TWI743412B - Photo-curable and thermo-curable copolymer, and photosensitive resin composition using the same, photosensitive resin film and method for preparing thereof, and color filter - Google Patents

Abstract

The present invention relates to photo-curable and thermo-curable copolymer that has excellent thermo-curability even at a relatively low temperature, can be photo-cured by light irradiation, and has excellent durability, chemical resistance, and storage stability through sufficient curing, and a photosensitive resin composition, a photosensitive resin film and a method of preparing thereof, and a color filter using the same.

Description

Light-curable and heat-curable copolymers and the use of said copolymers Polymer photosensitive resin composition, photosensitive resin film, method for preparing the same, and color filter

[Cross reference of related applications]

This application claims the Korean Patent Application No. 10-2017-0149676 filed by the Korean Intellectual Property Office on November 10, 2017 and the Korean Patent Application No. 10-2018-0136598 filed on November 8, 2018 The rights and interests of the application, the disclosed content of the application is incorporated herein by reference in its entirety.

The present invention relates to a photocurable and thermally curable copolymer, a photosensitive resin composition using the copolymer, a photosensitive resin film, and a color filter. More specifically, the present invention relates to a photo-curable and heat-curable copolymer, and a photosensitive resin composition, photosensitive resin film, and color filter using the copolymer. It also has excellent thermal curability at low temperatures, can be photocured by light irradiation, and has excellent durability, chemical resistance and storage stability through sufficient curing.

During the color filter manufacturing process, in the case of RGB patterns, the photosensitive resin composition is mainly coated with a spin coater or a slit coater, and is pre-baked. , And then expose and develop it.

After development, a post-baking process of applying heat at 220°C or more is finally performed. Although commonly used glass does not deform at this temperature, it is used in flexible displays. Plastics will be severely deformed at temperatures exceeding 220°C.

In order to reduce such 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 photosensitive resin composition may not be completely cured. And therefore, the amount of gas generated may increase, afterimages may appear, and chemical resistance and heat resistance may decrease.

Therefore, it is necessary to develop a material and a photosensitive resin composition that can be cured to a high level even at a low temperature and therefore can form a cured film with excellent heat resistance and chemical resistance.

The object of the present invention is to provide a photocurable and thermally curable copolymer, which has excellent thermal curability even at a relatively low temperature, can be photocured by light irradiation, and can be cured by light Fully cured with excellent durability, chemical resistance and storage stability.

Another object of the present invention is to provide a photosensitive resin composition, a photosensitive resin film, and a color filter using a photo-curable and heat-curable copolymer.

Provided is a photo-curable and heat-curable copolymer comprising: a first (meth)acrylate repeating unit, in which an organic functional group containing an epoxy group is bonded to the end of a branched chain; and a second (meth)acrylate A repeating unit, wherein the organic functional group containing an alkenyl group is bonded to the end of the branched chain, wherein in the second (meth)acrylate repeating unit, the branched chain includes: a C1-20 alkyl ester group substituted by a hydroxyl group, a hydroxyl group Substituted C1-20 oxyalkyl ester group, C3-30 cycloalkyl substituted alkyl ester group substituted by hydroxy group, C7-30 polycyclic alkyl ester group substituted by hydroxy group or C7-30 polycyclic alkyl ester group substituted by hydroxy group Cycloalkoxy substituted alkyl ester group.

A photosensitive resin composition is also provided, comprising: a photo-curable and thermally curable copolymer; a photo-polymerizable monomer having two or more than two photo-curable unsaturated functional groups; and a photoinitiator.

A method for preparing a photosensitive resin film is also provided, which includes the following steps: 1) coating a photosensitive resin composition on a substrate to form a coating; 2) drying the coating; 3) irradiating light to the dried The coating is photocured; and 4) the photocured film is thermally cured at 50°C to 250°C.

A photosensitive resin film is also provided, comprising: a photocurable and thermally curable copolymer; and a cured product of a photopolymerizable monomer having two or more photocurable unsaturated functional groups.

A color filter including a photosensitive resin film is also provided.

Throughout the specification, when a component "comprises" construction elements, unless specifically described to the contrary, it does not exclude other construction elements, but it may further include other construction elements.

The term "substituted" means bonding to another functional group instead of The hydrogen atom in the compound, and the position of the substituted hydrogen atom is not limited, as long as it is a position that can be substituted by a substituent, and when it is substituted by two or more than two substituents, these two or more The two substituents may be the same or different from each other.

或

意指連接至另一取代基的鍵，且直接鍵意 指在由L指示的部分處不存在單獨原子的情況。 mark

or

It means a bond to another substituent, and a direct bond means a case where a separate atom does not exist at the portion indicated by L.

The term "(meth)acryl" means acrylic or methacryl.

The weight average molecular weight means the weight average molecular weight measured by the GPC method relative to the polystyrene standard conversion. During the process of measuring the weight average molecular weight converted to the polystyrene standard by the GPC method, commonly known analyzers, such as Refractive Index Detector (Refractive Index Detector), and analytical columns can be used. In addition, commonly used temperature conditions, solvents, and flow rates can be applied. For example, using 1,2,4-trichlorobenzene as the solvent at an evaluation temperature of 160°C, Waters with a 300 millimeter (mm) length column of Polymer Laboratories PLgel MIX-B (Waters) PL-GPC220 equipment prepares a sample with a concentration of 10 milligrams (mg)/10 milliliters (mL) at a flow rate of 1 ml/min, and then feeds the sample in an amount of 200 microliters (μL) , And a calibration curve (formed using polystyrene standards) can be used to obtain the molecular weight (Mw). As polystyrene standard products, 9 types having molecular weights of 2000/10,000/30,000/70,000/200,000/700,000/2,000,000/4,000,000/10,000,000 are used.

Throughout the specification, an alkyl group is a linear monovalent functional group, a branched chain monovalent functional group, or a cyclic monovalent functional group derived from an alkane, and it may be, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group , Second butyl, tertiary butyl, pentyl, hexyl, etc. One or more hydrogen atoms contained in the alkyl group may be substituted with other substituents, and examples of the substituents may include C1-10 alkyl, C2-10 alkenyl, C2-10 alkynyl, C6-12 aryl, C2-12 heteroaryl group, C6-12 aralkyl group, halogen atom, cyano group, amino group, formamidino group, nitro group, amide group, carbonyl group, hydroxyl group, sulfonyl group, carbamate group, C1 -10 Alkoxy and so on.

Throughout the specification, a cycloalkyl group (although not specifically limited) is a monovalent functional group derived from a monocyclic cycloalkane (cycloalkane), and its examples are not specifically limited, but it has a cycloalkane having a carbon number of 3 to 60 The group is preferred, and according to one embodiment, the carbon number of the cycloalkyl group is 3-30. According to another embodiment, the carbon number of the cycloalkyl group is 3-20. According to another embodiment, the carbon number of the cycloalkyl group is 3-6. Specifically, the cycloalkyl group may include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tertiarybutylcyclohexyl, cycloheptyl, cyclooctyl, etc., but not limited to this.

Throughout the specification, a polycyclic alkyl group (although not specifically limited) is a monovalent functional group derived from a polycyclic cycloalkane (cycloalkane), and examples thereof are not specifically limited, but those having a carbon number of 3 to 60 Polycyclic alkyl groups are preferred, and according to one embodiment, the carbon number of cycloalkyl groups is 3-30. Specifically, it may include norbonane, 2,3-trimethylenenorbonane, etc., but is not limited thereto.

基，茀基等， 但不限於此。芳基的一或多個氫原子可分別經取代基取代，就如同在烷基中那樣。 Throughout the specification, the aryl group is a monovalent functional group derived from arenes, and it may be monocyclic or polycyclic. Specifically, the monocyclic aryl group may include a phenyl group, a biphenyl group, a triphenyl group, a stilbenyl group, etc., but is not limited thereto. Polycyclic aryl groups may include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylene,

Ji, Chi Ji, etc., but not limited to this. One or more hydrogen atoms of an aryl group may be substituted with a substituent, respectively, as in an alkyl group.

Throughout the specification, the alkenyl group may be linear or branched, and the carbon number is not specifically limited, but is preferably 2-40. According to one embodiment, the carbon number of the alkenyl group is 2-20. According to one embodiment, the carbon number of the alkenyl group is 2-10. According to one embodiment, the carbon number of the alkenyl group is 2-6. Specific examples thereof may include: 1-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-phenylvinyl-1-yl, 2,2 -Diphenylvinyl-1-yl, 2-phenyl-2-(naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl- 1-base, stibenyl, styryl, etc., but not limited thereto.

Throughout the specification, an alkylene group is a divalent functional group derived from an alkane and has a carbon number of 1-20, 1-10, or 1-5. It may be linear, branched or cyclic, and examples thereof may include methylene, ethylene, propylene, isobutyl, ethylene, tertiary, and pentylene, Shen Heji and so on. One or more hydrogen atoms contained in the alkylene group may be substituted with a substituent, respectively, as in an alkyl group.

Throughout the specification, an oxyalkylene group is a functional group derived from an alkylene group, in which an ether group (-O-) is bonded to one end of the alkylene group, and the carbon number is 1 to 20, 1 to 10, or 1. To 5. It may be linear, branched or cyclic, and examples thereof may include oxymethylene, oxyethylene, oxyethylene, oxyn-butyl, oxyisobutyl, and oxyethylene , Oxybutylene, oxypentyl, oxyhexylene, etc. One or more hydrogen atoms contained in the oxyalkylene group may be substituted with a substituent, respectively, as in an alkyl group.

Throughout the specification, cycloalkylene is derived from cycloalkane (cycloalkane) The divalent functional group of and the carbon number is 3 to 30, 3 to 20, or 3 to 10. Examples thereof may include cyclopropylidene, cyclobutylene, cyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl , 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but not limited .

Throughout the specification, a polycyclic alkylene is a divalent functional group derived from a cycloalkane, in which one hydrogen atom of the polycyclic alkyl group is substituted with a functional group.

Throughout the specification, the carbon number of the carbonyl group is not specifically limited, but it may preferably be 1-30. Specifically, it may be a compound of the following structure, but is not limited thereto.

Throughout the specification, in the ester group, the oxygen of the ester group may be substituted with a C1-25 linear alkyl group, a branched chain alkyl group, or a cycloalkyl group or a polycyclic alkyl group. An ester group substituted with an alkyl group may be referred to as an "alkyl ester group", and an ester group substituted with a polycyclic alkyl group may be referred to as a "polycyclic alkyl ester group".

Hereinafter, the photo-curable and heat-curable copolymer, the photosensitive resin composition using the copolymer, the photosensitive resin film, and the color filter according to specific embodiments will be explained in detail.

I. Light-curable and thermally curable copolymers

One embodiment of the present invention provides a photo-curable and thermally curable co A polymer comprising: a first (meth)acrylate repeating unit, in which an organic functional group containing an epoxy group is bonded to the end of a branched chain; and a second (meth)acrylate repeating unit, in which an alkenyl group is contained The organic functional group is bonded to the end of the branched chain, where in the second (meth)acrylate repeating unit, the branched chain includes: a C1-20 alkyl ester group substituted by a hydroxyl group, and a C1-20 oxyalkyl group substituted by a hydroxyl group Ester group, C3-30 cycloalkyl substituted alkyl ester group substituted by hydroxy group, C7-30 polycyclic alkyl ester group substituted by hydroxy group or C7-30 polycyclic alkoxy substituted alkyl ester group substituted by hydroxy group base.

The present inventors confirmed that for the photo-curable and heat-curable copolymers containing two or more types of repeating units as described above, the second (meth)acrylate repeating unit contains The organic functional group of the alkenyl group can be photocured by light irradiation to form a primary curing structure, and even at a low temperature of less than 200°C, the epoxy-containing group contained in the first (meth)acrylate repeating unit The organic functional group can also form a secondary curing structure through thermal curing, and therefore, it can be sufficiently cured by thermal curing and photocuring even at a low temperature. It is also confirmed through experiments that the finally cured film can have excellent durability and chemical resistance, and the photosensitive resin composition before curing can also have excellent storage stability, and the present invention has been completed.

Specifically, the photo-curable and thermally curable copolymer may include a first (meth)acrylate repeating unit in which an epoxy-containing organic functional group is bonded to the end of the branched chain. By including the first (meth)acrylate repeating unit, even at a low temperature of less than 200°C, the dense curing structure can be cured by the epoxy group contained in the first (meth)acrylate repeating unit through thermal curing. form.

In the first (meth)acrylate repeating unit, the chain formed by the polymerization reaction of the double bond contained in the (meth)acrylate is called the main chain, And the chain that grows from the autonomous chain in a branched form is called a branched chain or a side chain.

The (meth)acrylate repeating unit is a repeating unit included in the homopolymer of the (meth)acrylate monomer, and the (meth)acrylate repeating unit can be included by being included in the (meth)acrylate monomer The polyethylene chain formed by the polymerization of the vinyl group in the body serves as the main chain and the ester functional group contained in the (meth)acrylate monomer serves as the branched chain. That is, in the first (meth)acrylate repeating unit, the end of the branched chain to which the epoxy-containing organic functional group is bonded means the ester functional group contained in the (meth)acrylate repeating unit The end.

In the first (meth)acrylate repeating unit, the branched chain may contain any of the following: carbonyl (-CO-); C1-20 alkyl ester group (R'COO-: R'is C1-20 alkane Group); or a C1-20 oxyalkyl ester group, and the organic functional group containing an epoxy group may be bonded to the carbonyl group or the end of the C1-20 alkyl group contained in the C1-20 alkyl ester group.

The organic functional group including an epoxy group may include a functional group composed only of an epoxy group or a functional group in which an epoxy group is bonded to other functional groups, and specifically, it may be a functional group represented by the following Chemical Formula 1; Any one of the functional groups represented by the following Chemical Formula 2; and the functional groups represented by the following Chemical Formula 3.

In Chemical Formula 1, each of R ₁ , R ₂ and R ₃ may independently be a direct bond, hydrogen or a C1-5 alkyl group, and preferably, all of R ₁ , R ₂ and R ₃ may be hydrogen .

[Chemical formula 2]

In Chemical Formula 2, each of R ₄ and R ₅ may independently be a direct bond or a C1-5 alkylene group, and preferably, R ₄ may be a methylene group, and R ₅ may be an ethylene group .

In Chemical Formula 3, each of R ₆ and R ₇ is independently a direct bond, hydrogen or a C1-5 alkyl group, and X is a direct bond, -O- or -S-.

Specifically, the first (meth)acrylate repeating unit may be represented by Chemical Formula 4 below.

In Chemical Formula 4, each of R ₈ to R ₁₀ is independently hydrogen or a C1-10 alkyl group; L ₁ is a direct bond, a C1-20 alkylene group or a C1-20 oxyalkylene group; and R ₁₁ It is an organic functional group containing an epoxy group.

Preferably, in Chemical Formula 4, each of R ₈ and R ₁₀ is independently hydrogen, R ₉ is a C1-3 alkyl group, L ₁ is a direct bond or a C1-3 alkylene group, and R ₁₁ is The functional group represented by Chemical formula 1, the functional group represented by Chemical formula 2, or the functional group represented by Chemical formula 3.

More preferably, in Chemical Formula 4, L ₁ may be a direct bond, and R ₁₁ may be a functional group represented by Chemical Formula 3. In addition, in Chemical Formula 4, L ₁ may be a C1-3 alkylene group, and R ₁₁ may be a functional group represented by Chemical Formula 1, a functional group represented by Chemical Formula 2, or a functional group represented by Chemical Formula 3.

Specifically, an example of the first (meth)acrylate repeating unit represented by Chemical Formula 4 may include the following Chemical Formula 4-1 derived from glycidyl methacrylate, derived from 3,4-epoxycyclohexylmethyl The following chemical formula 4-2 of methyl acrylate (3,4-epoxycyclohexyl methylmethacrylate), the following chemical formula 4-3 derived from chemical formula A of the following synthesis example 3, and the following chemical formula 4-4 derived from chemical formula B of the following synthesis example 4.

[Chemical formula 4-2]

The photo-curable and heat-curable copolymer may include a second (meth)acrylate repeating unit in which an alkenyl-containing organic functional group is bonded to the end of the branched chain. By including the second (meth)acrylate repeating unit, the alkenyl group included in the second (meth)acrylate repeating unit can be photocured by light irradiation to form a dense cured structure.

In the second (meth)acrylate repeating unit, the chain formed by the polymerization reaction of the double bond contained in the (meth)acrylate is referred to as the main chain, and will be branched as the main chain. The resulting chain is called a branched chain or a side chain.

The (meth)acrylate repeating unit is a repeating unit included in the homopolymer of the (meth)acrylate monomer, and the (meth)acrylate repeating unit can be included by being included in the (meth)acrylate monomer The polyethylene chain formed by the polymerization of the vinyl group in the body serves as the main chain and the ester functional group contained in the (meth)acrylate monomer serves as the branched chain. That is, in the second (meth)acrylate repeating unit, the end of the branched chain to which the alkenyl-containing organic functional group is bonded means the end of the ester functional group contained in the (meth)acrylate repeating unit End.

In the second (meth)acrylate repeating unit, the branched chain may include a C1-20 alkyl ester group or a C1-10 alkyl ester group substituted by a hydroxyl group (R'COO-: R'is a C1-10 alkyl group), A C1-20 oxyalkyl ester group substituted by a hydroxy group, a C3-30 cycloalkyl group or a C3-10 cycloalkyl group substituted by a hydroxy group, a C7-30 polycyclic alkyl ester group substituted by a hydroxy group, or C8-15 polycyclic alkyl ester group, or C7-30 polycyclic alkoxy group substituted by hydroxy group or C8-15 polycyclic alkoxy group substituted alkyl ester group.

Specifically, the C1-20 alkyl group contained in the C1-20 alkyl ester group substituted with a hydroxyl group or the C3-30 cycloalkane group contained in the C3-30 cycloalkyl substituted alkyl ester group substituted with the hydroxyl group At the end of the group, the organic functional group containing an alkenyl group may be substituted.

In addition, in the C7-30 polycyclic alkyl ester group substituted with a hydroxy group, at the end of the C7-30 polycyclic alkyl group contained in the C7-30 polycyclic alkyl ester group, the organic The functional group may be substituted.

In addition, in the alkyl ester group substituted with a C7-30 polycyclic alkoxy group substituted with a hydroxyl group, an alkenyl group is contained at the end of the C7-30 polycyclic alkyl group contained in the C7-30 polycyclic alkoxy group The organic functional group can be substituted.

At the same time, the hydroxyl group can be substituted at the C1-20 alkyl group contained in the C1-20 alkyl ester group, substituted at the C3-30 cycloalkyl group, or substituted at the C10-30 polycyclic alkyl ester group as a branched chain. The C10-30 polycyclic alkyl group of is substituted or the C10-30 polycyclic alkyl group contained in the C10-30 polycyclic alkoxy group is substituted.

The hydroxyl group can be induced via the ring-opening reaction of the epoxy group contained in the first (meth)acrylate repeating unit, and more specifically, the hydroxyl group can be induced via the ring-opening reaction of the epoxy group contained in the first (meth)acrylate repeating unit. It is induced by the reaction between the epoxy group and the compound containing the alkenyl group-containing organic functional group.

The organic functional group including an alkenyl group may include a functional group composed only of an alkenyl group and a functional group in which the alkenyl group is bonded to other organic functional groups, and specifically, a (meth)acrylic group, (methyl) An acryloxy group and the like, and preferably, a methacryloxy group may be used.

Specifically, the second (meth)acrylate repeating unit may be represented by the following Chemical Formula 5.

In Chemical Formula 5, each of R ₁₂ to R ₁₄ is independently hydrogen or a C1-10 alkyl group; L ₂ is a direct bond, a C1-20 alkylene group or a C1-20 oxyalkylene group; L ₃ is C1-20 alkylene substituted by hydroxy, C1-20 oxyalkylene substituted by hydroxy, C3-30 cycloalkylene substituted by hydroxy or C7-30 polycyclic alkylene substituted by hydroxy; and R ₁₅ is an organic functional group containing an alkenyl group.

Preferably, in the chemical formula 5, each of R ₁₂ and R ₁₄ is independently hydrogen; R _{13 is} independently a C1-3 alkyl group; L ₂ is a direct bond, a C1-10 alkylene group or a C1- 10 oxyalkylene; and L ₃ is a C1-5 alkylene substituted with a hydroxy group, a C3-10 cycloalkylene substituted with a hydroxy group, or a C8-15 polycyclic alkylene substituted with a hydroxy group.

More specifically, in Chemical Formula 5, L ₂ may be a direct bond, and L ₃ may be a C10-20 polycyclic alkylene group substituted with a hydroxyl group. In addition, in the chemical formula 5, L ₂ may be a C1-10 alkylene group or a C1-10 oxyalkylene group, and L ₃ may be a C1-5 alkylene group substituted with a hydroxy group, or a C3-10 alkylene group substituted with a hydroxy group. Cycloalkyl or C8-15 polycyclic alkylene substituted by hydroxy.

Specifically, examples of the second (meth)acrylate repeating unit represented by Chemical Formula 5 may include the following Chemical Formula 5-1 to Chemical Formula 5-4, which may be described by It is prepared by the reaction of epoxy group and (meth)acrylic acid at the ends of Chemical Formula 4-1 to Chemical Formula 4-4 described in the text.

[Chemical formula 5-1]

The molar ratio of the first (meth)acrylate repeating unit to the second (meth)acrylate repeating unit may be 99:1 to 1:99. According to this, since the photo-curable and thermally curable copolymer includes both the first (meth)acrylate repeating unit and the second (meth)acrylate repeating unit, the photo-curable and thermally curable copolymer It can simultaneously realize light curability and low temperature thermal curability.

Preferably, based on 100 mol of the first (meth)acrylate repeating unit, the second may be included in a ratio of 10 mol to 90 mol, 20 mol to 70 mol, or 30 mol to 50 mol. (Meth)acrylate repeating unit. If the content of the second (meth)acrylate repeating unit based on 100 mol of the first (meth)acrylate repeating unit is excessively reduced, a residue problem may occur in the synthetic copolymer.

On the contrary, if the content of the second (meth)acrylate repeating unit based on 100 mol of the first (meth)acrylate repeating unit is increased to more than 90 mol, the dyeing properties and chemical resistance of the synthetic copolymer May be reduced.

At the same time, the photocurable and thermally curable copolymer may further include one or more repeating units selected from the group consisting of: the third (meth)acrylate repeating unit represented by the following chemical formula 6; The maleimide repeating unit represented by the following Chemical Formula 7; and the vinyl repeating unit represented by the following Chemical Formula 8. Thereby, the heat resistance and chemical resistance of the photocurable and thermally curable copolymer can be improved.

In Chemical Formula 6 to Chemical Formula 8, each of R ₁₆ to R ₂₆ is independently hydrogen; deuterium; halo; C1-20 alkyl; C1-20 alkoxy; C6-30 monocyclic or polycyclic aromatic Group; C2-20 alkenyl group; or C3-30 monocyclic or polycyclic cycloalkyl group, and L ₄ is a direct bond, C1-20 alkylene group or C1-20 oxyalkylene group.

More specifically, in the third (meth)acrylate repeating unit represented by Chemical Formula 6, R ₁₆ and R ₁₈ may be hydrogen, R ₁₇ may be a methyl group, L ₄ may be a methylene group, and R ₁₉ Can be phenyl. That is, the third (meth)acrylate repeating unit may be a repeating unit derived from benzyl methacrylate.

In addition, in the maleimide repeating unit represented by Chemical Formula 7, R ₂₀ and R ₂₁ may be hydrogen, and R ₂₂ may be a phenyl group. In the vinyl repeating unit represented by Chemical Formula 8, R ₂₃ , R _24, and R ₂₅ 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 (N-phenylmaleimide), and the vinyl repeating unit represented by Chemical Formula 8 The unit may be a repeating unit derived from styrene.

The molar ratio of the third (meth)acrylate repeating unit to the first (meth)acrylate repeating unit can be 1:99 to 99:1, and the third (meth)acrylate repeating unit and the second ( The molar ratio of the meth)acrylate repeating unit may be 1:99 to 99:1. According to this, by using the first (meth)acrylate repeating unit, the second (meth)acrylate repeating unit, and the third (meth)acrylate repeating unit in combination, heat resistance and chemical resistance can be improved .

The weight average molecular weight of the light-curable and heat-curable copolymer (measured by GPC) can range from 1000 grams/mole (g/mol) to 100,000 grams/mole.

At the same time, the photo-curable and heat-curable copolymer may be composed of the following: the first (meth)acrylate repeating unit, in which an organic functional group containing an epoxy group is bonded to the end of the branched chain; the second (a Group) acrylate repeating unit, in which an organic functional group containing an alkenyl group is bonded to the end of the branched chain; the third (meth)acrylate repeating unit represented by Chemical Formula 6; Maleic acid represented by Chemical Formula 7 Amine repeating unit; and a vinyl repeating unit represented by Chemical Formula 8.

That is, the photo-curable and thermally curable copolymers may not contain more The five types of repeating units described in this article are extra repeating units. Therefore, the spontaneous side reaction in the molecule can be suppressed before the photocurable and thermally curable copolymer is cured, thereby ensuring high reliability.

For example, suppose that the photo-curable and thermally curable copolymer includes a repeating unit obtained by the reaction of the second (meth)acrylate repeating unit with an acid anhydride as the repeating unit in addition to the five types described above The side reaction with the (meth)propenyl functional group or epoxy group may be carried out by the terminal carboxyl group (the terminal carboxyl group is formed by the ring-opening reaction of acid anhydride), and therefore it is difficult to fully realize the light Properties of curable and thermally curable copolymers.

The method of synthesizing the photocurable and thermally curable copolymer is not particularly limited, but for example, the copolymer may be formed by including (meth)acrylate substituted with an epoxy-containing organic functional group at the end. The monomer mixture of monomers is polymerized and then reacted with a compound containing an alkenyl group-containing organic functional group to prepare it. Examples of the (meth)acrylate monomer substituted with an epoxy-containing organic functional group at the end may include glycidyl methacrylate, 3,4-epoxycyclohexyl methyl methacrylate, derived from The following Chemical Formula 4-3 of Chemical Formula A of Synthesis Example 3, the following Chemical Formula 4-4 of Chemical Formula B of Synthesis Example 4 below, etc., and examples of the compound including an alkenyl-containing organic functional group may include methacrylic acid. In addition, in the monomer mixture, benzyl methacrylate, N-phenyl maleimide, or styrene may be added as other monomers used in the synthesis of the copolymer.

II. Photosensitive resin composition

Another embodiment of the present invention provides a photosensitive resin composition comprising: the photocurable and thermally curable copolymer of one embodiment; a photocurable resin having two or more photocurable unsaturated functional groups; Polymerized monomer; and photoinitiator.

The details of the photo-curable and thermally curable copolymer are as described above in one embodiment.

The photopolymerizable monomer may be a compound having two or more than two photocurable unsaturated functional groups (such as a polyfunctional vinyl group, etc.), and the photopolymerizable monomer may be the same as the photocurable and The unsaturated functional groups of the thermally curable copolymer form crosslinks, thereby forming a crosslinked structure by photocuring when exposed to light. Therefore, when the pattern film described below is formed, the photosensitive resin composition in the exposed area may not undergo alkaline development, but may continue to exist on the substrate.

As the photopolymerizable monomer, those photopolymerizable monomers that are liquid at room temperature can be used, and thus the viscosity of the photosensitive resin composition can be controlled according to the coating method, or the non-exposed area can be further increased. Alkaline developability.

As the photopolymerizable monomer, an acrylic compound having two or more than two photocurable unsaturated functional groups can be used, and more specifically, a compound composed of the following can be used alone or in combination One or more compounds selected from the group: acrylate compounds containing hydroxyl groups, such as 2-hydroxyethylacrylate, 2-hydroxypropylacrylate, pentaerythritol triacrylate, dipentaerythritol five Acrylate, etc.; water-soluble acrylate compounds, such as polyethylene glycol diacrylate, polypropylene glycol diacrylate, etc.; polyol-based polyfunctional polyester acrylate (polyester acrylate) compounds, such as trimethylolpropane Trimethylol propane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, etc.; polyfunctional alcohol ethylene oxide adduct and/or propylene oxide adduct acrylic compound, such as trihydroxy Methyl propane, hydrogenated bisphenol A, etc., or polyphenols, such as bisphenol A, biphenol, etc.; polyfunctional or monofunctional polyurethane acrylic Ester compounds, which are acrylates containing isocyanate-modified hydroxyl groups; epoxy acrylate compounds, which are bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether and hydrogenated bisphenol A diglycidyl ether; A diglycidyl ether) or (meth)acrylic acid adduct of phenol novolac epoxy resin; caprolactone-modified acrylate compounds, such as caprolactone-modified bis(trimethylolpropane) tetraacrylate ( caprolactone-modified ditrimethylolpropane tetraacrylate, ε-caprolactone-modified dipentaerythritol acrylate, caprolactone-modified hydroxy pivalic acid neopentyl glycol ester diacrylate (caprolactone-modified hydroxy pivalic acid neopentyl glycol ester diacrylate) ) Etc.; and photosensitive (meth)acrylate compounds, such as methacrylate compounds corresponding to the above-mentioned acrylate compounds.

Among them, as the photopolymerizable monomer, a polyfunctional (meth)acrylate compound having two or more (meth)acrylic groups in one molecule can be preferably used, and in particular, Pentaerythritol triacrylate, trimethylolpropane triacrylate, dipentaerythritol hexaacrylate, caprolactone-modified di(trimethylolpropane) tetraacrylate, etc. are suitably used. Examples of commercially available photopolymerizable monomers may include Kayarad's DPEA-12 and the like.

Based on the total weight of the photosensitive resin composition, the content of the photopolymerizable monomer described above may be 0.1% by weight (wt%) to 30% by weight or 1% to 20% by weight. If the content of the photopolymerizable monomer is excessively reduced, the photocuring may be insufficient, and if the content is excessively increased, the dryness of the cured film may decrease, and the characteristics may decrease.

At the same time, for example, the photoinitiator is used to initiate the interaction between the photocurable and thermally curable copolymer and the photopolymerizable monomer in the exposed area of the photosensitive resin composition. Free radical light curing.

Generally known photoinitiators can be used, and specifically, benzoin and its alkyl ethers, such as benzoin, methyl benzoin, ethyl benzoin, etc.; acetophenone, such as acetophenone, 2,2-dibenzoin Methoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 4-(1-tertiary butyldioxy-1-methylethyl)acetophenone, etc.; anthraquinone, Such as 2-methylanthraquinone, 2-pentylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.; thioxanthones, such as 2,4-dimethylthioxanthone, 2,4 -Diisopropylthioxanthone, 2-chlorothioxanthone, etc.; ketals, such as acetophenone dimethyl ketal, benzyl dimethyl ketal, etc.; benzophenone, Such as benzophenone, 4-(1-tertiary butyldioxy-1-methylethyl) benzophenone, 3,3',4,4'-four (tertiary butyl dioxycarbonyl) ) Benzophenone and so on.

As a preferred photoinitiator, mention may be made of 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinoacetone-1,2-benzyl-2-dimethylamine 1-(4-morpholinophenyl)butan-1-one (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)-butane-1-one); 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino) Phenyl]-1-butanone; α-aminoacetophenones, such as N,N-dimethylaminoacetophenone (as a commercial product, Ciba Specialty Chemicals) (now steam Irgacure (registered trademark) 907, Irgacure 369, Irgacure 379, etc. from Pakistan Japan Company); phosphine oxides such as 2,4,6-trimethylbenzyl diphenyl Phosphine oxide, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, bis(2,6-dimethoxybenzyl)2,4,4-trimethyl -Pentyl phosphine oxide (commercial products, Lucirin (registered trademark) TPO from BASF, and Yanjiagu 819 from Ciba Fine Chemicals, etc.).

In addition, preferred photoinitiators may include oxime esters. Specific examples of oxime esters may include 2-(acetoxyiminomethyl)thioxanthene-9-one, (1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzyl oxime)), (ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-,1 -(O-acetoxime)) and so on. As commercial products, we can mention Ciba's GGI-325, Yanjiagu OXE01, Yanjiagu OXE02; ADEKA's N-1919; Ciba's Darocur TPO Wait.

Based on the total weight of the resin composition, the content of the photoinitiator may be 0.1% to 20% by weight or 1% to 10% by weight. If the content of the photoinitiator is too low, photocuring may not be properly achieved, and on the contrary, if the content is too high, the resolution of the photosensitive resin composition may decrease, or the reliability of the pattern film may be insufficient.

The photosensitive resin composition may further include one or more selected from the group consisting of solvents, fillers, pigments, and additives.

The added filler plays a role in improving the heat resistance and stability of the resin, dimensional stability against heat, and adhesion. In addition, it acts as a synergist pigment by enhancing the color. As fillers, inorganic fillers or organic fillers can be used, and for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, fused silica, spherical silica, talc, clay, magnesium carbonate, carbonic acid can be used Calcium, aluminum oxide (alumina), aluminum hydroxide, mica, etc.

Pigments exhibit visibility and hiding power, and as pigments, red pigments, blue pigments, green pigments, yellow pigments, black pigments, etc. can be used. As the blue pigment, Phthalocyanine Blue, Pigment Blue 15:1, Pigment Blue 15:2, Pigment Blue 15:3, Pigment Blue 15:4, Pigment Blue 15: 6. Pigment Blue 60 and so on. As the green pigment, Pigment Green 7, Pigment Green 36, Solvent Green 3, Solvent Green 5, Solvent Green 20, Solvent Green 28, and the like can be used. As a yellow pigment, it can be Anthraquinones, isoindolinones, condensed azos, benzimidazolones, etc. can be used. For example, Pigment Yellow 108, Pigment Yellow 147, Pigment Yellow 151, Pigment Yellow 166, Pigment Yellow 181, and pigments can be used. Huang 193 and so on. As the red pigment, Pigment Red 254 or the like can be used.

Based on the total weight of the resin composition, the content of the pigment may preferably be 0.1% to 10% by weight or 0.5% to 5% by weight.

Additives can be added to remove bubbles of the resin composition, remove bumps or pits on the surface during film coating, provide flame retardancy, control viscosity, act as a catalyst, and the like.

Specifically, commonly used known additives can be used, such as: thickeners, such as micronized silica, organic bentonite, montmorillonite, etc.; defoamers and/or leveling agents, such as silicones, fluorine , Polymers and other defoamers and/or leveling agents; silane coupling agents, such as imidazoles, thiazoles, triazoles, etc.; and flame retardants, such as phosphorus-containing flame retardants Agent, antimony flame retardant, etc.

Among them, the leveling agent performs the function of removing bumps or pits on the surface during coating, and can be used, for example, BYK-380N, BYK-307, BYK-378, and BYK of BYK-Chemie GmbH. -350.

Based on the total weight of the resin composition, the content of the additive may preferably be 0.01% to 10% by weight.

The solvent can be used in combination of one or more solvents to dissolve the resin composition or provide suitable viscosity.

As the solvent, mention may be made of ketones such as methyl ethyl ketone, cyclohexanone, etc.; aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, etc.; glycol ethers (Serosol) such as ethylene glycol monoethyl ether, Ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol diethyl ether , Triethylene glycol monoethyl ether, etc.; acetate, such as 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 acetate, etc.; alcohols, such as ethanol, propanol, ethylene glycol, propylene glycol, carbitol, etc.; aliphatic hydrocarbons, such as octane, decane, etc.; petroleum solvents, such as petroleum ether, Naphtha, hydrogenated naphtha, solvent naphtha, etc.; and amides, such as dimethyl acetamide, dimethyl formamide (DMF) and the like. These solvents can be used alone or in a combination of two or more types of the solvents.

Based on the total weight of the resin composition, the content of the solvent may be 5% to 50% by weight. If the content is less than 5% by weight, coatability may be reduced due to higher viscosity, and if the content is more than 50% by weight, the resin composition may not be dried well, thereby increasing the viscosity.

The photosensitive resin composition may further include acid-modified oligomers or thermosetting binders as needed, and as acid-modified oligomers and thermosetting binders, it can be used (but not limited to) in photosensitive resins. Various compounds, oligomers or polymers are well known in the field of composition.

III. Photosensitive resin film

Another embodiment of the present invention provides a photosensitive resin film comprising: the photocurable and thermally curable copolymer of one embodiment; and a photocurable resin having two or more than two photocurable unsaturated functional groups. The cured product of polymerized monomers.

The photosensitive resin film may be a single film that does not include a pattern, or may include a patterned film including a pattern formed by exposure.

The photosensitive resin film can be prepared by a method of preparing a photosensitive resin film, and the method includes the following steps: 1) Coating another embodiment of the photosensitive resin on the substrate Grease composition to form a coating; 2) drying the coating; 3) irradiating light to the dried coating for photocuring; and 4) applying light to the photocured coating at 50°C to 250°C The layer is thermally cured.

In the step of coating the photosensitive resin composition of another embodiment on the substrate to form a coating layer (step 1), the photosensitive resin composition is as described above in another embodiment.

The method of coating the photosensitive resin composition on the substrate is not specifically limited, and, for example, screen printing, offset printing, flexographic printing, inkjet printing, etc. can be used.

In addition, the photosensitive resin composition can be formed by the following steps: dissolving or dispersing the photo-curable and thermally curable copolymer of one embodiment in an organic solvent, having two or more than two photo-curable unsaturated functions -Based photopolymerizable monomers and photoinitiators.

The step of drying the coating layer (step 2) is to remove the solvent and the like used in the photosensitive resin composition, and a method such as heating or vacuum evaporation of the coating layer can be used. Preferably, drying can be performed at 50°C to 130°C, more preferably at 70°C to 120°C.

The step of irradiating light to the dried coating to perform photocuring (step 3) is a step of irradiating light to the dried coating in step 2 to cure it. As explained above, the alkenyl-containing organic functional group in the second (meth)acrylate repeating unit included in the photocurable and thermally curable copolymer of one embodiment can be photocured by light irradiation , Thereby forming a cured structure.

In the step of irradiating light to perform photocuring, exposure is performed by light (UV, etc.) rays in a specific wavelength range. The exposure can be performed by selective exposure using a photomask or direct pattern exposure using a laser direct stepper. The amount of exposure varies according to the thickness of the coating, but is preferably 0.1 millijoules/cm² (mJ/cm ² ) to 1000 millijoules/cm².

After the step of irradiating light to the dried coating to perform photocuring (step 3), a step of development using an alkaline solvent or the like may be performed as necessary. As the alkaline solvent, alkaline aqueous solvents such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, and amines can be used. By developing, only the film in the exposed area can continue to exist.

That is, if exposure is performed, for example, photocuring occurs at the exposed area to form a crosslink between the photocurable and thermally curable copolymer and the unsaturated functional group contained in the photopolymerizable monomer, and therefore , It may not be removed by subsequent development.

The step of thermally curing the photocured coating at 50°C to 250°C (step 4) is a step of performing low-temperature heat treatment on the photocured coating in step 3. The temperature of the low-temperature heat treatment is preferably 200°C or less. Preferably, the temperature of the low temperature heat treatment is 50°C to 250°C, more preferably 70°C to 150°C or 80°C to 120°C. Here, the member used for the heat treatment is not specifically limited, and the heat treatment can be performed by heating members such as a heating plate, a hot air circulating reactor, an infrared furnace, and the like.

As explained above, the epoxy-containing organic functional group in the first (meth)acrylate repeating unit included in the photocurable and thermally curable copolymer of one embodiment can be thermally cured by heat treatment To form a cured structure.

When the photosensitive resin film undergoes photo-curing and thermal curing via the method described above, it may include the photo-curable and thermal-curable copolymer of one embodiment, and having two or more photo-curables. Photopolymerization of unsaturated functional groups The cured product of the combined monomer. More specifically, the cured product may include: a cross-linked structure in which the epoxy group of the photo-curable and thermally curable copolymer and the thermally curable functional group are cross-linked by thermal curing; and a cross-linked structure in which The alkenyl group of the first (meth)acrylate repeating unit and the unsaturated functional group of the photopolymerizable monomer are crosslinked with each other by photocuring.

In addition, the photosensitive resin film may further contain a small amount of photoinitiator that continues to exist after receiving light curing, or optionally added pigments or additives dispersed in the cured product.

The thickness of the photosensitive resin film is not specifically limited, but it can be freely controlled within a range of 0.01 micrometers (μm) to 1000 micrometers, for example. If the thickness of the photosensitive resin film is increased or decreased by a specific value, the characteristics measured in the photosensitive resin film may change as much as the specific value.

IV. Color filter

Another embodiment of the present invention provides a color filter including the photosensitive resin film of another embodiment.

The details of the photosensitive resin film are as described above in another embodiment. The photosensitive resin film used in the color filter may contain a pigment dispersed in the cured product.

For the details of the color filter, various technical configurations that are well-known in the field of color filters can be applied (but not limited to).

According to the present invention, there is provided a photo-curable and heat-curable copolymer, and a photosensitive resin composition, a photosensitive resin film, and a color filter using the copolymer, even if the copolymer is at a relatively low temperature It also has excellent thermal curability It can be cured by light irradiation, and has excellent durability, chemical resistance and storage stability through sufficient curing.

Hereinafter, the present invention will be explained in detail in the following examples. However, these examples are only presented as illustrations of the present invention, and the scope of the present invention is not limited thereto.

<Synthesis example: Synthesis of photocurable and thermally curable copolymers>

Synthesis Example 1

In the reaction vessel, 5.1% by weight of benzyl methacrylate, 0.8% by weight of N-phenylmaleimide, 0.6% by weight of styrene, and 13.2% by weight of glycidyl methacrylate It was placed together with 78.9% by weight of propylene glycol methyl ether acetate (PGMEA) solvent to dissolve it, and then the temperature of the solution was increased to 75°C under a nitrogen atmosphere. When the temperature of the reactant reached 75°C, 1.2% by weight of the thermal initiator V-65 was added, and then the reactant was allowed to react for 12 hours. A thermal polymerization inhibitor and a catalyst were added to the obtained resin solution, and then 0.1% by weight of methacrylic acid was introduced in an air atmosphere, and the reactants were allowed to react for 16 hours while maintaining the temperature at 120°C. The prepared light-curable and heat-curable copolymer has a weight average molecular weight of 4500 g/mol, and the content of (meth)acrylate repeating units substituted by epoxy groups at the end of the branched chain is 49 mol% , And the content of the (meth)acrylate repeating unit substituted with an alkenyl group at the end of the branched chain is 21 mol%.

Synthesis example 2

Except that 3,4-epoxycyclohexyl methyl methacrylate was used instead of glycidyl methacrylate, the photo-curable and heat-curable copolymers were synthesized by the same method as in Synthesis Example 1. The weight-average molecular weight of the prepared photo-curable and heat-curable copolymer is 4700 g/mol, and the content of (meth)acrylate repeating units substituted by epoxy groups at the end of the branched chain is 49 mol% , And the content of the (meth)acrylate repeating unit substituted with an alkenyl group at the end of the branched chain is 21 mol%.

Synthesis Example 3

The photo-curable and heat-curable copolymers were synthesized by the same method as Synthesis Example 1, except that the compound represented by the following chemical formula A was used instead of glycidyl methacrylate.

Synthesis Example 4

The photo-curable and heat-curable copolymers were synthesized by the same method as Synthesis Example 1, except that the compound represented by the following Chemical Formula B was used instead of glycidyl methacrylate.

[Chemical formula B]

<Comparative synthesis example>

Comparative Synthesis Example 1

In the reaction vessel, 9.3% by weight of benzyl methacrylate, 1.5% by weight of N-phenylmaleimide, 1.1% by weight of styrene, and 6.8% by weight of glycidyl methacrylate It was placed together with 74.6% by weight of propylene glycol methyl ether acetate (PGMEA) solvent to dissolve it, and then the temperature of the solution was increased to 65° C. under a nitrogen atmosphere. When the temperature of the reactant reaches 65°C, 0.7% by weight of the thermal initiator V-65 is added. A thermal polymerization inhibitor and a catalyst were added to the obtained resin solution, and then 4.3% by weight of methacrylic acid was introduced in an air atmosphere, and the reactants were allowed to react for 16 hours while maintaining the temperature at 120°C. The temperature of the prepared resin solvent was lowered to 90° C., and 5.5% by weight of 1,2,5,6-tetrahydrophthalic anhydride was introduced in an air atmosphere, and the reactants were allowed to react for 24 hours. The prepared light-curable and heat-curable copolymer has a weight average molecular weight of 8100 g/mol, an acid value of 83KOH mg/g (mg/g), and an epoxy group substituted at the end of the branched chain (former The content of the (meth)acrylate repeating unit is 0 mol%, and the content of the (meth)acrylate repeating unit substituted with an alkenyl group at the end of the branched chain is 40 mol%.

<Examples and Comparative Examples: Preparation of photosensitive resin composition and photosensitive resin pattern film>

Example 1

(1) Photosensitive resin composition

In 35 grams of propylene glycol methyl ether acetate (PGMEA) solvent, stir and dissolve 1 gram of the photoinitiator Irgacure 369 (manufactured by Ciba Fine Chemicals) at room temperature for 30 minutes, and Then introduce 7.5 grams of the photocurable and thermally curable copolymer obtained in Synthesis Example 1 and 5 grams of dipentaerythritol pentaerythritol pentaerythritol pentaerythritol penta/hexaacrylate; DPHA, manufactured by Nippon Kayaku (Nippon Kayaku), and the reaction mixture was stirred at room temperature for 1 hour, and then, 50 grams of 15% dispersion of CI Pigment Red 254 as a pigment and 0.2 grams were introduced , And the reaction mixture was stirred at room temperature for 1 hour. The composition obtained by the above reaction is filtered twice or more to remove impurities, thereby preparing a photosensitive resin composition.

(2) Photosensitive resin pattern film

The photosensitive resin composition was coated on a 5 cm x 5 cm (cm) glass substrate at a rate of 230 revolutions per minute, and prebaked at 100°C for 100 seconds. Thereafter, the photosensitive resin composition was exposed and developed with an energy of 40 mJ/cm², and then post-baked at 100°C for 30 minutes, thereby preparing a photosensitive resin patterned film.

Example 2

The photosensitive resin composition was prepared by the same method as in Example 1, except that C.I. Pigment Green 7 was used instead of C.I. Pigment Red 254 when preparing the photosensitive resin composition Finished product and photosensitive resin pattern film.

Example 3

Except that C.I. Pigment Blue 15:6 was used instead of C.I. Pigment Red 254 when preparing the photosensitive resin composition, the photosensitive resin composition and the photosensitive resin pattern film were prepared by the same method as in Example 1.

Example 4

In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 2 to replace the photo-curable and heat-curable copolymer obtained in Synthesis Example 1 when preparing the photosensitive resin composition, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 1.

Example 5

In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 2 to replace the photo-curable and heat-curable copolymer obtained in Synthesis Example 1 when preparing the photosensitive resin composition, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 2.

Example 6

In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 2 to replace the photo-curable and heat-curable copolymer obtained in Synthesis Example 1 when preparing the photosensitive resin composition, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 3.

Example 7

In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 3 in the preparation of the photosensitive resin composition instead of the photo-curable and heat-curable copolymer obtained in Synthesis Example 1, by Prepared in the same way as in Example 1. The photosensitive resin composition and the photosensitive resin pattern film.

Example 8

In addition to using the photo-curable and heat-curable copolymer obtained in Synthesis Example 4 in the preparation of the photosensitive resin composition instead of the photo-curable and heat-curable copolymer obtained in Synthesis Example 1, by The photosensitive resin composition and the photosensitive resin pattern film were prepared in the same manner as in Example 1.

Comparative example 1

Except that the thermosetting resin represented by the following chemical formula C (bisphenol type of novolac epoxy resin: KBPN-110 manufactured by Kukdo Chemicals) was used in the preparation of the photosensitive resin composition instead of the synthesis example 1 Except for the obtained photo-curable and thermally curable copolymer, a photosensitive resin composition and a photosensitive resin pattern film were prepared by the same method as in Example 1.

Comparative example 2

Except that the thermosetting resin used in Comparative Example 1 was used in the preparation of the photosensitive resin composition instead of the photo-curable and thermally curable copolymer obtained in Synthesis Example 1, the same as in Example 2 Method to prepare photosensitive resin composition And photosensitive resin pattern film.

Comparative example 3

Except that the thermosetting resin used in Comparative Example 1 was used in the preparation of the photosensitive resin composition instead of the photocurable and thermally curable copolymer obtained in Synthesis Example 1, the same as in Example 3 The method prepares the photosensitive resin composition and the photosensitive resin pattern film.

Comparative example 4

Except that the copolymer resin obtained by Comparative Synthesis Example 1 was used in the preparation of the photosensitive resin composition instead of the photocurable and thermally curable copolymer obtained by Synthesis Example 1, by the same method as Example 1 To prepare a photosensitive resin composition and a photosensitive resin pattern film.

Comparative example 5

Except that the copolymer resin obtained in Comparative Synthesis Example 1 was used in the preparation of the photosensitive resin composition instead of the photo-curable and thermally curable copolymer obtained in Synthesis Example 1, the same method as in Example 2 was used. To prepare a photosensitive resin composition and a photosensitive resin pattern film.

Comparative example 6

Except that the copolymer resin obtained by Comparative Synthesis Example 1 was used in the preparation of the photosensitive resin composition instead of the photocurable and thermally curable copolymer obtained by Synthesis Example 1, by the same method as Example 3 To prepare a photosensitive resin composition and a photosensitive resin pattern film.

<Experimental example: Measurement of the characteristics of the photosensitive resin composition and photosensitive resin pattern film obtained in the examples and comparative examples>

Measure the photosensitive resin composition obtained in the examples and comparative examples as follows And the characteristics of the photosensitive resin pattern film, and the results are shown in the following table.

1. Experimental example 1: Dyeing characteristics

The photosensitive resin pattern film obtained in the examples and comparative examples was coated with a photosensitive resin composition containing a pigment (the pigment has a color different from the pigment contained in the photosensitive resin pattern film)/the photosensitive resin composition The photosensitive resin composition is developed, and then, for the photosensitive resin patterned film, the color change is measured as the minimum perceptible color difference (MPCD), and the pattern movement and swelling are observed using an optical device, and according to the following Standards are used to determine whether the pigment is dissolved, and the results are shown in Table 1 below.

○: The pigment is not dissolved at all

△: A slight amount of dissolution of the pigment is observed.

X: The film peeled off while dissolving with the pigment.

2. Experimental example 2: Chemical resistance

On the photosensitive pattern films obtained in the Examples and Comparative Examples, a protective layer (over coat) photoresist was coated/exposed the protective layer photoresist/the protective layer photoresist was developed, and then, the photoresist For the resin pattern film, the color change is measured as the Minimum Perceptible Color Difference (MPCD), the pattern movement and swelling are observed using an optical device, and whether the pigment is dissolved is determined according to the following criteria, and the results are shown below in FIG. 1.

○: The pigment is not dissolved at all

△: A slight amount of dissolution of the pigment is observed.

X: The film peeled off while dissolving with the pigment.

3. Experimental example 3: Storage stability

The photosensitive resin composition obtained in the examples and comparative examples was used to manufacture On the date and 2 weeks thereafter, let it stand at room temperature, and then measure the development time (seconds). The results are shown in Table 1 below. It can be seen that between the manufacturing date and the next 2 weeks, the smaller the change in the development time, the better the storage stability.

As shown in Table 1, it was confirmed that compared with Comparative Examples 1 to 3 using ordinary thermosetting resins, the photo-curable and thermally curable copolymers obtained in the synthesis examples were used as examples of binder resins. Even if the photosensitive resin composition is post-baked at a temperature of 100°C, it has excellent chemical resistance and dyeing properties through subsequent processes.

It was also confirmed that the resin obtained in the comparative synthesis example does not contain the first (meth)acrylate repeating unit (in which the organic functional group containing an epoxy group is bonded to the end of the branched chain) of the comparative example 4 to the comparative example. Compared with Example 6, the photosensitive resin composition also has excellent chemical resistance and dyeing properties through subsequent processes.

Therefore, it can be confirmed that compared with the existing thermosetting adhesive resin, the The photo-curable and heat-curable copolymer obtained in the example exhibits excellent curability even at low temperatures, and therefore, a cured film having excellent heat resistance and chemical resistance can be formed.

In addition, it was confirmed that the photosensitive resin composition of the example may have storage stability equivalent to the photosensitive resin composition of the comparative example or much better than the photosensitive resin composition of the comparative example. Therefore, it can be confirmed that the photo-curable and heat-curable copolymer obtained in the synthesis example can form sufficient bonding during curing, thereby achieving excellent storage stability, even when compared with existing thermosetting binder resins. sex.

Claims (11)

A photocurable and thermally curable copolymer, comprising: a first (meth)acrylate repeating unit, in which an organic functional group containing an epoxy group is bonded to the end of a branched chain; and a second (meth)acrylic acid An ester repeating unit, in which an organic functional group containing an alkenyl group is bonded to the end of a branched chain, is included in a ratio of 10 mol to 90 mol based on 100 mol of the first (meth)acrylate repeating unit The second (meth)acrylate repeating unit, wherein in the second (meth)acrylate repeating unit, the branched chain comprises: a C1-20 alkyl ester group substituted with a hydroxyl group; C1-20 oxyalkyl ester group; C3-30 cycloalkyl substituted alkyl ester group substituted by hydroxyl group; C7-30 polycyclic alkyl ester group substituted by hydroxyl group; or C7-30 polycyclic ring substituted by hydroxyl group An alkoxy-substituted alkyl ester group, wherein the weight average molecular weight (measured by GPC) of the photo-curable and heat-curable copolymer is 1,000 g/mol to 100,000 g/mol, wherein The first (meth)acrylate repeat unit is represented by the following chemical formula 4:

Wherein, in Chemical Formula 4, each of R ₈ to R ₁₀ is independently hydrogen or a C1-10 alkyl group, L ₁ is a direct bond, a C1-20 alkylene group or a C1-20 oxyalkylene group, and R ₁₁ is an organic functional group containing an epoxy group, wherein the second (meth)acrylate repeating unit is represented by the following chemical formula 5:

Wherein, in the chemical formula 5, each of R ₁₂ to R ₁₄ is independently hydrogen or a C1-10 alkyl group, L ₂ is a direct bond, a C1-20 alkylene group or a C1-20 oxyalkylene group, L ₃ is C1-20 alkylene substituted by hydroxy, C1-20 oxyalkylene substituted by hydroxy, C3-30 cycloalkylene substituted by hydroxy or C7-30 polycyclic alkylene substituted by hydroxy; And R ₁₅ is an organic functional group containing an alkenyl group. The photo-curable and heat-curable copolymer described in the first item of the scope of patent application, wherein in the first (meth)acrylate repeating unit, the branched chain includes a carbonyl group and a C1-20 alkyl ester group Or C1-20 oxyalkyl ester group. The photo-curable and thermally curable copolymer as described in the first item of the patent application, wherein the epoxy-containing organic functional group includes a functional group represented by the following chemical formula 1; a functional group represented by the following chemical formula 2 ; Or a functional group represented by the following chemical formula 3:

Wherein, in Chemical Formula 1, each of R ₁ , R ₂ and R ₃ is independently a direct bond, hydrogen or a C1-5 alkyl group,

Wherein, in the chemical formula 2, each of R ₄ and R ₅ is independently a direct bond or a C1-5 alkylene group,

Wherein, in Chemical Formula 3, each of R ₆ and R ₇ is independently a direct bond, hydrogen or a C1-5 alkyl group, and X is a direct bond, -O- or -S-. The photo-curable and thermally curable copolymer as described in the first item of the patent application, wherein the alkenyl-containing organic functional group includes a (meth)acryloyl group or a (meth)acryloyloxy group. The photo-curable and thermally curable copolymer as described in item 1 of the scope of the patent application further includes one or more types of repeating units selected from the group consisting of: the third represented by the following chemical formula 6 (Meth)acrylate repeating unit; maleimide repeating unit represented by the following Chemical Formula 7; and vinyl repeating unit represented by the following Chemical Formula 8:

Wherein, in Chemical Formula 6 to Chemical Formula 8, each of R ₁₆ to R ₂₆ is independently hydrogen; deuterium; halo; C1-20 alkyl; C1-20 alkoxy; C6-30 monocyclic or polycyclic Cyclic aryl group; C2-20 alkenyl group; or C3-30 monocyclic or polycyclic cycloalkyl group, and L ₄ is a direct bond, C1-20 alkylene group or C1-20 oxyalkylene group. A photosensitive resin composition comprising: the photo-curable and heat-curable copolymer as described in item 1 of the scope of the patent application; a photo-polymerizable monomer having two or more than two photo-curable unsaturated functions Base; and Light initiator. The photosensitive resin composition according to claim 6, wherein the photopolymerizable monomer includes an acrylic compound having two or more photocurable unsaturated functional groups. The photosensitive resin composition described in item 6 of the scope of patent application further includes pigments. A method for preparing a photosensitive resin film, comprising the following steps: 1) coating the photosensitive resin composition as described in item 6 of the scope of patent application on a substrate to form a coating film; 2) drying the coating film 3) irradiating light to the dried coating film for photocuring; and 4) thermally curing the photocured coating film at 50°C to 250°C. A photosensitive resin film, comprising: the photo-curable and thermally curable copolymer as described in item 1 of the scope of the patent application; and a cured product of a photo-polymerizable monomer, the photo-polymerizable monomer having two or More than two light-curable unsaturated functional groups. A color filter includes the photosensitive resin film as described in item 10 of the scope of patent application.