KR100972625B1 - Ultraviolet hardening type resin, making method thereof, and pattern film manufacturing method using it

Info

Publication number: KR100972625B1
Application number: KR1020100023455A
Authority: KR
Inventors: 김필융
Original assignee: 주식회사 신광화학산업
Priority date: 2010-03-16
Filing date: 2010-03-16
Publication date: 2010-07-27

Abstract

PURPOSE: A UV-curable resin is provided to have a fast hardening rate and hardness more than 2H, to obtain excellent adhesive force with a substrate, abrasion resistance, and deaeration property, and to be used for manufacturing a pattern film. CONSTITUTION: A UV-curable resin includes 20-60 weight% of a polyurethane acrylate polymer having a low molecular weight, 0.5-10 weight% of a photoinitiator, and 0.01-5 weight% of an additive. The polyurethane acrylate polymer having the low molecular weight is a material including chemical formula (a) and chemical formula (b) at the same time. The additive includes a wetting agent and an antifoaming agent. A method for manufacturing a pattern film comprise the following steps: coating a mold for forming a pattern with the UV-curable resin; laminating a film on the mold; irradiating ultraviolet ray to the laminated film and the mold; and coating metal or metal oxide on the molded pattern and printing colors.

Description

Ultraviolet Hardening Type Resin, Manufacturing Method And Pattern Film Manufacturing Method Using The Same {Ultraviolet Hardening Type Resin, Making Method Thereof, and Pattern Film manufacturing Method Using It}

The present invention relates to an ultraviolet curable resin, a method for manufacturing the same, and a method for manufacturing a pattern film using the same, and particularly relates to an ultraviolet curable resin, a method for manufacturing the same, and a method for manufacturing a pattern film using the same, wherein a fast curing speed and high hardness can be obtained.

In recent years, electronics have emphasized not only functional aspects but also design aspects. On the other hand, the application of patterns has been popularized to give decorative beauty to the keypad and the exterior of a portable terminal, the appearance of a flat panel display, or the surface of home appliances such as a refrigerator or a microwave oven, and for a luxurious design. Among them, patterns using specific patterns are the most commercialized.

Patterns using patterns are divided into hairlines and spins. The hairline pattern is for realizing the luxurious metal texture, and the spin pattern is for improving the luxury by giving the effect of rotating according to the viewing angle.

In the case of the hairline pattern, the surface of the metal cannot be given a luxurious texture alone, so the surface of the metal must be scratched or worn with a steel brush to form a hairline. In order to form a hairline, it must be scraped with a steel brush one by one, so the work efficiency is low and the metal surface is not easily worn, so processing is not easy. In addition, the metal dust generated during wear clings to the surface of the product by static electricity, which requires additional work to remove it, which is not easy to apply because it has a problem of low productivity.

Another method for forming the hairline is printing the hairline on a light-transmissive mask film, and then applying a photoresist to a silkscreen to set the light-transmissive mask film to develop only the hairline portion, and then transfer it to the screen first. After screen printing to form a hairline on the film and subsequently screen printing to cover the hairline portion on the transfer film secondly, the transfer film having the printed layer is formed by injection molding to form a metallic hairline on the surface of the injection molded product. . However, this process is complicated by its operation and somewhat high defect rate, increasing the production cost.

In addition to the above method, after the UV curable resin is injected into the mold in which the hairline is formed and the film is bonded, the hairline film may be manufactured by irradiating ultraviolet rays. Although this method produces a high production speed, it is difficult to expect that UV curable resins that are generally used have a high shrinkage rate when they are cured, and thus a pattern of a desired shape can be formed as it is. It may be difficult to release the pattern film from the mold. This is a phenomenon caused by the hardness of 2H or more due to the characteristics of the pattern film that can be used for the exterior of the final product. After curing, a trifunctional or higher polyfunctional polyurethane acrylate oligomer having a relatively high hardness and shrinkage and low adhesion to a substrate or This is because a bifunctional or higher functional epoxy acrylate oligomer is mainly used.

In the case of the spin pattern, since the depth of the pattern is difficult to manufacture the transfer film, the spin pattern may be manufactured by injection molding a synthetic resin, but the spin pattern is not largely applied. At present, the manufacturing method of a spin pattern is mainly commercialized the same method as the manufacturing method of said hairline film mainly using an ultraviolet curable resin. But this too has the same problem.

In order to overcome the above disadvantages, an ultraviolet curable resin may be applied which excludes the use of some polyfunctional polyurethane acrylate oligomers or bifunctional or more epoxy acrylate oligomers. In this case, the shrinkage rate during curing and the adhesion to the substrate may be increased, but the curing speed is somewhat slow and the durability and hardness are low, which reduces the production speed and when pattern film is used on the outer surface, it is easily scratched by a nail or the like. Symptoms may occur. Due to these problems, the application of UV curable resins is not used in various ways in pattern film manufacturing.

The present invention has been made to solve the above problems of the prior art, the object of the present invention is to provide an ultraviolet curable resin having a high curing speed, hardness of 2H or more, and excellent adhesion to a substrate, and a method of manufacturing the same.

In addition, an object of the present invention is to provide a method for producing a pattern film using the ultraviolet curable resin produced by the present invention.

UV-curable resin according to the present invention for solving the above problems is 20 to 60% by weight polyurethane acrylate oligomer, 30 to 70% by weight acrylate monomer, 0.5 to 10% by weight photoinitiator, 0.01 to 5% by weight additive It is configured to include.

In addition, the manufacturing method of the ultraviolet curable resin according to the present invention is to mix 20 to 60% by weight of polyurethane acrylate oligomer, 30 to 70% by weight of acrylate monomer, 0.5 to 10% by weight of photoinitiator, 0.01 to 5% by weight of additive It consists of steps.

In addition, the pattern film manufacturing method using an ultraviolet curable resin according to the present invention comprises the steps of applying an ultraviolet curable resin to the pattern molding mold; Laminating the film to the mold; Irradiating ultraviolet rays to the film and the mold; Printing a metal or metal oxide coating and color for the formed pattern; wherein the UV curable resin comprises 20 to 60 wt% of polyurethane acrylate oligomer, 30 to 70 wt% of acrylate monomer, and 0.5 to photoinitiator. 10 wt%, 0.01-5 wt% of the additive.

The ultraviolet curable resin according to the present invention configured as described above has a high curing rate, hardness of 2H or more, and excellent adhesion to a substrate. Therefore, there is an advantage that can be used to manufacture a pattern film while overcoming the disadvantages of the conventional manufacturing method using a steel brush, a manufacturing method using injection molding, a manufacturing method using a mask film, a conventional manufacturing method using a UV curable resin. have.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the state which laminated | stacked the film on the mold by which the pattern was shape | molded using the ultraviolet curable resin which concerns on this invention.
Figure 2 is a perspective view of a film molded hairline pattern produced using an ultraviolet curable resin according to the present invention.
3 is a perspective view and a cross-sectional view of a film with a spin pattern produced using the ultraviolet curable resin according to the present invention.
4 is a flowchart of a method for producing a pattern film using the ultraviolet curable resin according to the present invention.

Hereinafter, with reference to the accompanying drawings an embodiment of the ultraviolet curable resin according to the present invention, a manufacturing method thereof and a pattern film manufacturing method using the same will be described in detail.

BRIEF DESCRIPTION OF THE DRAWINGS It is sectional drawing which shows the state which laminated | stacked the film on the mold by which the pattern was shape | molded using the ultraviolet curable resin which concerns on this invention. The ultraviolet curable resin 110 is coated on the mold 120, and the film 100 is laminated thereon. The molding groove of the mold 120 varies according to the pattern to be manufactured.

In general, the film 100 is mainly composed of polycarbonate (PC), poly ethylene terephthalate (PET), poly ethylene methacrylate (PMMA), and the like. PC and PET are most commonly used. Depending on the application used, a film hard-coated on the back side may be used to prevent damage to the film on which the pattern is formed.

In addition, it is preferable that the mold 120 in which the pattern is formed is made of a stainless steel material plated with nickel or chromium. If the surface of the mold 120 is not plated, after the ultraviolet irradiation, the ultraviolet curable resin 110 is adhered to the mold 120 and it is difficult to release the molded pattern film.

FIG. 2 is a perspective view of a film in which a hairline pattern manufactured using an ultraviolet curable resin according to the present invention is molded. FIG. The ultraviolet curable resin 110 cured on the film 100 forms the hairline pattern 111.

3 is a perspective view and a cross-sectional view of a film in which a spin pattern manufactured using an ultraviolet curable resin according to the present invention is molded. According to the perspective view shown in (a) of FIG. 3, the ultraviolet curable resin 110 cured on the film 100 is formed with a concentric spin pattern 112. The cross section of the spin pattern 112 usually has a triangular shape, and when viewed from above, the spin pattern 112 generally has a concentric or spiral shape. 3B illustrates a cross section of the spin pattern 112 formed in a triangular shape.

4 is a flowchart of a method for producing a pattern film using the ultraviolet curable resin according to the present invention. The ultraviolet curable resin by this invention is apply | coated to the mold in which the pattern molding groove was formed, and the film is laminated | stacked on the ultraviolet curable resin (S11). Ultraviolet rays are irradiated onto the mold and the film stacked up and down (S12). The film in which the pattern is molded is released from the mold (S13). A metal or metal oxide coating and color are printed on the formed pattern (S14).

When curing the UV-curable resin in step S12 described above, it is possible to use various light sources such as mercury lamps or metal lamps, but the irradiated wavelength is 200 nm to 450 nm and the light amount is the sum of all A, B, C, and V wavelengths. It is preferable that it is 200mJ / cm <2> -3,000mJ / cm <2>. When the wavelength to be cured is less than 200nm or more than 450nm, decomposition of the photoinitiator contained in the ultraviolet curable resin is not smoothly performed. In addition, if the amount of light is less than 200 mJ / cm², radicals do not occur smoothly in the photoinitiator in the UV-curable resin, and thus the UV-curable resin may not be cured, and thus, the pattern may not be formed. Shrinkage may occur in the pattern film due to heat generated by over-curing and ultraviolet irradiation, which may cause the pattern film to bend.

Hereinafter, the ultraviolet curable resin used for this invention is described in detail.

The ultraviolet curable resin according to the present invention comprises 20 to 60 wt% of polyurethane acrylate oligomer, 30 to 70 wt% of acrylate monomer, 0.5 to 10 wt% of photoinitiator, and 0.01 to 5 wt% of additive.

The polyurethane acrylate oligomer included in the ultraviolet curable resin according to the present invention is produced by the following method.

That is, mixing and synthesizing 1 mole of trifunctional isocyanate compound and 2.5 mole of diol type polyol in a reactor, and 2.5 mole to a compound formed by reacting the isocyanate compound and polyol. Synthesizing a urethane prepolymer by mixing and reacting diisocyanates of the isocyanate, and the urethane prepolymer and (meth) acrylate synthesized to induce reaction with radicals generated from photoinitiators decomposed by ultraviolet rays. Through the step of introducing a monomer and a monomole diol for reducing the curing density is to synthesize a polyurethane acrylate oligomer introduced at the same time the acrylate group and a hydroxyl group. At this time, 2 mol-3 mol of (meth) acrylate monomers and 1 mol or less of monomolecular diol are added with respect to 1 mol of urethane prepolymers.

In the above reaction, in order to proceed with only one desired reaction, only one of the three NCO reactors needs to have a slow reaction rate to achieve a smooth synthesis. It is preferable that a trifunctional isocyanate compound has a structure of following [Formula 1]. In Formula 1, (b) represents a three-dimensional structural formula of (a). Of the three NCOs, the reaction rates of zones (A) and (C) are the same, but zone (B) has steric hindrance due to other molecules in the structure, so the reaction rate is slower than that of (A) and (C). However, among trifunctional isocyanate compounds, compounds having a symmetrical structure, such as trimer type isocyanurate, have the same reaction rate for all NCOs. In this case, it is difficult to react only in one desired place.

[Formula 1]

(a)

(b)

The structural formula of the urethane composite synthesized using the trifunctional isocyanate compound having the structure of [Formula 1] is shown in the following formula (2). 50% of the structures of (a) and (b) are synthesized, respectively.

[Formula 2]

(a)

(b}

In [Formula 2], R is a hydrocarbon compound, depending on the polyol used.

The polyol may be ethylene glycol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexane dimethanol, bisphenol A , Any one selected from bisphenol F, reduced bisphenol A, reduced bisphenol F, dicyclopenta diol, and tricyclodecanediol is used.

Alternatively, the polyol may be a mixture of one or more of glycerol, trimethylol ethane, trimethylolpropane, pentaerythritol, sorbose, and sorbitol.

Alternatively, the polyol may be a mixture of one or two or more of polyester polyol, polycaprolactone polyol or polyether polyol.

Alternatively, the polyol may be one in which a polyester polyol, a polycaprolactone polyol, or a polyether polyol is mixed with a single molecule diol. Here, the polyol has a diol form having two hydroxyl groups, it is preferable to use a number average molecular weight of less than 500 to 2,000 g / mol. If there is only one hydroxyl group, no further process is possible, and if more than two, there is a high possibility of forming a gel by side reaction in the synthesis process. In addition, when the number average molecular weight is less than 500 g / mol, the number of reactors per weight of the final composition increases, the curing density increases to cause an increase in the shrinkage rate to reduce the adhesive force, and if it is more than 2,000 g / mol soft segment (soft The characteristics of the polyol, which acts as a segment, are greatly highlighted, so that the hardness after the curing of the final composition decreases, making it difficult to apply to the pattern film manufacturing process.

On the other hand, the polyester polyol is ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, polytetramethylene glycol, tetramethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl One of glycol, 1,4-cyclohexanedimethanol, 3-methyl-1,8-octanediol, or a polyester polyol or a copolymer thereof produced by reacting an acid with a single molecule diol is used.

The polycaprolactone polyol is used by polymerizing a single molecule ε-caprolactone.

The polyether polyol is used by polymerizing a single molecule of propylene epoxide and tetramethylene epoxide, respectively, or by mixing.

The structural formula of the urethane prepolymer synthesized using the composite having the structure of [Formula 2] is as shown in [Formula 3]. 50% each of the structures of (c) and (d) is synthesized, and X depends on the structure of the diisocyanate used.

The diisocyanate is 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, toluene diisocyanate mixture, naphthalene 1,5-diisocysi Anato, diphenyl oxy 4,4-diisocyanate, 4,4-methylenediphenyl diisocyanate, 2,4-methylenediphenyl diisocyanate, 2,2-diisocyanatodiphenylmethane, diphenylmethane diisocyanate , 3,3-dimethyl-4,4-biphenylene isocyanate, 3,3-dimethoxy-4,4-biphenylene diisocyanate, benzene 1-[(2,4-diisocyanatophenyl) methyl] 3-isocyanato-2-methyl, 2,4,6-triisopropyl-meth-phenylene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate, 1,3 -Bis (1-isocyanato-1-methylethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) benzene, 1,6-hex Samethylene isocyanate, 1,5-diisocyanato-2-methylpentane, methyl 2,6-diisocyanatohexanoate, bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocy Anatomethyl) cyclohexane, 2,2,4-trimethylhexane 1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate, 2,5 (6) -trimethyl-1- (iso Cyanatomethyl) -5-isocyanatocyclolonehexane, 1,8-diisocyanato-2,4-dimethyloctane, octahydro-4,7-methano-1H-indenodimethyl diisocyanate, 1 , 1-methylenebis (4-isocyanatocyclohexane), 1,6-hexamethylene isocyanate, 1,5-diisocyanato-2-methylpentane, methyl 2,6-diisocyanatohexanoate , Bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 2,2,4-trimethylhexane 1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diiso-shi Anate, 2,5 (6) -trimethyl-1- (isocyanatomethyl) -5-isocyanatocyclolonehexane, 1,8-diisocyanato-2,4-dimethyloctane, octahydro- Preference is given to using at least one of 4,7-methano-1H-indenodimethyl diisocyanate and 1,1-methylenebis (4-isocyanatocyclohexane).

(3)

(c)

(d)

The structural formula of the polyurethane acrylate oligomer synthesized using the prepolymer having the structure of [Formula 3] is as shown in [Formula 4]. (e) and (f) are each synthesized by 50% and W, Y and Z depend on the monomolecular diol and (meth) acrylate monomers used.

The single molecule diol is represented by the following Chemical Formula 5. W may include hetero atoms as aliphatic or aromatic hydrocarbons having 1 to 15 carbon atoms and ethylene oxide propylene oxide may be present repeatedly.

As said (meth) acrylate monomer, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylamide, ( Preference is given to using at least one of a meta) acrylamide mixture, beta carboxyethyl acrylate, pentaerythritol triacrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, dipentaerythritol pentaacrylate Do.

[Formula 4]

(e)

(f)

[Chemical Formula 5]

HO-W-OH

Monofunctional monomers among the acrylate monomers included in the ultraviolet curable resin include diethylaminoethyl acrylate, dimethylaminoethyl acrylate, t-octyl acrylate, N, N-dimethyl acrylamide, N-vinyl caprolactam, and N-vinyl Pyrrolidone, acryloyl morpholine, isobutoxymethyl acrylamide, diacetone acrylamide, carbonyl (meth) acrylate, isobornyl (meth) acrylate, tricyclotecanyl acrylate, 2-phenoxyethyl (meth Acrylate, dicyclopentanyl acrylate, dicyclopentadiene acrylate, methoxy polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, ethoxyethoxyethyl acrylate, methoxyethylene glycol acrylate, polypropylene glycol Mono acrylate, polyethylene glycol mono acrylate, phenoxy Acrylate, cyclohexyl acrylate, benzyl acrylate, epoxydiethylene glycol acrylate, (meth) acrylic acid, butoxyethyl acrylate, tetrahydrofurfuryl (meth) acrylate, β-methacryloyloxyethyl hydride Rosen salate, styryl acrylate, octadecyl acrylate, lauryl acrylate, undecyl acrylate, isodecyl acrylate, decyl acrylate, nonyl acrylate, lauryl (meth) acrylate, 2-ethylhexyl ( Meta) acrylate, isooctyl acrylate, octyl acrylate, heptyl acrylate, hexyl acrylate, isoamyl acrylate, pentyl acrylate, t-butyl acrylate, isobutyl acrylate, amyl acrylate, butyl acrylate, Isopropyl acrylate, propyl acrylate, ethyl acrylate , Methyl acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl acryl One, two or more of latex, N, N-diethyl (meth) acrylamide and N, N'-dimethyl-aminopropyl (meth) acrylate can be used.

The polyfunctional monomers among the ultraviolet curable acrylate monomers include trimethylol propane triacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol diacrylate, One or more of trimethylolpropanetrioxyethyl acrylate, tricyclodecanedimethanol diacrylate and tris (2-hydroxyethyl) isocyanurate diacrylate can be used.

The photoinitiator included in the ultraviolet curable resin is 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, 1-hydroxycyclohexylphenyl ketone, benzaldehyde, anthraquinone, 3-methylacetophenone, 1- (4 Isopropyl-phenol) -2-hydroxy-2-methyl propane-1-one, thioxanthone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, One or more of benzoin propyl ether and benzoinethyl ether can be used.

Micure TPO, PBZ, BP, EPD, DETX, BMS, MS-7, HP-8, CP-4, BK-6 and Ciba Geigy's Irgacure 184, 500, 1173, which are commercially supplied products of the photoinitiator 2959, MBF, 754, 651, 369, 907, 1300, 4265, 819, 819DW, 2022, 2100, 784, 250, Darocure TPO, and the like.

As the additive included in the ultraviolet curable resin, a wetting agent and an antifoaming agent are used. The wetting agent is to reduce the surface tension of the resin when the surface tension of the adhered surface is low to improve the spreadability, and the antifoaming agent is used for smooth removal of bubbles generated by the vortex when the resin is injected into the mold and applied.

The additives include dimethyl polysiloxane emulsion, polydimethyl siloxane, mineral oil compound, modified soy lecithin, soy lecithin, polymethyl-phenyl silicone, hydroxy polydimethyl siloxane, modified polysiloxane, alkyl-aryl modified polysiloxane, hydroxy silicone polyacrylate, Organomodified polysiloxanes, polysiloxane copolymers, polyether siloxane copolymer emulsions, fluorinated silicones, unsaturated polycarboxylic acids, polycarbonate acids, amino-polyesters, sodium polyacrylates, silicone acrylates, silicone polyesters, epoxysiloxanes, silicone polysiloxanes One or more of the ether acrylates are used.

Therefore, A530, 011, 018, 019, 020, 021, 022, 023, 024, 025, 028, 031, 032, 033 034, 035, 036, 037, 038, 044, 045, 094, 1610, 1615, 051, 052, 053, 055, 057, 060N, 065, 066N, 067N, 070, 071, 080, 088, 141 and TEGO ( Germany, Daegu) Airex980, Airex985, Foamex800 Foamex805, Foamex815, Foamex825, Foamex835, Foamex1435, Foamex1488, Foamex1495, Foamex7447, Foamex8020, Foamex8030, Foamex810, Foamex840, Foamex3062, FoamexN, FoamexK3, FoamexKS4, Foamex842, Rad2, Rad 200, Rad 200 One or more of 2018, 2020, 2021, 2023, 2025, 2028, 2035, 2038, 2040, 2048, 2526, 2527, 2550, 2720, 2721, 2722, 2723 from Rad2300, Rad2500, Rad2700 and EFKA.

[Example]

Into a 5 liter round bottom flask equipped with a stirrer, 340 g of polymethylene polyphenyl isocyanate and 0.15 g of 1,4-diazo- [2,2,2] -bicyclo octane as a reaction catalyst were stirred and the reactor temperature was adjusted to 45 ° C. 1.25 g of methylhydroquinone was added first, and then 2,500 g of polyether polyol having a number average molecular weight of 1,000 g / mol was slowly added in order to suppress side reactions that may be generated by heat during synthesis. After the addition, the reactor was maintained at 70 ° C. and stirred for 3 hours to synthesize.

Then, 435.5 g of 2,6-toluene diisocyanate was slowly added while maintaining the reactor temperature at 50 ° C., and the reaction temperature was increased to 70 ° C. for 2 hours and 30 minutes.

Then, 290 g of 2-hydroxyethyl acrylate and 45.06 g of 1,4-butanediol were slowly added to proceed with the reaction.

The reactor temperature was maintained at 70 ° C. for 3 hours after the addition was complete.

The first two to the conclusion of the first of the polyurethane reaction measuring the amount of NCO remaining using the titration when the content of the NCO as desired remained was conducted in the following reactions, the conclusion of the final polyurethane reaction infrared spectroscopy 2270cm ^{- It} was confirmed that the NCO peak of ¹ disappeared, and that hydroxy reacted with isocyanate group. The peak was detected at the number average molecular weight of 3,700 g / mol and 2,400 g / mol simultaneously using gel permeation chromatography. When comparing the area, it was confirmed that the ratio of the area is about 1: 1.

Thus, a number average molecular weight of 3,700 g / mol, an average number of urethane group bonds of 9, three acrylate groups, a number average molecular weight of 2,400 g / mol, an average number of urethane group bonds of 7, two acrylate groups, and one hydroxy group Mixed polyurethane acrylate oligomers in a 1: 1 ratio were synthesized.

42.0 g of the synthesized polyurethane acrylate oligomer was added to a 250 ml blender, 12.5 g of 1,6-hexane diol diacrylate, 15 g of dicyclopentyl acrylate, 7.5 g of trimethylol propane triacrylate, and 19.3 isobornyl acrylate. g and photoinitiator, Miwon B. Micure BP 1.75g, Micure CP-4 1.25g, Micure TPO 0.5g and additives EFKA 2020 0.15g, TEGO Foamex825 0.05g is added, the total weight is 100.0g, at room temperature Stir for 60 minutes. After stirring for 60 minutes, it was filtered using a filter.

Thus, an ultraviolet curable resin composition having a viscosity of 500 cPs at 25 ° C. was obtained.

Comparative Example 1

In the same manner as in the above-described embodiment, a polyurethane acrylate oligomer and an ultraviolet curable resin composition were synthesized using 2,4-toluene diisocyanate trimer instead of polymethylene polyphenyl isocyanate.

Thus, an ultraviolet curable resin composition having a viscosity of 850 cPs was obtained at 25 ° C.

Comparative Example 2

The polyurethane acrylate oligomer and the ultraviolet curable resin composition were synthesized using the hexamethylene diisocyanate burette having the structure of the following [Formula 5] instead of the polymethylene polyphenyl isocyanate.

However, gelation due to side reactions during synthesis occurred, and thus the polyurethane acrylate oligomer and the ultraviolet curable resin were not synthesized.

[Chemical Formula 5]

Comparative Example 3

In the same manner as in the above-described embodiment, using polyurethane 2,6-toluene diisocyanate instead of polymethylene polyphenyl isocyanate, a polyurethane acrylate oligomer and an ultraviolet curable resin composition were synthesized.

Thus, an ultraviolet curable resin composition having a viscosity of 330 cPs was obtained at 25 ° C.

[Comparative Example 4]

In the same manner as in the above-described examples, however, 232 g of 2-hydroxyethyl acrylate and 90.12 g of 1,4-butanediol were added thereto to synthesize a polyurethane acrylate oligomer and an ultraviolet curable resin composition.

Thus, an ultraviolet curable resin composition having a viscosity of 400 cPs at 25 ° C. was obtained.

[Comparative Example 5]

In the same manner as in the above-described example, polyurethane acrylate oligomer and UV curable resin composition were synthesized by adding 348 g of 2-hydroxyethyl acrylate instead of 2-hydroxyethyl acrylate and 1,4-butanediol.

Thus, an ultraviolet curable resin composition having a viscosity of 520 cPs was obtained at 25 ° C.

[Comparative Example 6]

Polyurethane acrylate oligomer and ultraviolet curable resin composition were synthesized using polytetramethylene ether glycol having the same method as Example described above, but having a number average molecular weight of 2,000 g / mol instead of 1,4-butanediol.

Thus, an ultraviolet curable resin composition having a viscosity of 790 cPs at 25 ° C. was obtained.

Comparative Example 7

Synthesis of polyurethane acrylate oligomer and ultraviolet curable resin composition using the same method as the above-described embodiment, but using a polyether polyol having a number average molecular weight of 3,000 g / mol instead of a polyether polyol having a number average molecular weight of 1,000 g / mol It was.

Thus, an ultraviolet curable resin composition having a viscosity of 1,480 cPs at 25 ° C. was obtained.

Comparative Example 8

Polyurethane acrylate oligomer and ultraviolet curable resin composition were synthesized in the same manner as in the above-described example, using neopentyl glycol instead of polyether polyol having a number average molecular weight of 1,000 g / mol.

Thus, an ultraviolet curable resin composition having a viscosity of 270 cPs at 25 ° C. was obtained.

[Comparative Example 9]

42.0 g of the synthesized polyurethane acrylate oligomer was added to a 250 ml blender, 12.5 g of 1,6-hexane diol diacrylate, 15 g of dicyclopentyl acrylate, 7.5 g of trimethylol propane triacrylate, and 19.3 isobornyl acrylate. As g and photoinitiator, Miwon B. Micure BP 1.75g, Micure CP-4 1.25g, Micure TPO 0.5g was added, the total weight was 99.8g, and stirred at room temperature for 60 minutes. After stirring for 60 minutes, it was filtered using a filter.

[Comparative Example 10]

100.0 g of the synthesized polyurethane acrylate oligomer was added to a 250 ml blender, 12.5 g of 1,6-hexane diol diacrylate, 15 g of dicyclopentyl acrylate, 7.5 g of trimethylol propane triacrylate, and 19.3 isobornyl acrylate. g and photoinitiator, Miwon B. Micure BP 1.75g, Micure CP-4 1.25g, Micure TPO 0.5g, and additives EFKA 2020 0.15g, TEGO Foamex825 0.05g, the total weight is 158.0g, at room temperature Stir for 60 minutes. After stirring for 60 minutes, it was filtered using a filter.

Thus, an ultraviolet curable resin composition having a viscosity of 2,300 cPs was obtained at 25 ° C.

Comparative Example 11

12.0 g of the synthesized polyurethane acrylate oligomer was added to a 250 ml blender, 12.5 g of 1,6-hexane diol diacrylate, 15 g of dicyclopentyl acrylate, 7.5 g of trimethylol propane triacrylate, and 19.3 isobornyl acrylate. g and photoinitiator, Miwon B. Micure BP 1.75g, Micure CP-4 1.25g, Micure TPO 0.5g, and additives EFKA 2020 0.15g, TEGO Foamex825 0.05g, the total weight is 70.0g, at room temperature Stir for 60 minutes. After stirring for 60 minutes, it was filtered using a filter.

Thus, an ultraviolet curable resin composition having a viscosity of 160 cPs at 25 ° C. was obtained.

Adhesion Test Evaluation

Specimens are manufactured and evaluated according to ASTM (American Society for Testing Materials) D 3359. Draw 10 lines at intervals of 1mm in width and length, attach 3M # 610 tapes five times, remove them immediately, and count the remaining spaces among the 100 spaces.

[Pencil hardness test evaluation]

Produce and evaluate the specimens in accordance with ASTM D 3363. Tilt at 45 degrees with Mitsubishi High-Uni Pencil and measure 1 kg load. Five times while changing the position of the scratch of about 20mm at a speed of about 3mm / sec in the direction of the pencil lead, wipe the graphite of the pencil attached to the test surface with a rubber eraser or a gauze to examine the groove of the test surface. At this time, do not scratch more than three times, starting with a soft pencil five times. The hardness of the pencil is higher and higher in the order of 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H and 6H.

[High temperature, high humidity leaving test evaluation]

After leaving the specimen for 24 hours at 80 ° C and 80% humidity, the naked eye is inspected for abnormality of the cured coating film.

[Abrasion Resistance Test Evaluation]

After the resin is coated on the film to a thickness of 20 μm, the coated film is subjected to a load of 275 g using an abrasion resistance tester and the abrading wheel is rotated 50 times so that the coating surface is worn out so that the base film is not exposed. Examine the base film for exposure.

[Hardening Speed Test Evaluation]

A 50-mm x 50-mm PET film was coated with a zirconia curable resin at a thickness of 20 μm and irradiated with UV light with a 250 mW metal lamp to calculate the energy required to completely cure the resin.

[Defogging test evaluation]

The resin is injected into the mold in which the pattern is formed, and the film is laminated and irradiated with ultraviolet light to investigate whether bubbles exist in the cured coating film. At this time, lamination of the film should be carried out 15 seconds after the resin is injected, and ultraviolet irradiation should be carried out 60 seconds after the lamination of the film. The presence or absence of bubbles in the cured coating film is determined by using an optical device having a magnification of 10 times or more.

Test evaluation results of Examples and Comparative Examples are shown in Tables 1 and 2 below.

Item Example Comparative example
One Comparative example
2 Comparative example
3 Comparative example
4 Comparative example
5 Polyurethane acrylate oligomer (Examples) (g) 42 - Gelling does not synthesize oligomers - - - Polyurethane acrylate oligomer (Comparative Example 1) (g) - 42 - - - Polyurethane acrylate oligomer (Comparative Example 2) (g) - - Polyurethane acrylate oligomer (Comparative Example 3) (g) - - 42 Polyurethane acrylate oligomer (Comparative Example 4) (g) - - - 42 Polyurethane acrylate oligomer (Comparative Example 5) (g) - - - - 42 Polyurethane acrylate oligomer (Comparative Example 6) (g) - - - - - Polyurethane acrylate oligomer (Comparative Example 7) (g) - - - - - Polyurethane acrylate oligomer (Comparative Example 8) (g) - - - - - Trimethylol propane triacrylate (g) 7.5 7.5 7.5 7.5 7.5 Isobonyl acrylate (g) 19.3 19.3 19.3 19.3 19.3 1,6-hexanediol diacrylate (g) 12.5 12.5 12.5 12.5 12.5 Dicyclopentyl acrylate (g) 15 15 15 15 15 Micure BP (g) 1.75 1.75 1.75 1.75 1.75 Micurfe TPO (g) 0.5 0.5 0.5 0.5 0.5 Micure CP-4 (g) 1.25 1.25 1.25 1.25 1.25 TEGO Foamex825 (g) 0.05 0.05 0.05 0.05 0.05 EFKA 2020 (g) 0.15 0.15 0.15 0.15 0.15 Adhesion test (number of remaining cells out of 100) 100 75 100 100 90 Pencil hardness test (final hardness notation) 2H 2H HB HB 2H High temperature, high humidity standing test Pass Pass Pass Pass Pass Wear resistance test (with or without base film) Pass Pass exposure exposure Pass Cure Speed Test (mJ / cm ² ) 250 250 350 400 250 Defoaming test (with or without bubbles) none none none none none

Item Comparative example
6 Comparative example
7 Comparative example
8 Comparative example
9 Comparative example
10 Comparative example
11 Polyurethane acrylate oligomer (Examples) (g) - - - 42 100 12 Polyurethane acrylate oligomer (Comparative Example 1) (g) - - - - - - Polyurethane acrylate oligomer (Comparative Example 2) (g) - - - - - - Polyurethane acrylate oligomer (Comparative Example 3) (g) - - - - - - Polyurethane acrylate oligomer (Comparative Example 4) (g) - - - - - - Polyurethane acrylate oligomer (Comparative Example 5) (g) - - - - - - Polyurethane acrylate oligomer (Comparative Example 6) (g) 42 - - - - - Polyurethane acrylate oligomer (Comparative Example 7) (g) - 42 - - - - Polyurethane acrylate oligomer (Comparative Example 8) (g) - - 42 - - - Trimethylol propane triacrylate (g) 7.5 7.5 7.5 7.5 7.5 7.5 Isobonyl acrylate (g) 19.3 19.3 19.3 19.3 19.3 19.3 1,6-hexanediol diacrylate (g) 12.5 12.5 12.5 12.5 12.5 12.5 Dicyclopentyl acrylate (g) 15 15 15 15 15 15 Micure BP (g) 1.75 1.75 1.75 1.75 1.75 1.75 Micurfe TPO (g) 0.5 0.5 0.5 0.5 0.5 0.5 Micure CP-4 (g) 1.25 1.25 1.25 1.25 1.25 1.25 TEGO Foamex825 (g) 0.05 0.05 0.05 - 0.05 0.05 EFKA 2020 (g) 0.15 0.15 0.15 - 0.15 0.15 Adhesion test (number of remaining cells out of 100) 52 100 18 15 72 100 Pencil hardness test (final hardness notation) HB B 4H 2H 2H H High temperature, high humidity standing test Occur Pass Occur Occur Pass Pass Wear resistance test (with or without base film) exposure exposure Pass Pass Pass exposure Cure Speed Test (mJ / cm ² ) 450 1,000 200 250 250 250 Defoaming test (with or without bubbles) none none none Occur Occur none

As shown in Table 1, the UV-curable resin according to the embodiment has an adhesive strength of 100, a pencil hardness of 2H, excellent wear resistance and high temperature and high humidity resistance characteristics, fully cured at 250mJ / cm ² , and excellent defoaming property. Giving.

In Comparative Example 1 in which the oligomers were synthesized by using toluene diisocyanate trimers having the same curing rate of all three isocyanate groups, it can be seen that other properties are excellent but the adhesion is low compared to the examples. This is a value that can cause peeling of the pattern film.

In Comparative Example 2 in which the oligomer was synthesized using the hexamethylene diisocyanate biuret, the synthesis of the oligomer was not achieved. This is because the main chain and the isocyanate group are connected by linear hydrocarbons and the length thereof is relatively long, and thus the flexibility of the chain is high, which causes side reactions when the polyol reacts with the isocyanate. This produced gel during synthesis, making it impossible to prepare oligomers.

In Comparative Example 3 in which a low polymer was synthesized using toluene diisocyanate having two isocyanate groups, it can be seen that the pencil hardness and the wear resistance were lower than those of the examples, and the curing rate was slow. This value is not suitable for the production of pattern films.

In the case of Comparative Example 4 in which the synthesis ratio of 2-hydroxyethyl acrylate was 2 mol each, it showed similar characteristics to Comparative Example 3 above, which was not suitable for the production of a pattern film, and in the case of Comparative Example 5 in which the synthesis ratio was 3 mol, It can be seen that the properties are good but the adhesion is somewhat low.

In Comparative Example 6 in which the oligomer was synthesized using polyol instead of monomolecular diol, almost all of the properties showed numerical values which were not suitable for the production of pattern films.

In Comparative Example 7, in which the oligomer was synthesized using a polyol having a molecular weight of 3,000 g / mol, the soft segment and the molecular weight in the oligomer were greatly increased, resulting in lower pencil hardness and abrasion resistance and a lower curing rate than those of the Examples. Able to know.

In Comparative Example 8 in which the oligomer was synthesized using monomolecular diol, the curing rate was slightly increased compared to the example, but the adhesion was greatly decreased, and thus the peeling of the pattern was observed even at high temperature and high humidity storage.

From the comparison between Example 9 and Comparative Example 9, it can be seen that the use of the additive increases the wettability, thereby increasing the adhesion, thereby preventing the peeling of the pattern in the high temperature and high humidity state, and improving the defoaming property.

In Comparative Example 10 in which the oligomer content is increased and Comparative Example 11 in which the oligomer content is reduced compared to the Examples, the increase in the oligomer causes an increase in the viscosity, resulting in a decrease in the wettability, resulting in a decrease in adhesion and defoamability. It can be seen that the reduction of the oligomer causes the decrease of the pencil hardness and the wear resistance property.

100: film 110: UV curable resin
111: hairline pattern 112: spin pattern
120: mold

Claims

In the ultraviolet curable resin comprising 20 to 60% by weight of polyurethane acrylate oligomer, 30 to 70% by weight of acrylate monomer, 0.5 to 10% by weight of photoinitiator, and 0.01 to 5% by weight of additive.
The polyurethane acrylate oligomer is a material containing at the same time (a) and (b) of the general formula (I),
The additives include a wetting agent for reducing the surface tension of the ultraviolet curable resin and an antifoaming agent for removing bubbles, and include dimethyl polysiloxane emulsion, polydimethyl siloxane, mineral oil compound, modified soy lecithin, soy lecithin, and polymethyl. -Phenyl silicones, hydroxy polydimethyl siloxanes, modified polysiloxanes, alkyl-aryl modified polysiloxanes, hydroxy silicone polyacrylates, organo-modified polysiloxanes, polysiloxane copolymers, polyether siloxane copolymer emulsions, fluorinated silicones, unsaturated polycarboxylic acids, poly An ultraviolet curable resin comprising at least one of carbonic acid, amino-polyester, sodium polyacrylate, silicone acrylate, silicone polyester, epoxysiloxane, and silicone polyacrylate acrylate.
[Formula I]
(a)

(b)

The method according to claim 1,
The acrylate monomer is diethylaminoethyl acrylate, dimethylaminoethyl acrylate, t-octyl acrylate, N, N-dimethyl acrylamide, N-vinyl caprolactam, N-vinyl pyrrolidone, acryloyl morpholine , Isobutoxymethyl acrylamide, diacetone acrylamide, carbonyl (meth) acrylate, isobornyl (meth) acrylate, tricyclotecanyl acrylate, 2-phenoxyethyl (meth) acrylate, dicyclopentanyl acrylate , Dicyclopentadiene acrylate, methoxy polypropylene glycol acrylate, methoxy polyethylene glycol acrylate, ethoxyethoxyethyl acrylate, methoxyethylene glycol acrylate, polypropylene glycol mono acrylate, polyethylene glycol mono acrylate Phenoxyethyl acrylate, cyclohexyl acrylate, Vaginal acrylate, epoxydiethylene glycol acrylate, (meth) acrylic acid, butoxyethyl acrylate, tetrahydrofurfuryl (meth) acrylate, β-methacryloyloxyethylhydrogen salate, styryl acrylate , Octadecyl acrylate, lauryl acrylate, undecyl acrylate, isodecyl acrylate, decyl acrylate, nonyl acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl acryl Latex, octyl acrylate, heptyl acrylate, hexyl acrylate, isoamyl acrylate, pentyl acrylate, t-butyl acrylate, isobutyl acrylate, amyl acrylate, butyl acrylate, isopropyl acrylate, propyl acrylate , Ethyl acrylate, methyl acrylate, 2-hydroxybutyl (meth) Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl acrylate, N, N-diethyl (meth) acrylamide, N, N'-dimethyl-aminopropyl (meth) acrylate, trimethylol propanetriacrylate, pentaerythritol triacrylate, ethylene glycol diacrylate, 1,6-hexanediol diacrylate, tripropylene glycol di An ultraviolet curable resin comprising at least one of acrylate, trimethylolpropanetrioxyethyl acrylate, tricyclodecanedimethanol diacrylate, and tris (2-hydroxyethyl) isocyanurate diacrylate.

The method according to claim 1,
The photoinitiator is 2,2-dimethoxy-2-phenyl-acetophenone, xanthone, 1-hydroxycyclohexylphenyl ketone, benzaldehyde, anthraquinone, 3-methylacetophenone, 1- (4-isopropyl-phenol) -2-hydroxy-2-methyl propane-1-one, thioxanthone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone, 4,4'-diaminobenzophenone, benzoin propyl ether, benzo Ultraviolet curable resin, characterized in that it comprises at least one of phosphorus ether.

delete

In the method for producing an ultraviolet curable resin comprising 20 to 60% by weight polyurethane acrylate oligomer, 30 to 70% by weight acrylate monomer, 0.5 to 10% by weight photoinitiator, 0.01 to 5% by weight additives,
Mixing and synthesizing a trifunctional isocyanate compound and a polyol in a reactor;
Synthesizing a urethane prepolymer by mixing and reacting a diisocyanate to a composite formed by rebounding a trifunctional isocyanate crosslinker and a polyol;
Including a (meth) acrylate monomer and a monomolecular diol to synthesize a polyurethane acrylate oligomer introduced at the same time the acrylate group and a hydroxyl group;
The trifunctional isocyanate compound is a substance of the following general formula (II),
The polyol includes at least one of polyester polyol, polycaprolactone polyol or polyether polyol,
The polycaprolactone polyol is a polymerized ε-caprolactone, the polyether polyol is a method for producing an ultraviolet curable resin, characterized in that the polymerized by mixing each or a propylene epoxide and tetramethylene epoxide.
[Formula II]

In the method for producing an ultraviolet curable resin comprising 20 to 60% by weight polyurethane acrylate oligomer, 30 to 70% by weight acrylate monomer, 0.5 to 10% by weight photoinitiator, 0.01 to 5% by weight additives,
Mixing and synthesizing a trifunctional isocyanate compound and a polyol in a reactor;
Synthesizing a urethane prepolymer by mixing and reacting a diisocyanate to a composite formed by rebounding a trifunctional isocyanate crosslinker and a polyol;
Including a (meth) acrylate monomer and a monomolecular diol to synthesize a polyurethane acrylate oligomer introduced at the same time the acrylate group and a hydroxyl group;
The trifunctional isocyanate compound is a substance of the following general formula (II),
The polyol is composed of any one of a polyester polyol, polycaprolactone polyol or polyether polyol mixed with a single molecule diol,
The polycaprolactone polyol is a polymerized ε-caprolactone, the polyether polyol is a method for producing an ultraviolet curable resin, characterized in that the polymerized by mixing each or a propylene epoxide and tetramethylene epoxide.
[Formula II]

The method according to claim 11 or 12,
The polyol has a diol (diol) form having two hydroxyl groups, the number average molecular weight is 500 to 2,000g / mol less than a method for producing a UV curable resin.

The method according to claim 11 or 12,
The diisocyanate is 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, toluene diisocyanate mixture, naphthalene 1,5-diisocysi Anato, diphenyl oxy 4,4-diisocyanate, 4,4-methylenediphenyl diisocyanate, 2,4-methylenediphenyl diisocyanate, 2,2-diisocyanatodiphenylmethane, diphenylmethane diisocyanate , 3,3-dimethyl-4,4-biphenylene isocyanate, 3,3-dimethoxy-4,4-biphenylene diisocyanate, benzene 1-[(2,4-diisocyanatophenyl) methyl] 3-isocyanato-2-methyl, 2,4,6-triisopropyl-meth-phenylene diisocyanate, 1,4-xylene diisocyanate, 1,3-xylene diisocyanate, 1,3 -Bis (1-isocyanato-1-methylethyl) benzene, 1,4-bis (1-isocyanato-1-methylethyl) benzene, 1,6-hex Samethylene isocyanate, 1,5-diisocyanato-2-methylpentane, methyl 2,6-diisocyanatohexanoate, bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocy Anatomethyl) cyclohexane, 2,2,4-trimethylhexane 1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate, 2,5 (6) -trimethyl-1- (iso Cyanatomethyl) -5-isocyanatocyclolonehexane, 1,8-diisocyanato-2,4-dimethyloctane, octahydro-4,7-methano-1H-indenodimethyl diisocyanate, 1 , 1-methylenebis (4-isocyanatocyclohexane), 1,6-hexamethylene isocyanate, 1,5-diisocyanato-2-methylpentane, methyl 2,6-diisocyanatohexanoate , Bis (isocyanatomethyl) cyclohexane, 1,3-bis (isocyanatomethyl) cyclohexane, 2,2,4-trimethylhexane 1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diiso-shi Anate, 2,5 (6) -trimethyl-1- (isocyanatomethyl) -5-isocyanatocyclolonehexane, 1,8-diisocyanato-2,4-dimethyloctane, octahydro- A method for producing an ultraviolet curable resin, comprising at least one of 4,7-methano-1H-indenedimethyl diisocyanate and 1,1-methylenebis (4-isocyanatocyclohexane).

The method according to claim 11 or 12,
The acrylate monomer is 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, (meth) acrylamide, (meth) acrylamide UV curable type comprising at least one of a mixture of id, beta carboxyethyl acrylate, pentaerythritol triacrylate, trimethylolpropane diallyl ether, pentaerythritol triallyl ether, dipentaerythritol pentaacrylate Method for producing a resin.

Applying an ultraviolet curable resin to a pattern forming mold made of stainless steel whose surface is plated with nickel or chromium;
Laminating the film to the mold;
Irradiating ultraviolet rays to the film and the mold;
Printing a metal or metal oxide coating and color on the molded pattern;
The UV-curable resin is a pattern film manufacturing method comprising 20 to 60% by weight of polyurethane acrylate oligomer, 30 to 70% by weight of acrylate monomer, 0.5 to 10% by weight of photoinitiator, 0.01 to 5% by weight of additive.

The method according to claim 16,
The wavelength of the irradiated ultraviolet light is 200nm or more and less than 450nm, the irradiation amount is a pattern film manufacturing method characterized in that less than 200 mJ / cm² 3,000 mJ / cm².