TWI643876B - Photosensitive resin composition, photocurable pattern formed from the same and image display comprising the pattern - Google Patents

Abstract

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the same. More specifically, the photosensitive resin composition includes an alkali-soluble resin (A) and a photopolymerizable compound. (B), a photopolymerization initiator (C), a solvent (D), and an additive (E), the alkali-soluble resin (A) includes a specific resin having a repeating unit containing an oxo-functional group, and is composed of The repeating unit represented by Chemical Formula 1 has a high cured density of the photosensitive resin composition and excellent adhesion, chemical resistance, storage stability, and the like. In the chemical formula 1, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[Chemical Formula 1]

Description

Photosensitive resin composition, light-cured pattern formed therefrom, and image display device including the pattern

The present invention relates to a photosensitive resin composition, a photocurable pattern formed therefrom, and an image display device including the photocurable pattern.

In the display field, a photosensitive resin composition is used in order to form various photocurable patterns such as a photoresist, an insulating film, a protective film, a black matrix, and a column spacer. Specifically, although a photoresist process can be used to selectively expose and develop the photosensitive resin composition to form a desired photocurable pattern, in order to increase the productivity of the process and increase the application target Physical properties require a photosensitive resin composition having high sensitivity.

The patterning of the photosensitive resin composition uses a photo-etching method, that is, a change in the polarity of a polymer and a cross-linking reaction by a photoreaction. In particular, the change characteristics of the solubility in a solvent such as an alkaline aqueous solution after exposure are used.

The pattern formation using the photosensitive resin composition is classified into a positive type and a negative type according to the solubility of the photosensitive portion in the developing solution. Positive photoresist is the exposed part The pattern is divided into solutions that are dissolved by the developing solution. The negative type photoresist is a method in which the exposed part is insoluble in the developing solution and the unexposed part is dissolved to form a pattern. Agents and other aspects are different from each other.

The conventional photosensitive resin composition has problems in that the thickness changes before and after the thermal process, it is difficult to form a fine pattern, and the developability is insufficient.

Recently, in order to solve such a problem, a method of adding an inorganic substance powder to a photosensitive resin composition is disclosed in Japanese Patent Application Publication No. 2000-095896. However, the compatibility of the photosensitive resin composition and the inorganic substance powder is reduced. There is a problem that the developability is lowered due to the adhesion to the substrate, etc., and there is a problem that the content of the inorganic powder cannot be sufficiently increased. As a result, there is a limitation that the problem of the photosensitive resin composition cannot be sufficiently solved.

Prior art literature Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2000-095896

An object of the present invention is to provide a photosensitive resin composition having a high curing density and improved adhesion, chemical resistance, storage stability, and the like.

Another object of the present invention is to provide a photocurable pattern formed from the photosensitive resin composition and an image display device including the same.

1. A photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (D), and an additive (E), and the alkali-soluble resin ( A) contains a first resin (A-1) having a repeating unit containing an oxetane functional group and a repeating unit represented by the following Chemical Formula 1: (In the formula, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

2. The photosensitive resin composition according to the above item 1, wherein the repeating unit containing an oxetane functional group is represented by the following chemical formula 2: (In the formula, R ₃ is a hydrogen atom or a methyl group, R ₄ is an alkylene group having 1 to 6 carbon atoms, and R ₅ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

3. The photosensitive resin composition according to the above item 1, wherein the first resin (A-1) further includes a repeating unit represented by the following chemical formula 3 and a repeating unit represented by the following chemical formula 4: (Wherein R ₆ is a hydrogen atom or a methyl group; R ₇ is a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or -COO-R ₇ ′, and the aforementioned R ₇ ′ is At least one of a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, and the cycloalkyl group or the hydrogen atom of the aryl group is further linear or branched by 1 to 5 carbon atoms. Chain alkyl substituted or unsubstituted). (Wherein R ₈ is a hydrogen atom or a methyl group).

4. The photosensitive resin composition according to the above item 1, wherein the first resin (A-1) is represented by the following Chemical Formula 5: [Chemical Formula 5] (Wherein R ₁ , R ₃ , R ₆ and R ₈ are each independently hydrogen or methyl; R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₄ is a carbon atom having 1 to 6 carbon atoms; Alkylene; R ₅ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₇ is a cycloalkyl group having 3 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, the above cycloalkyl group or the above At least one of the hydrogen atoms of the aryl group is further substituted or unsubstituted with a linear or branched alkyl group having 1 to 5 carbon atoms; a = 0.1 to 50 mole%, b = 2 to 50 mole%, c = 2 to 95 mole%, d = 2 to 70 mole%).

5. The photosensitive resin composition according to the above item 1, in the photosensitive resin composition, the alkali-soluble resin (A) is contained in an amount of 5 to 90 parts by weight based on 100 parts by weight of the solid content, The photopolymerizable compound (B) is included at 1 to 90 parts by weight, the photopolymerization initiator (C) is included at 0.1 to 20 parts by weight, and the additive (E) is 0.001 to 1 part by weight Served.

6. The photosensitive resin composition according to the above item 1, wherein the alkali-soluble resin (A) further includes a second resin (A-2) represented by the following Chemical Formula 6: [Chemical Formula 6] (Wherein R ₉ and R ₁₂ are each independently a hydrogen atom or a methyl group, X is a single bond or an alkylene group having 1 to 6 carbon atoms, the alkylene group contains a hetero atom or does not include a hetero atom, e = 60 to 95 mole%, f = 5 to 40 mole%).

7. A photocurable pattern produced from the photosensitive resin composition according to any one of the above items 1 to 6.

8. The photocurable pattern according to the item 7, wherein the photocurable pattern is selected from the group consisting of an adhesive layer, an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, and a color filter. Device pattern, black matrix pattern, and spacer pattern.

9. An image display device comprising the photo-curable pattern of item 7 above.

The photosensitive resin composition according to the present invention has high curing density, good line width and pattern shape, and is excellent in adhesion, chemical resistance, storage stability, and fine pattern formation properties.

The photosensitive resin composition according to an embodiment of the present invention further includes a second resin (A-2), so that a stronger pattern can be formed by radical polymerization of the first resin and thermal curing reaction of the second resin. .

One embodiment of the present invention relates to a photosensitive resin composition including an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (D), and an additive (E ), The alkali-soluble resin (A) includes a first resin (A-1), and the first resin (A-1) has a repeating unit containing an oxetane functional group and a repeating unit represented by the following Chemical Formula 1, Therefore, it has a high curing density and can provide excellent adhesion, chemical resistance, storage stability, and the like.

In the present invention, when the repeating unit, compound, or resin represented by a chemical formula has an isomer, it means that the corresponding chemical formula representing the repeating unit, compound, or resin is a representative chemical formula included in its isomer.

In the present invention, "(meth) acrylic-" means "acrylic-", "methacrylic-", or both.

In the present invention, "first" in the "first resin" is only a term used to distinguish the resin to be described below from other resins that may be further added as necessary, and it is not a premise that other resins are used in combination.

In the present invention, each of the repeating units represented by the first and second resins described above cannot be interpreted directly and in a limited state, and the sub repeating units in parentheses may be within a specified mole range Inside is freely located anywhere on the chain. That is, the parentheses of each repeating unit are represented by one block in order to indicate Moire%, but as long as each sub-repeating unit is within the corresponding resin, it may be placed without restriction as a segment or separately.

<Photosensitive resin composition>

The photosensitive resin composition of the present invention includes an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), a solvent (D), and an additive (E).

Alkali soluble resin (A)

The alkali-soluble resin (A) used in the present invention is a component that imparts solubility to an alkaline developing solution used in a development process when forming a pattern, and includes a first resin (A-1) and a first resin (A-1). ) Has a repeating unit containing an oxetane functional group and a repeating unit represented by the following Chemical Formula 1.

The first resin according to the present invention has a repeating unit containing an oxetane functional group and a repeating unit represented by the following Chemical Formula 1, so that the curing density can be increased. In this way, the line width and pattern shape of the photocurable pattern formed by including the same can be made excellent, and the adhesiveness, chemical resistance, storage stability, and fine pattern formation property can be excellent.

(In the formula, R ₁ is a hydrogen atom or a methyl group, and R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

When the oxonium functional group according to the present invention is represented by the above Chemical Formula 1 In the case where the functional groups contained in the repeating unit are coexisted in one resin, the composition can be simultaneously cured by heat and light when the composition is cured. Therefore, it is not only excellent in curability, but also when contained in different resins. In the case of the same resin, since it is excellent in reactivity with cross-linking and the like and is significantly excellent in curing density, when forming a pattern using a composition containing the same, it is necessary to ensure excellent developability and adhesion, chemical resistance, Aspects such as storage stability are clearly advantageous.

Considering from this aspect, preferably, the repeating unit including the above-mentioned oxetane functional group according to an embodiment of the present invention may be represented by the following Chemical Formula 2.

(In the formula, R ₃ is a hydrogen atom or a methyl group, R ₄ is an alkylene group having 1 to 6 carbon atoms, and R ₅ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms).

Thereby, the object and effect of the present invention described above can be achieved more effectively.

The first resin according to the present invention may further have a repeating unit formed of other monomers known in the art in addition to the repeating unit of Chemical Formula 1 described above.

According to need, the first resin (A-1) according to an embodiment of the present invention may further preferably have a repeating unit represented by the following Chemical Formula 3 and The repeating unit represented by the following Chemical Formula 4.

(Wherein R ₆ is a hydrogen atom or a methyl group, R ₇ is a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 18 carbon atoms, or -COO-R ₇ ′, and the aforementioned R ₇ ′ is a carbon At least one of a cycloalkyl group having 3 to 8 carbon atoms and an aryl group having 6 to 18 carbon atoms may be further linear or branched with 1 to 5 carbon atoms. Substituted by alkyl).

(Wherein R ₈ is a hydrogen atom or a methyl group).

The first resin (A-1) according to an embodiment of the present invention contains a ring structure in the resin by containing a cycloalkyl group having 3 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms. It can be excellent in chemical resistance, heat resistance, etc. For example, it can have effects such as a pattern that can well resist a stripper in a subsequent process, and can contribute to improving developability. In addition, by having a repeating unit of the above Chemical Formula 4, alkaline solubility can be imparted to the resin.

As long as the first resin according to the present invention has oxygen-containing fluorene (oxetane) The repeating unit of the functional group and the alkali-soluble resin of the repeating unit represented by the above Chemical Formula 1 are not particularly limited, and as a preferable example, the repeating unit represented by the following Chemical Formula 5 may be included.

(Wherein R ₁ , R ₃ , R ₆ and R ₈ are each independently hydrogen or methyl; R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₄ is a carbon atom having 1 to 6 carbon atoms; Alkylene; R ₅ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₇ is a cycloalkyl group having 3 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, the above cycloalkyl group or the above At least one of the hydrogen atoms of the aryl group may be further substituted with a linear or branched alkyl group having 1 to 5 carbon atoms; a = 0.1 to 50 mole%, b = 2 to 50 mole%, c = 2 to 95 mole%, d = 2 to 70 mole%, preferably a = 25 to 45 mole%, b = 20 to 40 mole%, c = 10 to 30 mole%, d = 20 To 50 mol%).

The weight average molecular weight of the first resin is preferably 10,000 to 30,000 in terms of exhibiting the most excellent pattern formability and developability. In the above molecular weight range, the most excellent pattern formation property, developability, and the like can be exhibited.

If necessary, the above-mentioned alkali-soluble resin (A) according to the present invention may further include a second resin (A-2) represented by the following Chemical Formula 6. The alkali-soluble resin (A) of the present invention includes a second resin (A-2), and undergoes a thermal curing reaction through a ring-opening polymerization reaction of an epoxy functional group and a carboxylic acid in a post-baking step. Therefore, the pattern formed from the photosensitive resin composition of the present invention can be more firmly formed by radical polymerization of the first resin and thermal curing reaction of the second resin.

(Wherein R ₉ and R ₁₂ are each independently a hydrogen atom or a methyl group, X is a single bond or an alkylene group having 1 to 6 carbon atoms, and the above alkylene group contains a hetero atom or does not include a hetero atom, e = 60 to 95 mole%, f = 5 to 40 mole%).

From the viewpoint of further improving the adhesion, the weight average molecular weight of the second resin is preferably 2,000 to 30,000.

In addition, different repeating units may be independently added to the first resin and the second resin according to an embodiment of the present invention. As a comonomer which can form such a repeating unit, what is necessary is just a comonomer which can achieve the objective of this invention, The comonomer conventionally known in the art can be used without a restriction | limiting in particular.

For an alkali-soluble resin according to an embodiment of the present invention (A), the mixed weight ratio of the first resin and the second resin may be 20:80 to 80:20, and preferably 30:70 to 70:30. Within the above range, the most excellent adhesion, developability, and T / B ratio can be exhibited. The T / B is defined as follows: from the bottom of the hole pattern to 5% of the total height as the bottom CD (a), and from the bottom to 95% of the total height as the top CD (b), and dividing the length of (b) by the length of (a) and multiplying by 100 (= b / a × 100) is defined as "T / B ratio".

The acid value of the alkali-soluble resin (A) is preferably in the range of 20 to 200 (KOH mg / g (mg / g)). When the acid value is in the above range, excellent developability and stability over time can be obtained.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the alkali-soluble resin (A) is preferably 1.5 to 6.0, more preferably 1.8 to 4.0. When the said molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] exists in the said range, since developability becomes excellent, it is preferable.

The content of the alkali-soluble resin (A) is not particularly limited. For example, the alkali-soluble resin (A) may be contained in an amount of 5 to 90 parts by weight based on 100 parts by weight of the solid content in the photosensitive resin composition, and may preferably be 10 to 70. The weight part contains the said alkali soluble resin (A). When included in the above range, the solubility in the developing solution is sufficient and the developability is excellent, and a photocurable pattern having excellent mechanical properties can be formed.

Photopolymerizable compound (B)

The photopolymerizable compound (B) used in the photosensitive resin composition of the present invention is a compound capable of polymerizing by the action of light and a photopolymerization initiator (C) described later, During the manufacturing process, the crosslinking density can be increased, and the mechanical characteristics of the photo-curable pattern can be enhanced.

In order to improve the developability, sensitivity, adhesion, surface problems, and the like of the resin composition, the photopolymerizable compound (B) may be a mixture of two or more photopolymerizable compounds having different functional group structures or functional group numbers. The photopolymerizable compound used in the art is not particularly limited, and examples thereof include the following compounds as monofunctional monomers, difunctional monomers, and other polyfunctional monomers.

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropylacrylate, 2-ethylhexylcarbitol acrylate, and 2-hydroxy Ethyl acrylate, N-vinyl pyrrolidone and the like. Specific examples of the difunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Triethylene glycol di (meth) acrylate, bis (propenyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like. Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trihydroxy Methylpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, dinepentaerythritol penta (meth) acrylate, ethoxylate Dimethylpentaerythritol hexa (meth) acrylate, dioxypentaerythritol hexa (meth) acrylate, dioxypentaerythritol hexa (meth) acrylate, and the like. Among these, a difunctional or more polyfunctional monomer is preferably used.

The content of the photopolymerizable compound (B) is not particularly limited. For example, based on the solid content in the photosensitive resin composition, it is preferably 1 to 90 parts by weight based on 100 parts by weight of the alkali-soluble resin (A). The photopolymerizable compound (B) is used in a range of 10 to 80 parts by weight. When the content of the photopolymerizable compound (B) is within the above-mentioned content range, it can have excellent durability and can improve the developability of the composition.

Photopolymerization initiator (C)

As the photopolymerization initiator according to the present invention, a photopolymerization initiator generally used in the field can be used without limitation without departing from the object of the present invention. Considering the high sensitivity and the strength or surface smoothness of the photocurable pattern formed from the photosensitive resin composition of the present invention, three examples are mentioned. Compounds, acetophenone compounds, biimidazole compounds, oxime compounds, benzoin compounds, benzophenone compounds, 9-oxysulfur Compounds, anthracene compounds, and the like, but are not limited thereto. These can be used individually or in combination of 2 or more types.

In addition, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzoin, 9,10 -Phenanthrenequinone, camphorquinone, methyl benzamate, titanocene compounds, etc.

In addition, as the photopolymerization initiator, a photopolymerization initiator having a group capable of causing chain transfer can also be used. Examples of such a photopolymerization initiator include a photopolymerization initiator described in Japanese Patent Publication No. 2002-544205.

The photopolymerization initiator may be used in combination with a polymerization initiation aid. When the photopolymerization initiator and the polymerization initiation aid are used in combination, the photosensitive resin composition containing them can be further increased in sensitivity, and productivity in forming a photocurable pattern can be improved.

As said polymerization initiation adjuvant, the polymerization initiation adjuvant normally used in this field can be used in the range which does not deviate from the objective of this invention, and the kind is not specifically limited. Specifically, an amine compound and a carboxylic acid compound can be preferably used.

The content of the photopolymerization initiator is not particularly limited. For example, the content of the photopolymerization initiator may be 0.1 to 20 parts by weight based on 100 parts by weight of the solid content in the photosensitive resin composition. Within the above range, since the photosensitive resin composition is made more sensitive and the exposure time is shortened, productivity is improved, high resolution can be maintained, and the strength of the formed pixel portion and the smoothness of the surface of the pixel portion can be improved. In this respect, it is better.

Solvent (D)

The solvent according to the present invention can be used without limitation as long as it is a solvent generally used in the art.

Specific examples of the solvent include ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, ethylene glycol alkyl ether acetates, alkylene glycol alkyl ether acetates, and alkoxylates. Butyl acetate, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, propylene glycol alkyl ether propionate, butanediol monoalkyl ether, butanediol monoalkyl ether acetate, Butanediol monoalkyl ether propionates, alkoxyethyl propionates, dipropylene glycol dialkyl ethers, aromatic hydrocarbons, ketones, alcohols, esters, alkoxyalkanols , Cyclic ethers, cyclic esters, etc. When considering coating properties and drying properties, Preferred are methyl ethyl diethylene glycol, propylene glycol monomethyl ether acetate, 3-methoxy-1-butanol, and the like. These can be used individually or in mixture of 2 or more types.

The content of the solvent is not particularly limited, and for example, the content of the solvent may be 40 to 90 parts by weight in a total of 100 parts by weight of the photosensitive resin composition. In the case where the above range is satisfied, coating is performed from a spin coater, a slit spin coater, a slit coater (sometimes referred to as a die coater, a curtain flow coater), an inkjet printer, and the like. It is preferable that the coating property is good when the device performs coating.

Additive (E)

The photosensitive resin composition according to the present invention may further contain additives such as fillers, other polymer compounds, curing agents, adhesion promoters, antioxidants, ultraviolet absorbers, anticoagulants, and chain transfer agents as necessary.

These additives may be used alone or in combination of two or more.

The content of the above additives is not particularly limited, and for example, the content of the additives may be 0.001 to 1 part by weight relative to 100 parts by weight of the solid content in the photosensitive resin composition.

<Light-cured pattern and image display device>

An object of the present invention is to provide a photocurable pattern produced from the photosensitive resin composition and an image display device including the photocurable pattern.

The photocurable pattern produced using the photosensitive resin composition can be controlled for CD deviation (CD-Bias), and has excellent T / B ratio, developability, adhesion and mechanical properties. Therefore, it can be used as various patterns in image display devices, such as adhesives. Layers, array planarization films, protective films, insulating film patterns, etc. can also be used as photoresist, black matrix, spacer patterns, etc., but are not limited to this.

Examples of the image display device provided with such a photo-curable pattern or using the pattern in a manufacturing process include a liquid crystal display device, an OLED, and a flexible display. However, it is not limited to this, and all image display devices known in the art can be cited.

The photo-curable pattern can be produced by applying the above-mentioned photosensitive resin composition of the present invention to a substrate and, after undergoing a development process as necessary, forming a photo-curable pattern.

Specifically, first, a photosensitive resin composition is applied to a substrate and then heated and dried to remove volatile components such as solvents, thereby obtaining a smooth coating film.

Examples of the coating method include a spin coating method, a cast coating method, a roll coating method, a slit spin coating method, and a slit coating method. After the application, heat drying (pre-baking) or drying under reduced pressure is performed to heat to volatilize volatile components such as solvents. Here, the heating temperature is a relatively low temperature of 70 to 100 ° C. The thickness of the coating film after heating and drying is usually about 1 to 8 microns. The thus-obtained coating film is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, in order to uniformly irradiate parallel light rays throughout the exposure section and to align the mask and the substrate at a correct position, it is preferable to use a mask aligner or a stepper. After the ultraviolet rays are irradiated, the portions irradiated with the ultraviolet rays are cured.

As the ultraviolet rays, g rays (wavelength: 436 nm), h rays, i rays (wavelength: 365 nm), and the like can be used. The amount of ultraviolet radiation can be as required Instead, it is appropriately selected and is not limited in the present invention. If the cured coating film is contacted with a developing solution as needed, and the non-exposed portion is dissolved and developed, the target pattern shape can be formed.

The development method may be any of a liquid addition method, a dipping method, and a spray method. In addition, the substrate can be tilted at an arbitrary angle during development. The developing solution is usually an aqueous solution containing a basic compound and a surfactant.

The concentration of the surfactant in the developing solution is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, and more preferably 0.1 to 5% by weight. After development, it is washed with water and post-baked at a relatively low temperature of 100 to 150 ° C for 10 to 60 minutes.

In the following, preferred embodiments are disclosed in order to facilitate understanding of the present invention, but these embodiments are only used to illustrate the present invention, and do not limit the scope of the appended claims. It is clear to a person skilled in the art that various changes and modifications can be made to the embodiments within the scope of the present invention and the technical idea, and such changes and modifications naturally also fall within the scope of protection claimed in the present invention.

<Synthesis example 1> Synthesis of first resin A-1-1

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was flowed in at 0.02 liters / minute to form a nitrogen atmosphere, and 250 grams of propylene glycol monomethyl ether acetate was charged. After the temperature was raised to 100 ° C, a solution containing 36.0 g (0.50 mole) of acrylic acid, 51.1 g (0.30 mole) of 3-ethyl-3-oxomethyl methacrylate, 23.6 g (0.20 mole) of vinyl toluene, and A solution of 150 g of propylene glycol monomethyl ether acetate was added to 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to obtain a solution, and the solution was added dropwise from the dropping funnel to the solution over 2 hours. The flask was further stirred at 100 ° C for 5 hours.

Next, the atmosphere in the flask was changed from nitrogen to air, and 49.8 g of glycidyl methacrylate [0.35 mol (70 mol% relative to the acrylic acid used in the reaction)] was put into the flask at 110 ° C. The reaction was continued for 6 hours. Thus, an unsaturated group-containing resin (A-1-1) having a solid content acid value of 70 mg KOH / g was obtained. The polystyrene equivalent weight average molecular weight measured by GPC was 24,100, and the molecular weight distribution (Mw / Mn) was 2.30.

<Synthesis example 1-2> Synthesis of first resin A-1-2

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was flowed in at 0.02 liters / minute to form a nitrogen atmosphere, and 250 grams of propylene glycol monomethyl ether acetate was charged. After the temperature was raised to 100 ° C, 36.0 g (0.50 mol) of acrylic acid, 51.1 g (0.30 mol) of 3-ethyl-3-oxomethyl methacrylate, and 33.6 g (0.20 mol) of cyclohexyl methacrylate were contained. Ear) and a mixture of 150 g of propylene glycol monomethyl ether acetate were added to a solution of 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to obtain a solution, and the solution was removed from the dropping funnel over 2 hours. The mixture was dropped into the flask, and further stirred at 100 ° C. for 5 hours.

Next, the atmosphere in the flask was changed from nitrogen to air, and 49.8 g of glycidyl methacrylate [0.35 mol (70 mol% relative to the acrylic acid used in the reaction)] was put into the flask at 110 ° C. The reaction was continued for 6 hours. Thus, an unsaturated group-containing resin (A-1-2) having an acid value of 71 mg KOH / g as a solid content was obtained. The polystyrene equivalent weight average molecular weight measured by GPC was 23,900, and the molecular weight distribution (Mw / Mn) was 2.34.

<Synthesis example 2> Synthesis of first resin A-1-3

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was flowed in at 0.02 liters / minute to form a nitrogen atmosphere, and 250 grams of propylene glycol monomethyl ether acetate was charged. After the temperature was raised to 100 ° C, it contained 36.0 g of acrylic acid (0.50 mol), 51.1 g of 3-ethyl-3-oxomethyl methacrylate (0.30 mol), 20.8 g of styrene (0.20 mol), and propylene glycol. A solution of 150 g of monomethyl ether acetate was added to 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) to obtain a solution, and the solution was added dropwise from a dropping funnel to the flask over 2 hours. The stirring was continued at 100 ° C for 5 hours.

Next, the atmosphere in the flask was changed from nitrogen to air, and 49.8 g of glycidyl methacrylate [0.35 mol (70 mol% relative to the acrylic acid used in the reaction)] was put into the flask at 110 ° C. The reaction was continued for 6 hours. Thus, an unsaturated group-containing resin (A-1-3) having an acid value of 71 mg KOH / g as a solid content was obtained. The polystyrene equivalent weight average molecular weight measured by GPC was 23,900, and the molecular weight distribution (Mw / Mn) was 2.31.

<Synthesis example 3> Synthesis of second resin A-2-1

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was flowed in at 0.02 liters / minute to form a nitrogen atmosphere. 150 grams of diethylene glycol methyl ether was charged, and the mixture was heated to 70 ° C while being stirred. Next, 210.2 g (0.95 mol) of a mixture of the following chemical formulas 16 and 17 (molar ratio 50:50) and 14.5 g (0.17 mol) of methacrylic acid were dissolved in diethylene glycol methyl ether 150 grams to prepare a solution. After the prepared dissolved solution was dropped into the flask using a dropping funnel, 27.9 g (0.11 mole) of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in diethyl 200 g of glycol methyl ether was obtained to obtain a solution, and the above-mentioned polymerization initiator was dissolved. The solution was dropped into the flask over 4 hours using another dropping funnel. After the dropwise addition of the solution of the polymerization initiator was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. Thus, a solution of a copolymer having a solid content of 41.6% by mass and an acid value of 65 mg-KOH / g (in terms of solid content) was obtained. The weight average molecular weight Mw of the obtained resin (A-2-1) was 8,300, and the molecular weight distribution was 1.85.

At this time, the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the above-mentioned dispersion resin was performed using an HLC-8120GPC (manufactured by Tosoh Corporation). The column was used in series with TSK-GELG4000HXL and TSK-GELG2000HXL. The column temperature is 40 ° C, the mobile phase solvent is tetrahydrofuran, the flow rate is 1.0 ml / min, the injection volume is 50 microliters (μl), the detector uses RI, and the measurement sample concentration is 0.6 mass% (solvent = tetrahydrofuran). TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, and A-500 (manufactured by Tosoh Corporation) were used as reference materials.

The ratio of the weight-average molecular weight to the number-average molecular weight obtained as described above was taken as the molecular weight distribution (Mw / Mn).

<Synthesis Example 4> Synthesis of unsaturated group-containing resin A-4

In a 1 liter flask equipped with a reflux condenser, a dropping funnel and a stirrer, Nitrogen was flowed in at a rate of 1 liter / minute to form a nitrogen atmosphere, and 200 g of propylene glycol monomethyl ether acetate was charged. After raising the temperature to 100 ° C, a mixture containing 150 g of acrylic acid 33.9 g (0.47 mol), norberene 4.7 g (0.05 mol), vinyl toluene 56.7 g (0.48 mol), and propylene glycol monomethyl ether acetate was prepared. 3.6 g of 2,2'-azobis (2,4-dimethylvaleronitrile) was added to obtain a solution, and the solution was added dropwise from a dropping funnel to a flask over 2 hours, and further stirred at 100 ° C for 5 hours. hour.

Next, the atmosphere in the flask was changed from nitrogen to air, and 42.6 g of glycidyl methacrylate [0.30 mol (64 mol% relative to the acrylic acid used in this reaction)] was put into the flask at 110 ° C. The reaction was continued for 6 hours. Thus, an unsaturated group-containing resin A-4 having a solid content acid value of 79 mg KOH / g was obtained. The polystyrene-equivalent weight average molecular weight measured by GPC was 6,600, and the molecular weight distribution (Mw / Mn) was 1.9.

<Synthesis Example 5> Synthesis of Oxygen Resin A-5

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was flowed in at 0.02 liters / minute to form a nitrogen atmosphere. 150 grams of diethylene glycol methyl ether was charged, and the mixture was heated to 70 ° C while being stirred. Next, a mixture of the following Chemical Formulas 16 and 17 (molar ratio of 50:50) 132.2 g (0.60 mol) and 5-ethyl 3-oxomethyl methacrylate (51.1 g (0.30 mol) ) And 8.6 g (0.10 mole) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ether to prepare a solution.

After the prepared dissolved solution was dropped into the flask using a dropping funnel, 27.9 g (0.11 mole) of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in diethyl A solution of 200 g of diol methyl ether was obtained, and the solution of the polymerization initiator was added dropwise to the flask over a period of 4 hours using another dropping funnel. After the dropwise addition of the solution of the polymerization initiator was completed, the solution was maintained at 70 ° C. for 4 hours, and then cooled to room temperature. Thus, a solution of a copolymer (resin A-5) having a solid content of 41.8% by mass and an acid value of 62 mg-KOH / g (in terms of solid content) was obtained.

The weight average molecular weight Mw of the obtained resin A-5 was 7,700, and the molecular weight distribution was 1.82.

<Synthesis Example 6> Synthesis of Resin (A-6) containing Oxygen alone

In a 1-liter flask equipped with a reflux condenser, a dropping funnel, and a stirrer, nitrogen gas was flowed in at 0.02 liters / minute to form a nitrogen atmosphere. 150 grams of diethylene glycol methyl ether was charged, and the mixture was heated to 70 ° C while stirring. 161.7 g (0.95 mol) of 3-ethyl-3-oxomethyl methacrylate and 14.5 g (0.17 mol) of methacrylic acid were dissolved in 150 g of diethylene glycol methyl ether to prepare a solution.

After the prepared dissolved solution was dropped into the flask using a dropping funnel, 27.9 g (0.11 mole) of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in diethyl A solution of 200 g of diol methyl ether was obtained, and the solution of the polymerization initiator was added dropwise to the flask over a period of 4 hours using another dropping funnel. Polymerization initiator After the dropwise addition of the solution was completed, the solution was maintained at 70 ° C for 4 hours, and then cooled to room temperature. Thus, a solution of a copolymer (resin A-6) having a solid content of 41.6% by mass and an acid value of 65 mg-KOH / g (in terms of solid content) was obtained. The weight average molecular weight Mw of the obtained resin A-6 was 8,300, and the molecular weight distribution was 1.85.

At this time, the measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the above-mentioned dispersing resin is performed by using an HLC-8120GPC (manufactured by Tosoh Corporation). The column temperature is 40 ° C, the mobile phase solvent is tetrahydrofuran, the flow rate is 1.0 ml / min, the injection volume is 50 microliters, the detector uses RI, and the measurement sample concentration is 0.6% by mass (solvent = tetrahydrofuran). The calibration standard material TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation) were used.

The ratio of the weight-average molecular weight to the number-average molecular weight obtained as described above was taken as the molecular weight distribution (Mw / Mn).

The weight-average molecular weight (Mw) and the number-average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (series)

Column temperature: 40 ° C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection volume: 50 μl

Detector: RI

Measurement sample concentration: 0.6% by mass (solvent = tetrahydrofuran)

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight-average molecular weight to the number-average molecular weight obtained as described above was taken as the molecular weight distribution (Mw / Mn).

A photosensitive resin composition having the composition and content (parts by weight) described in Table 1 below was produced.

The components used in the above Table 1 are as follows:

A-1-1: Resin produced in Synthesis Example 1

A-1-2: Resin produced in Synthesis Example 1-2

A-1-3: Resin produced in Synthesis Example 2

A-2-1: Resin produced in Synthesis Example 3

A-4: Resin produced in Synthesis Example 4

A-5: Resin produced in Synthesis Example 5

A-6: Resin produced in Synthesis Example 6

B: Dipentaerythritol hexaacrylic acid (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)

C: 1,2-octanedione-1- [4- (phenylthio) phenyl] -2-o-benzidine oxime (Ciba Refinery Company)

C-1: 4,4'-bis (diethylamino) benzophenone (EAB-F; manufactured by Hodogaya Chemical Co., Ltd.)

D-1: Propylene glycol monomethyl ether acetate

D-2: 3-ethoxyethylpropionate

D-3: 3-methoxy-1-butanol

D-4: 3-methoxybutyl acetate

E (Antioxidant): 1,3,5-tris (3,5-di-tertiary-butyl-4-hydroxybenzyl) -1,3,5-tris -2,4,6 (1H, 3H, 5H) -trione (Irganox 3114, manufactured by Ciba Fine Chemicals)

<Experimental example>

A 2-inch square glass substrate (Eagle 2000, manufactured by Corning) was sequentially washed with a neutral detergent, water, and ethanol, and then dried. After the photosensitive resin compositions produced in the above examples and comparative examples were spin-coated on the glass substrate, they were pre-baked at 90 ° C. for 3 minutes in a clean oven. After the pre-baked substrate was cooled to normal temperature, the distance between the pre-baked substrate and the quartz glass light mask was set to 150 μm, and an exposure machine (TME-150RSK, manufactured by Topcon Corporation) was used at 60 mJ / sq. An exposure amount (cm: 405 nm) of cm (mJ / cm ² ) was irradiated with light. At this time, the irradiation of the polymerizable resin composition is performed using the light emitted from the ultra-high pressure mercury lamp, and the light emitted from the ultra-high pressure mercury lamp is blocked by an optical filter (LU0400, manufactured by Asahi Spectroscopy Corporation). Turn off light below 400 nm. In this case, a light mask in which the following pattern was formed on the same plane was used.

The pattern has a light-transmitting portion (pattern) with a square of 10 μm on one side, and the pitch of the square is 100 μm. After light irradiation, the coating film was immersed at 25 ° C. for 100 seconds in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, and then washed with water. It was then post-baked at 220 ° C for 20 minutes in an oven. The obtained film thickness was 3 micrometers. The film thickness was measured using a film thickness measuring device (DEKTAK 6M, manufactured by Veeco). The obtained pattern was evaluated for physical properties as follows, and the results are shown in Table 2 below.

Transmittance evaluation

The transmittance (%) of the cured film obtained at 400 nm was measured using a microscope spectrophotometer (OSP-SP200, manufactured by OLYMPUS). The transmittance is the transmittance when converted to a film thickness of 3.0 μm and is shown in Table 2 below. The closer the transmittance is to 100%, the better.

2. Line width and section shape

The cured film obtained above was measured for line width using a scanning electron microscope (S-4200, manufactured by Hitachi, Ltd.), and the cross-sectional shape was evaluated as follows. The cross-sectional shape is judged to be tapered when the angle of the pattern of the substrate is less than 90 degrees, and is greater than It was judged as an inverted cone at 90 degrees.

If it is a forward taper, a short circuit of the ITO wiring is less likely to occur when a display device is formed, so it is preferable.

3. Mechanical characteristics (total displacement and recovery rate)

For the cured film obtained above, the total displacement amount (micrometer) and the elastic displacement amount (micrometer) were measured using a dynamic ultra-micro hardness meter (DUH-W201, manufactured by Shimadzu Corporation) under the following measurement conditions, and the measured values were used. The value of is calculated as the recovery rate (%) as follows. If the total amount of displacement is small and the recovery rate is large, it is determined to be hard.

Recovery rate (%) = [Elastic displacement (micron)] / [Total displacement (micron)] × 100

Measurement conditions:

Test mode: load-unload (load-unload) test

Test force: 5 grams of force (gf) [SI unit conversion value: 49.0 millinewtons (mN)]

Load speed: 0.45 gf / sec (gf / sec) [SI unit conversion value; 4.41 millinewtons Ton / second (mN / sec)]

Duration: 5 seconds

Indenter: conical indenter (50 microns in diameter)

4. Adhesiveness

Regarding the development adhesiveness, a light mask having 1,000 circular patterns having a diameter of 5 to 20 micrometers and a interval of 1 micrometer was used, and the pattern formed with a film thickness of 3 micrometers was observed without a defect using a microscope. The size of the mask when 100% remained was evaluated.

The smaller the size of the mask, the better the sensitivity.

5. Chemical resistance

The coating film that was heated at 90 ° C for 1 hour and cured, was etched at 50 ° C (MA-S02, manufactured by Toyo Fine Chemical Co., Ltd.) solution (acid resistance evaluation), or peeled at 50 ° C. Agent (SAM-19, manufactured by Toyo Fine Chemical Co., Ltd.) in a solution (peel resistance evaluation) for 10 minutes. The chemical resistance was evaluated by observing the change in thickness when left in the above-mentioned various solutions. The thickness change rate is calculated using the following mathematical formula 1. The smaller the thickness change rate, the better. The evaluation results are shown in Table 2 below.

[Mathematical formula 1] Thickness change rate (%) = {(film thickness before placing in solution-film thickness after placing in solution) / (film thickness before placing in solution)} * 100 (%)

When the thickness change rate obtained by the above formula 1 is 5% or less, the evaluation is "○", when it is more than 5% and 10% or less, the evaluation is "△", and when it is more than 10%, the evaluation is "X". .

6. Evaluation Criteria for Storage Stability

Viscosity change above 2cp: X

Viscosity change less than 2cp: ○

As shown in Tables 2 and 3 above, the alkali-soluble properties according to the present invention are used. In Examples 1 to 6 of the resin, compared with Comparative Examples 1 to 5 in which the alkali-soluble resin according to the present invention was not used, it was confirmed that the line width and pattern shape with respect to the substrate were good and dense at low exposure. Excellent bonding properties, and excellent chemical resistance and storage stability.

Claims (6)

A photosensitive resin composition comprising an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C), and a solvent (D), and the alkali-soluble resin (A) and a photopolymerizable compound Based on the mixed content of (B), the alkali-soluble resin (A) contains 15% by weight or more of the first resin (A-1), and the first resin (A-1) is a repeating unit represented by the following chemical formula 5 Formed: In the formula, R ₁ , R ₃ , R _6, and R ₈ are each independently hydrogen or methyl; R ₂ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₄ is a carbon atom having 1 to 6 carbon atoms. Alkyl; R ₅ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ₇ is a cycloalkyl group having 3 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, a cycloalkyl group or an aryl group At least one of the hydrogen atoms is further substituted or unsubstituted with a linear or branched alkyl group having 1 to 5 carbon atoms; a = 0.1 to 50 mol%, b = 2 to 50 mol%, c = 2 to 95 mole%, d = 2 to 70 mole%. The photosensitive resin composition according to claim 1, in the photosensitive resin composition, the alkali-soluble resin (A) is contained in an amount of 5 to 90 parts by weight based on 100 parts by weight of the solid content, and the photopolymerizable property is The compound (B) is contained in an amount of 1 to 90 parts by weight, and the photopolymerization initiator (C) is contained in an amount of 0.1 to 20 parts by weight. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (A) further includes a second resin (A-2) represented by the following chemical formula 6: In the formula, R ₉ and R ₁₂ are each independently a hydrogen atom or a methyl group, X is a single bond or an alkylene group having 1 to 6 carbon atoms, the alkylene group contains a hetero atom or does not include a hetero atom, and e = 60 to 95 mole%, f = 5 to 40 mole%. A photocurable pattern is manufactured from the photosensitive resin composition as described in any one of Claims 1-3. The photocurable pattern as described in claim 4, the photocurable pattern is selected from the group consisting of an adhesive layer, an array flattening film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a color filter pattern, and black A matrix pattern and a spacer pattern. An image display device including the photocurable pattern according to claim 4.