WO2012086959A2 - Photo-curable resin composition for printing process - Google Patents

Abstract

The present invention relates to a photo-curable resin composition for a printing process and more specifically to a photo-curable resin composition comprising a polysilazane compound. The composition according to the invention comprises the polysilazane compound, thereby ensuring an excellent adhesive force to a substrate, heat resistance, durability (against high temperature, high pressure, and high humidity) and lower layer protection property while maintaining high permeability even after high temperature treatment. Therefore, the photo-curable resin composition can be useful in the formation of a fine pattern and a protective layer.

Description

Photocurable resin composition for printing process

The present invention relates to photocurable resin compositions for printing processes useful for the production of micropatterns and protective films used in imprint lithography and roll printing processes.

In general, the process of forming a fine pattern applied to information storage, small sensor, photonic crystal and optical device, microelectromechanical device, display device, display and semiconductor using photolithography to form a fine pattern using light It is a way.

In the conventional photolithography method, the circuit line width or pattern line width is determined by the wavelength of light used in the exposure process. Given the current state of the art, photolithography processes are difficult to form fine patterns of 50 nm or less on a substrate because of light interference. In addition, as the pattern becomes very fine, the initial investment costs increase due to expensive equipment such as exposure equipment, and the price of high-resolution masks soars, resulting in a decrease in efficiency. It is also acting as another factor.

In addition, the process takes a long time because the exposure, the post-exposure bake, the development, the post-development bake, the etching process, the cleaning process, and the like every time the pattern is formed, the productivity is increased because the photo process must be repeated several times. The problem of deterioration was highlighted.

Imprint lithography and roll printing techniques have emerged as a way to solve this problem. Imprint lithography is the first method invented by Stephen chou of Princeton University in order to imprint nanoscale. The fine pattern is formed by painting. Specifically, a method of forming a pattern by bonding to a curable composition coated on a metal film or an organic film using an inorganic material or a polymer mold (Mold) in which a desired fine pattern is formed in advance, and forming a pattern by heat or photocuring, as compared with the conventional photolithography method. There is an advantage to simplify the process and to form a fine pattern. Such an imprint method is disclosed in US Patent No. 5,772,905, US Patent No. 5,259,926, and Japanese Patent Publication No. 2007-244984 (Korean Patent Publication No. 10-2009-0031274).

In addition, Korean Patent Application No. 2006-0005482 (Publication Patent Publication No. 10-2007-76292) discloses a roll printing apparatus and a manufacturing method of a display device using the same, and roll printing using one or more rolls. The method is applicable to devices such as FED (Field Emission Display), OLED (Organic Light Electroluminescent Display), PDP (Plasma Display Panel), etc., and that the manufacturing process of the device will be simplified. It is disclosed that precision will be secured.

The roll printing method may form a fine pattern by using a plate, a roll, a roll, and the like on a roll instead of a high-resolution mask used when forming a pattern in conventional photolithography. This roll printing method improves productivity and work efficiency through a simplified process. In addition, it has been proposed as an alternative that can drastically reduce the complicated process that proceeds through various processes, such as exposure or development of photolithography and the resulting process costs.

Japanese Patent Laid-Open No. 2005-197699 discloses an imprint composition for semiconductor microlithography in connection with such a printing technique for pattern formation that can be performed at low cost. Further, Japanese Laid-Open Patent Publication No. 2005-301289 as a member of LCD or the like also discloses the application of photocurable printing lithography to a transparent protective film material, a spacer and the like. Resists such as transparent protective films, spacers, and the like, disclosed in Japanese Patent Laid-Open No. 2005-301289, are called protective films (permanent films) because, unlike etching resists, materials are finally left.

This protective film (permanent film), unlike the etching resist, is an element left in the TFT display panel. In the case of a TFT substrate, a transparent protective film is formed to protect the thin film transistor. The conventional protective film (permanent film) is mostly formed through a photolithography process through a photoresist material. Similarly, in the case of the protective film (permanent film) formed after the color filter is formed on the LCD top plate, a photocurable resin is coated on the color filter, the electrode lead portion is removed by photolithography, and a thermosetting process is performed to perform the protective film (permanent film). ). The protective film (permanent film) for the color filter reduces the step between the color filters and enables resistance to high temperature processes in forming the transparent electrode (ITO).

Conventionally, photocurable resins and thermosetting resins, such as a siloxane polymer, a silicone polyimide, an epoxy resin, and an acrylic resin, have been used as a transparent protective film (permanent film) for color filters.

In addition, the existing protective film (permanent film) formed silicon nitride (SiNx) on the metal and formed a protective film (permanent film) thereon. However, in order to perform the silicon nitride free (SiNx free) process, since the photocurable resin composition must be formed directly on the metal, the role of the protective film is also increased. As the SiNx) formation process can be eliminated, there are many advantages in realizing low cost.

In the formation of a fine pattern and a protective film (permanent film) through the imprint and roll printing process, a resin composition on substrates of various materials such as inorganic layers such as Cu, SiNx, Mo, and film layers such as organic layers, PET, PES, etc. The adhesion to the lower substrate of the coating film formed after coating and photocuring is essential.

In addition, when the photocurable resin composition is formed on a substrate, depending on the type of metal patterned on the substrate at the time of performing a high temperature thermal process, the metal material may be modified due to oxidation and diffusion of the metal material. . Representative of such a metal material is copper. When a high temperature thermal process is performed during formation of a protective film (permanent film) on copper with a TFT electrode by using an imprint process, defects due to black spots and stains on the coating film are generated due to oxidation and diffusion of the copper layer. This defect is pointed out as the biggest problem in the process of forming an organic material on the copper layer.

As a protective film (permanent film), the main technical problems must be carried out, such as adhesiveness, permeability after high temperature treatment, excellence in mechanical properties, chemical resistance, and outgas reduction. However, since organic materials have many limitations such as temperature, pressure, moisture, and hardness, some limitations are imposed on the use of materials due to these limitations. Thus, resin compositions that can satisfy the above conditions have not been readily presented. In addition, in the case of the coating resin composition that can be applied to the silicon nitride free (SiNx free), the reality is not presented even more for reasons of the modification of the underlying film material and the limitation of material properties.

In order to solve the problems as described above, the present invention can be applied to a variety of substrates such as plastic, metal, glass, such as excellent adhesiveness, durability against high temperature, high humidity and high pressure conditions, excellent permeability and heat resistance after high temperature treatment, And an object of the present invention is to provide a photocurable resin composition for a printing process with a low degree of modification of the lower film.

The present invention also provides a method for producing a protective film for a printing process using the photocurable resin composition and the method, which can stably and easily form fine patterns required for various electronic device industrial processes including semiconductors, displays, and the like. It is an object to provide a protective film.

In order to achieve the above object, the present invention

(1) polysilazane compounds;

(2) ethylene monomers;

(3) crosslinkable monomers having at least two ethylenic double bonds;

(4) photopolymerization initiators; And

(5) It provides the photocurable resin composition for printing processes containing surfactant.

The present invention also provides a method for producing a protective film for a printing process comprising applying and exposing the photocurable resin composition to a substrate.

In addition, the present invention provides a protective film for a printing process produced by the manufacturing method.

Since the photocurable resin composition according to the present invention comprises a polysilazane compound, when the protective film is formed, compared with the coating film using the resin composition used in the conventional imprint lithography and roll printing process, the adhesive strength with the substrate, high transmittance even after high temperature treatment, It shows excellent performance as a protective film (permanent film) by simultaneously improving the durability, heat resistance, and prevention of underlayer film deterioration by high temperature processes in harsh conditions such as high temperature and high humidity.

1 is an electron microscope photograph of a lower film before thermosetting a protective film prepared from the composition of Example 1 according to the present invention.

2 to 5 are photographs of the degree of denaturation of the lower layer after thermosetting the protective film made of the compositions of Examples 1 to 3 and Comparative Example 1, respectively, with an electron microscope.

The photocurable resin composition for a printing process according to the present invention comprises a polysilazane compound for improving the adhesion, durability, permeability and heat resistance of the cured polymer resin, that is, the protective film, and preventing the underlayer of the composition. Characterized in that.

Specifically, the photocurable resin composition for a printing process according to the present invention,

(1) 1 to 60 weight percent of a polysilazane compound;

(2) 10 to 80 wt% of an ethylene monomer;

(3) 10 to 80% by weight of a crosslinkable monomer having at least two or more ethylenic double bonds;

(4) 0.1 to 12 wt% of a photopolymerization initiator; And

(5) 0.001 to 5% by weight of surfactant.

Each component is demonstrated below.

(1) polysilazane compound

The polysilazane compound used for this invention is not specifically limited, It can select arbitrarily unless the effect of this invention is impaired. These may be presented as either inorganic or organic compounds.

The amount of the polysilazane compound according to the present invention is preferably used in 1 to 60% by weight, preferably 10 to 40% by weight.

The amount of the polysilazane compound used is 1% by weight If less than, there is a tendency that the lower film denaturation prevention, adhesion and the like of the obtained thin film is lowered, and when it exceeds 60% by weight, printing characteristics may be deteriorated due to the increase in viscosity.

The polysilazane compound used in the present invention includes a linear structure having a structural unit represented by the following formula (1), has a molecular weight of 300 to 2,000, has 3 to 10 SiH ₃ groups in one molecule, and is used for chemical analysis. Perhydropolysilazane having an element ratio of Si: 59-62, N: 31-34, and H: 6.5-7.5 per weight% by weight, and perhydropolysilazane having a polystyrene reduced average molecular weight in the range of 2,000 to 20,000. This is preferred.

[Formula 1]

Wherein n is an integer.

The perhydropolysilazane may be prepared according to a conventional method in the art, for example, according to the method described in Japanese Patent Laid-Open No. 63-16325, and basically a chain portion in a molecule and It may be represented by the following formula (2) to include a cyclic moiety.

[Formula 2]

Preferred examples of the perhydropolysilazane include compounds having the structure of Formula 3 or 4 below.

[Formula 3]

[Formula 4]

In which R is_One, R₂ And R₃Each independently represent a group in which a group directly connected to silicon, such as a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group or a fluoroalkyl group, is carbon, an alkylsilyl group, an alkylamino group, or an alkoxy group, n is an integer. (At this time, R_One, R₂ And R₃ At least one of them is a hydrogen atom.)

In the present invention, polysilazane having a number average molecular weight of about 100 to 50,000 having a skeleton composed of the above structural units or a modified product thereof is included.

As an example of a preferable compound including the structure of Formula 4, a method for producing polysilazane having a hydrogen atom in R ₁ and R ₂ and a methyl group in R ₃ is described in D. Seyferth et al . Polym. Prepr. Am. Chem. Soc. Div. Polym. Chem. 25.10 (1984). The polysilazane obtained by this method is a chain polymer and a cyclic polymer, and both do not have a crosslinked structure.

In the formula (4), in the case of the polyorgano (hydro) silazane having a hydrogen atom at R ₁ and R ₂ and an organic group at R ₃ , the polymer has a cyclic structure having a polymerization degree of 3 to 5, or a chain in the molecule. There is one having a structure and a ring structure at the same time.

In addition, the organic group in the polysilazane, and R ₁ and R ₂ having in the general formula (4) in the R ₁ an organic group to a hydrogen atom, and R ₂ and R _3, and R ₃ is a polymerization degree having a hydrogen atom a 3-5 degree There are also polysilazanes having a cyclic structure.

In the present invention, as an organic polysilazane other than the compound having the structure of Formula 4, polyorgano (hydro) silazane having a crosslinked structure of Formula 5 below, and R1SiX3 (X: halogen) obtained by ammonia decomposition Polysilazane having a structure of formula (6) obtained by co-ammonia decomposition of polysilazane, R1Si (NH) X, or R1SiX3 having a crosslinked structure (see Japanese Patent Application Laid-Open No. 49-69717) Can be.

[Formula 5]

[Formula 6]

In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and m and n each independently represent an integer.

In addition to the above compounds, inorganic silazane copolymers or modified polysilazanes having increased molecular weight or improved hydrolysis resistance (Japanese Patent Application Laid-Open No. H1-138108, H11-138107, H1-203429 and 1-203430), copolymerization silazane (Japanese Patent Publication No. Hei 2-175726, Hei 5-86200, Hei 5-331293), which is advantageous for the thickening of the organic component into polysilazane. Etc.) may be included.

The polysilazane compounds presented above may be used alone or in combination of two or more thereof.

(2) ethylene monomer

In the photocurable resin composition of the present invention, the amount of the ethylene monomer used is preferably 10 to 80% by weight, more preferably 20 to 60% by weight.

When the amount of the ethylene-based monomer is less than 10% by weight, the obtained thin film molecular weight is not sufficient, and the strength tends to be lowered. When the amount of the ethylene monomer is more than 80% by weight, the unreacted material increases, which may cause shrinkage.

Specific examples of the ethylene monomers are isobutyl acrylate, tert-butyl acrylate, lauryl acrylate, methyl methacrylate, alkyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl methacrylate, benzyl Acrylate, 2-hydroxyacrylate, trimethoxybutyl acrylate, ethylcarbidol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxypolyethylene glycol acrylate, 2-hydroxyethyl Acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate and methacrylates thereof; Acrylates including halogen compounds such as 3-fluoroethyl acrylate and 4-fluoropropyl acrylate and methacrylates thereof; Acrylates containing siloxane groups such as triethylsiloxane ethyl acrylate and methacrylates thereof; And olefins having aromatics such as styrene and 4-methoxystyrene, but are not limited thereto, and these may be used alone or in combination of two or more thereof.

(3) crosslinkable monomers having at least two ethylenic double bonds

In the photocurable resin composition of the present invention, the amount of the crosslinkable monomer having at least two or more ethylenic double bonds is preferably 10 to 80% by weight, more preferably 20 to 60% by weight. good.

When the amount of the crosslinkable monomer is less than 10% by weight, the degree of curing is insufficient, which is detrimental to the pattern formation. When the amount of the crosslinkable monomer is greater than 80% by weight, the hardness is excessively high due to the increase of the degree of curing or rather, the unreacted substances are increased, causing the shrinkage. This can be

Specific examples of the crosslinkable monomer include diethylene glycol monoethyl ether, dimethylol dicyclopentane diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, and 1,6-hexanediol Diacrylate, aryloxy polyethylene glycol acrylate, dicyclopentenyl acrylate, hydroxy pivalate neopentyl glycol diacrylate, neopentyl glycol diacrylate, 1, 9-nonane diol diacrylate, polyethylene glycol diacryl Acrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate, and methacrylates thereof, but are not limited thereto, and these may be used alone or in combination of two or more thereof.

Moreover, as a polyfunctional crosslinkable monomer which has three or more functional groups, EO modified glycerol triacrylate, PO modified glycerol triacrylate, trimethylol propane triacrylate, pentaerythritol ethoxy tetraacrylate, dipentaerythritol hexa Acrylate, EO modified trimethylol propane triacrylate, and these methacrylates, etc. are mentioned, It is not limited to these, These can be used individually or in mixture of 2 or more types.

(4) photopolymerization initiator

In the photocurable resin composition of the present invention, the amount of the photopolymerization initiator used is preferably from 0.1 to 12% by weight, more preferably from 0.5 to 8% by weight.

When the amount of the photopolymerization initiator is less than 0.1% by weight, photocuring is slow or difficult, and when the amount of the photopolymerization initiator is more than 12% by weight, a reaction suppression effect occurs, so that a film property, a transmittance, or a curing margin tends to decrease.

Specific examples of the photopolymerization initiator include Irgacure 369, Igacure 907, Igacure184, Igacure 651, Igacure 819, Igacure 2959, Igacure 1800, Darocur 1173, Darocur 1116 and Darocur 1020; 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxy Acetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-mo Acetophenone compounds such as polynophenyl) -butan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone and 4,4'-bis (diethyl amino) benzo Benzophenone compounds such as phenone; Thioxanthone, 2-Chrol Thioxanthone, 2-Methyl Thioxanthone, Isopropyl Thioxanthone, 2,4-Diethyl Thioxanthone, 2,4-Diisopropyl Thioxanthone and 2-Chloro Thioxide Thioxanthone type compounds, such as Santon; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl dimethyl ketal; And 2,4,6, -trichloro s-triazine, 2-phenyl 4,6-bis (trichloro methyl) -s-triazine, 2- (3 ', 4'-dimethoxy styryl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy Phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl 4,6- Bis (trichloro methyl) -s-triazine, bis (trichloro methyl) -6-styryl s-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloro methyl) -s -Triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2-4-trichloro methyl (piperonyl) -6-tri Triazine compounds such as azine and 2-4-trichloromethyl (4'-methoxy styryl) -6-triazine, and the like, but are not limited thereto, and these may be used alone or in combination of two or more thereof. .

Preferably the acetophenone system is advantageous to secure a curing margin

(5) surfactant

The photocurable resin composition of this invention may contain surfactant. The surfactant may be used as long as it can improve the coating property of the photocurable resin composition, the amount of the surfactant used in the present invention is preferably 0.001 to 5% by weight, more preferably based on the total composition It is preferable to use 0.01 to 2% by weight. If two or more surfactants are used in combination, the total content is as indicated above.

When the surfactant is contained in an amount of 0.001% by weight or less, uniform coating may be limited, and when 5% by weight or more may cause problems in mold transfer properties and formation of additional materials in a later process.

It is preferable that the said surfactant contains at least 1 type from silicone type and a fluorine type surfactant, It is also possible to mix and use 2 or more types.

Specific examples of the surfactant may include, but are not limited to, fluorine-based surfactants from Dainippon Ink Chemical Co., Ltd., 3M and Shin-Etsu Chemical Co., Ltd., and silicone-based surfactants from Dow, BK, and Evonik.

In addition, the photocurable resin composition of the present invention may further include a solvent.

Generally, a solvent is not used in the case of the photocurable resin composition for a printing process, but in the present invention, a solvent may be added for dissolution of polysilazane and compatibility with the photocurable resin composition. The amount of the solvent is preferably 0 to 70% by weight, more preferably 0 to 50% by weight.

Specific examples of the solvent include acetonitrile, glycerol, dimethyl sulfoxide, nitromethane, dimethyl formamide, phenol, N-methylpyrrolidone, pyridine perfluorotributylamine, perfluoro decalin, 2-butanone, Alcohols such as methylene carbonate methanol, ethanol, ethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, propylene ethylene glycol, diethylene glycol, butanediol, benzyl alcohol and hexyl alcohol; Ethers such as propylene carbonate, tetrahydrofuran, 1,4-dioxane, 1-methoxy-2-propanol, methoxybenzene, dibutyl ether and diphenol ether; Ethyl acetate, propyl acetate, butyl acetate, ethyl propion, ethyl ester, butyl ester, methyl-2-hydroxyisobutyrate, 2-methoxy-1-methylethyl ester, 2-methoxyethanol acetate and 2-ethoxy Esters such as ethanol acetate; Ethylene glycol alkyl ether acetates such as ethylene glycol methyl ether acetate and ethylene glycol ethyl ether acetate; Ethylene glycol alkyl ether propionates such as ethylene glycol methyl ether propionate and ethylene glycol ethyl ether propionate; Ethylene glycol monoalkyl ethers such as ethylene glycol methyl ether and ethylene glycol ethyl ether; Diethylene glycol alkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate and propylene glycol propyl ether acetate; Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate and propylene glycol propyl ether propionate; Propylene glycol monoalkyl ethers such as propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether and propylene glycol butyl ether; Dipropylene glycol alkyl ethers such as dipropylene glycol dimethyl ether and diporoethylene glycol diethyl ether; Butylene glycol monomethyl ether, such as butylene glycol monomethyl ether and butylene glycol monoethyl ether; And dibutylene glycol alkyl ethers, such as dibutylene glycol dimethyl ether and dibutylene glycol diethyl ether, etc. are mentioned, It is not limited to these, These can be used individually or in mixture of 2 or more types.

The viscosity of the composition according to the invention is 2 mPa · s to 25 mPa · s at 25 ° C., preferably 3 mPa · s to 20 mPa · s, more preferably 5 mPa · s to 15 mPa · s to be.

At this time, when the composition viscosity of the present invention is 2 mPa · s or less, it is limited to the desired coating film thickness formation, and when the composition viscosity is 25 mPa · s or more, it may be difficult to apply the material to the substrate.

The present invention also provides a method for producing a protective film and a fine pattern for a printing process using the photocurable resin composition, and a protective film and a fine pattern produced by the method.

Specifically, the method for producing a protective film for a printing process according to the present invention includes applying and exposing a photocurable composition according to the present invention to a substrate.

In addition, according to the present invention, after applying the composition to the substrate, by using an imprint lithography or roll printing process to form a coating film and exposed to it, it is possible to stably and easily fine patterns required for various electronic device industrial processes including semiconductors and displays Can be formed.

At this time, the composition is applied to a substrate (for example, silicon substrate, ceramic substrate, metal layer, polymer layer, etc.) by applying a suitable method such as spin coating, roller coating, slit, inkjet coating, etc. in a thickness of 0.5 to 10 ㎛ It is preferable.

As a light source used for exposure, UV of 190-450 nm, Preferably 200-400 nm area is used, and electron beam irradiation is also possible. In addition, a high temperature heat treatment process may be subsequently performed to improve the use and properties of the film.

The protective film and the micropattern manufactured according to the present invention have excellent adhesion to a substrate, durability against high temperature, high humidity, and high pressure conditions, high permeability and heat resistance after high temperature treatment, and a low degree of modification of the lower layer, and thus include a semiconductor and a display. It can be usefully used as a protective film and a fine pattern required for various electronic device industry process, the composition of the present invention is the imprint lithography and roll printing process using the conventional photolithography process by replacing the photolithography process for forming a fine pattern In addition to simplifying the steps of exposure, development, cleaning, etc., the manufacturing process time can be shortened, thereby reducing manufacturing costs and improving productivity.

Hereinafter, preferred examples are provided to help understanding of the present invention, but the following examples are merely to illustrate the present invention, and the scope of the present invention is not limited to the following examples.

Example 1

5 parts by weight of polysilazane SN-1 having a structure of Formula 1, molecular weight of 500, 30 parts by weight of 4-hydroxybutyl acrylate and 30 parts by weight of phenoxyethyl acrylate as an ethylene monomer, an ethylene double bond 30 parts by weight of 1,4-butanediol diacrylate as a crosslinkable monomer having 3 parts by weight, 3 parts by weight of Igacure 369 (manufactured by Ciba) as a photopolymerization initiator, and 0.1 parts by weight of BYK's silicone-based surfactant as a surfactant for 6 hours or more at room temperature. Mixing produced a photocurable composition according to the present invention.

Further, each of the photocurable compositions prepared above was applied on a degreasing-washed metal substrate with a thickness of 0.5 to 5 μm, bonded to a polymer mold and exposed using a lamp having a wavelength of 365 nm, and then formed thin film and polymer. The mold was released to form a protective film.

Example 2

A photocurable composition and a protective film according to the present invention were prepared in the same manner as in Example 1, except that 10 parts by weight of polysilazane SN-1 having a structure of Formula 1 and a molecular weight of 500 was used.

Example 3

The photocurable composition and the protective film according to the present invention in the same manner as in Example 1, except that 10 parts by weight of polysilazane SN-2 having a structure of Formula 1 and having a molecular weight of 1500 was used instead of polysilazane SN-1. Was prepared.

Comparative Example 1

A photocurable composition and a protective film were prepared in the same manner as in Example 1, except that 4-hydroxybutyl acrylate was used in an amount of 40 parts by weight without using polysilazane.

[Experiment]

The protective film prepared in Examples 1 to 3, and Comparative Example 1 was measured for adhesion, durability, permeability, heat resistance, and lower film deterioration degree with respect to the substrate by the following method, and the results are shown in Table 1 below. It was.

A) adhesion (substrate adhesion)

After making 100 cells horizontally and vertically and using 3M's 610 adhesive tape to closely contact the substrate with the protective film as described above, when the tape was slowly peeled off, the number of remaining cells on the substrate was designated as 1% per one. Adhesiveness and adhesiveness evaluation were implemented as a reference.

A: When the number of remaining cells on the substrate is 100% to 80%

B: When the number of remaining cells on the substrate is 80% to 50%

C: The number of cells remaining on the substrate is 50% to 15%

D: When the number of remaining cells on the substrate is 15% to 0%

B) durability (high temperature, high humidity, high pressure)

The substrate on which the protective film was formed as described above was thermally cured in an oven at 230 ° C. for 30 minutes, and the adhesive strength was checked in the same manner as in the above a) to confirm 100% adhesion.

The substrate was treated at 120 ° C., 100% humidity, 2 atmospheres, and left for 24 hours in a device capable of high temperature, high pressure, and high humidity, and then the surface state and adhesion state of the substrate were rechecked. Evaluation was based on the same criteria.

At this time, since the adhesive 100% state was checked before the equipment was put in place, the poor adhesive state means that the moisture penetrated into the coating film and the lower substrate and the lifting phenomenon occurred.

C) permeability

As described above, the substrate on which the protective film was formed was thermally cured in an oven at 230 ° C. for 150 minutes, and the substrate on which the coating film was formed was measured at 400 nm using a transmittance equipment, and evaluated according to the following criteria.

A: When the transmittance is 98% or more

B: transmittance is 97% or more

C: When the transmittance is 96% or more

D: When the transmittance is 95% or more

D) heat resistance

The weight loss was measured by a thermogravimetric analyzer (TGA) while thermally curing the substrate having the protective film formed thereon at 230 ° C. for 30 minutes in an oven, and evaluated according to the following criteria.

A: If the weight loss is less than 1%

B: Weight loss is more than 1% but less than 3%

C: Weight loss is more than 3% and less than 5%

D: Weight loss is more than 5%

E) Lower layer degeneration prevention

The substrate on which the protective film was formed as described above was thermally cured in an oven at 230 ° C. for 150 minutes, and the substrate on which the coating film was formed was checked by visual inspection and SEM (Self-scanning microscope), and evaluated according to the following criteria. In addition, the SEM photograph is shown in Figs.

A: 20% or less surface stain

B: 20% or more of surface stains, 40% or less

C: More than 40% of surface stains, less than 60%

D: 60% or more surface stain

Table 1

division	Adhesion	durability	Transmittance	Heat resistance	Lower film degeneration prevention
Example 1	B	B	A	B	B
Example 2	A	A	A	A	A
Example 3	A	A	A	B	A
Comparative Example 1	D	D	C	C	D

As shown in Table 1, in the case of the composition of Comparative Example 1 that does not include a polysilazane compound, the adhesion, durability, permeability, heat resistance and the degree of prevention of underlayer film deterioration are significantly reduced, but according to the present invention, the polysilazane compound The compositions of Examples 1 to 3, including the, exhibited excellent effects in terms of adhesion, durability, permeability, heat resistance, and lower film deterioration. In particular, Examples 2 and 3 containing 10% by weight or more of the polysilazane compound showed more excellent effects in terms of adhesion, durability, heat resistance, and lower film deterioration.

Since the photocurable resin composition according to the present invention comprises a polysilazane compound, when the protective film is formed, compared with the coating film using the resin composition used in the conventional imprint lithography and roll printing process, the adhesive strength with the substrate, high transmittance even after high temperature treatment, It shows excellent performance as a protective film (permanent film) by simultaneously improving the durability, heat resistance, and prevention of underlayer film deterioration by high temperature processes in harsh conditions such as high temperature and high humidity.

Claims (23)

1. (1) polysilazane compounds;

   (2) ethylene monomers;

   (3) crosslinkable monomers having at least two ethylenic double bonds;

   (4) photopolymerization initiators; And

   (5) A photocurable resin composition for a printing process, comprising a surfactant.
2. The method of claim 1,

   The photocurable resin composition

   (1) 1 to 60 weight percent of a polysilazane compound;

   (2) 10 to 80 wt% of an ethylene monomer;

   (3) 10 to 80% by weight of a crosslinkable monomer having at least two or more ethylenic double bonds;

   (4) 0.1 to 12 wt% of a photopolymerization initiator; And

   (5) 0.001 to 5 wt% surfactant

   Photocurable resin composition for a printing process comprising a.
3. The method of claim 1,

   The polysilazane compound includes a linear structure having a structural unit represented by the following formula (1), has a molecular weight of 300 to 2,000, has 3 to 10 SiH ₃ groups in one molecule, and the element ratio by chemical analysis is each It is perhydropolysilazane which is Si: 59-62 , N: 31-34, and H: 6.5-7.5 per weight%, The photocurable resin composition for printing processes.

   [Formula 1]

   

   Wherein n is an integer.
4. The method of claim 3,

   The polysilazane compound has a structure of formula (2) in the molecule and comprises a chain or cyclic moiety, the photocurable resin composition for a printing process.

   [Formula 2]

   
5. The method of claim 4, wherein

   A photocurable resin composition for a printing process, wherein the polysilazane compound has a structure of the following Chemical Formula 3 or 4 and has a number average molecular weight of 100-50000;

   [Formula 3]

   

   [Formula 4]

   

   Wherein R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a group in which the group directly connected to silicon is carbon, an alkylsilyl group, an alkylamino group, and an alkoxy group, n is an integer. (At least one of R ₁ , R ₂ and R ₃ is a hydrogen atom.)
6. The method of claim 5,

   The polysilazane compound is polysilazane having a number average molecular weight of 100 to 50,000 or a modified product thereof, The photocurable resin composition for a printing process.
7. The method of claim 5,

   The compound of formula (4) is a polysilazane having a hydrogen atom in R ₁ and R ₂ , and a methyl group in R ₃ , the photocurable resin composition for a printing process.
8. The method of claim 5,

   The compound of formula 4 is a polyorgano (hydro) silazane having a hydrogen atom in R ₁ and R ₂ , and an organic group in R ₃ , the photocurable resin composition for a printing process.
9. The method of claim 8,

   The compound of formula 4 has a cyclic structure having a degree of polymerization of 3 to 5 or a photocurable resin composition for a printing process, characterized in that it has a chain structure and a cyclic structure in the molecule at the same time.
10. The method of claim 5,

    The compound of formula (4) is a polysilazane having a hydrogen atom in R ₁ , and an organic group in R ₂ and R ₃ , the photocurable resin composition for a printing process.
11. The method of claim 5,

    The compound of formula 4 is a polysilazane having a cyclic structure having a degree of polymerization of 3 to 5 having an organic group in R ₁ and R ₂ , and a hydrogen atom in R ₃ , a photocurable resin composition for a printing process.
12. The method of claim 1,

    A polysilazane having a crosslinked structure obtained by ammonia decomposition of a polyorgano (hydro) silazane having a crosslinked structure represented by the following formula (5) as a polysilazane compound in a molecule, and R1SiX3 (X: halogen), It is polysilazane which has a structure of following General formula (6) obtained by R1Si (NH) X or co-ammonia decomposition of R1SiX3. The photocurable resin composition for printing processes.

    [Formula 5]

    

    [Formula 6]

    

    In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an aryl group, and m and n each independently represent an integer.
13. The method of claim 1,

    The polysilazane compound is an inorganic silazane copolymer, a modified polysilazane, or a copolymerized silazane having an organic component introduced into the polysilazane, a photocurable resin composition for a printing process.
14. The method of claim 1,

    The ethylene monomer is isobutyl acrylate, tert- butyl acrylate, lauryl acrylate, methyl methacrylate, alkyl acrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl methacrylate, benzyl acrylate, 2 -Hydroxy acrylate, trimethoxybutyl acrylate, ethyl carbidol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate, 2 Hydroxypropyl acrylate, 2-acryloxyethyl-2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate and methacrylates thereof; Acrylates including halogen compounds such as 3-fluoroethyl acrylate and 4-fluoropropyl acrylate and methacrylates thereof; Acrylates containing siloxane groups such as triethylsiloxane ethyl acrylate and methacrylates thereof; Olefins having aromatics such as styrene and 4-methoxystyrene; And a photocurable resin composition for a printing process, characterized in that selected from the group consisting of.
15. The method of claim 1,

    The crosslinkable monomer having at least two ethylenic double bonds may include diethylene glycol monoethyl ether, dimethylol dicyclopentane diacrylate, 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, 1,6-hexanediol diacrylate, aryloxy polyethylene glycol acrylate, dicyclopentenyl acrylate, hydroxy pivalate neopentyl glycol diacrylate, neopentyl glycol diacrylate, 1,9-nonanediol diacryl A sight for a printing process, characterized in that selected from the group consisting of latex, polyethylene glycol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate, methacrylates thereof and mixtures thereof Chemical composition.
16. The method of claim 1,

    The photopolymerization initiator is Irgacure 369, Igacure 907, Igacure184, Igacure 651, Igacure 819, Igacure 2959, Igacure 1800, Darocur 1173, Darocur 1116 and Darocur 1020, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoxanthone compounds A photocurable resin composition for a printing process, which is selected from the group consisting of a phosphorus compound, a triazine compound, and a mixture thereof.
17. The method of claim 1,

    Said surfactant is selected from the group consisting of a silicone type surfactant, a fluorine type surfactant, and mixtures thereof, The photocurable resin composition for a printing process.
18. The method of claim 1,

    The photocurable resin composition for a printing process, wherein the photocurable resin composition further comprises a solvent.
19. The method of claim 18,

    The solvent is acetonitrile, glycerol, dimethyl sulfoxide, nitromethane, dimethyl formamide, phenol, N-methylpyrrolidone, pyridine perfluorotributylamine, perfluoro decalin, 2-butanone, methylene carbonate, propylene Carbonates, alcohols, ethers; Esters, ethylene glycol alkyl ether acetates, ethylene glycol alkyl ether propionates, ethylene glycol monoalkyl ethers, diethylene glycol alkyl ethers, propylene glycol alkyl ether acetates, propylene glycol alkyl ether propionates, propylene Glycol monoalkyl ethers, dipropylene glycol alkyl ethers, butylene glycol monomethyl ethers, dibutylene glycol alkyl ethers, and mixtures thereof, the photocurable resin composition for a printing process .
20. The method of claim 1,

    The photocurable resin composition has a viscosity of 2 mPa · s to 25 mPa · s at 25 ° C. The photocurable resin composition for a printing process.
21. A method of manufacturing a protective film for a printing process comprising applying and exposing a photocurable resin composition for a printing process for a printing process to a substrate.
22. A method of manufacturing a micropattern comprising applying a photocurable resin composition for a printing process according to claim 1 to a substrate, forming a coating film by using an imprint lithography or roll printing process, and then exposing it.
23. A protective film or fine pattern produced by the manufacturing method according to claim 21 and 22.

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