TW201335284A - Curable resin composition comprising organopolysiloxane - Google Patents

Abstract

Provided is a curable resin composition comprising (a-1) an organopolysiloxane containing a siloxane unit having one or more functional groups selected from the group consisting of vinyl, (meth)acrylate and epoxy; (a-2) an organopolysiloxane containing a siloxane unit having one or more functional groups selected from the group consisting of hydroxyl, amino and thiol; and (b) an acrylic compound having one or more ethylenically unsaturated double bonds. The curable resin composition cures to form a uniform and stable coating when applied on a substrate, which has good light transmittance, adhesion, heat resistance and photosensitive properties such as pattern development and resolution, as well as a good film retension rate, and particularly, exhibits good hardness even after cured at a relatively low temperature.

Description

Curable resin composition containing organic polyoxyalkylene

The present invention relates to a curable resin composition comprising an organopolysiloxane. In particular, the present invention relates to a curable resin composition comprising an organopolyoxane which forms a uniform and stable coating on a substrate. When cured, the coating has good light transmission, adhesion, heat and photographic properties (such as pattern development and resolution), and good film retention. In particular, the coating exhibits good hardness even when cured at relatively low temperatures. The present invention also relates to a cured coating film prepared from a curable resin composition, and an electronic component comprising the cured coating film.

Semiconductor devices, such as touch panel displays (TPDs), liquid crystal displays (LCDs), charge coupled devices (CCDs), and complementary metal oxide semiconductors (CMOS), are typically covered with a protective film to protect their internal devices.

These devices undergo various processing steps during fabrication, such as heat treatment, exposure, alignment alignment layers, sputtering to form electrodes, and cleaning with ultrapure water. Therefore, the protective film must have good heat resistance and light resistance, as well as long-term discoloration resistance, yellowing resistance and whitening resistance. The protective film must form a uniform and stable coating film on the substrate and must have good pattern developing properties. When cured, even at a relatively low temperature of 150 ° C or lower and cured For about 10 minutes, it should also exhibit high hardness to protect other devices that are susceptible to heat damage. In particular, the protective film must have scratch resistance of 95% or more for a wavelength of 400 to 800 nm, adhesion of 5B or higher, high resolution, and pencil hardness of 7H or more.

However, conventional protective film compositions do not meet all of the above requirements. In particular, when the conventional protective film is cured at a relatively low temperature, the hardness is defective.

PCT Publication No. WO 2007/001039 discloses a curable organopolyoxane composition which has a transmittance of 80% or higher when cured, and an optical element comprising the composition. Although it has good adhesion and transparency, and the amount of transmittance reduction at low temperatures is low, it needs to be cured at 150 ° C for 15 minutes or longer, resulting in insufficient hardness of the coating film.

Accordingly, it is an object of the present invention to provide a curable resin composition comprising an organopolyoxane to form a uniform and stable coating on a substrate, wherein the coating has good transparency and adhesion upon curing. Properties, heat resistance and photosensitivity (such as pattern development and resolution), and good film retention; and, in particular, the coating exhibits good hardness even when cured at relatively low temperatures.

According to one aspect of the present invention, there is provided a curable resin composition comprising: (a) (a-1) an organopolyoxyalkylene having a siloxane unit having a selected from the group consisting of vinyl And (a-2) an organopolyoxane containing a siloxane unit having a selected from One or more functional groups of a group consisting of a hydroxyl group, an amine group and a thiol group; and (b) an acrylic acid compound having one or more ethylenically unsaturated double bonds.

The cured coating film formed by the curable resin composition of the invention has good anti-dyeing power, surface hardness, adhesion, heat resistance, light transmittance, and excellent photosensitive properties (such as pattern developability, high resolution) With film retention rate. Therefore, the cured coating film is suitable for the manufacture of various semiconductor devices such as TPD, LCD, CCD and CMOS.

The structure and properties of the siloxane polymer depend on the number of networks formed between the ruthenium atom and the oxygen atom. In other words, when the number of organic groups bonded to the ruthenium atom is from 1 to 1.5, the siloxane polymer is a highly crosslinked three-dimensional rigid structure (crosslinked with a large amount of Si-O bonds). When the number of organic groups bonded to the ruthenium atom is 2 or more, the siloxane polymer is in a liquid or elastic state.

The repeating unit of the siloxane polymer is classified according to the number of oxygen atoms bonded to the ruthenium atom, as shown in Table 1 below.

As indicated above, the ruthenium atom of the oxoxane unit is bonded to an oxygen atom, which is called a monofunctional unit (M type); the ruthenium atom of the oxirane unit is connected to two oxygen atoms, which is called a bifunctional unit (D). Type); the helium atom of the oxane unit is connected to the third One oxygen atom, which is called a trifunctional unit (T type); and the helium atom of the oxoxane unit are connected to four oxygen atoms, which is called a tetrafunctional unit (Q type).

In the oxoxane compound, if any two of the above-mentioned oxoxane units are connected, it is a oxoxane dimer (dioxane); in the oxoxane compound, if there are any three of the above-mentioned oxime The alkane unit is connected to a helium oxide trimer (trioxane); and in the oxoxane compound, if a network of the above-mentioned oxoxane unit is formed, it is a siloxane polymer (polyoxane). .

In the polymerization of a siloxane, a hydroxy group is bonded to a ruthenium atom (Si-OH), that is, a decyl group is used as a reactive group, which generates a siloxane polymer via condensation polymerization. Thus, the preparation of a siloxane polymer can be divided into two main steps: the synthesis of a sterol monomer, and the condensation polymerization thereof to obtain a decane polymer.

Although chlorodecane is commonly used in the synthesis of sterol monomers, it can also be substituted with alkoxy decanes such as methoxy decane and ethoxy decane.

In the case of chlorodecane, as shown below, the Si-Cl bond is highly reactive with water and is easily hydrolyzed to form decyl alcohol, which produces a decane by condensation polymerization.

Hydrolysis reaction: ≡SiCl+H ₂ O --> ≡Si-OH+HCl

Condensation reaction: ≡Si-OH+OH-Si≡ --> ≡Si-O-Si≡+H ₂ O

In the case of alkoxydecane, as shown below, the Si-OR bond is hydrolyzed to form an alcohol and a sterol. Subsequently, a condensation reaction is carried out with a decyl alcohol and a residual alkoxy decane or other sterol moiety to form a decane.

Hydrolysis reaction: ≡Si-OR+H ₂ O --> ≡Si-OH+ROH

Condensation reaction: ≡Si-OH+≡Si-OH --> ≡Si-O-Si≡+H ₂ O, or ≡Si-OH+≡Si-OR --> ≡Si-O-Si≡+ROH

The monofunctional, dimorphic, trifunctional and tetrafunctional units in the polyoxyalkylene can be obtained by hydrolysis and condensation of the chlorodecane or alkoxydecane as described above.

For example, forming a polymer with a difunctional siloxane unit is carried out by hydrolyzing dichlorodimethyl decane or dimethoxy dimethyl decane, followed by subjecting the resulting silanediol to a condensation reaction.

In the following, the components of the invention are described in detail.

(a) Organic polyoxane (a-1) an organopolyoxane containing a siloxane unit having one or more functional groups selected from the group consisting of a vinyl group, a (meth) acrylate, and an epoxy group. base

The curable resin composition of the present invention comprises an organopolyoxane (a-1) containing a siloxane unit having a selected from the group consisting of a vinyl group, a (meth) acrylate and an epoxy group. One or more functional groups of the group formed. In particular, the oxoxane unit may be selected from one or more of the group consisting of Chemical Formulas I and II.

In the above formulae I and II, each of A is independently a single bond, a C ₁ -C ₉ alkylene group, a C ₃ -C ₁₄ -cycloalkylene group, a C ₆ -C ₁₄ extended aryl group, a C ₇ - a C ₁₄ alkyl extended aryl group or a C ₇ -C ₁₄ arylalkylene group, preferably a C ₁ -C ₉ alkylene group or a C ₆ -C ₁₄ extending aryl group, more preferably a C ₁ -C ₅ alkylene group or C ₆ -C ₁₀ exoaryl, most preferably C ₁ -C ₅ alkyl; and each of X is independently vinyl, (meth) acrylate, -Z or -O(CH ₂ ) _n Z Wherein Z is an epoxy group and n is an integer from 0 to 5.

(a-2) an organopolyoxane containing a oxoxane unit having one or more functional groups selected from the group consisting of a hydroxyl group, an amine group and a thiol group

The curable resin composition of the present invention comprises an organopolyoxane (a-2) containing a siloxane unit having a group selected from the group consisting of a hydroxyl group, an amine group and a thiol group. One or more functional groups. In particular, the oxoxane unit may be one or more selected from the group consisting of Chemical Formulas III and IV.

In the above Chemical Formulas III to IV, each of B is independently a single bond, a C ₁ -C ₉ alkylene group, a C ₃ -C ₁₄ cycloalkylene group, a C ₆ -C ₁₄ aryl group, a C ₇ - C ₁₄ alkyl extended aryl, or C ₇ -C ₁₄ arylalkylene, preferably C ₁ -C ₉ alkyl or C ₆ -C ₁₄ aryl, more preferably C ₁ -C ₅ alkyl Or a C ₆ -C ₁₀ extended aryl group, most preferably a C ₁ -C ₅ alkylene group; and each of Y is independently -OH, -NH ₂ or -SH.

According to the present invention, the weight ratio of the organopolyoxane (a-1) to the organopolyoxane (a-2) may range from 1:99 to 99:1, preferably from 20:80 to 80: 20, better from 30:70 to 70:30.

When the weight ratio falls within the above range, the vinyl group, (meth) acrylate or epoxy group of the organopolyoxane (a-1), which is in the form of a ring or contains an unsaturated π bond, The unshared electron pair of the thiol group, the hydroxyl group or the thiol group of the organopolyoxane (a-2) is crosslinked. Crosslinking between the organopolyoxane (a-1) and (a-2) increases the density of the formed film, thereby improving its hardness. In addition, the film retention rate may increase due to low shrinkage after heat curing.

The organopolyoxane (a-1) may comprise a oxoxane unit having one or more functional groups selected from the group consisting of a vinyl group, a (meth) acrylate and an epoxy group, to be organic The content of the constituent unit of the polyoxyalkylene (a-1) is from 1 to 90 mol%, preferably from 3 to 85 mol%, more preferably from 5 to 80 mol%, based on the total number of moles. The organopolyoxane (a-2) may further comprise a oxoxane unit having one or more functional groups selected from the group consisting of a hydroxyl group, an amine group and a thiol group, and an organopolyoxyalkylene oxide. The content of the constituent unit of (a-2) is from 1 to 90 mol%, preferably from 3 to 85 mol%, more preferably from 5 to 80 mol%, based on the total number of moles. When the content of the oxoxane unit having one or more functional groups is 1 mol% or more, more functional molecules are involved in the crosslinking reaction of the heat curing, and the organic polyoxyalkylene can be crosslinked. More sexual. In this case, the hardness of the film at low temperatures is improved. Further, when the content of the siloxane unit having one or more functional groups is 90 mol% or less, the storage stability and heat resistance of the film are increased, and at the same time, micropores formed on the film are prevented from being caused. The film hardness is deteriorated.

One or both of the organopolyoxanes (a-1) and (a-2) may further comprise one or more oxoxane units selected from the group consisting of Chemical Formulas V, VI and VII. In particular, it is preferred to have a siloxane unit of the formula VII because the organopolyoxane containing the siloxane unit has a higher crosslinkability. In addition, the hardness of the film is enhanced by the increase in density of the film, and the smoothness of the film due to uneven density is prevented.

In the above Chemical Formulas V to VII, each of R is independently H, C ₁ -C ₉ alkyl, C ₃ -C ₁₄ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ alkylaryl Or a C ₇ -C ₁₄ arylalkyl group, preferably H, C ₁ -C ₉ alkyl or C ₆ -C ₁₄ aryl, more preferably C ₁ -C ₃ alkyl or C ₆ -C ₁₀ aryl The base is preferably a methyl group or a phenyl group.

Each of the organic polyoxyalkylenes (a-1) and (a-2) may have a weight average molecular weight of 1,000 to 500,000, preferably 1,500 to 100,000, more preferably 2,000 to 50,000. When the weight average molecular weight is 1,000 or more, not only the surface of the film coating layer can be prevented from being cracked due to a decrease in shrinkage property during the curing step, but also the film thickness can be prevented from being reduced by etching of the developer during the development step. In addition, the present invention can provide a film having a more uniform thickness and improved heat resistance and surface hardness. A weight average molecular weight of 500,000 or less maintains a proper degree of composition viscosity while ensuring fluidity of the composition which will improve film surface smoothness and allow for uniform lamination in the coating and curing steps. Therefore, it is possible to reduce problems such as a decrease in density and a deterioration in hardness due to micropores formed in the film. It also improves the transparency of the film, in particular, the solubility of the composition in the developer, which results in a high resolution pattern after the photocuring and development steps.

(b) an acrylic compound having one or more ethylenically unsaturated double bonds

The curable resin composition of the present invention is an acrylic compound having one or more ethylenically unsaturated double bonds, which enhances the surface hardness, maintenance rate and sensitivity of the film formed by the curable resin composition.

The acrylic compound having one or more ethylenically unsaturated double bonds may be an acrylic compound having one or more reactive ethylenically unsaturated double bonds, preferably two or more reactive ethylenically unsaturated doubles. key. Specific examples thereof may include, but are not limited to, selected from ethylene glycol di(meth)acrylate, propylene glycol di(methyl) Acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, polyethylene glycol di(methyl) Acrylate, polypropylene glycol di(meth)acrylate, tris(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, neopentyl Tetraol tri(meth)acrylate succinic acid monoester, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylic acid Ester, dipentaerythritol penta (meth) acrylate succinic acid monoester, caprolactone modified dine pentaerythritol hexa(meth) acrylate, neopentyl alcohol triacrylate hexamethylene di Isocyanate (reaction product of pentaerythritol triacrylate and hexamethylene diisocyanate), pentaerythritol hepta (meth) acrylate, tripentenol octa (meth) acrylate, bisphenol A One or more of the group consisting of epoxy acrylates and ethylene glycol monomethyl ether acrylates.

In the present invention, the terms "(meth)acrylic" and "(meth)acrylate" mean "acrylic and/or methacrylic" and "acrylate" and/or methacrylate, respectively. ".

The curable resin composition of the present invention may comprise an acrylic compound having one or more ethylenically unsaturated double bonds, and the total solid amount of the organopolyoxane (a-1) and (a-2) is 100% by weight. The content is from 1 to 80 parts by weight. When the content falls within this range, an appropriate degree of light transmittance and workability can be maintained, and adhesion and surface smoothness can be improved.

(c) decane coupling agent

The curable resin composition of the present invention may further comprise a decane coupling agent. The decane coupling agent improves the adhesion of the cured film to the substrate.

The decane coupling agent may be a functional decane compound having at least one reactive functional group, and examples of the reactive group include a carboxyl group, a (meth) acrylonitrile group, and a different Cyanate ester, epoxy group, but is not limited thereto. Such decane coupling agents are well known in the art.

Specific examples of decane coupling agents include, but are not limited to, selected from the group consisting of trimethoxymercaptobenzoic acid, γ-methylpropoxypropyltrimethoxydecane, vinyltriethoxydecane, and ethylene. Trimethoxy decane, γ-isocyanate propyl triethoxy decane, γ-glycidoxypropyl trimethoxy decane, γ-glycidoxypropyl triethoxy decane, and β-( One or more of the groups consisting of 3,4-epoxycyclohexyl)ethyltrimethoxynonane.

The curable resin composition of the present invention may comprise a decane coupling agent in an amount of from 0.01 to 10 parts by weight based on 100 parts by total of the total solids of the organopolysiloxanes (a-1) and (a-2) It is preferably from 0.1 to 5 parts by weight. When the content of the decane coupling agent is 0.01 parts by weight or more, the adhesion between the curable resin composition and the substrate may be sufficient. Further, when the content is 10 parts by weight or less, the thermal stability of the composition at a high temperature can be improved, and formation of a shift point after the development step can be prevented.

(d) Photopolymerization initiator

The curable resin composition of the present invention may further comprise a photopolymerization initiator. The photopolymerization initiator serves to initiate polymerization of the crosslinkable monomer when it is exposed to visible light, ultraviolet light, extreme ultraviolet light or the like.

The photopolymerization initiator may be any conventional photopolymerization initiator known in the art, preferably selected from the group consisting of acetophenones, diimidazoles, and trisole. Classes, phosphonium salts, benzoin, benzophenone, diketones, α-diketones, polynuclear steroids, thioxanthone, diazo, quinone One or more of the group consisting of sulfonates, anthraquinones, oxazoles and strontium borate salts. The preferred ones are cockroaches, which are disclosed in Korean Laid-Open Patent Publication No. 2004-0007700, 2005-0084149, 2008-0083650, 2008-0080208, 2007-0044062, 2007-0091110, 2007-0044753, 2009-0009991. 2009-0093933, 2010-0097658 and 2011-0059525, and PCT Publication Nos. WO 10/102502 and WO 10/133077. Commercially available products such as OXE-01, OXE-02 (Ciba), N-1919 (ADEKA), etc., which are preferably highly sensitive and analytical.

The curable resin composition of the present invention may comprise a photopolymerization initiator, in an amount of from 0.5 to 10 based on 100 parts by weight of the total solids of the organopolyoxane (a-1) and (a-2). The parts by weight are preferably from 1 to 5 parts by weight. When the content of the photopolymerization initiator is 0.5 parts by weight or more, the hardness and sensitivity of the film, and the linearity of the pattern may be sufficient. When the content is 10 parts by weight or less, good resolution may be provided due to the appropriate hardness of the film, and residual film formation in other regions than the pattern after the development step may be prevented.

(e) Surfactant

The curable resin composition of the present invention may further comprise a surfactant to enhance its coating properties.

The surfactant may include a fluorine-based surfactant, a ruthenium-based surfactant, a nonionic surfactant, and the like. Specific examples of surfactants may include, but are not limited to, surfactants based on fluorine or hydrazine, such as FZ2122 (Dow Corning Toray), BM-1000 and BM-1100 (BM CHEMIE), Megapack F142 D, Megapack F172. , Megapack F173 and Megapack F183 (Dai-Nippon Ink Chemicals), Fluorad FC-135, Fluorad FC-170 C, Fluorad FC-430 and Fluorad FC-431 (Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145, Surfron S-382, Surfron SC-101, Surfron SC-102, Surfron SC-103, urfron SC-104, Surfron SC-105 and Surfron SC-106 (Asahi Glass), Eftop EF301, Eftop 303 and Eftop 352 (Shin-Akida Kasei), and SH-28 PA, SH-190, SH-193, SZ-6032 , SF-8428, DC-57 and DC-190 (Toray Silicon), etc. (above trade name); nonionic surfactants, such as polyoxyethylene alkyl ethers, such as polyoxyethylene lauryl ether, polyoxygen Ethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene aryl ethers, such as polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether, and polyoxyethylene dialkyl esters, Such as polyoxyethylene dilaurate and polyoxyethylene distearate; organosiloxane polymer KP341 (Shin-Etsu Chemical); and (meth)acrylic copolymer Polyflow No. 57 and 95 (Kyoei Yushi Chemical) . The surfactants can be used singly or in combination.

The curable resin composition of the present invention may comprise a surfactant in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the total solids of the organopolyoxane (a-1) and (a-2). It is preferably from 0.1 to 5 parts by weight. When the amount of the surfactant is 0.05 parts by weight or more, the coating property of the curable resin composition can be improved, and cracks on the surface of the coating can be prevented. Further, when the amount of the surfactant is 10 parts by weight or less, the manufacturing cost is advantageous.

(f) organic solvent

The curable resin composition of the present invention may further comprise an organic solvent. The curable resin composition may comprise an organic solvent in an amount such that the solid content of the curable resin composition is from 10 to 50% by weight, wherein the solid represents a component in a solid form in the curable resin composition.

The organic solvent is any organic solvent which is soluble in each of the above components and is chemically stable. Specific examples may include a solvent selected from the group consisting of propylene glycol methyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol methyl ether, ethyl acetate, ethyl acetate. Ethyl lactate, celecoxib ethyl acetate, γ-butyrolactone, 2-methoxyethyl acetate, β-ethoxypropionate ethyl ester, n-propyl acetate and n-butyl acetate One or more, preferably selected from the group consisting of propylene glycol methyl ether acetate, 4-hydroxy-4-methyl-2-pentanone, propylene glycol methyl ether and ethyl acetate. Or more.

The curable resin composition of the present invention can be applied to form a film by any conventional method known in the art. Specific examples may include spray coating, roll coating, spin coating, and the like.

The curable resin composition of the present invention can be applied to a substrate to form a uniform and stable film after curing. The cured film has resistance to stains and improved pattern development properties. The resulting film is cured at a relatively low temperature of 150 ° C or lower, and has good heat resistance, resolution and film retention. At the same time, the transmittance in the wavelength range of 400 to 800 nm is 95% or more, and the adhesion is 5 B or more.

In particular, during the photocuring and thermal curing steps, the hydroxyl group of the organopolyoxyalkylene (a-1), the amine group and the thiol group do not share an electron pair, and participate in the formation of a π-bonding or ring-opening reaction to The vinyl group and the (meth) acrylate of the polyoxyalkylene (a-2) form a covalent bond with the epoxy group. The increased cross-linking condition provides a film having a high density and a significantly improved hardness after the thermal curing step, such as 7H or greater, or even close to 8H.

Hereinafter, the present invention will now be described in more detail with reference to Preparation Examples, Examples and Comparative Examples, and the scope of the invention is not limited thereto. It is to be understood that the invention may be modified and altered by those skilled in the art, which are also within the scope of the invention.

In the following examples, the weight average molecular weight was determined by gel permeation chromatography (GPC) using polystyrene standards.

Preparation Example 1: Preparation of Organic Polyoxane (IPL-001)

633 g of distilled water was placed in a three-necked round bottom flask equipped with a cooling jacket and a condenser, followed by mixing 30 g of acetic acid into distilled water. To cool the medium at 3 ° C in the jacket, the temperature of the mixture was cooled to about 5 ° C and the mixture was stirred at about 300 rpm with a stirrer. 160 g of γ-propylene decyloxypropyltrimethoxydecane was added to the mixture using a metering pump at a rate of 1.3 g/min. The reaction temperature was maintained below 10 ° C for 3 hours of hydrolysis and condensation polymerization. After the completion of the polymerization, the reaction mixture was allowed to stand for 30 minutes. Next, propylene glycol methyl ether acetate was added to the reaction mixture, and allowed to react for about 30 minutes to dissolve the organodecane. Subsequently, methanol and water contained in the reaction mixture were removed by atmospheric distillation. 633 g of distilled water was added to the remaining reaction mixture, which was then stirred for 1 hour to remove acetic acid and alcohol. After removing water by low-temperature vacuum distillation, the reaction product was aged at 40 ° C for 72 hours to obtain an organic decane polymer (IPL001). The organosiloxane polymer had an adhesion of 43.8 cP and a yield of 88.2%.

Preparation Example 2: Preparation of Organic Polyoxane (IPL-002)

The procedure of Preparation Example 1 was repeated except that 160 g of vinyltrimethoxydecane was used instead of 160 g of γ-acrylenyloxypropyltrimethoxydecane to obtain an organic decane polymer (IPL002). The adhesion of the product was determined to be 42.1 cP by a Brookfield viscometer, and the yield was 81.2%.

Preparation Example 3: Preparation of Organic Polyoxane (IPL-003)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-glycidoxypropyltrimethoxydecane was used instead of 160 g of γ-propylene decyloxypropyltrimethoxydecane to obtain an organic oxirane. Alkane polymer (IPL003). The adhesion of the product was determined to be 46.8 cP by a Brookfield viscometer and the yield was 86.1%.

Preparation Example 4: Preparation of Organic Polyoxane (IPL-004)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-mercaptopropyltrimethoxydecane was used instead of 160 g of γ-acrylenyloxypropyltrimethoxydecane to obtain an organic decane polymer (IPL004). ). Adhesion of the product via Brinell The meter measured 40.2 cP and the yield was 83.3%.

Preparation Example 5: Preparation of Organic Polyoxane (IPL-005)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-hydroxypropyltrimethoxydecane was used instead of 160 g of γ-propylene decyloxypropyltrimethoxydecane to obtain an organic decane polymer (IPL005). . The adhesion of the product was determined to be 38.5 cP by a Brookfield viscometer and the yield was 84.9%.

Preparation Example 6 Preparation of Organic Polyoxane (IPL-006)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-aminopropyltrimethoxydecane was used instead of 160 g of γ-acrylenyloxypropyltrimethoxydecane to obtain an organomethoxyalkylene polymer ( IPL006). The adhesion of the product was determined to be 44.1 cP by a Brookfield viscometer and the yield was 83.6%.

Preparation Example 7 Preparation of Organic Polyoxane (IPL-007)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-propenyloxypropyltrimethoxydecane/tetramethoxydecane (molar ratio of 8:2) was used instead of 160 g of γ-acrylonitrile. In addition to oxypropyltrimethoxydecane, an organic decane polymer (IPL007) was obtained. The adhesion of the product was determined to be 44.1 cP by a Brookfield viscometer and the yield was 83.6%.

Preparation Example 8 Preparation of Organic Polyoxane (IPL-008)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-mercaptopropyltrimethoxydecane/tetramethoxydecane (molar ratio of 8:2) was used instead of 160 g of γ-acryloxypropylpropyl. In addition to trimethoxy decane, an organic decane polymer (IPL008) was obtained. The adhesion of the product was determined to be 37.1 cP by a Brookfield viscometer and the yield was 83.4%.

Preparation Example 9 Preparation of Organic Polyoxane (IPL-009)

The procedure of Preparation Example 1 was repeated except that 160 g of vinyltrimethoxydecane/γ-glycidoxypropyltrimethoxydecane/tetramethoxydecane was used (the molar ratio was 4:4:2). In place of 160 g of γ-acrylenyloxypropyltrimethoxydecane, an organic decane polymer (IPL009) was obtained. The adhesion of the product was determined to be 41.6 cP by a Brookfield viscometer and the yield was 84.2%.

Preparation 10: Preparation of an organic polyoxane (IPL-010)

The procedure of Preparation Example 1 was repeated except that 160 g of γ-hydroxypropyltrimethoxydecane/γ-aminopropyltrimethoxydecane/tetramethoxydecane (molar ratio of 4:4:2) was used. Instead of 160 g of γ-acrylenyloxypropyltrimethoxydecane, an organic decane polymer (IPL010) was obtained. The adhesion of the product was determined to be 43.2 cP by a Brookfield viscometer and the yield was 85.9%.

Example 1

The liquid curable resin composition was prepared by mixing the following components: 50 parts by weight of organopolyoxyalkylene IPL-001 (based on solid content) and 50 parts by weight of organopolyoxyalkylene IPL-004 (in terms of solid content) a mixture of 50 parts by weight of M-520 (Toagosei Co., Ltd.) as an acrylic compound having an ethylenically unsaturated double bond; 0.3 part by weight of GPTMS (γ-glycidoxypropyl) Trimethoxydecane, Aldrich) as a decane coupling agent; 2.5 parts by weight of N-1919 (Adeka) as a photopolymerization initiator; 0.16 parts by weight of FZ2122 (Dow Corning Toray) as a surfactant; and propylene glycol A The base ether acetate is used as an organic solvent in an amount such that the weight ratio of (a+b+c+d+e)/(a+b+c+d+e+f) is 25%.

The resulting curable resin composition was aged at 4 ° C for 12 hours and filtered through a 1.0 μm filter. The resulting composition is spin coated onto a glass or tantalum substrate and pre-baked and exposed, followed by development to form a negative pattern. Finally, the coating was post-baked at 150 ° C for 10 minutes to obtain a cured film. Determining the mechanical properties of the cured film, Including development properties, transmittance, film retention, adhesion, heat resistance and surface hardness.

Example 2

The procedure of Example 1 was repeated except that a mixture of IPL-002 and IPL-004 (50:50 by weight) obtained from Preparation Examples 2 and 4, respectively, was used as the organic polyoxoxane to obtain a cured film.

Example 3

The procedure of Example 1 was repeated except that a mixture of IPL-003 and IPL-004 (50:50 by weight) obtained from Preparation Examples 3 and 4, respectively, was used as the organopolyoxane to obtain a cured film.

Example 4

The procedure of Example 1 was repeated except that a mixture of IPL-001 and IPL-005 (50:50 by weight) obtained from Preparation Examples 1 and 5, respectively, was used as the organic polyoxoxane, and a cured film was obtained.

Example 5

The procedure of Example 1 was repeated except that a mixture of IPL-002 and IPL-005 (50:50 by weight) obtained in Preparation Examples 2 and 5, respectively, was used as the organic polyoxoxane, and a cured film was obtained.

Example 6

The procedure of Example 1 was repeated except that a mixture of IPL-003 and IPL-005 (50:50 by weight) obtained from Preparation Examples 3 and 5, respectively, was used as the organic polyoxoxane, and a cured film was obtained.

Example 7

The procedure of Example 1 was repeated except that the use was obtained from the preparation examples. A cured film was obtained as a mixture of IPL-001 and IPL-006 of 1 and 6 (weight ratio of 50:50) as an organic polyoxoxane.

Example 8

The procedure of Example 1 was repeated except that a mixture of IPL-002 and IPL-006 (50:50 by weight) obtained in Preparation Examples 2 and 6, respectively, was used as the organopolyoxane to obtain a cured film.

Example 9

The procedure of Example 1 was repeated except that a mixture of IPL-003 and IPL-006 (50:50 by weight) obtained in Preparation Examples 3 and 6, respectively, was used as the organopolyoxane, and a cured film was obtained.

Example 10

The procedure of Example 1 was repeated except that a mixture of IPL-007 and IPL-008 (50:50 by weight) obtained from Preparation Examples 7 and 8, respectively, was used as the organic polyoxoxane to obtain a cured film.

Example 11

The procedure of Example 1 was repeated except that a mixture of IPL-009 and IPL-004 (50:50 by weight) obtained from Preparation Examples 9 and 4, respectively, was used as the organic polyoxoxane to obtain a cured film.

Example 12

The procedure of Example 1 was repeated except that a mixture of IPL-003 and IPL-010 (50:50 by weight) obtained from Preparation Examples 3 and 10, respectively, was used as the organic polyoxoxane to obtain a cured film.

Example 13

The procedure of Example 1 was repeated except that the use was obtained from the preparation examples. A mixture of IPL-003 and IPL-004 (weight ratio of 30:70) of 3 and 4 was used as an organic polyoxoxane to obtain a cured film.

Example 14

The procedure of Example 1 was repeated except that a mixture of IPL-003 and IPL-004 (70:30 by weight) obtained from Preparation Examples 3 and 4, respectively, was used as the organic polyoxoxane to obtain a cured film.

Comparative example 1

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-001 obtained in Preparation Example 1 was used as the organic polyoxoxane to obtain a cured film.

Comparative example 2

The procedure of Example 1 was repeated except that 100 parts by weight of the IPL-002 amount obtained in Preparation Example 2 was used as the organopolyoxane to obtain a cured film.

Comparative example 3

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-003 from Preparation Example 3 was used as the organopolyoxane to obtain a cured film.

Comparative example 4

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-004 obtained in Preparation Example 4 was used as the organopolyoxane to obtain a cured film.

Comparative Example 5

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-005 from Preparation Example 5 was used as the organic polyoxoxane to obtain a cured film.

Comparative Example 6

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-006 obtained in Preparation Example 6 was used as the organic polyoxoxane to obtain a cured film.

Comparative Example 7

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-001 derived from Preparation Example 1 was used as the organopolyoxane, and M-520 (Toagosei) having an ethylenically unsaturated double bond was not used. A cured film was obtained in addition to the acrylic compound.

Comparative Example 8

The procedure of Example 1 was repeated except that 100 parts by weight of IPL-004 obtained in Preparation Example 4 was used as the organopolyoxane, and M-520 (Toagosei) having an ethylenically unsaturated double bond was not used as A cured film was obtained in addition to the acrylic compound.

In Tables 2 and 3, the trifunctional oxirane unit is abbreviated as "T"; the tetrafunctional siloxane unit is abbreviated as "Q"; an acrylic compound having one or more ethylenically unsaturated double bonds The abbreviation is "MM"; and the methoxyalkane unit derived from tetramethoxy decane is abbreviated as "TEOS".

The cured films obtained in the examples and the comparative examples were tested in accordance with the following methods to evaluate their physical properties.

Test Example 1: Developing properties

The curable resin composition was spin-coated on the ruthenium substrate, prebaked, and dried on a hot plate at 110 ° C for 90 seconds to produce a coating film having a thickness of 2.5 μm. The coated film was exposed through a mask with an exposure of about 30 mJ/cm ² based on an aligner (MA6) using a wavelength of 365 nm with an emission wavelength of 200 to 450 nm. The film was then developed by spraying a developer through a nozzle at 25 ° C, which was an aqueous solution containing 2.38% tetramethylammonium hydroxide. The developed film was heated at 150 ° C for 10 minutes to obtain a cured film.

The developing properties of the cured film were evaluated in accordance with the shape of the developed micropattern. Observing the cured film with a line by scanning electron microscope according to the following standards The pattern formed in the contact hole having a width of 10 μm was evaluated, and the shape of the developed micropattern was evaluated.

○: The rectangle is clear and no bottom smearing is observed.

△: The rectangle is clear, but the surface of the cured film is not smooth or the film spots remain.

X: The rectangle is not clear, or the cured film is not developed.

Test Example 2: Transmittance

A cured film having a thickness of 2.5 μm was prepared in the same manner as described above except that the glass substrate was used instead of the tantalum substrate. The transmittance of the obtained cured film in the wavelength range of 400 to 800 nm was measured by ultraviolet/visible spectroscopic analysis.

Test Example 3: Adhesion

The cured film cross-cut test was carried out in accordance with ASTM D3359 using the 2.5 μm thick cured film prepared above, wherein the adhesion of the cured film was evaluated according to the following criteria.

OB: The cured film is broken into a thin layer, and more than 65% of the film is delaminated from the substrate.

1B: The end of the cut portion of the cured film and the crystal lattice are delaminated from the substrate, and the delamination region is more than 35% and less than or equal to 65%.

2B: The crystal lattice of the portion of the cured film cutting portion is delaminated from the substrate, and the delamination region is more than 15% and less than or equal to 35%.

3B: The crystal lattice of the portion of the cured film cut portion is delaminated from the substrate, and the delamination region is more than 5% and less than or equal to 15%.

4H: The crystal lattice of the portion of the cured film cut portion is delaminated from the substrate, and the delamination region is 5% or less.

5H: The end of the cured portion of the cured film was smooth, and no lattice was delaminated from the substrate.

Test Example 4: Surface hardness

The evaluation of the surface hardness of the cured film was based on the pencil hardness test of ASTM D3363. Specifically, the Mitsubishi pencil is brought into contact with the cured film formed on the substrate. It was placed thereon with a weight of 500 g to increase the load, and then the surface of the cured film was cut at a speed of 50 mm/sec. The surface of the film was observed with the naked eye, and the highest pencil hardness of the damage such as abrasion, delamination, tearing, and scratching was not observed on the cured film as its surface hardness.

Test Example 5: Heat resistance

The heat resistance of the cured film was evaluated by thermo-gravimetric analysis (TGA) under the following test conditions. The cured film was heated from 30 ° C to 130 ° C at a heating rate of 10 ° C / min, and heated at 130 ° C for 5 minutes to remove moisture, followed by dropping the temperature to 30 ° C. Subsequently, the sample was heated to 150 ° C at a heating rate of 10 ° C / min, and heated at 150 ° C for 30 minutes. The sample was cooled to 30 ° C, then the change in weight was measured and recorded as a percentage (%). The lower the weight loss, the better the heat resistance.

Test Example 6: Film retention rate

The film retention rate of the cured film at 30 mJ/cm ² was measured and expressed as a percentage (%), and the thickness of the cured film after post-baking was compared with that after prebaking using a surface analyzer (ALPHA-STEP IQ). Thickness (2.5 μm).

[Test Results]

The development properties, light transmittance, adhesion, surface hardness, heat resistance and film maintenance ratio of the samples obtained in the examples and the comparative examples are shown in Table 4 below.

Table 4 lists samples prepared according to (i) examples (in which a mixture of organopolyoxane (a-1) and (a-2) is used), and a sample prepared according to (ii) a comparative example (in which organic is used) Test results of polyoxyalkylene (a-1) and (a-2).

According to an embodiment of the present invention, a mixture of organopolyoxane (a-1) and (a-2) in a ratio of 1:1, 3:7 and 7:3 is used to form a curable resin composition. The film prepared by subjecting the composition to exposure, development, and heat curing has improved resolution, hardness, heat resistance, and light transmittance.

The vinyl group, the acrylate group and the epoxy group of the organic polyoxyalkylene (a-1) are in the form of a ring or contain an unsaturated π bond. Hydroxyl, amine and sulfur of organic polyoxane (a-2) The alcohol group has an unshared electron pair and is nucleophilic. The functional group of the organopolyoxyalkylene (a-1) and the nucleophilic functional group of the organopolyoxane (a-2) are involved in the crosslinking reaction during the curing step, thereby improving the hardness of the film while improving the film maintenance. Rate, surface hardness and heat resistance.

According to an embodiment of the present invention, a curable resin composition comprising both of the organopolyoxane (a-1) and (a-2) is confirmed to have good developing properties at the developing step without exhibiting the following defects, Such as the formation of insoluble residual film, irregular surface smoothness, reduced light transmission and the like. After heat curing, the film density is increased by cross-linking, thereby improving the hardness and heat resistance of the film and avoiding any cracks on the surface caused by shrinkage. Further, the film of the present invention is suitable for forming a micropattern due to low shrinkage after heat curing, has good adhesion, and has excellent film maintenance ratio.

On the other hand, in the comparative example, since the curable resin composition was prepared by using one of the organopolyoxanes (a-1) and (a-2), crosslinking did not occur as in the examples. reaction. Therefore, the film has a relatively low density and a reduced hardness. Films formed from these compositions also have problems of poor adhesion and heat resistance. Since the load resistance is poor, heat resistance is insufficient even after heat treatment.

While the invention has been described with respect to the specific embodiments described above, it is understood that the invention may be modified and modified by those skilled in the art and still fall within the scope of the invention. As defined in the scope.

Claims (9)

A curable resin composition comprising: (a) (a-1) an organopolyoxane containing a siloxane unit having a selected from the group consisting of a vinyl group, a (meth) acrylate, and a ring One or more functional groups of the group consisting of oxy groups; (a-2) an organopolyoxane containing a siloxane unit having a selected from the group consisting of a hydroxyl group, an amine group and a thiol group One or more functional groups that make up the group; and (b) an acrylic compound having one or more ethylenically unsaturated double bonds. The curable resin composition according to claim 1, wherein the organopolyoxane (a-1) comprises one or more siloxane units selected from the group consisting of Chemical Formulas I and II. And the organopolyoxane (a-2) comprises one or more oxoxane units selected from the group consisting of Chemical Formulas III and IV: Wherein each of A is independently a single bond, a C ₁ -C ₉ alkylene group, a C ₃ -C ₁₄ cycloalkylene group, a C ₆ -C ₁₄ aryl group, a C ₇ -C ₁₄ alkyl aryl group or a C _7- C ₁₄ arylalkylene; and each of X is independently vinyl, (meth) acrylate, -Z or -O(CH ₂ ) _n Z, wherein Z is an epoxy group, and n is 0 To an integer of 5, Wherein each of B is independently a single bond, a C ₁ -C ₉ alkylene group, a C ₃ -C ₁₄ cycloalkylene group, a C ₆ -C ₁₄ aryl group, a C ₇ -C ₁₄ alkyl aryl group, or C ₇ -C ₁₄ arylalkylene; and each of Y is independently -OH, -NH ₂ or -SH. The curable resin composition according to claim 2, wherein any one or both of the organopolyoxane (a-1) and (a-2) are further selected from the chemical formula V, One or more oxoxane units of the group consisting of VI and VII: Wherein each of R is independently H, C ₁ -C ₉ alkyl, C ₃ -C ₁₄ cycloalkyl, C ₆ -C ₁₄ aryl, C ₇ -C ₁₄ alkylaryl or C ₇ -C ₁₄ Arylalkyl. The curable resin composition according to claim 3, wherein either or both of the organopolyoxanes (a-1) and (a-2) comprise a oxoxane unit of the formula VII. The curable resin composition according to claim 3, wherein the organopolyoxane (a-1) comprises a content based on the total number of moles of the organopolysiloxane (a-1) 1 to 90 mol% of a oxoxane unit having one or more functional groups selected from the group consisting of a vinyl group, a (meth) acrylate and an epoxy group; and the organopolyoxane ( A-2) comprising a group selected from the group consisting of a hydroxyl group, an amine group and a thiol group, in an amount of from 1 to 90 mol% based on the total moles of the organopolysiloxane (a-2) One or more functional group of oxane units. The curable resin composition according to claim 5, wherein the weight ratio of the organopolyoxane (a-1) to the organopolyoxane (a-2) of the curable resin composition The range is from 1:99 to 99:1. The curable resin composition according to claim 1, which further comprises a (c) decane coupling agent, (d) a photopolymerization initiator, (e) a surfactant, and (f) One or more of the groups of organic solvents. The curable resin composition according to claim 3, which further comprises a (c) decane coupling agent, (d) a photopolymerization initiator, and (e) a surfactant. And (f) one or more groups of organic solvents. The curable resin composition according to claim 8, which comprises, based on the solid content, 100 parts by weight of the organopolyoxane (a-1) and (a-2); 80 parts by weight of the acrylic compound (b) having one or more ethylenically unsaturated double bonds; 0.01 to 10 parts by weight of the decane coupling agent (c); 0.5 to 10 parts by weight of the photopolymerization initiation The agent (d); and 0.05 to 10 parts by weight of the surfactant (e), wherein the curable resin composition contains the organic solvent in an amount such that the solid content of the curable resin composition is 10 to 50% by weight (f).