TWI769821B - Photosensitive resin composition, photosensitive resin layer and color filter layer - Google Patents

Abstract

Disclosed are a photosensitive resin composition including (A) a colorant including a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength region of 350 nm to 450 nm; (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, a photosensitive resin layer manufactured using the photosensitive resin composition, and a color filter layer.

Description

Photosensitive resin composition, photosensitive resin layer, and color filter layer

The present invention relates to a photosensitive resin composition, a photosensitive resin layer using the composition, and a color filter layer including the photosensitive resin layer. [Cross-reference to related applications]

This application claims priority to and the benefit of Korean Patent Application No. 10-2018-0147495 filed in the Korean Intellectual Property Office on November 26, 2018, the entire contents of which are incorporated herein by reference.

Among many types of displays, liquid crystal display devices have advantages in brightness, thinness, low cost, low operating power consumption, and improved adhesion to integrated circuits, and have been more widely used in notebook computers, monitor and TV screen. The liquid crystal display device includes a lower substrate on which a black matrix (light shielding layer), a color filter and an ITO pixel electrode are formed, and an active circuit including a liquid crystal layer, a thin film transistor and a capacitor layer formed thereon part and the upper substrate of the ITO pixel electrode.

Formed in the pixel area by sequentially stacking a plurality of color filters (usually, formed of three primary colors such as red (R), green (G), and blue (B) in a predetermined order to form each pixel) A color filter, and a black matrix (light shielding layer) are disposed on a transparent substrate in a predetermined pattern to form boundaries between pixels.

The pigment dispersion method, which is one of methods for realizing a color filter, provides a colored film by repeating a series of processes such as coating a photopolymerizable composition containing a colorant on a transparent substrate containing a black matrix on, exposing the formed pattern to light, removing the unexposed portion with a solvent, and thermally curing the composition. The coloring photosensitive resin composition for producing a color filter according to the pigment dispersion method generally contains an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent, other additives, and the like. The pigment dispersion method having the above-mentioned characteristics is actively used in the manufacture of liquid crystal displays for mobile phones, notebook computers, monitors, and TVs.

However, the photosensitive resin composition in the color filter using the pigment dispersion method with many advantages has some drawbacks because of difficulty in finely pulverizing the powder, thereby requiring various additives for use even in dispersion and complicated processes It stabilizes the dispersions without any problems and further maintains the optimum quality of the pigment dispersions under complex storage and transportation conditions.

In addition, the color filter produced by using the pigment-type photosensitive resin composition has limitations in brightness and contrast ratio due to the particle size of the pigment. Color image sensor devices for image sensors require smaller dispersed particle sizes to form fine patterns. In response to this demand, attempts have been made to achieve color filters having improved color characteristics such as brightness, contrast ratio, etc., by introducing dyes instead of pigments or preparing photosensitive resin compositions together with pigments, but not with pigment-type Compared with the photosensitive resin composition, the dye-type photosensitive resin composition has a problem of light-resistance deterioration.

Attempts have been made to apply C.I. Pigment Blue 15:3 (β-type) or C.I. Pigment Blue 15:4 (β-type) pigments in place of Pigment Blue 15:6 (ε-type) pigments, but in this case, although improved lightfastness , but the Bx color coordinate increases in a high-color blue resist, which is a problem because it does not suit the recent trend of increasing demand for high color reproduction.

Therefore, research on a photosensitive resin composition capable of simultaneously performing high color reproduction (with a small Bx color coordinate in a high-color blue resist) without causing deterioration in light resistance has been continued.

Examples provide photosensitive resin compositions having high color reproduction while having improved light resistance.

Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

Another embodiment provides a color filter layer including a photosensitive resin layer.

Embodiments of the present invention provide a photosensitive resin composition comprising: (A) a colorant including a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength range of 350 nm to 450 nm ( azaporphyrin-based dye); (B) a binder resin; (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.

The azaporphyrin-based dyes may contain Cu or V(=O) as the central metal.

在化學式1中， M是Cu或V(=O)，且 R¹ 到R²⁰ 獨立地是氫原子、鹵素原子、取代或未取代的C1到C20烷基、取代或未取代的C1到C20烷氧基、取代或未取代的C6到C20芳基、磺酸基、取代或未取代的磺醯胺基或取代或未取代的C1到C20烷基酯基， 條件為，R¹ 到R⁵ 中的至少一個、R⁶ 到R¹⁰ 中的至少一個、R¹¹ 到R¹⁵ 中的至少一個以及R¹⁶ 到R²⁰ 中的至少一個不是獨立的氫原子。The azaporphyrin-based dye may be represented by Chemical Formula 1. [Chemical formula 1]

In Chemical Formula 1, M is Cu or V(=O), and R ¹ to R ²⁰ are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkane Oxy group, substituted or unsubstituted C6 to C20 aryl, sulfonic acid, substituted or unsubstituted sulfonamido, or substituted or unsubstituted C1 to C20 alkyl ester, provided that R ¹ to R ⁵ At least one of , at least one of R ⁶ to R ¹⁰ , at least one of R ¹¹ to R ¹⁵ , and at least one of R ¹⁶ to R ²⁰ are not independent hydrogen atoms.

在化學式2中， R²¹ 是取代或未取代的C1到C20烷基。One of R ¹ to R ⁵ , one of R ⁶ to R ¹⁰ , one of R ¹¹ to R ¹⁵ , and one of R ¹⁶ to R ²⁰ may be independently represented by Chemical Formula 2. [Chemical formula 2]

In Chemical Formula 2, R ²¹ is a substituted or unsubstituted C1 to C20 alkyl group.

在化學式3中， L¹ 是取代或未取代的C1到C20伸烷基（alkylene group），且 R²² 和R²³ 獨立地是取代或未取代的C1到C20烷基。R ³ , R ⁸ , R ¹³ and R ¹⁸ may be independently represented by Chemical Formula 3. [Chemical formula 3]

In Chemical Formula 3, L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, and R ²² and R ²³ are independently a substituted or unsubstituted C1 to C20 alkyl group.

[化學式1-2]

The azaporphyrin-based dye may be represented by Chemical Formula 1-1 or Chemical Formula 1-2. [Chemical formula 1-1]

[Chemical formula 1-2]

The azaporphyrin-based dye may be contained in an amount of 0.1 wt % to 5 wt % based on the total solid content of the photosensitive resin composition.

The colorant may further comprise a violet pigment.

The blue pigment may be C.I. Pigment Blue 15:6.

Based on the total amount of the photosensitive resin composition, the photosensitive resin composition may include 2 to 40 wt % of a colorant; 3 to 20 wt % of a binder resin; 1 to 20 wt % of a photosensitive resin A polymeric compound; 0.1 wt % to 5 wt % of a photopolymerization initiator; and the balance of a solvent.

The photosensitive resin composition may further contain an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof.

Another embodiment provides a photosensitive resin layer manufactured using the photosensitive resin composition.

Another embodiment provides a color filter layer including a photosensitive resin layer.

Other aspects of the invention are included in the following detailed description.

The photosensitive resin composition according to the embodiment includes a compound that blocks light in a wavelength range of 350 nm to 450 nm, so as to improve the color filter of a panel constituting an optical display device such as a liquid crystal display (LCD), etc. The color reproducibility of the light sheet layer and thus relatively high light fastness can be maintained even at high color coordinates. In particular, the compound has the property of strongly absorbing light in a very narrow wavelength region, and thus can block the spectrum of the corresponding region and achieve high color (blue).

Embodiments of the present invention are hereinafter described in detail. However, these examples are exemplary, the invention is not limited thereto and the invention is defined by the scope of the claims.

In this specification, when no specific definition is otherwise provided, "substituted" means substitution by a substituent selected from the group consisting of halogen (F, Br, Cl or I), hydroxyl, nitro, cyano, amino (NH ₂ , NH(R ²⁰⁰ ) or N(R ²⁰¹ )(R ²⁰² ), wherein R ²⁰⁰ , R ²⁰¹ and R ²⁰² are the same or different, and are independently C1 to C10 alkyl), amidino group, hydrazine group (hydrazine group), hydrazone group (hydrazone group), carboxyl, substituted or unsubstituted alkyl, substituted or unsubstituted alkenyl, substituted or unsubstituted alkynyl, substituted or unsubstituted alicyclic organic group, substituted or unsubstituted aryl and substituted or unsubstituted heterocyclyl.

In this specification, when a specific definition is not otherwise provided, "alkyl" refers to C1 to C20 alkyl, and specifically C1 to C15 alkyl, "cycloalkyl" refers to C3 to C20 cycloalkyl, and Specifically C3 to C18 cycloalkyl, "alkoxy" refers to C1 to C20 alkoxy, and specifically C1 to C18 alkoxy, "aryl" refers to C6 to C20 aryl, and specifically Speaking of C6 to C18 aryl, "alkenyl" refers to C2 to C20 alkenyl, and specifically C2 to C18 alkenyl, and "alkylene" refers to C1 to C20 alkylene, and specifically C1 to C18 Alkylene, and "aryl" refers to C6 to C20 aryl, and specifically C6 to C16 aryl.

In this specification, when a specific definition is not otherwise provided, "(meth)acrylate" refers to "acrylate" and "methacrylate", and "(meth)acrylic" refers to "acrylic acid" and "methacrylate" Methacrylate".

In this specification, when no definition is otherwise provided, the term "combination" refers to mixing or copolymerization. In addition, "copolymerization" refers to block copolymerization to random copolymerization, and "copolymer" refers to block copolymerization to random copolymer.

In the chemical formulae of the present specification, unless a specific definition is provided otherwise, when a chemical bond is not drawn at the position where it should be given, the hydrogen bond is at the position.

In this specification, "*" indicates a point connecting the same or different atoms or chemical formulas when no specific definition is otherwise provided.

Also, when any member is positioned "on" another member in this specification, not only can the member contact the other member, but the other member may also be present between the two members.

Furthermore, in this specification, unless expressly described to the contrary, the word "comprise" and variations thereof (such as comprises/comprising) should be understood to imply the inclusion of stated elements but not the exclusion of any other components.

The embodiment provides a photosensitive resin composition comprising: (A) a colorant including a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength range of 350 nm to 450 nm; (B) an adhesive (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent.

Hereinafter, each component is described in detail. (A) Colorants

The photosensitive resin composition according to the embodiment includes a blue pigment and an azaporphyrin-based dye as colorants.

Azaporphyrin dyes have maximum absorption wavelengths in the wavelength range of 350 nm to 450 nm, eg, in the wavelength range of 400 nm to 440 nm.

In order to achieve high color blue (high color blue resist), it is necessary to achieve a low Bx color coordinate, and therefore the combination and amount of colorants that can minimize deterioration in light resistance and workability are important of. In order to achieve high color blue, a method of increasing the amount of colorant while blue-shifting the light absorption of the blue colorant is generally used. However, the method has a problem of greatly reducing the durability characteristics such as light fastness due to the increased amount of colorant. Therefore, a method of mixing different dyes with blue colorants has been proposed, but when different dyes are applied to the blue colorants, the light resistance is greatly reduced by the different dyes, and therefore, it is difficult to maintain excellent light resistance and At the same time, high color blue is realized. For example, attempts have been made to use conventional azo-based yellow dyes to absorb light in the wavelength range of 380 nm to 420 nm, but here, the azo-based yellow dyes should be used in relatively large amounts, and Therefore, there is a problem that the process margin of the entire composition cannot be ensured, and it is not commercially available. Furthermore, when a conventional azo-based yellow dye is used together with a conventional blue pigment (ε blue), since the transmission spectrum and the absorption spectrum overlap, the blue transmission region is damaged, and thus brightness loss is increased, and thus light resistance may be deteriorated.

According to the embodiment, a mixture of blue pigments and azaporphyrin-based dyes can be used as a colorant to minimize the above-mentioned problem of light resistance deterioration while achieving high-color blue, azaporphyrin-based dyes at 350 nm to It has a maximum absorption wavelength in the wavelength range of 450 nm.

For example, the azaporphyrin-based dyes may include Cu or V(=O) as the central metal. The type of the central metal of the azaporphyrin-based dye is very important since high color reproduction and light resistance characteristics vary depending on the central metal of the azaporphyrin-based dye. For example, when the central metal of the azaporphyrin-based dye is Zn, Co, Pt, etc., even if a mixture thereof with the above-mentioned blue pigment is used as a colorant, the light resistance is not improved.

The azaporphyrin-based dye may be represented by Chemical Formula 1. [Chemical formula 1]

In Chemical Formula 1, M is Cu or V(=O), and R ¹ to R ²⁰ are independently a hydrogen atom, a halogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkane Oxygen, substituted or unsubstituted C6 to C20 aryl, sulfonic acid group, substituted or unsubstituted sulfoneamide group or substituted or unsubstituted C1 to C20 alkylester group, condition For, at least one of R ¹ to R ⁵ , at least one of R ⁶ to R ¹⁰ , at least one of R ¹¹ to R ¹⁵ , and at least one of R ¹⁶ to R ²⁰ are not independent hydrogen atoms.

For example, in Chemical Formula 1, one of R ¹ to R ⁵ , one of R ⁶ to R ¹⁰ , one of R ¹¹ to R ¹⁵ , and one of R ¹⁶ to R ²⁰ can be independently represented by Chemical Formula 2 express. [Chemical formula 2]

In Chemical Formula 2, R ²¹ is a substituted or unsubstituted C1 to C20 alkyl group.

For example, in Chemical Formula 1, R ³ , R ⁸ , R ¹³ and R ¹⁸ may be independently represented by Chemical Formula 3. [Chemical formula 3]

In Chemical Formula 3, L ¹ is a substituted or unsubstituted C1 to C20 alkylene group, and R ²² and R ²³ are independently a substituted or unsubstituted C1 to C20 alkyl group.

[化學式1-2]

For example, the azaporphyrin-based dye may be represented by Chemical Formula 1-1 or Chemical Formula 1-2. [Chemical formula 1-1]

[Chemical formula 1-2]

The azaporphyrin-based dye may be contained in an amount smaller than that of the blue pigment. Azaporphyrin-based dyes are auxiliary dyes that function to absorb light in the wavelength range of 350 nm to 450 nm, and when included in an amount smaller than that of the blue pigment, high performance can be obtained in a blue resist. Color reproduction, but when the azaporphyrin-based dye is included in an amount larger than that of the blue pigment, the azaporphyrin-based dye is used in excess, and thus high color reproduction may not be achieved in the blue resist.

Even if the azoporphyrin-based dye is used in a large amount, it is not difficult to obtain high color reproduction and realize color coordinates, but even transmittance may deteriorate, and thus, luminance may decrease, or other performance (reliability) is expected to deteriorate.

The azaporphyrin-based dye may be included in an amount of 0.1% by weight to 5% by weight based on the total solid content of the photosensitive resin composition. Within the volume range, sufficiently high color reproduction is possible, and an excellent processing margin can be obtained.

For example, colorants may include violet pigments in addition to blue pigments and azaporphyrin-based dyes.

For example, the blue pigment may be an epsilon blue pigment. It may be the blue pigment used in the composition according to one embodiment, and the use of ε blue pigment instead of β blue pigment helps to improve brightness (light fastness).

For example, the blue pigment may be C.I. Pigment Blue 15:6.

The colorant may be included in an amount of 2 wt % to 40 wt % based on the total solid content of the photosensitive resin composition according to the embodiment. Improved lightfastness can be achieved at high color coordinates when colorants are included in the range. (B) Binder resin

The binder resin may include an acryl-based binder resin. For example, the adhesive resin may be an acrylic adhesive resin.

The propylene-based binder resin is a copolymer of a first ethylenic unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable therewith, and is a resin containing at least one propylene-based repeating unit.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group and/or a hydroxyl group, and examples of the monomer include acrylic acid, methacrylic acid, maleic acid (maleic acid), itaconic acid (itaconic acid), fumaric acid (fumaric acid) or a combination thereof.

The first ethylenically unsaturated monomer may be included in an amount of 5% to 50% by weight, for example, 10% to 40% by weight, based on the total amount of the propylene-based binder resin.

The second ethylenically unsaturated monomer can be an aromatic vinyl compound, such as styrene, α-methyl styrene, vinyl toluene, vinyl benzyl methyl ether, etc.; unsaturated carboxylate compounds, Such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-hydroxyethyl(meth)acrylate (2-hydroxyethyl(meth)acrylate), 2-hydroxy(methyl)acrylate 2-hydroxybutyl(meth)acrylate, benzyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, etc.; unsaturated aminoalkyl carboxylic acid Ester compounds, such as 2-aminoethyl (meth)acrylate, 2-dimethylaminoethyl (meth)acrylate, etc.; carboxylate vinyl ester compounds, such as vinyl acetate (vinyl acetate), vinyl benzoate (vinyl benzoate), etc.; unsaturated glycidyl carboxylate (glycidyl carboxylate ester) compounds, such as glycidyl (meth)acrylate (glycidyl (meth)acrylate), etc. ; Vinyl cyanide (vinyl cyanide) compounds, such as (meth)acrylonitrile ((meth)acrylonitrile), etc.; unsaturated amide compounds, such as (meth)acrylamide ((meth)acrylamide), etc.; and similar compounds , and can be used alone or as a mixture of two or more.

Specific examples of the acrylic binder resin may be (meth)acrylic acid/benzyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene copolymer, (meth)acrylic acid/methyl methacrylate Benzyl methacrylate/2-hydroxyethyl methacrylate copolymer, (meth)acrylic acid/benzyl methacrylate/styrene/2-hydroxyethyl methacrylate copolymer and the like, but not Limited to this, and can be used alone or as a mixture of two or more.

The weight average molecular weight of the acrylic binder resin may be from 3,000 grams/mol (g/mol) to 150,000 grams/mol, such as 5,000 grams/mol to 50,000 grams/mol, such as 20,000 grams /mol to 30,000 g/mol. When the weight average molecular weight of the acrylic binder resin is within the range, the photosensitive resin composition can have excellent physical properties and chemical properties and suitable viscosity, maintain suitable developability and sensitivity, and can be used in the manufacture of color It exhibits excellent intimate contact properties with the substrate during the filter layer.

The acid value of the acrylic binder resin may be 15 milligrams KOH/gram (mgKOH/g) to 60 milligrams KOH/gram, eg, 20 milligrams KOH/gram to 50 milligrams KOH/gram. Excellent pixel resolution is obtained when the acrylic binder resin has an acid value in the range.

The binder resin may be included in an amount of 3% by weight to 20% by weight, for example, 5% by weight to 15% by weight, based on the total amount of the photosensitive resin composition. When the binder resin is included in the range, developability can be improved and surface smoothness can be improved due to improved cross-linking during manufacture of the color filter layer. (C) Photopolymerizable compound

The photopolymerizable compound may be a monofunctional or polyfunctional ester of (meth)acrylic acid containing at least one ethylenically unsaturated double bond.

The photopolymerizable compound has an ethylenically unsaturated double bond, and thus can cause sufficient polymerization and form a pattern having excellent heat resistance, light resistance, and chemical resistance during exposure during pattern formation.

Specific examples of the photopolymerizable compound may be ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate (neopentyl glycol di(meth)acrylate), 1,4-butanediol di(meth)acrylate (1,4-butanediol di(meth)acrylate), 1,6-hexanediol di(meth)acrylate Ester (1,6-hexanediol di(meth)acrylate), bisphenol A di(meth)acrylate (bisphenolA di(meth)acrylate), pentaerythritol di(meth)acrylate (pentaerythritol di(meth)acrylate), pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol hexa(meth)acrylate , dipentaerythritol di(meth)acrylate (dipentaerythritol di(meth)acrylate), dipentaerythritol tri(meth)acrylate (dipentaerythritol tri(meth)acrylate), dipentaerythritol penta(meth)acrylate (dipentaerythritol penta(meth)acrylate) meth)acrylate), dipentaerythritol hexa(meth)acrylate (dipentaerythritol hexa(meth)acrylate), bisphenol A epoxy(meth)acrylate (bisphenol A epoxy(meth)acrylate), ethylene glycol monomethyl Ethylene glycol monomethylether (meth)acrylate, trimethylol propane tri(meth)acrylate, trimethylol propane tri(meth)acrylate Esters (tris(meth )acryloyloxyethyl phosphate), novolac epoxy (meth)acrylate, and similar compounds.

Examples of commercially available photopolymerizable compounds are as follows. Monofunctional (meth)acrylates may include Aronix M-101 ^® , M-111 ^® , M-114 ^® (Toagosei Chemistry Industry Co., Ltd.); card KAYARAD TC-110S ^® , TC-120S ^® (Nippon Kayaku Co., Ltd.); V-158 ^® , V-2311 ^® (Osaka Organic Chemical Industry Co., Ltd. Organic Chemical Ind., Ltd.)), and the like. Examples of difunctional (meth)acrylates may include Anix M-210 ^® , M-240 ^® , M-6200 ^® (Toa Gosei Chemical Co., Ltd.); Kayarad HDDA ^® , HX-220 ^® , R-604 ^® (Nihon Kayaku Co., Ltd.); V-260 ^® , V-312 ^® , V-335 HP ^® (Osaka Organic Chemical Industry Co., Ltd.), and the like. Examples of trifunctional (meth)acrylates may include Anix M- ^309® , M-400®, M- ^405® , M- ^450® , M- ^710® , M- ^8030® , M- ^{8060® (} Toagosei Chemicals Co., Ltd.); Kayarad TMPTA ^® , DPCA-20 ^® , DPCA-30 ^® , DPCA-60 ^® , DPCA-120 ^® (Nihon Kayaku Co., Ltd.); V-295 ^® , V-300 ^® , V-360 ^® , V-GPT ^® , V-3PA ^® , V-400 ^® (Osaka Yuki Kayaku Kogyo Co. Ltd.), and the like. These can be used alone or in a mixture of two or more.

The photopolymerizable compound may be treated with an acid anhydride to improve developability.

The photopolymerizable compound may be included in an amount of 1% by weight to 20% by weight, for example, 3% by weight to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable compound is included in the range, the photopolymerizable monomer is sufficiently cured during exposure in a pattern formation process with excellent reliability, and developability of an alkaline developer can be improved. (D) Photopolymerization initiator

The photopolymerization initiator may be an initiator commonly used in photosensitive resin compositions, for example, acetophenone-based compounds, benzophenone-based compounds, thioxanthone-based compounds ) compounds, benzoin-based compounds, triazine-based compounds, oxime-based compounds, or combinations thereof.

Examples of acetophenone compounds can be 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyl Trichloroacetophenone, p-tert-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1-(4- (Methylthio)phenyl)-2-morpholinopropan-1-one (2-methyl-1-(4-(methylthio)phenyl)-2-morpholinopropan-1-one), 2-benzyl- 2-Dimethylamino-1-(4-morpholinophenyl)-butan-1-one (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one), and similar compounds .

Examples of benzophenone compounds can be benzophenone, benzyl benzoate, benzyl methylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4 ,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichloro Benzophenone, 3,3'-dimethyl-2-methoxybenzophenone, and similar compounds.

Examples of thioxanthones may be thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone, and similar compounds.

Examples of benzoin compounds may be benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal, and the like.

Examples of triazine compounds can be 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(3', 4'-Dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4'-methoxynaphthyl)-4,6-bis(trichloromethyl) Methyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis (Trichloromethyl)-s-triazine, 2-biphenyl-4,6-bis(trichloromethyl)-s-triazine (2-biphenyl-4,6-bis(trichloromethyl)-s-triazine ), bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthyl-1-yl)-4,6-bis(trichloromethyl)-s-triazine (2 -(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine), 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl) -s-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-s-triazine (2,4-bis(trichloromethyl)-6-piperonyl-s-triazine), 2-4- Bis(trichloromethyl)-6-(4-methoxystyryl)-s-triazine, and similar compounds.

Examples of oxime-based compounds may be O-acyloxime-based compounds, 2-(o-benzoyl oxime)-1-[4-(phenylthio)phenyl]-1,2- Octanedione (2-(o-benzoyloxime)-1-[4-(phenylthio)phenyl]-1,2-octandione), 1-(o-acetyloxime)-1-[9-ethyl-6-( 2-Methylbenzoyl)-9H-carbazol-3-yl]ethanone (1-(o-acetyloxime)-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3 -yl]ethanone), O-ethoxycarbonyl-α-oxyamino-1-phenylpropan-1-one, and similar compounds. Specific examples of O-oxime compounds may be 1,2-octanedione, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- Phenyl)-butan-1-one, 1-(4-phenylthiophenyl)-butane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl) phenyl)-octane-1,2-dione-2-oxime-O-benzoate, 1-(4-phenylthiophenyl)-oct-1-one oxime-O-acetate , 1-(4-phenylthiophenyl)-butan-1-one oxime-O-acetate, and similar compounds.

The photopolymerization initiator may contain both an oxime-based initiator and an acetophenone-based initiator. In this case, as compared with the case of using one type of photopolymerization initiator alone, an excellent processing margin can be ensured by improving the curing efficiency. Further, in this case, the oxime-based initiator may be contained in a larger amount than the amount of the acetophenone-based initiator. When the oxime-based initiator is included in an amount equal to or less than the amount of the acetophenone-based initiator, the sensitivity is low (the sensitivity is excellent), and thus the desired CD can be performed.

In addition to the compounds, the photopolymerization initiator may further include azole-based compounds, diketone-based compounds, sulfonium borate-based compounds, diazo-based compounds, imidazole-based compounds ) compounds, biimidazole-based compounds, fluorene-based compounds, and similar compounds.

The photopolymerization initiator can be used together with a sensitizer capable of causing a chemical reaction by absorbing light and becoming excited and then transferring its energy.

Examples of the photosensitive agent may be tetraethylene glycol bis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, pentaerythritol tetrakis-3-mercapto propionate, dipentaerythritol tetrakis-3-mercapto propionate, and similar compounds.

The photopolymerization initiator may be included in an amount of 0.1% by weight to 5% by weight, for example, 0.1% by weight to 3% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included within the range, sufficient photopolymerization occurs during exposure during pattern formation, excellent reliability can be achieved, and heat resistance, light resistance, and chemical resistance, resolution, and compactness of the pattern can be improved Contact characteristics, and can prevent the decrease in transmittance due to non-reactive initiators. (E) Solvent

The solvent is a material that has compatibility with, but does not react with, colorants, binder resins, photopolymerizable compounds, and photopolymerization initiators.

Examples of the solvent may include, but are not limited to, alcohols, such as methanol, ethanol, and the like; ethers, such as dichloroethyl ether, n-butyl ether, diisoamyl ether, methyl phenyl ether, Tetrahydrofuran and the like; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and the like; cellosolve acetate such as methyl glycol ethyl acetate, Ethyl Glycol Ethyl Acetate, Diethyl Glycol Ethyl Acetate and Similar; , diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and the like; propylene glycol alkylether acetates, such as propylene glycol methyl ether Ether acetate, propylene glycol propyl ether acetate and the like; aromatic hydrocarbons such as toluene, xylene and the like; ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl Alkyl-2-pentanone, methyl-n-acetone, methyl-n-butanone, methyl-n-pentanone, 2-heptanone and the like; saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate , n-butyl acetate, isobutyl acetate and the like; lactic acid esters such as methyl lactate, ethyl lactate and the like; oxy acetic acid alkyl esters such as Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate and the like; alkyl alkoxyacetates such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate Esters, methyl ethoxyacetate, ethyl ethoxyacetate and the like; 3-oxy propionic acid alkylesters such as methyl 3-oxypropionate, 3-oxypropionic acid alkylesters Ethyl oxypropionate and the like; alkyl 3-alkoxypropanoates such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Ethyl esters, methyl 3-ethoxypropionate and the like; alkyl 2-oxypropionates such as methyl 2-oxypropionate, ethyl 2-oxypropionate, 2-oxypropionate Propionate and the like; Alkyl 2-alkoxypropionates such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate , 2-ethoxy methyl propionate and the like; 2-oxy-2-methyl propionate esters, such as 2-oxy-2-methyl propionate Ethyl methylpropionate and the like; 2-alkoxy-2-methylpropionic acid alkyl esters of monooxymonocarboxylic acid alkyl esters, such as 2-methoxy-2-methylpropionate Methyl 2-ethoxy-2-methylpropionate and the like; esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl glycolate ester, methyl 2-hydroxy-3-methylbutyrate with and the like; ketoesters such as ethyl pyruvate and the like. In addition, high boiling point solvents such as N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylformamide can also be used Methyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ether, dihexyl ether, acetone acetone, isophorone, caproic acid, caprylic acid , 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate (ethyl benzoate), diethyl oxalate (diethyl oxalate), diethyl maleate (diethyl maleate), Gamma-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

In view of miscibility and reactivity, ketones such as cyclohexanone and the like; ethylene glycol alkylether acetates such as ethyl cellosolve acetic acid can be preferably used Esters (ethyl cellosolve acetate) and the like; Esters, such as ethyl 2-hydroxypropionate and the like; Carbitols, such as diethylene glycol monomethyl ether and the like; Propylene glycol alkyl ether acetates, such as Propylene glycol methyl ether acetate, propylene glycol propyl ether acetate.

The solvent is used in a balance amount of, for example, 20 to 80% by weight, for example, 25 to 60% by weight, based on the total amount of the photosensitive resin composition. When the solvent is contained within the range, the photosensitive resin composition can have an appropriate viscosity, thereby improving the coating characteristics of the color filter layer. Other additives

The photosensitive resin composition according to the embodiment may further include an epoxy compound in order to improve the close contact property with the substrate.

Examples of epoxy compounds may include phenol novolac epoxy compounds, tetramethylbiphenyl epoxy compounds, bisphenol A epoxy compounds, cycloaliphatic epoxy compounds, or combinations thereof.

The epoxy compound may be included in an amount of 0.01 parts by weight to 20 parts by weight, for example, 0.1 parts by weight to 10 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included in the range, intimate contact properties, storage properties, and the like can be improved.

In addition, the photosensitive resin composition may further contain a silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group, and the like, in order to improve its adhesion to the substrate.

Examples of the silane-based coupling agent may include trimethoxysilyl benzoic acid, gamma methacryl propoxy trimethoxy silane, vinyl triacetoxy silane, vinyl trimethoxy silane, gamma isocyanate propyl trimethoxysilane Ethoxysilane, gamma glycidoxypropyltrimethoxysilane, beta epoxycyclohexylethyltrimethoxysilane, vinylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2 -(3,4-Epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidyl Glyceryloxypropyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-Methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane , 3-propenyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-amino Propyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-triethoxysilyl-N-(1,3-dimethylbutylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, 3-isocyanatopropyltriethoxysilane and the like compounds, and may be used alone or in a mixture of two or more.

The silane coupling agent may be included in an amount of 0.01 parts by weight to 10 parts by weight based on 100 parts by weight of the photosensitive resin composition. When a silane coupling agent is included in the range, intimate contact properties, storage properties, and the like can be improved.

Furthermore, if necessary, the photosensitive resin composition may further contain a surfactant to improve coating properties and prevent defects.

Examples of surfactants may be commercially available fluorochemical surfactants of BM- ^1000® , BM- ^1100® and similar products from BM Chemie Inc.; Dainippon Ink Kagaku Kogyo MEGAFACE F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^® , F 554 ^® and similar products from Sumitomo 3M Co., Ltd) FULORAD FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^® and similar products; SURFLON S-112 from ASAHI Glass Co., Ltd ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^® and similar products; SH-28PA ^® , SH-190 ^® , SH-193 ^® , SZ-6032 ^® , SF-8428 ^® and similar product.

The surfactant may be included in an amount of 0.001 parts by weight to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the surfactant is included within the range, coating uniformity is ensured, no stain is found, and the wetting characteristics of the glass substrate are excellent.

In addition, the photosensitive resin composition may further contain predetermined amounts of other additives, such as oxidation inhibitors, stabilizers, and the like, unless the performance is deteriorated.

According to another embodiment, there is provided a photosensitive resin layer manufactured using the photosensitive resin composition according to the embodiment.

The pattern formation process in the photosensitive resin layer is as follows.

The process includes coating the photosensitive resin composition according to the embodiment on a support substrate by spin coating, slit coating, inkjet printing, etc.; drying the coated photosensitive resin composition to form the photosensitive resin composition layer; exposing the photosensitive resin composition; developing the exposed photosensitive resin composition in an alkaline aqueous solution to obtain a photosensitive resin layer; and heat-treating the photosensitive resin layer. The conditions of the patterning process are well known in the related art and are not described in detail in this specification.

According to an embodiment, a color filter layer including a photosensitive resin layer is provided.

Hereinafter, the present invention is explained in more detail with reference to examples, which, however, are not to be construed as limiting the scope of the present invention in any sense. ( Synthesis of Dye ) Synthesis Example 1 : Synthesis of Dye Represented by Chemical Formula 1-1

30 grams (0.2 moles) of p-aldehyde benzoic acid was placed in a round bottom flask, 600 grams of propionic acid was added thereto, and the mixture was stirred. To this was added 13.5 g (0.2 moles) of pyrrole, and the resulting mixture was heated to 80°C, stirred for 1 hour, heated to 130°C, and stirred for 1.5 hours to complete the reaction. The reaction was cooled to room temperature (23°C), 300 g of acetone was added thereto, and the resulting mixture was stirred at room temperature for 1 hour and filtered. Subsequently, the solid compound on the screen was collected, washed with acetone, and dried to synthesize 8.3 g (26%) of intermediate (A).

Then, 24.5 g (30.1 mmol) of Intermediate A and 34.3 g (241 mmol) of K ₂ CO ₃ were placed in a round bottom flask, to which was added 250 g of dimethylformamide (DMF), and The resulting mixture was stirred. To this was added 46.5 g (241 mmol) of 1-bromo-2-ethylhexane, and the resulting mixture was stirred at 100°C for 24 hours. After the reaction was completed, the temperature was lowered to room temperature, dimethylformamide was removed by distillation, extracted with methylene chloride (MC), and the obtained product was washed with 10% sodium chloride and DI water. Subsequently, the solvent was removed by distillation, MeCN was added thereto, and the resulting mixture was washed and dried to obtain 28.9 g (75%) of compound (B).

Then, 1.0 g (0.81 mmol) of intermediate (B) and 0.44 g (2.42 mmol) Cu(OAc) ₂ H ₂ O were placed in a round bottom flask, 10 g of DMF was added thereto, and the mixture was mixed Stir at 100°C for 15 hours. When the reaction was complete, the temperature was lowered to room temperature, DMF was removed by distillation, extracted with MC, and the product was washed with 10% sodium chloride and DI. Subsequently, the solvent was removed by distillation, the reactants were dissolved by using a minimum amount of MC, and the solution was slowly added dropwise to 100 g of MeCN for precipitation. The thus obtained precipitate was filtered, washed with MeCN, and dried to obtain 0.9 g (86%) of the compound represented by Chemical Formula 1-1.

[Chemical formula 1-1]

LC Mass: 1299 m/z Synthesis Example 2 : Synthesis of Dye Represented by Chemical Formula 1-2

Except using vanadium oxide sulfate hydrate (2.42 mmol) instead of Cu(OAc) ₂ H ₂ O based on 1.0 g (0.81 mmol) of intermediate (B) and increasing the temperature to 120 0.84 g (80%) of the compound represented by Chemical Formula 1-2 was obtained according to the same method as in Synthesis Example 1 except that the reaction was carried out.

[Chemical formula 1-2]

LC Mass: 1303 m/z Comparative Synthesis Example 1 : Synthesis of Compounds Represented by Chemical Formulas 1-3

3.2 g (2.58 mmol) of intermediate (B) was placed in a round bottom flask, 160 g of chloroform was added thereto, and the mixture was stirred at 60°C. 1.42 g (7.74 mmol) of Zn(OAc) ₂ was placed in another round bottom flask, 30 g of MeOH was added to it, and the resulting mixture was stirred at room temperature to dissolve the Zn(OAc) ₂ . Subsequently, the Zn(OAc) ₂ solution was added to the flask containing the intermediate (B), and the mixture was stirred for 2 hours for reaction. After the reaction was completed, the temperature was lowered to room temperature, extracted with MC, and washed with 10% NaCl and DI water. After distilling off the solvent, the reactants were dissolved with a minimal amount of MC, and the resulting solution was slowly added dropwise to 100 g of MeCN for precipitation. The thus obtained precipitate was filtered, washed with MeCN, and dried to obtain 3.1 g (92%) of the compound represented by Chemical Formula 1-3.

[Chemical formula 1-3]

LC Mass: 1300 m/z (synthetic photosensitive resin composition) Example 1 , Example 2 , and Comparative Examples 1 to 3

The following components were mixed in the compositions shown in Table 1 to prepare photosensitive resin compositions according to Example 1, Example 2, and Comparative Examples 1 to 3.

Specifically, the photopolymerization initiator was dissolved in the solvent, the solution was stirred at room temperature for 2 hours, the binder resin and the photopolymerizable compound were added thereto, and the resulting mixture was stirred at room temperature for 2 hours. Subsequently, the blue pigment dispersion, colorant, and other additives were added to the reactants, and the resulting mixture was stirred at room temperature for 1 hour. Subsequently, the product obtained therefrom was filtered three times to remove impurities, thereby preparing each photosensitive resin composition.

[Table 1] (unit: % by weight) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 (A) Colorants (A-1) 33.86 33.86 33.86 48.71 - (A-2) 1.95 1.95 1.95 - 48.71 (A-3) - - 0.65 - - (A-4) 0.65 - - - - (A-5) - 0.65 - - - (B) Binder resin 10.25 10.25 10.25 10.25 10.25 (C) Photopolymerizable compound 7.53 7.53 7.53 7.53 7.53 (D) Photopolymerization initiator 0.62 0.62 0.62 0.62 0.62 (E) Solvent 44.83 44.83 44.83 44.83 44.83 (F) Other additives 0.15 0.15 0.15 0.15 0.15 ( A ) Colorants

(A-1) C.I. Pigment Blue 15:6 Pigment Dispersion (GC1679, SANYO; Pigment Solid Content 10%)

(A-2) C.I. Pigment Blue 15:6 Pigment Dispersion (GC1207, Sanyo; Pigment Solid Content 10%)

(A-3) Compound of Comparative Synthesis Example 1 (dye represented by Chemical Formula 1-3)

(A-4) Compound of Synthesis Example 1 (dye represented by Chemical Formula 1-1)

(A-5) Compound of Synthesis Example 2 (dye represented by Chemical Formula 1-2) ( B ) Binder resin

Acrylic adhesive resin (CRB-400H, SMS) ( C ) Photopolymerizable compound

Dipentaerythritol hexaacrylate (DPHA) (Nihon Kayaku Co., Ltd.) ( D ) Photopolymerization initiator

Oxime compounds (OXE01, BASF) ( E ) solvent

Propylene Glycol Methyl Ether Acetate (Kyowa Co., Ltd.) ( F ) Additive

Fluorosurfactant (F-554, DIC Co., Ltd.) evaluation : Bx color coordinates and light fastness

Each of the photosensitive resin compositions of Example 1, Example 2, and Comparative Examples 1 to 3 were mixed on a 1 mm thick degreasing and washed glass substrate at 250 revolutions per minute (rpm) to 350 revolutions per minute (rpm) It was coated to a thickness of 1 micrometer to 3 micrometers, and then dried on a hot plate at 90° C. for 2 minutes to obtain a thin film. Subsequently, the film was exposed to light at 50 millijoules per square centimeter (mJ/cm ² ) by using a high pressure mercury lamp with a dominant wavelength of 365 nm, and by using KOH developer (111 times dilute solution) in wash/developer = The membrane was developed at 1/0.8 for 60 seconds and washed for an additional 60 seconds. Subsequently, the film was dried in a forced convection drying oven at 230° C. for 20 minutes to obtain each color sample (color chip).

The CIE color coordinates and luminance (Y) of each color sample were measured before and after lightfastness evaluation using a spectrophotometer (MCPD3000, Otsuka Electronics), and the results of changes according to lightfastness evaluation are shown in Table 2 and Table 3.

*Lightfastness evaluation: Xenon lamp (0.68W), under respective ambient conditions of air and _N2 gas, at 60°C for 20 hours

[Table 2] del(x) del(y) del Y del(E*) Lightfast air (xenon 20 hours) Example 1 0.0008 -0.002 0.05 2.58 Example 2 0.0001 0.0013 -0.04 1.74 Comparative Example 1 0.0025 -0.0044 -0.03 5.32 Comparative Example 2 0.003 0.002 0.08 2.85 Comparative Example 3 0.0018 0.003 0.05 2.62

[table 3] del(x) del(y) del Y del(E*) Lightfastness N ₂ (Xenon 20 hours) Example 1 0.0004 -0.0008 0.04 1.04 Example 2 -0.0001 0.0006 -0.1 1.18 Comparative Example 1 0.0011 -0.0026 -0.06 2.69 Comparative Example 2 0.0025 0.0012 0.02 1.21 Comparative Example 3 0.00015 0.0018 0.04 1.85

From Table 2 and Table 3, when the azaporphyrin-based dye represented by Chemical Formula 1-1 or Chemical Formula 1-2 was used together with a blue pigment, it was confirmed that blue resistance was achieved while maintaining sufficient improvement in light resistance in a small amount. High color in etch.

While the present invention has been described in connection with what are presently considered to be practical example embodiments, it is to be understood that the invention is not limited to the disclosed embodiments. On the contrary, it is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.

none.

none.

none.

Claims (8)

A photosensitive resin composition, comprising: (A) a colorant comprising a blue pigment and an azaporphyrin-based dye having a maximum absorption wavelength in a wavelength range of 350 nm to 450 nm; (B) a binder resin (C) a photopolymerizable compound; (D) a photopolymerization initiator; and (E) a solvent, wherein the azaporphyrin-based dye includes a central metal of Cu or V(=O), and the azaporphyrin-based dye The coordination number of phospholine dyes is 2. The photosensitive resin composition according to claim 1, wherein the azaporphyrin-based dye is contained in an amount of 0.1 wt % to 5 wt % based on the total solid content of the photosensitive resin composition. The photosensitive resin composition according to claim 1, wherein the colorant further includes a violet pigment. The photosensitive resin composition according to claim 1, wherein the blue pigment is C.I. Pigment Blue 15:6. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition includes 2% by weight to 40% by weight of the colorant based on the total amount of the photosensitive resin composition; 3% by weight to 20% by weight of the binder resin; 1 to 20% by weight of the photopolymerizable compound; 0.1 wt % to 5 wt % of the photopolymerization initiator; and the balance of the solvent. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises an epoxy compound, a silane coupling agent, a surfactant, or a combination thereof. A photosensitive resin layer produced using the photosensitive resin composition according to any one of Claims 1 to 6. A color filter layer comprising the photosensitive resin layer according to claim 7.