WO2019093827A1 - Copolymer having photocurable and thermosetting property, and photosensitive resin composition, photosensitive resin film, and color filter using same - Google Patents

Abstract

The present invention relates to a copolymer having photocurable and thermosetting properties, which shows excellent thermosetting at relatively low temperatures and can also undergo a photocuring process upon light exposure, thus ensuring excellent durability, chemical resistance, and storage stability through the sufficient hardening, and a photosensitive resin composition, a photosensitive resin film, and a color filter using the same.

Description

 Title of the Invention

 A photosensitive resin composition using the same, a photosensitive resin film, and a color filter

 TECHNICAL FIELD

Cross-reference with related application (s)

 This application claims the benefit of priority based on Korean Patent Application No. 10-20Γ7-0149676 dated November 10, 2017, and Korean Patent Application No. 10-2018-0136598 dated November 8, 2018, All of which are incorporated herein by reference.

 The present invention relates to a copolymer having photo-curable properties and thermosetting properties, a photosensitive resin composition using the same, a photosensitive resin film, and a color filter. More specifically, the present invention relates to a thermosetting resin composition which has an excellent thermosetting property at a relatively low temperature and can proceed with photo-curing by light irradiation, and has a photocurable property and a thermosetting property capable of having excellent durability, , A photosensitive resin composition using the same, a photosensitive resin film, and a color filter.

 TECHNICAL BACKGROUND OF THE INVENTION

 In the case of the RGB pattern in the color filter process, the photosensitive resin composition is coated using a spin or a slit coater, pre-baked, exposed, and developed.

Following the development, a final post-baking process of 220 ^° C or more is carried out. Generally used glasses do not deform at this temperature, but they can be applied to flexible displays. The plastic used has a problem that severe deformation occurs at a temperature of 220 ^° C or higher.

In order to reduce the deformation of the substrate, a method of lowering the temperature of the post-baking process is used. However, when the temperature of the post-baking process is lowered, the curing of the photosensitive resin composition becomes complete There is a problem that the residual gas phase is generated due to an increase in the amount of generated gas because the gas is not generated, and the chemical resistance and the heat resistance are lowered. Therefore, development of a material and a photosensitive resin composition for forming a cured film having excellent heat resistance and chemical resistance, which can be cured at a high level even at a low temperature, is required.

 DISCLOSURE OF THE INVENTION

 [Problem to be solved]

 The present invention provides a copolymer having photo-curability and thermosetting property which can have excellent durability, chemical resistance and storage stability through layered curing, which has an excellent thermosetting property at a relatively low temperature and can proceed with photo-curing by light irradiation .

 The present invention also provides a photosensitive resin composition, a photosensitive resin film, and a color filter using the copolymer having the photocurable and thermosetting properties.

 MEANS FOR SOLVING THE PROBLEMS

 In the present specification, a first (meth) acrylate repeating unit in which an organic functional group including an epoxy group is bonded to a branched chain terminal; And a second (meth) acrylate repeating unit in which an organic functional group including an alkenyl group is bonded to the branched chain terminal, wherein in the second (meth) acrylate repeating unit, the branch chain has a substitution An alkyl ester group having 1 to 20 carbon atoms; Or an oxyalkyl ester group having 1 to 20 carbon atoms substituted with a hydroxy group; Or an alkyl ester group substituted by a cycloalkyl group having 3 to 30 carbon atoms in which the hydroxy group is substituted; Or a multi-GLA alkyl ester group having 7 to 30 carbon atoms substituted with a hydroxy group; Or an alkyl ester group substituted by a multicyclic alkyloxy group having 7 to 30 carbon atoms substituted with a hydroxy group.

 The present specification also includes copolymers having the photocurable and thermosetting properties described above; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a photo-initiator.

The present invention also includes: 1) coating the photosensitive resin composition on a substrate to form a coating film; 2) drying the coating film; 3) irradiating the dried coating film with light to cure the coating; And 4) thermosetting the photocured film at 50 ^° C to 250 ^° C. A manufacturing method is provided.

 The present specification also includes copolymers having the photocurable and thermosetting properties described above; And a photopolymerizable monomer having two or more photocurable avidity functional groups.

 In this specification, there is also provided a color filter including the above photosensitive resin film. In this specification, when a component is referred to as " comprising ", it means that it can include other components, aside from other components, unless specifically stated otherwise.

 In the present specification, the term " substituted " means that a different functional group is bonded in place of a hydrogen atom in a compound, and the position to be substituted is not limited as long as the position where the hydrogen atom is substituted, , Two or more substituents may be the same as or different from each other.

 In the present specification, "+" or "*" means a bond connected to another substituent, and a direct bond means a case where no separate atom exists in a portion represented by "L".

 As used herein, "(meth) acryl" may mean acryl or methacryl.

In the present specification, the weight average molecular weight refers to the weight average molecular weight in terms of polystyrene measured by the GPC method. In the process of measuring the weight average molecular weight in terms of polystyrene measured by the GPC method, a detector such as a known analyzer and a refractive index detector may be used, and a column for analysis may be used. The silver condition, solvent, f low rat e can be applied. As a specific example of the above measurement conditions, the evaluation temperature is 160 ^° C using a Waters PL-GPC220 instrument using a Polymer Laboratories PLeg MIX-B 300 osmagnetic column and 1, 2, 4-trichlorobenzene Was used as a solvent. The flow rate was adjusted to a flow rate of ImL / min, the sample was adjusted to a concentration of 10 mg / lOmL, and the solution was supplied in an amount of 200 iiL. The value of Mw was determined using a calibration curve formed using polystyrene standards . The molecular weight of the polystyrene standards was 2,000 I 10,000 I 30,000 I 70,000 I 200,000 I 700,000 / 2,000,000 / 4,000,000 / 10,000,000. In the present specification, the alkyl group is a monovalent functional group derived from an alkane, for example, straight, branched or cyclic, and includes methyl, ethyl, propyl, isobutyl, secbutyl, tert -Butyl, pentyl, or novolac. One or more hydrogen atoms included in the alkyl group may be substituted with another substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, an alkynyl group having 6 to 10 carbon atoms An aryl group having 2 to 12 carbon atoms, a heteroaryl group having 2 to 12 carbon atoms, an arylalkyl group having 6 to 12 carbon atoms, a halogen atom, a cyano group, an amino group, an amidino group, a nitro group, an amide group, a carbonyl group, A methine group, and an alkoxy group having 1 to 10 carbon atoms.

 In this specification, the cycloalkyl group is not particularly limited, and examples thereof include monovalent functional groups derived from monocyclic cycloalkane. Examples thereof include, but are not limited to, preferably 3 to 60 carbon atoms, , The cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another state, the number of carbon atoms of the cycloalkyl group is 3-6. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- , 4, 5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like.

 In the present specification, the multi-ring alkyl group is not particularly limited, but is a monovalent functional group derived from a polycyclic cycloalkane. Examples thereof include, but are not particularly limited to, preferably 3 to 60 carbon atoms, The cycloalkyl group has 3 to 30 carbon atoms. Specific examples thereof include, but are not limited to, Nor bornane, 2,3-tr imethylenenorbornane, and the like.

In the present specification, the aryl group is a monovalent functional group derived from arene For example, monocyclic or polycyclic. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a stilbenyl group, or the like, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group, a fluorenyl group, and the like, but is not limited thereto. At least one hydrogen atom in each of these aryl groups may be substituted with the same substituent as in the case of the alkyl group.

 In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl,

Propenyl isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1-butenyl; 1, 3-butadienyl, allyl, 1-phenylvinyl-1-yl,

2-phenyl-2- (naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl- 1-yl) vinyl-1-yl, stilbenyl, styrenyl, and the like.

 In the present specification, an alkylene group is a divalent functional group derived from an alkane, and has 1 to 20, or 1 to 10, or 1 to 5 carbon atoms. For example, it may be a straight chain, branched or cyclic group such as a methylene group, an ethylene group, a propylene group, an isobutylene group, a sec-butylene group, a tert-butylene group, a pentylene group and a nuclear silicone group. The at least one hydrogen atom contained in the lower alkylene group may be substituted with the same substituent as in the case of the above alkyl group.

In the present specification, the oxyalkylene group is a functional group derived from the alkylene group and has a structure in which an ether group (-O-) is bonded to one terminal of the alkylene group, and the number of carbon atoms is 1 to 20, or 1 to 10, or 1 To 5. Examples of the hydrocarbon group include straight chain, branched or cyclic groups such as an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxy n-butylene group, an oxyisobutylene group, an oxy sec-butylene group, A pentylene group, an oxyhexylene group and the like. The at least one hydrogen atom contained in the oxyalkylene group may be substituted with the same substituent as in the case of the alkyl group. In the present specification, the cycloalkylene group is a divalent functional group derived from cycloalkane and has 3 to 30 carbon atoms, or 3 to 20 carbon atoms, or 3 to 10 carbon atoms. Examples of the cyclic olefins include cyclopentylene, cyclopentylene, cyclopentylene, 3-methylcyclopentylene, 2,3-dimethylcyclopentylene, cyclohexylene, 3-methylcyclohexylene, 4-methylcyclohexylene, But are not limited to, 3-dimethylcyclonucleosilane, 3,4,5-trimethylcyclohexylsilane, 4-tert-butylcyclonucleosilane, cycloheptylene, cyclooctylene and the like.

 In the present specification, the multi-ring alkylene group means a divalent functional group derived from a multi-ring alkane, which is a polycyclic cycloalkane, in which one hydrogen atom has been substituted with a functional group in the multi-middle alkyl group.

 In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 30 carbon atoms. Specifically, the compound may be a compound having the following structure. .

 In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group or a multi-ring alkyl group having 1 to 25 carbon atoms in the ester group. The ester group substituted with the alkyl group may be referred to as an " alkyl moiety group ", and the ester moiety substituted with the polyhydric allyl group may be referred to as a " multi-ring alkyl ester group ". BEST MODE FOR CARRYING OUT THE INVENTION Copolymers having photo-curable properties and thermosetting properties, photosensitive resin compositions using them, photosensitive resin films, and color filters according to specific embodiments of the present invention will be described in detail below.

I. Copolymers having photo-curable and thermosetting properties

According to one embodiment of the present invention, there is provided a resin composition comprising: a first (meth) acrylate repeating unit having a branched functional group bonded to a branched functional group containing an epoxy group; And at the branched end (Meth) acrylate repeating unit in which an organic functional group including an alkenyl group is bonded, and in the second (meth) acrylate repeating unit, the branched chain is an alkyl ester group having 1 to 20 carbon atoms substituted with a hydroxy group ; Or an alkyl ester group substituted by a cycloalkyl group having 3 to 30 carbon atoms in which a hydroxy group is substituted; Or a multicyclic alkyl ester group having 7 to 30 carbon atoms substituted with a hydroxy group; Or an alkyl ester group substituted by a multicyclic alkyloxy group having 7 to 30 carbon atoms in which the hydroxyl group has been substituted can be provided.

 The present inventors have found that, in the case of a copolymer having photo-curable and thermosetting properties containing the above two types of repeating units, an organic functional group containing an alkenyl group contained in the repeating unit of (meth) The photo-curing can be carried out to form a primary curing structure, and an organic functional group including an epoxy group contained in the repeating unit of (meth) acrylate can be thermally cured at a low temperature of less than 200 ° C to form a secondary As the cured structure is formed, sufficient curing can proceed by thermal curing and light curing at low temperatures. Through this experiment, it was confirmed through experiments that the final cured film can have excellent durability and chemical resistance and that the photosensitive resin composition before curing is also excellent in storage stability, and completed the invention.

Specifically, the photopolymerizable and thermosetting copolymers may include a first (meth) acrylate repeating unit having an organic functional group including an epoxy group bonded to the branched chain terminal. (Meth) acrylate repeating unit, the epoxy group contained in the first (meth) acrylate repeating unit can form a cured structure through thermal curing even at a temperature of less than 200 ^° C .

 In the first (meth) acrylate repeating unit, a chain formed through the double bond-containing reaction of (meth) acrylate is referred to as a main chain, and a chain branched from the main chain Branched chain or side chain.

The repeating unit of the (meth) acrylate is a repeating unit contained in the homopolymer of the (meth) acrylate monomer, and the repeating unit of the main chain (meth) acrylate monomer May contain an ester functional group contained in a polyethylene chain or a branched (meth) acrylate monomer by polymerization of a vinyl group contained in the polymer. That is,

In the (meth) acrylate repeating unit, the branch chain terminal at which the organic functional group including the epoxy group is combined can terminate the ester functional group contained in the (meth) acrylate repeating unit.

 In the above-mentioned 1 (meth) acrylate repeating unit, the branched chain may be a carbonyl group (-C0-) or an alkyl ester group having 1 to 20 carbon atoms (R 'COO-; R' is an alkyl group having 1 to 20 carbon atoms); Or an oxyalkyl ester group having 1 to 20 carbon atoms; And the organic functional group including the epoxy group may be bonded to the terminal of the carbonyl group or the alkyl group having 1 to 20 carbon atoms contained in the alkyl ester group having 1 to 20 carbon atoms.

 The organic functional group including the epoxy group may include a functional group composed of only an epoxy group or a functional group having an epoxy group bonded to another organic functional group, and specifically includes a functional group represented by the following formula (1); Or a functional group represented by the following formula (2); Or a functional group represented by the following formula (3).

■

In Formula 1, R _1; R ₂ and R ₃ may each independently be a direct bond, hydrogen, or an alkyl group having 1 to 5 carbon atoms, and preferably R ₂ and R ₃ may be two hydrogen atoms.

 (2)

상기 화학식 2에서， I ᅳ 및 ¾는 각각 독립적으로 직접결합， 또는 탄 소수 1 내지 5의 알킬렌기 중 어느 하나일 수 있고， 바람직하게는 는 탄소 수 1의 메틸렌기， ¾는 탄소수 2의 에틸렌기일 수 있다.

In the general formula (2), I ᅳ and 는 each independently represents a direct bond or an alkylene group having 1 to 5 carbon atoms, preferably a carbon A methylene group of a number of 1, and an ethylene group of 2 carbon atoms.

 (3)

상기 화학식 3에서， , 및 R₇는 각각 독립적으로 직접결합， 또는 탄 소수 1 내지 5의 알킬렌기 중 어느 하나이고, X는 직접결합， -0-， 또는 -S- 중 어느 하나이다.

In Formula 3, R ₁ and R ₂ are each independently a direct bond or an alkylene group having 1 to 5 carbon atoms, and X is a direct bond, -O-, or -S-.

 Specifically, the repeating unit of the system 1 (meth) acrylate may be represented by the following formula (4).

 [Chemical Formula 4]

In the general formula (4), each of ¾ to R ₁₀ is independently hydrogen or an alkyl group having 1 to 10 carbon atoms, and the total number of carbon atoms in the alkylene group is 1 to 20, And Ru is an organic functional group including an epoxy group.

Preferably, in Formula 4, ¾ and R ₁₀ are each independently hydrogen, R ₇ is an alkyl group having 1 to 3 carbon atoms, and R is any one of a direct bond and an alkylene group having 1 or less carbon atoms, and R _u Is a functional group represented by the formula (1), a functional group represented by the formula (2), or a functional group represented by the formula (3). More preferably, in the formula (4), R is a direct bond, and R _n is a functional group represented by the formula (3). In the formula (4), silver is an alkylene group having 1 to 3 carbon atoms, and R _n may be a functional group represented by the formula (1), a functional group represented by the formula (2), or a functional group represented by the formula (3).

 Specifically, examples of the first (meth) acrylate repeating unit represented by Formula 4 include a repeating unit derived from glycidyl methacrylate represented by the following Formula 4-1 or 3, 4-epoxycyclohexylmethylmethacrylate 4-2 derived from the formula (A) shown below in Synthesis Example 3, and the following Formula (4-4) derived from the formula (B) shown in the following Synthesis Example 4,

 -One]

[화학식 4-3]

[Formula 4-3]

 The photopolymerizable and thermosetting copolymers may contain a repeating unit of the (meth) acrylate system in which an organic functional group including an alkenyl group is bonded to the branched chain end. The second (meth) acrylate repeating unit is contained in the second (meth) acrylate repeating unit, and the photocuring is performed by the light irradiation with the alkenyl group contained in the second (meth) acrylate repeating unit to form a dense cured structure have.

In the second (meth) acrylate repeating unit, when a chain formed through polymerization reaction of a double bond contained in (meth) acrylate is referred to as a main chain, a chain extending in a branch shape from the main chain is branched Or side chain (side chain).

 The repeating unit of the (meth) acrylate is a repeating unit contained in the homopolymer of the (meth) acrylate monomer. The repeating unit is a repeating unit derived from the polymerization of a vinyl group contained in the main chain (meth) ) ≪ / RTI > acrylate monomers. That is, in the second (meth) acrylate repeating unit, the branched chain terminal at which the organic functional group including an alkenyl group is bonded may mean the terminal of the ester functional group contained in the (meth) acrylate repeating unit.

 In the repeating unit of the (meth) acrylate, the branch chain is an alkyl ester group (R 'COO- wherein R' is an alkyl group having 1 to 10 carbon atoms) substituted with a hydroxyl group and having 1 to 20 carbon atoms or a carbon number of 1 to 10, Or an oxyalkyl ester group having 1 to 20 carbon atoms substituted with a hydroxy group, or an alkyl ester group substituted with a hydroxy group-substituted C3-C30, or C3-C10 cycloalkyl group, 30, or a multi-ring alkyl ester group having 8 to 15 carbon atoms, or an alkyl ester group substituted with a hydroxyl group-substituted multi-ring alkyloxy group having 7 to 30 carbon atoms or 8 to 15 carbon atoms.

 Specifically, the alkyl group having 1 to 20 carbon atoms contained in the alkyl ester group having 1 to 20 carbon atoms substituted with the hydroxy group, or the carbon number in the alkyl ester group substituted with the hydroxy group-substituted cycloalkyl group having 3 to 30 carbon atoms The organic functional group including the alkenyl group may be substituted at the terminal of the cycloalkyl group having 3 to 30 carbon atoms.

 In the multi-ring alkyl ester group having 7 to 30 carbon atoms substituted with a hydroxy group, the alkenyl group may be bonded to the end of the multi-ring alkyl group having 7 to 30 carbon atoms and contained in the polycyclic alkyl ester group having 7 to 30 carbon atoms Containing organic functional groups may be substituted.

Further, in the alkyl ester group substituted with the substituted polycyclic alkyloxy group having 7 to 30 carbon atoms, the terminal of the polycyclic alkyl group having 7 to 30 carbon atoms contained in the polycyclic alkyloxy group having 7 to 30 carbon atoms The organic functional group including the alkenyl group may be substituted. On the other hand, the hydroxy group may be substituted with a branched alkyl group having 1 to 10 carbon atoms in the alkyl ester group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or a polycyclic alkyl having 10 to 30 carbon atoms May be substituted with 10 to 30 multibranched alkyl groups contained in the stator group or 10 to 30 multibranched alkyl groups included in the above multichannel alkyloxy groups having 10 to 30 carbon atoms.

 The hydroxy group can be derived through the ring opening reaction of an epoxy group contained in the above-mentioned first (meth) acrylate repeating unit, more specifically, the epoxy group contained in the first (meth) acrylate repeating unit, And a compound containing an organic functional group including an alkenyl group ol.

 The organic functional group including the alkenyl group may include both a functional group composed solely of an alkenyl group or a functional group having an alkenyl group bonded to another organic functional group. Specifically, a (meth) acryloyl group, a (meth) acryloyloxy And the like can be used, and a methacryloyloxy group can be preferably used. Specifically, the second (meth) acrylate repeating unit may be represented by the following general formula (5).

 [Chemical Formula 5]

In the formula (5), R ₁₂ to R ₁₄ are each independently any one of hydrogen and an alkyl group having 1 to 10 carbon atoms, L ₂ is a direct bond or an alkylene group having 1 to 20 carbon atoms, And L ₃ represents an alkylene group having 1 to 20 carbon atoms substituted with a hydroxyl group or a cycloalkylene group having 3 to 30 carbon atoms substituted with a hydroxy group or a poly ring alkyl group having 7 to 30 carbon atoms substituted with a hydroxy group And R < ₁₅ > represents an alkenyl group Containing organic functional groups.

Preferably, R ₁₂ and R ₁₄ are each independently hydrogen, R ₁₃ is an alkyl group having 1 to 3 carbon atoms, L ₂ is a direct bond or an alkylene group having 1 to 10 carbon atoms, L ₃ is an alkylene group having 1 to 5 carbon atoms substituted with a hydroxy group, or a cycloalkylene group having 3 to 10 carbon atoms substituted with a hydroxy group, or a cycloalkylene group having a carbon number of 8 To 15 < RTI ID = 0.0 > polycyclic < / RTI >

More preferably, in the above formula (5), L ₂ is a direct bond and L ₃ is a polycyclic alkylene group having 10 to 20 carbon atoms substituted with a hydroxy group. Further, in Formula 5, L ₂ is a group having 1 to 10 carbon atoms, yet of an alkylene group, or a carbon number from 1 to ^'10 oxyalkylene groups, L ₃ is of a carbon number of 1 within the five substituted with hydroxy alkylene group, or a hydroxyl group A substituted cycloalkylene group having 3 to 10 carbon atoms, or a multi-ring alkylene group having 8 to 15 carbon atoms substituted with a hydroxy group. .

 Specifically, examples of the repetitive units of the geranyl (meth) acrylate represented by the formula (5) include the following formulas (5-1) to (5-4) Terminal epoxy group may be prepared by reacting with (meth) acrylic acid.

 ... -

[화학식 5-2]

[Formula 5-2]

[화학식 5-4]

[Formula 5-4]

 The molar ratio between the repeating unit of the (meth) acrylate and the repeating unit of the second (meth) acrylate may be from 99: 1 to 1:99. As described above, the photopolymerizable and thermosetting copolymers contain both the first (meth) acrylate repeating unit and the twelve (meth) acrylate repeating unit, so that the photocuring property and the low-temperature thermosetting property can be realized at the same time.

 (Meth) acrylate repeating unit is preferably used in an amount of 10 to 90 moles, or 20 to 70 moles, or 30 to 50 moles, based on 100 moles of the first (meth) acrylate repeating unit . If the content of the second (meth) acrylate repeating unit is less than 10 moles per 100 moles of the above-mentioned (meth) acrylate repeating units, the residual copolymer may cause a residue problem.

On the other hand, if the content of the repeating unit of (meth) acrylate is excessively increased to more than 90 moles relative to 100 moles of the first (meth) acrylate repeating unit, there is a problem that the conversion characteristics and chemical resistance of the resultant copolymer deteriorate Lt; / RTI > On the other hand, the copolymer having the photocurable property and the thermosetting property, (Meth) acrylate repeating unit represented by the following formula A maleimide repeating unit represented by the following formula (7); And a vinyl repeating unit represented by the following formula (8). Accordingly, the heat resistance and chemical resistance of the copolymer having the photo-curability and the thermosetting property can be improved.

 [Chemical Formula 6]

， R₁₆ 내지 R₂₆은 각각 독립적으로, 수소; 중 수소; 할로겐기; 탄소수 1 내지 20의 알킬기; 탄소수 1 내지 20의 알콕시기; 탄소수 6 내지 30의 단환 또는 다환의 아릴기; 탄소수 2 내지 20의 알케닐 기 ; 또는 탄소수 3 내지 30의 단환 또는 다환의 시클로알킬기 중 어느 하나 이고， L₄는 직접결합 또는 탄소수 1 내지 20의 알킬렌기，_.탄소수 1 내지 20 의 옥시알킬렌기 중 어느 하나이다.

, R ₁₆ to R ₂₆ each independently represent hydrogen; Hydrogen; A halogen group; An alkyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; A monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Or any one of a monocyclic or polycyclic cycloalkyl group having a carbon number of 3 to 30, and, L ₄ is a bond or an alkylene group having 1 to 20 carbon _atoms. And an oxyalkylene group having 1 to 20 carbon atoms.

More specifically, in the third (meth) acrylate repeating unit represented by Formula 6, R ₁₆ and R ₁₈ are hydrogen, R ₁₇ is a methyl group, L ₄ is a methylene group, Ri ₉ may be a phenyl group. That is, the third (meth) acrylate repeating unit may be a repeating unit derived from benzyl methacrylate.

In the maleimide repeating unit represented by Formula 7, R ₂₀ and R ₂₁ may be hydrogen, and R ₂₂ may be a phenyl group. In the vinyl repeat unit represented by the formula (8), ¾ ₃ , ¾ ₄ and 5 may be hydrogen and R ₂₆ may be a phenyl group. That is, the maleimide repeating unit represented by Chemical Formula 7 may be a repeating unit derived from N-phenylmaleimide, and the vinyl repeating unit represented by Chemical Formula 8 may be a styrene derived repeating unit. (Meth) acrylate repeating unit and the first (meth) acrylate repeating unit is in the range of 1:99 to 99: 1, and the second (meth) acrylate repeating unit and the second ) Acrylate repeat units may be from 1:99 to 99: 1. As described above, when the first (meth) acrylate repeating unit, the second (meth) acrylate repeating unit, and the third (meth) acrylate repeating unit are used together, technical and chemical resistance Effects can be realized.

 The weight average molecular weight (GPC measurement) of the photopolymerizable and thermosetting copolymers may be from 1,000 g / mol to 100,000 g / m.

 On the other hand, the copolymer having photo-curable properties and thermosetting properties is a copolymer of a 1 (meth) acrylate repeating unit in which an organic functional group including an epoxy group is bonded to a branched chain terminal; A second (meth) acrylate repeating unit in which an organic functional group containing an alkenyl group is bonded to a branched chain terminal; The crab 3 represented by the above formula (6)

(Meth) acrylate repeating units; A maleimide repeating unit represented by the above formula (7); And the vinyl repeating unit represented by the formula (8). That is, the copolymer having the photocurable property and the thermosetting property may not further contain additional repeating units other than the above-mentioned five repeating units. Accordingly, the copolymer having photo-curing property and thermosetting property can secure high reliability by suppressing spontaneous intracellular reaction before curing proceeds.

 For example, when the copolymer having the photocurable property and the thermosetting property is the above-mentioned

As additional repeating units other than the five repeating units, the second

(Meth) acrylate repeating units and acid anhydrides, the terminal carboxyl group formed by the ring opening reaction of the acid anhydride (Meth) acryl functional group or an epoxy group, the physical properties of the copolymer having the photo-curability and the thermosetting property are difficult to be realized.

 Examples of the method of synthesizing the copolymer having the photocurable property and the thermosetting property are not limited. For example, a method of synthesizing a monomer mixture containing a (meth) acrylate monomer substituted with an organic functional group containing an epoxy group at the terminal And then reacting a compound containing an organic functional group including an alkenyl group. Examples of the (meth) acrylate monomer having an epoxy group-substituted organic functional group at the terminal thereof include glycidyl methacrylate or 3,4-epoxycyclohexylmethyl methacrylate, And the following formula 4-4 derived from the formula B of the following synthesis example 4, and the like. Examples of the compound containing an organic functional group containing the alkenyl group include methacrylic acid, . In addition, as the monomer mixture, benzyl methacrylate, N-phenylmaleimide, and styrene may be added as other monomers used in the synthesis of co-polymers.

Π. Photosensitive resin composition

 According to another embodiment of the invention, there is provided a photopolymerizable and thermosetting copolymer of this embodiment; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a photoinitiator may be provided.

 The contents of the copolymer having the photocurable property and the thermosetting property are all included in the above embodiment.

 The photopolymerizable monomer may be a compound having a photocurable unsaturated functional group such as, for example, two or more polyfunctional vinyl groups. The photopolymerizable monomer may form a crosslinked structure with the unsaturated functional group of the copolymer having photocurable and thermosetting properties A cross-linking structure due to photo-curing can be formed during exposure. Thus, when forming the pattern film described later, the light-sensitive resin composition in the exposed portion can be left on the substrate without being subjected to alkali development.

Such a photopolymerizable monomer may be a liquid at room temperature, Accordingly, the viscosity of the phase-inversion photosensitive resin composition can be adjusted according to the application method, and the alkali developability of the non-visible portion can be further improved.

As the photopolymerizable monomer, an acrylate compound having at least two photocurable unsaturated functional groups can be used. As specific examples, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, pentaerythritol Acrylate compounds containing a hydroxyl group such as triacrylate or dipentaerythritol pentaacrylate; Water-soluble acrylate compounds such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, and polypropylene glycol diacrylate; Polyfunctional polyester acrylate compounds of polyhydric alcohols such as trimethyl acrylate, propane triacrylate, pentaerythritol tetraacrylate, or dipentaerythritol hexaacrylate; Acrylate compounds of polyfunctional alcohols such as trimethylol propane or hydrogenated bisphenol A or phenol oxidized adducts of polyhydric phenols such as bisphenol A and biphenol and / or propylene oxide adducts; A polyfunctional or monofunctional polyurethane acrylate-based compound which is an isocyanate-modified product of the hydroxyl group-containing acrylate; An epoxy acrylate-based compound which is a (meth) acrylic acid adduct of bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether or phenol novolac epoxy resin; Caprolactone-modified ditrimethylolpropane tetraacrylate, acrylate of _? -Caprolactone-modified dipentaerythritol, or caprolactone-modified hydroperoxide-derived neopentylglycollate and? -Stearyl acrylate Acrylate compounds modified with caprolactone, and photosensitive (meth) acrylate compounds such as a methacrylate compound which reacts with the above-mentioned acrylate compounds can be used, and these compounds can be used alone Or two or more of them may be used in combination. Among these, as the photopolymerizable monomer, a polyfunctional (meth) acrylate compound having at least two (meth) acryloyl groups in one molecule can be preferably used. Particularly, pentaerythritol can be used as triacrylate, trimethylol Propane triacrylate, dipentaerythritol hexaacrylate, or caprolactone modified ditrimethyl propane tetraacrylate can be suitably used. Examples of commercially available photopolymerizable monomers include DPEA-12 of Kayarad and the like. The content of the photopolymerizable monomer may be 0.1 wt% to 30 wt%, or 1 wt% to 20 wt% based on the total weight of the photosensitive resin composition. If the content of the photopolymerizable monomer is too small, the photocuring may become insufficient. If the content of the photopolymerizable monomer is excessively large, the dryability of the cured film may deteriorate and the physical properties may be deteriorated.

 On the other hand, the photoinitiator has a role of initiating radical photocuring between a photopolymerizable monomer and a copolymer having photo-curable properties and thermosetting properties, for example, in the exposed portion of the photosensitive resin composition.

 As the photoinitiator, known ones can be used, benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and the like, and alkyl ethers thereof; Acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4- (1-t-butyldoxy-

Acetophenones such as 1-methylethyl) acetophenone; Anthraquinones such as 2-methyl anthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone; Thioxanthones such as 2, 4-dimethylthioxanthone, 2,4-diisopropylthioxanthone and 2-chlorothioxanthone; Ketal such as acetophenone dimethyl ketal and benzyl dimethyl ketal; Benzophenones such as benzophenone, 4- (l-butyldioxy-1-methylethyl) benzophenone, and 3,3'-benzophenone such as 4,4'-tetrakis (t-butyldioxycarbonyl) You can use the same materials. Further, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-

2- (4-methylphenyl) methyl] -1- [4- (4-morpholino) Nyl) phenyl] -1-butanone, N, N-dimethylaminoacetophenone (commercially available as Irgacure (registered trademark) 907, Irgacure 369, Irgacure 369 manufactured by Ciba Specialty Chemicals (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2, 6-dimeroxycibenzoyl) -2, 4, 4-trimethyl-pentylphosphine oxide (commercially available as Lucyl (registered trademark)

TPO, IRGACURE 819, manufactured by Ciba Specialty Chemicals, etc.) and the like can be mentioned as preferred photoinitiators.

Examples of preferred photoinitiators include oxime esters. Specific examples of the oxime ester include 2- (acetyloxyiminomethyl) thioxanthien-9-one, (1, 2-octanediyl, 1- [4- (phenylthio) phenyl] Benzoyloxime)), (ethanone, 1 [9-ethyl Yl] -, 1- (0-acetyloxime)), and the like. Examples of commercially available products include GGI-325, Irugacure 0XE01, Irugacure 0XE02, ADEKA N-1919, and Chiron Specialty Chemicals Darocur TP0 from Chiba Specialty Chemicals.

The content of the photoinitiator is based on the total amount of resin composition 0.1 ^"increase% to

20% by weight, or 1% by weight to 10% by weight. If the content of the photoinitiator is too small, photocuring may not occur properly. On the contrary, if the content is excessively large, the resolution of the photosensitive resin composition may be lowered or the reliability of the patterned film may not be uniform.

 On the other hand, the photosensitive resin composition includes a solvent; And at least one selected from the group consisting of fillers, pigments and additives.

 The filler added in this way enhances thermal stability, dimensional stability by heat, and resin adhesion. It also acts as an extender pigment by enhancing the color. As the filler, inorganic or organic layer precursors can be used, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide ), Aluminum hydroxide, mica, and the like.

 The pigment exhibits visibility and hiding power, and as the pigment, red, blue, green, yellow, and a color pigment can be used. Pigment Blue 15: 1, Pigment Blue 15: 2, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 60, have. Pigment Green 7, Pigment Gran 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used as green pigments. Examples of the yellow pigments include anthraquinone pigments, isoindolinone pigments, condensed azo pigments, and benzimidazolone pigments. Examples of pigments include Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Yellow 181, Pigment Yellow 193, and the like. As the red pigment, 254 pieces of Pigment Red can be used.

The content of the pigment is preferably 0.1 wt% to 10 wt%, or 0.5 wt% to 5 wt% with respect to the total weight of the resin composition. The additive may be added in the role of removing bubbles of the resin composition or removing the popping or crater on the surface during the film coating, imparting flame retardancy, controlling the viscosity, and catalyst.

 Concretely, thickeners such as fine silica, organic bentonite, montmorillonite and the like; Defoaming agents and / or leveling agents such as silicones, fluorides, and polymers; Silane coupling agents such as imidazole, thiazole and triazole; Flame retardants such as phosphorus flame retardants and antimony flame retardants, and the like.

 For example, BYK-380N, BYK-307, BYK-378, and BYK-350 of BYK-Chemie GmbH can be used as the leveling agent in removing the surface popping or crater during film coating.

 The content of the additive is preferably 0.01 wt% to 10 wt% with respect to the total weight of the resin composition.

 The solvent may be used by dissolving the resin composition or by intensively using one or more solvents to give an appropriate viscosity.

Examples of the solvent include ketones such as methyl ethyl ketone and cyclohexanone; Aromatic hydrocarbons such as rubrene, xylene, and tetramethylbenzene; Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether; Glycol ethers (salosorb) such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetic acid esters such as acetates; Alcohols such as ethanol, propanol, ethylene glycol, propylene glycol, and carbinols; Aliphatic hydrocarbons such as octane and decane; Petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha and solvent naphtha; Amides such as dimethylacetamide and dimethylformamide (DMF), and the like. These solvents may be used alone or as a mixture of two or more kinds. The content of the solvent may be 5% by weight to 50% by weight based on the total weight of the resin composition. When the content is less than 5% by weight, the viscosity is high and the coating property is poor. When the content is more than 50% by weight, the drying is not performed well, and the stickiness is increased.

 The photosensitive resin composition may further include an acid-denaturated or thermosetting binder, if necessary. Specific examples of the acid-modified oligomer and the thermosetting binder include various kinds of known various types of photosensitive resin compositions The compounds, oligomers, or polymers can be applied without limitation. m. Photosensitive resin film

 According to another embodiment of the invention, a copolymer having photo-curable and thermosetting properties of this embodiment; And a cured product of a photopolymerizable monomer having two or more photocurable unsaturated functional groups, may be provided.

 The photosensitive resin film may be a single film that does not include a pattern, or may include a pattern film including a pattern due to an exposure phenomenon.

The photosensitive resin film may be prepared by: 1) applying a photosensitive resin composition of another embodiment to a substrate to form a coating film; 2) drying the coating film; 3) irradiating the dried coating film with light to cure the coating; And 4) thermosetting the photocured film at 50 ^° C to 250 ^° C. ^'

 In the step (step 1) of applying the photosensitive resin composition of the another embodiment to a substrate to form a coating film, the photosensitive resin composition includes all the contents of the other embodiments described above.

 The method of applying the photosensitive resin composition to the substrate is not particularly limited, and for example, screen printing, offset printing, flexographic printing, ink jet, etc. can be used.

Also, the photosensitive resin composition may be a copolymer having photo-curable properties and thermosetting properties according to the embodiment of the present invention; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; And a photoinitiator dissolved or dispersed in an organic solvent have.

The step of drying the coating film (step 2) is for removing the solvent and the like used in the photosensitive resin composition. For example, heating of the coating film or evaporation of vacuum may be used. Preferably, the drying is performed at a temperature of preferably 50 ^° C to 130 ^° C, more preferably 70 ^° C to 120 ^° C.

The step (step 3) of irradiating light to the dried coating film by light irradiation is a step of irradiating light to the coating film dried in step 2 and curing the coating film. As described above, the organic functional group containing the alkenyl group in the second (meth) acrylate repeating unit contained in the copolymer having photo-curable and thermosetting properties of the embodiment is cured by light irradiation Structure can be formed. In the step of irradiating and curing the light, exposure is performed with a light beam (UV or the like) having a certain wavelength band. The exposure may be selectively exposed with a photomask, or may be directly pattern-exposed with a laser direct exposure apparatus. The amount of exposure depends on the thickness of the coating, but is preferably 0.1 mJ / cm ² to 1,000 mJ / cuf.

 After the dried coating film is irradiated with light and photo-cured (step 3), a development step may be performed using an alkali solution or the like, if necessary. The alkali solution may be an aqueous alkali solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amines and the like. By this phenomenon, only the film of the exposed portion can remain.

 That is, when the above-described exposure proceeds, for example, in the exposed portion, photocuring occurs and crosslinking can be formed between the copolymer having photocurable property and thermosetting property and the unsaturated functional groups contained in the photopolymerizable monomer or the like, And can not be removed by the subsequent phenomenon.

The step (step 4) of thermally curing the photocured coated film at 50 ^° C to 250 ^° C is a step of performing a low-temperature heat treatment on the photocured coating film in step 3. The low-temperature heat treatment temperature is preferably 200 ^° C or lower. Preferably, the low temperature heat treatment temperature is 50 ^° C to 250 ^° C, more preferably 70 ^° C to 150 ^° C, or 80 ^° C to 120 ^° C. At this time, But may be carried out by a heating means such as a hot plate, a hot air circulation path, an infrared ray furnace, or the like.

 As described above, the organic functional group including the epoxy group in the first (meth) acrylate repeating unit included in the copolymer having photo-curable and thermosetting properties of the above-mentioned embodiment is thermally cured by heat treatment to form a cured structure .

 Through the above-described method, the photosensitive resin film can be obtained by copolymerizing a photocurable and a curing-curable copolymer of the above-mentioned embodiment according to the photocuring and thermosetting; A cured product of a photopolymerizable monomer having two or more photocurable unsaturated functional groups. More specifically, the cured product is a crosslinked structure in which an epoxy group of the copolymer having photo-curable properties and thermosetting properties and a thermosetting functional group are crosslinked by thermosetting; The crosslinking structure in which the alkenyl group of the photopolymerizable and thermosetting copolymer and the unsaturated functional group of the photosensitizing monomer are cross-linked by photocuring.

 In addition, the photosensitive resin film may further include a small amount of a photoinitiator remaining in the photo-curing state, or a pigment or additive added as needed, dispersed in the cured product.

The thickness of the photosensitive resin film is not particularly limited, but is freely adjustable within a range of 0.01 _m to 1000, for example. When the thickness of the sense of polarization resin film is increased or decreased by a certain value can be changed as long as the physical ^properties, also a certain value, measured in the photosensitive resin film.

IV. Color filter

 According to another embodiment of the present invention, a color filter including the photosensitive resin film of the another embodiment may be provided.

 The content of the photosensitive resin film may include all of the above-mentioned contents in the other embodiments. The photosensitive resin film used for the color filter may contain the pigment dispersed in the cured product.

In addition to the other color filters, various technical configurations that are well known in the field of color filters can be applied without limitation. 【Effects of the Invention】

 According to the present invention, it is possible to provide a photocurable and thermosetting resin composition having excellent thermosetting property at a relatively low temperature and capable of progressing light curing by light irradiation and having excellent durability, chemical resistance and storage stability through layered curing , A photosensitive resin composition using the same, a photosensitive resin film, a color filter, and a color filter may be provided.

 DETAILED DESCRIPTION OF THE INVENTION

 The invention will be described in more detail in the following examples. It should be noted, however, that the following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.

≪ Synthesis Example: Synthesis of Copolymer Having Photocurable Property and Thermosetting Property >

 Synthetic ^ U

To the container was added 5.1 wt.% Of benzyl methacrylate, 0.8 wt.% Of N-phenylmaleimide, 0.6 wt.% Of styrene and 13.2 wt.% Of glycidyl methacrylate together with 78.9 wt.% Of propylene glycol methyl ether acetate (PGMEA) After dissolving, the temperature was raised to 75 ^° C in a nitrogen atmosphere. When the reaction temperature reached 75 ^° C, 1.2wt% of thermal initiator V-65 was added and the reaction was allowed to proceed for 12 hours. The resin solution thus obtained was subjected to air polymerization ^{at a} temperature of 120 ^° C for 16 hours while maintaining a temperature of not more than 50 ^° C. and a post-decarboxylic acid content of 0.1 wt%. The weight average molecular weight of the prepared photopolymerizable and thermosetting copolymers was 4,500 g / m 2, the content of the repeating unit of (meth) acrylate in which the branched chain terminal was replaced by the epoxide group was 49 mol%, the branched chain terminal The (meth) acrylate repeating unit content substituted with an alkenyl group was 21 mol%. Synthesis ^] 2

Copolymers having photocurable properties and thermosetting properties were synthesized in the same manner as in Synthesis Example 1, except that 3, 4-epoxycyclohexylmethyl methacrylate was used instead of glycidyl methacrylate. The prepared photo-curable and thermosetting copolymer had a weight average molecular weight of 4,700 g / mol, a content of (meth) acrylate repeating unit in which the branch chain terminal was substituted with an epoxy group, 49 mol / The content of (meth) acrylate repeating units whose terminals were substituted with alkenyl groups was 21 mol%. Synthetic F 13

 A copolymer having photo-curable properties and thermosetting properties was synthesized in the same manner as in Synthesis Example 1, except that the compound represented by the following formula (A) was used instead of glycidyl methacrylate.

합성^ ^·

Synthesis ^ ^·

Copolymers having photocurable properties and thermosetting properties were synthesized in the same manner as in Synthesis Example 1, except that the compound represented by the following formula (B) was used instead of glycidyl methacrylate.

[Chemical Formula B]

≪ Comparative Synthesis Example &

 Comparative synthetic fibers

To the vessel was added 9.3 wt.% Of benzyl methacrylate, 1.5 wt.% Of N-phenylmaleimide, lwt% of glycidyl methacrylate, 6.8% of glycidyl methacrylate was dissolved in 74.6% of propylene glycol methyl ether acetate (PGMEA) as a solvent, and the temperature was raised to 65 ^° C in a nitrogen atmosphere. When the reaction temperature reached 65 ^° C, 0.7wt% of thermal initiator V-65 was added and reacted for 12 hours. After adding a thermal polymerization inhibitor and a catalyst to the resultant resin solution, 4.3% of methacrylic acid was added in an air atmosphere and maintained at 120 ^° C for 16 hours. The temperature of the prepared resin solution was lowered to 90 ^° C and 5.5 wt% of 1, 2,5,6-tetrahydrophthalic anhydride was added in an air atmosphere for 24 hours. The prepared resin had a weight average molecular weight of 8, 100 g / m and an acid value of 83 KOH mg / g. The content of the (meth) acrylate repeating unit in which the branched chain terminal was substituted with an epoxy group was 0 and the branched chain terminal was an alkenyl group The substituted (meth) acrylate repeating unit content was 40 mol%.

≪ Examples and Comparative Examples: Preparation of Photosensitive Resin Composition and Photosensitive Resin Pattern Film > Example 1

 (1) Photosensitive resin composition

 1 g of Irgacure 369 (manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator was dissolved in 35 g of propylene glycol methyl ether acetate (PGMEA) as a polymerization initiator for 30 minutes at room temperature and stirred. Then, the copolymer having photocurable and thermosetting properties And 5 g of dipentaerythritol penta / nuclear acrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.) as a crosslinkable monomer having an ethylenic double bond and stirring at room temperature for 1 hour. 50 g of a 15% dispersion of Sigma Red 254 and 0.2 g of an additive, and the mixture was stirred at room temperature for 1 hour. The composition obtained by the above reaction was filtered twice more to remove impurities to prepare a photosensitive resin composition.

 (2) Photosensitive resin pattern film

The photosensitive resin composition was coated on a 5 cm x 5 cm glass at 230 rpm and prebaked at 100 ^° C for 100 seconds. Thereafter, the resist film was exposed to 40 mJ / cm ² of energy, developed, and post-baked at 100 ^° C for 30 minutes to prepare a photosensitive resin pattern film. Implementation 12

 In the preparation of the photosensitive resin composition, C.I. Pigment Red 254 instead of C.I. A photosensitive resin composition and a photosensitive resin pattern film were prepared in the same manner as in Example 1, except that Pigment Green 7 was used. Implementation ^ 13

 In the preparation of the photosensitive resin composition, C.I. Pigment Red 254 instead of C.I. A photosensitive resin composition and a photosensitive resin pattern film were prepared in the same manner as in Example 1, except that Pigment Blue 15: 6 was used. Implementation

In the production of the photosensitive resin composition, the photo-curability and heat resistance obtained in the above-mentioned Synthesis Example 2, instead of the copolymer having photo-curable property and thermosetting property, A photosensitive resin composition and a photosensitive resin pattern film were prepared in the same manner as in Example 1, except that a copolymer having curability was used. Implementation ^ 15

And, except for using the photosensitive resin composition during manufacture, the copolymer rather than copolymer having photo-curing and thermosetting obtained in the above Synthesis Example 1 having a photo-curable and thermosetting obtained in the above Synthesis Example ^2: the same as Example 2 To prepare a photosensitive resin composition and a photosensitive resin pattern film. Implementation ^] 6

 The same procedure as in Example 3 was carried out except that the copolymer having photo-curable and thermosetting properties obtained in Synthesis Example 2 was used instead of the copolymer having photo-curable property and thermosetting property obtained in Synthesis Example 1 To prepare a photosensitive resin composition and a photosensitive resin pattern film. Implementation ^ 17

 The same process as in Example 1 was carried out except that a copolymer having photo-curing property and thermal curability obtained in Synthesis Example 3 was used instead of the copolymer having photo-curable property and thermosetting property obtained in Synthesis Example 1 in the production of photosensitive resin composition To prepare a photosensitive resin composition and a photosensitive resin pattern film. Implementation ^ 18

 Except for using the copolymer having photo-curing property and thermosetting property obtained in Synthesis Example 4, instead of the copolymer having photo-curable property and thermosetting property, obtained in Synthesis Example 1, in the production of photosensitive resin composition, To prepare a photosensitive resin composition and a photosensitive resin pattern film. Compare ^] 1

In the production of the photosensitive resin composition, a thermosetting resin represented by the following formula (C) was used instead of the copolymer having photo-curing property and thermosetting property obtained in Synthesis Example 1 A sphenol-based novolac epoxy resin; A photosensitive resin composition and a photosensitive resin pattern film were prepared in the same manner as in Example 1, except that BPN-110 (Kukdo Chemical Co., Ltd.) was used.

 ≪ RTI ID = 0.0 &

비교^ 12

Compare ^ 12

 A photosensitive resin composition and a photosensitive resin composition were prepared in the same manner as in Example 2, except that the thermosetting resin used in Comparative Example 1 was used instead of the copolymer having photo-curable property and thermosetting property obtained in Synthesis Example 1, Thereby preparing a photosensitive resin pattern film. Comparative Example 3

 A photosensitive resin composition and a photosensitive resin composition were prepared in the same manner as in Example 3, except that the thermosetting resin used in Comparative Example 1 was used instead of the copolymer having photocurable property and thermosetting property obtained in Synthesis Example 1, Thereby preparing a photosensitive resin pattern film. Compare

A photosensitive resin composition was prepared in the same manner as in Example 1, except that the copolymer resin obtained in Comparative Synthesis Example 1 was used instead of the copolymer having photo-curable property and thermosetting property obtained in Synthesis Example 1, To prepare a composition and a photosensitive resin pattern film. Compare 15

 A photosensitive resin composition and a photosensitive resin composition were prepared in the same manner as in Example 2, except that the copolymer resin obtained in Comparative Synthesis Example 1 was used instead of the copolymer having photo-curable and thermosetting properties obtained in Synthesis Example 1, To prepare a resin pattern film. Comparative Example 6

 A photosensitive resin composition and a photosensitive resin composition were prepared in the same manner as in Example 3, except that the copolymer resin obtained in Comparative Synthesis Example 1 was used instead of the copolymer having photo-curable and thermosetting properties obtained in Synthesis Example 1, To prepare a resin pattern film. <Experimental Example> Measurement of physical properties of the photosensitive resin composition and photosensitive resin pattern film obtained in Examples and Comparative Examples>

 The physical properties of the photosensitive resin composition and the photosensitive resin pattern film obtained in the above Examples and Comparative Examples were measured by the following methods, and the results are shown in the table.

1. Experimental Example 1:

 A photosensitive resin composition containing a pigment having a color different from that of the pigment included in the light-sensitive resin pattern film was coated / developed on the photosensitive resin pattern film obtained in the above Examples and Comparative Examples, and then the photosensitive resin pattern film The color change was measured as MPCD (Minimum Perceptable Color Dielectric), and pattern shift and swelling were observed using optical equipment. The pigment elution was judged according to the following criteria, Table 1 shows the results.

 O: Pigment is not eluted at all

 Δ: Fine elution of pigment was observed

X: Pigment eluted and film peeled off 2. Experimental Example 2: Chemical resistance

 After coating / exposing / curing an overcoat photosensitive liquid on the photosensitive resin pattern film obtained in the above-mentioned Examples and Comparative Examples, the photosensitive resin pattern film was subjected to color evaluation as MPCD (Minimum Perceptable Color Dielectric) The pattern was shifted and swelling was observed using an optical instrument. The pigment elution was judged according to the following criteria, and the results are shown in Table 1 below.

 O: Pigment is not eluted at all

 Δ: Fine elution of pigment was observed

 X: the pigment is eluted and the film is peeled off at the same time

3. Experimental Example 3: Storage stability

 The photosensitive resin compositions obtained in the above Examples and Comparative Examples were measured for development time and the development time (second) after standing at room temperature for 2 weeks, and the results are shown in Table 1 below. The smaller the change in the development time after the production day and 2 weeks, the better the storage stability.

[Table 1]

 Experimental Example Result

상기 표 1에 나타난 바와 같이 , 상기 합성예에서 얻어진 광경화성 및 열경화성을 갖는 공중합체를 바인더 수지로 사용한 실시예의 감광성 수지 조성물은， 포스트베이킹을 100 ^°c온도에서 진행하더라도 일반 열경화성 수' 지를 적용한 비교예 1 내지 3과 달리 후공정에 의한 내화학성 및 이염특성이 우수한 것으로 확인되았다.

As shown in Table 1, the embodiment of the photosensitive resin composition using a copolymer having a photo-curable and thermosetting obtained in the Synthesis Example of a binder resin, even if progression of post-baking at 100 ^° c temperature applied if you general thermosetting "Comparison Unlike Examples 1 to 3, it was confirmed that the chemical resistance and the dye transfer property by the post-process were excellent.

Also, in comparison with Comparative Examples 4 to 6 in which the resin obtained in the Comparative Synthesis Example in which the first (meth) acrylate repeating unit having an organic functional group bonded to the branched chain is not present at the branched chain end, Chemical properties and salt characteristics. As a result, it can be seen that the copolymer having photo-curing property and thermosetting property obtained in the above Synthesis Example shows excellent curing property even at low temperature compared to conventional thermosetting binder resin and can form a cured film having excellent heat resistance and chemical resistance there was. ^"Further, the embodiment of the photosensitive resin composition was found to have excellent storage stability was more than equivalent to the level of the comparative example. As a result, it was confirmed that the copolymer having photo-curing property and thermosetting property obtained in the above-mentioned synthesis forms a stable bond even when compared with the conventional thermosetting binder resin due to the formation of a superficial bond during curing.

Claims

Claims:  [Claim 1]  The first branch having an organic functional group including an epoxy group bonded to the branched chain terminal (Meth) acrylate repeating units; And  And the second branch in which an organic functional group including an alkenyl group is bonded to the branched chain terminal (Meth) acrylate repeating units,  In the second (meth) acrylate repeating unit, the branched chain is an alkyl ester group having 1 to 20 carbon atoms substituted with a hydroxy group; Or an oxyalkyl ester group having 1 to 20 carbon atoms substituted with a hydroxy group; Or an alkyl ester group substituted by a cycloalkyl group having 3 to 30 carbon atoms in which the hydroxy group is substituted; Or a multicyclic alkyl ester group having 7 to 30 carbon atoms substituted with a hydroxy group; Or an alkyl ester group substituted by a multicyclic alkyloxy group having 7 to 30 carbon atoms substituted with a hydroxy group. [Claim 2]  The method according to claim 1,  Wherein the molar ratio of the repeating unit of (meth) acrylate to the repeating unit of second (meth) acrylate is from 1:99 to 99: 1. [Claim 3]  In Item 1,  The copolymer having photo-curability and thermosetting property has a weight-average molecular weight (GPC measurement) of from 1000 g / mol to 100000 g / irol. Claim 4  In Item 1, In the first (meth) acrylate repeating unit, the branched chain may be a carbonyl group; Or an alkyl ester group having 1 to 20 carbon atoms; Or an alkyl group having 1 to 20 carbon atoms A photo-curable and thermosetting copolymer comprising an oxyalkyl ester group. [Claim 5] ^: Wherein in claim 1  The organic functional group including the epoxy group may be a functional group represented by the following general formula (1); Or a functional group represented by the following formula (2); Or a functional group represented by the following general formula (3): &lt; EMI ID = [Chemical Formula 1]

In Formula (1),,, and ¾ are each independently a direct bond, hydrogen, or an alkyl group having 1 to 5 carbon atoms,  (2)

And R &lt; ₄ &gt; and R &lt; ₄ &gt; are each independently a direct bond or an alkylene group having 1 to 5 carbon atoms,  (3)

In the above formula (3), and R ₇ is a direct bond, each independently, or An alkylene group having 1 to 5 carbon atoms, X is a direct bond, 0-, or [Claim 6]  In Item 1,  The first (meth) acrylate repeating unit is represented by the following formula (4): &lt; EMI ID =  [Chemical Formula 4]

 In Formula 4,  8 to Rio are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms,  Is a direct bond or an alkylene group having 1 to 20 carbon atoms or an oxyalkylene group having 1 to 20 carbon atoms R _u is an organic functional group including an epoxy group Γ Claim 7]  The method according to claim 1,  The organic functional group containing the alkenyl group may be a (meth) acryloyl group or (Meth) acryloyloxy group. &Lt; / RTI &gt; 8.  In that U section, The repeating unit of the (meth) acrylate is a copolymer having photocurable and thermosetting properties represented by the following formula (5): [Chemical Formula 5]

 In Formula 5, R ₁₂ to R ₁₄ are each independently hydrogen or an alkyl group having 1 to 10 carbon atoms, L ₂ is a direct bond or an alkylene group having 1 to 20 carbon atoms or an oxyalkylene group having 1 to 20 carbon atoms, L ₃ represents an alkylene group having 1 to 20 carbon atoms substituted with a hydroxy group or an oxyalkylene group having 1 to 20 carbon atoms substituted with a hydroxy group or a cycloalkylene group having 3 to 30 carbon atoms substituted with a hydroxy group, Lt; / RTI &gt; to 30,  5 is an organic functional group including an alkenyl group. 9]  The method according to claim 1,  A third (meth) acrylate repeating unit represented by the following formula (6);  A maleimide repeating unit represented by the following formula (7); And  And at least one repeating unit selected from the group consisting of vinyl repeat units represented by the following general formula (8): &lt; EMI ID = [Chemical Formula 6]

 (7)

 In the above formulas (6) to (8)  R16 to R16 each independently represent hydrogen; heavy hydrogen; A halogen group; An alkyl group having 1 to 20 carbon atoms; An alkoxy group having 1 to 20 carbon atoms; A monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; An alkenyl group having 2 to 20 carbon atoms; Or a monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms, L ₄ is a direct bond, an alkylene group having 1 to 20 carbon atoms, or an oxyalkylene group having 1 to 20 carbon atoms. [Claim 10]  Copolymers having the photocurable and thermosetting properties of the term 1; A photopolymerizable monomer having at least two photocurable unsaturated functional groups; A photo-sensitive resin composition comprising: Claim 111  11. The method of claim 10,  Wherein the photopolymerizable monomer comprises an acrylate-based compound having at least two photocurable unsaturated functional groups. Claim 12  11. The method of claim 10,  Wherein the photosensitive resin composition further comprises a pigment. Claim 13  1) applying the photosensitive resin composition of claim 10 to a substrate to form a coating film;  2) drying the coating film; 3) irradiating the dried coating film with light to cure the coating; And 4) thermosetting the photocured film at 50 ^° C to 250 ^° C. [14] Comprising a cured photo-polymerizable monomer having a diameter between unsaturated functional groups: awesome-eu and two-over, a first optical claim ^ Mars-and-column screen _ _o sex ¾ is announcements polymer i Photosensitive water film. 15.  A color filter comprising the photosensitive resin film of claim 14. ᅳ