TW202315899A - Substrate with a cured film, photosensitive resin composition, method for manufacturing a substrate with a cured film, and display device - Google Patents

Abstract

Provided is a substrate with a cured film, which hardly cracks or fractures even when being bent and deformed, and yet still demonstrates good developability and adhesion. The substrate with a cured film of the present invention has a flexible substrate that can be bent and deformed repeatedly and yet can then return to its original shape, and a cured film formed on a surface of the flexible substrate, wherein the cured film is a cured film of a photosensitive resin composition that includes an unsaturated group-containing alkali-soluble resin and has a thickness of 1 to 30 [mu]m.

Description

Substrate with cured film, photosensitive resin composition, method for manufacturing substrate with cured film, and display device

The present invention relates to a substrate with a cured film, a photosensitive resin composition, a method for manufacturing a substrate with a cured film, and a display device.

In image display devices such as monitors, cured films cured from photosensitive resin compositions are used for various functional layers such as color filters, black matrices, protective films, and wavelength conversion layers.

In recent years, image display devices that can be repeatedly bent and deformed to return to the original shape have been developed. Therefore, the photosensitive resin composition is also required to be made into a cured film that can withstand repeated bending and deformation to return to its original shape (for example, Patent Document 1 to Patent Document 3).

[Prior Art Literature]

[Patent Document]

Patent Document 1: Japanese Patent Application Laid-Open No. 09-325493.

Patent Document 2: Japanese Patent Laid-Open No. 2017-84153.

Patent Document 3: Japanese Patent Laid-Open No. 2017-126003.

In a cured film used to form a substrate that can be deformed by bending or the like, flexibility to bend itself and adhesiveness that is not easily peeled off from the substrate during bending are required. However, a cured film that satisfies both of these requirements has not yet been obtained. In addition, depending on the application of the cured film, a large amount of non-resin components such as a light-shielding material for improving light-shielding properties may be mixed in the cured film. When the proportion of these components becomes high, the cured film becomes hard and fragile, so cracks, peeling, and the like are likely to occur during bending. On the other hand, if these conditions are to be improved, the resolution or linearity during development will be reduced, and the adhesion to the substrate will be reduced, so a cured film that can withstand repeated bending has not yet been obtained.

The present invention was made in view of the above-mentioned problems, and an object of the present invention is to provide a substrate with a hardened film that does not easily cause cracks or cracks even when the substrate is bent and deformed, and has good developability and adhesion, and a substrate with a hardened film for manufacturing a substrate with a hardened film. A photosensitive resin composition and a manufacturing method thereof, and a display device having the substrate with a cured film.

One aspect of the present invention for solving the above-mentioned problems relates to the substrate with a cured film of the following [1] to [3].

[1] A substrate with a cured film, comprising a flexible substrate that can be repeatedly bent and deformed to return to its original shape, and a cured film formed on the surface of the flexible substrate, wherein,

The aforementioned cured film is a cured film of a photosensitive resin composition having a film thickness of 1 to 30 μm, and the photosensitive resin composition includes an alkali-soluble resin containing an unsaturated group.

[2] The substrate with a cured film according to [1], wherein the cured film does not crack or peel when bent to a radius of curvature of 50 mm.

[3] The substrate with a cured film according to [1] or [2], wherein the optical density (OD value) of the cured film is 0.1 to 4.0/μm.

Another aspect of the present invention relates to the photosensitive resin composition of the following [4] to [11].

[4] A photosensitive resin composition for manufacturing the substrate with a cured film according to any one of [1] to [3],

Further, (A) an unsaturated group-containing alkali-soluble resin having an aromatic skeleton is included in the main chain.

[5] The photosensitive resin composition as described in [4], wherein the (A) unsaturated group-containing alkali-soluble resin has a bisphenol skeleton, a fenene group or a novolak skeleton in the main chain.

[6] The photosensitive resin composition as described in [5], wherein the bisphenol skeleton has a structure derived from bisphenol A or bisphenol F,

The aforementioned fennelyl is bisphenol fennelyl, biscresol fennelyl or bisnaphthyl fennelyl,

The aforementioned novolak skeleton contains a group selected from the group consisting of a phenol novolac structure, a cresol novolac structure, a trimethylphenol novolac structure, a biphenol novolak structure, a naphthol novolak structure, and a naphthol aralkyl structure. The novolac structure.

[7] The photosensitive resin composition according to any one of [4] to [6], which has:

(B) a photopolymerizable compound having at least 2 ethylenically unsaturated bonds;

(C) photopolymerization initiator;

(D) shades; and

(E) Epoxy resin.

[8] The photosensitive resin composition according to [7], wherein the component (E) has a weight average molecular weight (Mw) of 200 to 20,000 and an epoxy equivalent weight (EEW) of 100 g/eq to 10,000 g/eq. Epoxy resin below eq.

[9] The photosensitive resin composition according to [7] or [8], wherein the component (E) has an aromatic skeleton in the main chain.

[10] The photosensitive resin composition according to any one of [7] to [9], wherein the content of the component (E) is 0.4% by mass or more and 40% by mass or less based on the total solid content.

[11] The photosensitive resin composition according to any one of [7] to [10], wherein the total amount of the content of the aforementioned component (A) and the content of the aforementioned component (B) is relative to the solid content The total mass is not less than 4% by mass and not more than 93% by mass,

The blending ratio of the aforementioned (A) component to the aforementioned (B) component is 10/90 to 90/10 in terms of mass ratio (A)/(B),

The content of the above-mentioned (E) component is 0.4 mass % or more and 40 mass % or less with respect to the total mass of solid content.

Another aspect of the present invention relates to a method of manufacturing a substrate with a cured film according to the following [12].

[12] A method of manufacturing a substrate with a hardened film, comprising the steps of:

Coating the photosensitive resin composition as described in any one of [7] to [11] on a flexible substrate that can be repeatedly bent and deformed to return to its original shape to form a coating film;

A step of position-selectively exposing the aforementioned coating film;

A step of developing the above-mentioned exposed coating film to form a pattern; and

The step of baking the aforementioned patterned coating film.

Other aspects related to the present invention are the display devices of the following [13] to [15].

[13] A display device comprising the substrate with a cured film according to any one of [1] to [3] or the substrate with a cured film produced by the production method described in [12].

[14] The display device according to [13], comprising an organic electroluminescence (EL) light source or a laser light emitting diode (LED) light source.

[15] The display device according to [14], comprising a wavelength conversion layer containing quantum dots or a phosphor compound.

According to the present invention, it is possible to provide a substrate with a cured film, a substrate with a cured film that is less prone to cracks or cracks even when the substrate is bent and deformed, and has good developability and adhesion, a photosensitive resin composition for manufacturing a substrate with a cured film, and its production. A method, and a display device having the substrate with a cured film.

An embodiment of the present invention relates to a substrate with a cured film, including a flexible substrate and a cured film formed on the flexible substrate.

The flexible substrate only needs to be a substrate capable of repeated bending and deformation to return to the original shape (unbent flat plate shape). The flexible substrate may be a resin film such as polyimide, or flexible glass such as Willow glass manufactured by Corning Incorporated or Dragontrail manufactured by AGC Corporation. In addition, transparent electrodes such as ITO or gold can be evaporated or patterned on the surface of the flexible substrate.

When the device on which the substrate with a cured film is mounted is deformed (bent), the flexible substrate can be deformed (bent) into a shape corresponding to the deformation. For example, the flexible substrate is preferably bendable with a radius of curvature (r) of 50 mm, more preferably 40 mm, even more preferably 30 mm, and particularly preferably 10 mm. Next, when the above-mentioned substrate with a hardened film is bent with the above-mentioned curvature radii, no cracks or peeling will occur on the flexible substrate.

In addition, the above-mentioned cracks and peeling at the time of bending are opened by developing in advance, and a test piece with a width of 1 cm and a length of 12 cm is wound on the SUS with the above-mentioned radius of curvature so that the cured film of the substrate with a cured film faces outward. A cylinder was made and pulled out, and after such a bending test was performed 100 times, the number of cracks and peelings confirmed in the range of 1200 μm×1200 μm was observed using a microscope. In order to improve the reliability of the measurement, the average value of the number of cracks and peelings observed and confirmed in the range of 16 arbitrarily selected locations can be used as the number of cracks and peelings during bending.

The cured film may be a film formed by hardening a resin. The cured film may be a cured film of a photosensitive resin or a cured film of a thermosetting resin, but is preferably a cured film of a photosensitive resin from the viewpoint of fine pattern formation.

The hardened film can be endowed with characteristics corresponding to the application of the film. For example, when forming as a black matrix or a color filter, it is preferable to make the optical density (OD) per 1 micrometer of film thickness into 0.1/micrometer or more and 4.0/micrometer or less. The optical density of the cured film can be adjusted by adding an application-specific light-shielding material to the cured film.

Moreover, in order to raise an optical density (OD), it is necessary to add a large amount of light-shielding materials to a cured film. Next, if the amount of light-shielding material is too large, the toughness of the cured film will be reduced, and cracks or peeling will easily occur when bending. On the other hand, if the flexibility of the cured film is increased in order to suppress cracking or peeling, the developability will decrease, fine pattern formation will become difficult, and the adhesion of the cured film to the substrate will decrease. For this, For example, containing an aromatic ring in the main chain of the resin constituting the cured film can suppress the decrease in developability or adhesion, improve the flexibility of the cured film, and suppress the occurrence of cracks or peeling during bending.

In the present specification, the optical density (OD) of the cured film may be a value measured using a MACBETH transmission densitometer ("X-rite 361T(V)" manufactured by X-rite Corporation).

The film thickness of the cured film is preferably from 1 μm to 30 μm, more preferably from 2 μm to 15 μm, and still more preferably from 3 μm to 10 μm.

In this embodiment, not only the black matrix layer of the color filter or the light-shielding pixel division layer used in the organic EL display is thinner than 1 μm, but also the thickness of the light-shielding layer for the LED is 2 μm. A thicker layer of more than 3 μm or more is less prone to cracking or peeling when bent. Conventionally, cured films with a film thickness of 2 μm or more cracked when bent at a curvature of 50 mm, and cured films with a film thickness of 3 μm or more were not only cracked but also peeled when bent at a curvature of 50 mm. In contrast, as will be described later, the photosensitive resin composition contains (A) an alkali-soluble resin containing an unsaturated group having an aromatic skeleton in the main chain, and the substrate with a cured film formed of the photosensitive resin composition can be cured even after curing. When the film thickness of the film is 2 μm or more or 3 μm or more, the occurrence of cracks or peeling can be suppressed.

On the other hand, when the film thickness is 30 μm or less, it is easy to open into hole shapes such as via holes. As will be described later, if the photosensitive resin composition is contained in (A) unsaturated group-containing alkali-soluble resin having an aromatic skeleton in the main chain, a square shape of 200 μm×200 μm can be formed with high precision if the film thickness is 30 μm or less For the shape of the opening, if the film thickness is 15 μm or less, a quadrangular opening of 100 μm×200 μm can be formed with high precision, and if the film thickness is 10 μm or less, a quadrangular opening of 100 μm×100 μm can be formed with high precision.

In this specification, the film thickness of the cured film can be measured using a height difference meter ("TENCOR P-17" manufactured by KLA-Tencor Co., Ltd.) in a measurement range of 500 μm at a scanning speed of 50 μm/sec and a sampling rate of 20 Hz. The average thickness (μm).

The cured film can be obtained, for example, by exposing and curing a photosensitive resin composition containing (A) an unsaturated group-containing alkali-soluble resin having an aromatic skeleton in its main chain.

(A) The unsaturated group-containing alkali-soluble resin preferably has a polymerizable unsaturated group in one molecule and has an acidic group for exhibiting alkali solubility, and more preferably has a polymerizable unsaturated group and a carboxyl group. Component (A) has a polymerizable unsaturated group, so it can impart excellent photocurability to the photosensitive resin composition, and the molecular weight will increase when it is cured, and it can function as a binder. Moreover, since (A) component has an acidic group, it can improve the physical property of a cured resin film, such as developability and a patterning characteristic (pattern line width, pattern linearity).

At this time, if the cured film is produced using the component (A) having an aromatic skeleton in the main chain, a small space will be generated in the cured film by the bulky aromatic ring. It is considered that the molecules of the resin in the cured film can be easily expanded and contracted by this space, so that specific flexibility can be imparted to the cured film. On the other hand, alkali-soluble resins having an aromatic skeleton in the main chain have high developability and high adhesiveness after curing. Therefore, use the component (A) which has an aromatic skeleton in the main chain to make a cured film, thereby making the cured film more flexible, and obtaining a cured film that is less prone to cracking or peeling when bent, and has high developability and adhesion. membrane.

The above-mentioned aromatic skeleton is not particularly limited, and may be a bisphenol skeleton derived from bisphenol A and bisphenol F, a skeleton having a bisphenol fluorene group, a biscresol fluorene group, and a bisnaphthol fluorene group, etc. And phenolic novolak skeleton, etc. The above-mentioned novolac skeleton is obtained by condensation reaction of phenol and aldehyde who can. Examples of the above-mentioned phenol include phenol, cresol, ethylphenol, trimethylphenol, butylphenol, styrenated phenol, cumylphenol, naphthol, catechol, resorcinol, biphenol, Naphthalene diol, bisphenol A, and bisphenol F, etc. Examples of the above-mentioned aldehyde include formaldehyde, hydroxybenzaldehyde, salicylaldehyde and the like. In addition, the novolac skeleton also includes aralkyl type obtained by substituting these aldehydes with xylylene dimethanol, dichloroxylene, dichloromethylnaphthalene, and bischloromethylbiphenyl. Novolac backbone. Among the novolak skeletons, preferred are phenol novolak structure, cresol novolac structure, trimethylphenol novolac structure, biphenol novolac structure, naphthol novolak structure, and naphthol aralkyl structure.

Component (A) is preferably an unsaturated group-containing alkali-soluble resin obtained by reacting an epoxy compound having two or more epoxy groups and (meth)acrylic acid with a polybasic acid carboxylic acid or an anhydride thereof. . When producing the above-mentioned alkali-soluble resins containing unsaturated groups, polyesters can be formed by reacting hydroxyl groups with polybasic carboxylic acids. The component (A) is preferably a low-molecular-weight resin having an average degree of polymerization of the above-mentioned polyester of about 2 to 500. Also, "(meth)acrylic acid" refers to the collective name of acrylic acid and methacrylic acid, "(meth)acryl" refers to the collective name of acryl and methacryl, and "(meth)acrylate "is a collective term for acrylate and methacrylate, either of which represents one or both of them.

Examples of the above-mentioned epoxy compound having two or more epoxy groups include bisphenol A-type epoxy compound, bisphenol F-type epoxy compound, bisphenol-stilbene-type epoxy compound, bis-naphthol-stilbene-type epoxy compound, diphenyl Base stilbene type epoxy compound, phenol novolac type epoxy compound, (o, m, p) cresol novolak type epoxy compound, phenol aralkyl type epoxy compound, biphenyl type epoxy compound, containing naphthalene Skeleton phenol novolac compound (such as NC-7000L, manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy compound, trisphenol methane type epoxy compound (such as EPPN-501H, manufactured by Nippon Kayaku Co., Ltd.), tetraphenylphenol ethane-type epoxy compounds, and the like. These epoxy resins with aromatic rings are reacted with (meth)acrylic acid to form epoxy (meth)acrylate, and further reacted with polybasic acid carboxylic acid or its anhydride to introduce carboxyl groups, thereby obtaining Component (A) having an aromatic skeleton.

Moreover, as long as desired characteristics are acquired, (A) component may be the alkali-soluble resin containing an unsaturated group which does not have an aromatic frame|skeleton in a main chain.

The component (A) is preferably a compound having a weight average molecular weight (Mw) of 1,000 to 40,000, more preferably a compound of 2,000 to 20,000. The higher the Mw of the component (A), the higher the adhesiveness and flexibility of the resin cured film, and the easier it is to adjust the crosslinking density. On the other hand, the lower the Mw of component (A) is, the solvent solubility of component (A) can be improved, and the compatibility with other components in the photosensitive resin composition can be improved, and the white turbidity of the cured resin film can be improved. Inhibition, flatness and patterning.

From the same viewpoint, the component (A) preferably has an acid value of 30 mgKOH/g or more and 200 mgKOH/g or less.

In this specification, the weight average molecular weight (Mw) and number average molecular weight (Mn) of each component can be obtained by gel permeation chromatography (GPC) (for example, "HLC-8220GPC" (manufactured by TOSOH Co., Ltd.)) The conversion value of styrene. In addition, the acid value may be a value obtained using a potentiometric titration device (for example, "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.). However, for compounds such as monomers whose molecular weight can be calculated from the structure, the value calculated from the structure can be used as the molecular weight of the compound.

The content of the component (A) is preferably from 2% by mass to 84% by mass, more preferably from 6% by mass to 80% by mass, and still more preferably 10% by mass, based on the total mass of the solid content Above 76% by mass or less. (A) When the said content of a component is 2 mass % or more, it will become easy to improve the adhesiveness of the resin cured film with respect to a to-be-attached object. Moreover, if it is 84 mass % or less, a development speed can fully be made high, and an opening pattern can be obtained easily.

Moreover, (A) component can be used individually by 1 type or in combination of 2 or more types.

The photosensitive resin composition may contain (B) a photopolymerizable compound having at least 2 ethylenically unsaturated bonds, (C) a photopolymerization initiator, (D) a light-shielding material, (E) an epoxy resin, and the like.

Component (B) (a photopolymerizable compound having at least 2 ethylenically unsaturated bonds) can increase the exposure sensitivity of the photosensitive resin composition, and form a moderately cross-linked structure during curing to improve the adhesion of the cured film to the substrate, And improve the developability of the cured film (resolution, such as the linearity of the pattern).

Specific examples of the component (B) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, base) acrylate, tetramethylene glycol di(meth)acrylate, glyceryl di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate Base) Acrylate, Neopentylthritol Di(meth)acrylate, Neopentylthritol Tri(meth)acrylate, Neopentylthritol Tetra(meth)acrylate, Dineopentylthritol Tetra(meth)acrylate ) acrylate, glyceryl tri(meth)acrylate, sorbitol penta(meth)acrylate, diperythritol penta(meth)acrylate, dipenteoerythritol hexa(meth)acrylate, Sorbitol hexa(meth)acrylate, alkylene oxide-modified hexa(meth)acrylate of phosphazene, caprolactone-modified dipenteoerythritol hexa(meth)acrylate, etc. (meth) Acrylates, dendrimers having (meth)acryloyl groups as compounds having ethylenic double bonds, etc.

Examples of the aforementioned dendritic polymers include dendrites obtained by adding a part of the carbon-carbon double bond in the (meth)acryl group of the polyfunctional (meth)acrylate to a polyvalent mercapto compound. shape polymer. Specifically, it includes the branch obtained by reacting the (meth)acryl group of the polyfunctional (meth)acrylate represented by the following general formula (1) with the polyvalent mercapto compound represented by the following general formula (2) polymers etc.

(In formula (1), R ₁ is a hydrogen atom or a methyl group, and R ₂ is the remaining part after the n hydroxyl groups in the k hydroxyl groups of R ₃ (OH) _k are supplied to the ester bond in the formula. Preferred R ₃ (OH) _k is a polyhydric alcohol derived from a non-aromatic straight-chain or branched hydrocarbon skeleton with a carbon number of 2 to 8, a polyhydric alcohol formed by linking multiple molecules of the polyhydric alcohol through an ether bond through dehydration condensation of alcohol Alcohol ethers, or esters of these polyols or polyol ethers and hydroxy acids. k and n independently represent integers from 2 to 20, but k≧n.)

(In formula (2), R ₄ is a single bond or a hydrocarbon group with 1 to 6 carbon numbers of 2 to 6 valences, m is 2 when R ₄ is a single bond, and when R ₈ is a 2 to 6 valent base, it is the same as R ₄ has the same valence.)

Examples of polyfunctional (meth)acrylate represented by general formula (1) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, trimethylolpropane tri(methyl) ) acrylate, ethylene oxide modified trimethylolpropane tri(meth)acrylate, neopentylthritol di(meth)acrylate, neopentylthritol tri(meth)acrylate, dipentyl Tetrol penta(meth)acrylate, di-neopentyl tetra (meth)acrylates such as alcohol hexa(meth)acrylate, caprolactone-modified neopentylitol tri(meth)acrylate, etc.

Examples of polyvalent mercapto compounds represented by general formula (2) include trimethylolpropane tris(mercaptoacetate), trimethylolpropane tris(mercaptopropionate), neopentylitol tetrakis(mercaptoacetate), ), neopentylthritol tri(mercaptoacetate), neopentylthritol tetrakis(mercaptopropionate), diperythritol hexa(mercaptopropionate), diperythritol hexa(mercaptopropionate) )wait.

The component (B) preferably has 3 or more ethylenically unsaturated bonds, and more preferably has 5 or more ethylenically unsaturated bonds, from the viewpoint of increasing the crosslink density of the cured film and improving the adhesiveness. Even if the adhesiveness is improved by using the component (B) with a large number of ethylenically unsaturated bonds, by using a resin having an aromatic skeleton in the main chain as the component (A) or the component (E) described later, it can be cured The resin molecules in the film are easily stretched, and the cured film is given flexibility to withstand the bending of the substrate.

From the same viewpoint, the acrylic acid equivalent of the component (B) is preferably from 50 to 300, more preferably from 80 to 200. Moreover, (B) component does not have a free carboxyl group.

The content of the component (B) is preferably at least 2% by mass and not more than 84% by mass, more preferably at least 6% by mass and not more than 80% by mass, and more preferably at least 10% by mass and not more than 76% by mass relative to the total mass of the solid content . (B) If the said content of a component is 2 mass % or more, crosslinking becomes sufficient, and it becomes possible to form a film as a cured resin film. Moreover, if the said content of (B) component is 84 mass % or less, the adhesiveness of the resin cured film with respect to a to-be-attached body will fall easily.

The compounding ratio of (A) component and (B) component is mass ratio (A)/(B), Preferably it is 10/90-90/10, More preferably, it is 30/70-85/15. If the compounding ratio of (A) component is 10/90 or more, sufficient flexibility can be provided to a cured film. In addition, the acid value of the coating film is not easy to decrease, and the solubility with respect to the alkaline developer can be sufficiently improved, so the developability of the cured film can be further improved (resolution, such as linearity of the pattern). If the blending ratio of the component (A) is 90/10 or less, the crosslink density of the cured film can be further increased, and the adhesion can be further improved. In addition, since the acid value of the coating film is not too high, it is difficult to increase the solubility to an alkaline developer too much, and it is possible to suppress the formed pattern from being thinner than the target line width or lacking in the pattern.

In addition, the total amount of the content of the component (A) and the content of the component (B) is preferably from 4% by mass to 93% by mass, more preferably from 10% by mass to 90% by mass, based on the total mass of the solid content . When the said total amount is 4 mass % or more, it will become easy to form a film as a cured resin film. On the other hand, when the said total amount is 93 mass % or less, since the compounding ratio of (D) component and (E) component can fully increase, bendability and light-shielding property can fully be improved.

Moreover, (B) component can be used individually by 1 type or in combination of 2 or more types.

(C) Component (photopolymerization initiator) will not be specifically limited if it is a compound which may have a polymerizable unsaturated bond and can start polymerization of the compound which can add addition polymerize. Examples of the component (C) include photopolymerization initiators such as acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthene compounds, imidazole compounds, and acyl oxime ester compounds. Moreover, in this specification, a photopolymerization initiator also includes a sensitizer.

Examples of acetophenone compounds include acetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy -2-Methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl)propan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-hydroxy- Oligomers of 2-methyl-1-[4-(1-methylvinyl)phenyl]propan-1-one, etc.

Examples of triazine compounds include 2,4,6-tris(trichloromethyl)-1,3,5-triazine, 2-methyl-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-phenyl-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4- Chlorophenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)- 1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxy Styryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4,5-trimethoxystyryl)-4,6-bis(tri Chloromethyl)-1,3,5-triazine, 2-(4-methylthiostyryl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2- (Piperonyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, etc.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzoin tertiary butyl ether, and the like.

Examples of diphenyl ketone compounds include diphenyl ketone, methyl o-benzoyl benzoate, 4-phenyl diphenyl ketone, 4-benzoyl-4'-methyl diphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylcarbonylperoxide)diphenylketone, 2,4,6-trimethyldiphenylketone, 4,4'-bis(N,N- Diethylamino) diphenyl ketone, etc.

Examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

Examples of imidazole compounds include 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis(m-methoxyphenyl)imidazole dimer , 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2,4, 5-triaryl imidazole dimer, etc.

Examples of oxime ester compounds include 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-bicycloheptyl-1-ketoxime-O-acetic acid ester, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-ketoxime-O-benzoate, 1-[9-Ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-adamantylmethane-1-ketoxime-O-acetate, 1-[ 9-ethyl-6-(2-methyl Benzoyl)-9H-carbazol-3-yl]-tetrahydrofurylmethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl Base)-9H-carbazol-3-yl]-tetrahydrofurylmethane-1-ketoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H -carbazol-3-yl]-thiophenylmethane-1-ketoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carba Azol-3-yl]-thiophenylmethane-1-ketoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3 -yl]-morpholinylmethane-1-ketoxime-O-benzoate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl ]-morpholinylmethane-1-ketoxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethyl Alkane-1-ketoxime-O-bicycloheptanecarboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane- 1-ketoxime-O-tricyclodecane carboxylate, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-ethane-1 -Ketoxime-O-adamantanecarboxylate, 1-[4-(phenylthio)phenyl]octane-1,2-dione=2-phthaloyl oxime, 1-[9- Ethyl-6-(2-methylbenzoyl)carbazol-3-yl]ethanone-o-acetyloxime, (2-methylphenyl)(7-nitro-9,9-di Propyl-9H-Oxime-2-yl)-Acetyl oxime, Ethanone-1-[7-(2-Methylbenzoyl)-9,9-Dipropyl-9H-Oxime-2- Base]-1-(O-acetyl oxime), ethyl ketone-1-(-9,9-dibutyl-7-nitro-9H-fen-2-yl)-1-o-acetyl oxime , Ethanone-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1,2- Octanediene-1-[4-(phenylthio)-2-(O-benzoyl oxime)], ethyl ketone-1-[9-ethyl-6-(2-methylbenzyl Acyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 1-(4-phenylthio)butane-1,2-dione-2-oxime-O -benzoate, 1-(4-methylaminobenzenesulfonylphenyl)butane-1,2-dione-2-oxime-O-acetate, 1-(4-methylaminobenzenesulfonyl phenyl) butane-1-ketoxime-O-acetate, 4-ethoxy-2-methylphenyl-9-ethyl-6-nitro-9H-carbazolo-3-yl -O-acetyl oxime, etc.

Among them, the (C) component is preferably an oxime ester compound-based (ketoxime-containing) photopolymerization initiator. Oxime ester compound-based photopolymerization initiators have high sensitivity, so even when the content of the light-shielding material (D) is large, sufficient photosensitivity can be ensured, and the developability (resolution) of the cured film can be sufficiently improved.

Examples of the oxime ester compound-based photopolymerization initiator include oxime ester compound-based photopolymerization initiators represented by general formula (3) or general formula (4).

In formula (3), R ₅ and R ₆ are independently C1 to C15 alkyl, C6 to C18 aryl, C7 to C20 arylalkyl or C4 to C12 heterocyclyl, R ₇ is C1 Alkyl to C15, aryl from C6 to C18 or arylalkyl from C7 to C20. Here, the alkyl group and aryl group may be substituted by C1 to C10 alkyl group, C1 to C10 alkoxy group, C1 to C10 acyl group, halogen, and the alkylene part may contain unsaturated bond, ether bond, thioether bond, ester bond. Also, the alkyl group may be any of straight chain, branched or cyclic.

In formula (4), R ₈ and R ₉ are each independently a linear or branched alkyl group with 1 to 10 carbons, a cycloalkyl group with 4 to 10 carbons, a cycloalkylalkyl group or an alkyl ring An alkyl group, or a phenyl group which may be substituted by an alkyl group having 1 to 6 carbon atoms. R ₁₀ is independently a linear or branched alkyl or alkenyl group having 2 to 10 carbons, and a part of the -CH ₂ - group in the alkyl or alkenyl group may be substituted by an -O- group. Also, some of the hydrogen atoms in the groups of R ₈ to R ₁₀ may be substituted with halogen atoms.

Also, the molar absorption coefficient of component (C) at 365nm is preferably 10000L/mol. more than cm. The sensitivity of the photopolymerization initiator is high, so even the photosensitive resin composition containing the component (B) with a large equivalent of acrylic acid can ensure sufficient photosensitivity, and can fully improve the developability of the photosensitive resin composition (solution image rate). Examples of the photopolymerization initiator include Omnirad 1312 (manufactured by IGM Resins B.V., "Omnirad" is a registered trademark of the same company), and ADEKA ARKLS NCI-831 (manufactured by ADEKA Co., Ltd., "ADEKA ARKLS" is a registered trademark of the same company) )wait.

In this specification, the molar absorption coefficient of the photopolymerization initiator is measured in a 0.001% by weight acetonitrile solution in a quartz cell with an optical path of 1 cm using an ultraviolet-visible-infrared spectrophotometer "UH4150" (manufactured by Hitachi-Hightech Co., Ltd.) The absorbance value of .

Moreover, the compound which does not act as a photoinitiator or a sensitizer by itself but can increase the ability of a photoinitiator or a sensitizer by combining with the said compound can also be added. Examples of such compounds include amine compounds which are effective when used in combination with benzophenone. Examples of the above-mentioned amine compounds include triethylamine, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate, Isoamyl methylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4' - Bis(dimethylamino)diphenylketone, 4,4'-bis(diethylamino)diphenylketone, 4,4'-bis(ethylmethylamino)diphenylketone, etc.

The content of component (C) is preferably from 1 to 30 parts by mass, more preferably from 3 to 20 parts by mass, based on 100 parts by mass of the total of components (A) and (B) Down. If the content of the component (C) is 1 part by mass or more, it will have a moderate photopolymerization rate, and thus sufficient sensitivity can be ensured. Moreover, when the content of (C)component is 30 mass parts or less, the line width can be reproduced faithfully with respect to a mask line width, and a pattern edge can be made sharper.

Moreover, (C)component can be used individually by 1 type or in combination of 2 or more types.

(D) Component (light-shielding material) is added in order to provide the desired color tone according to the use of a cured film. For example, when the cured film is a black matrix, a black pigment or a mixed-color organic pigment obtained by mixing two or more types of organic pigments can be used. From the viewpoint of improving the dispersibility in the photosensitive resin composition, the average particle diameter of (D) component (the average particle diameter measured by the laser diffraction/scattering method particle size distribution meter or the dynamic light scattering method particle size distribution meter) Diameter) is preferably not less than 1 nm and not more than 1000.

Examples of the above-mentioned black pigments include: organic black pigments such as perylene black, indigo black, aniline black, and lactam black; Inorganic black pigments such as metal oxides or metal nitrides of one or more metal elements of the metal group composed of Ag, metal pigments of metal nitrogen oxides, etc.

Examples of the aforementioned organic pigments include azo pigments, condensed azo pigments, methine azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, bisoxazine pigments ( dioxazine dye), reduced pigments, perylene pigments, pyrene pigments, quinophthalone pigments, diketopyrrolopyrrole pigments, thioindigo pigments, etc.

Specific examples of the above-mentioned organic pigments include those with the following numbers in the pigment index, but are not limited thereto.

Pigment Red 2, 3, 4, 5, 9, 12, 14, 22, 23, 31, 38, 112, 122, 144, 146, 147, 149, 166, 168, 170, 175, 176, 177, 178, 179, 184, 185, 187, 188, 202, 207, 208, 209, 210, 213, 214, 220, 221, 242, 247, 253, 254, 255, 256, 257, 262, 264, 266, 272, 279, etc.;

Pigment Orange 5, 13, 16, 34, 36, 38, 43, 61, 62, 64, 67, 68, 71, 72, 73, 74, 81, etc.;

Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 55, 73, 74, 81, 83, 93, 95, 97, 109, 110, 111, 117, 120, 126, 127, 128, 129, 130, 136, 138, 139, 150, 151, 153, 154, 155, 173, 174, 175, 176, 180, 181, 183, 185, 191, 194, 199, 213, 214, etc.

Pigment green 7, 36, 58, etc.;

Pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, 80, etc.;

Pigment Violet 19, 23, 37, etc.

The content of the component (D) can be determined arbitrarily according to the desired light-shielding degree, but it is preferably at least 1% by mass and not more than 80% by mass, more preferably at least 2% by mass, relative to the total solid content of the photosensitive resin composition Above 70% by mass or less. When the content of (D) component is 1 mass % or more with respect to the total mass of solid content, sufficient light-shielding property can be acquired in the case of a thick film. If the content of the component (D) is 80% by mass or less relative to the total solid content, the content of the photosensitive resin originally used as a binder will not be reduced, so that the desired development characteristics and film forming performance can be obtained.

Component (D) is generally mixed with other compounding components as a dispersion dispersed in a solvent, and a dispersant can be added at this time. As the dispersant, known compounds used for dispersing pigments (light-shielding components) (compounds sold under the name of dispersant, dispersion wetting agent, dispersion accelerator, etc., etc.) can be used without any particular limitation.

Examples of dispersants include cationic polymer dispersants, anionic polymer dispersants, nonionic polymer dispersants, and pigment derivative type dispersants (dispersion aids).

Component (D) is basically a hard material in powder form, which will reduce the flexibility of the cured film and easily crack or peel off when bent. At this time, use a resin having an aromatic skeleton in the main chain as component (A) or component (E) described later, so that the resin molecules in the cured film can easily expand and contract, and the cured film can be given flexibility that can withstand the bending of the substrate .

Moreover, (D)component can be used individually by 1 type or in combination of 2 or more types.

Component (E) (epoxy resin) can improve the developability, adhesion, chemical resistance and water resistance of the cured film. Here, based on the findings of the inventors, the use of an epoxy compound having an aromatic skeleton in the main chain as the component (E) improves the flexibility of the cured film and suppresses the occurrence of cracks or peeling during bending. . The reason for this is considered to be that a small space is generated in the cured film by the large-volume aromatic ring, and the resin molecules in the cured film are easily stretched, thereby imparting specific flexibility to the cured film.

Examples of epoxy compounds having an aromatic skeleton in the main chain include bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol-stilbene-type epoxy compounds, biscresol-stilbene-type epoxy compounds, bis-naphthol Permeil-type epoxy compounds, diphenyl-stilbene-type epoxy compounds, phenol novolak-type epoxy compounds, (o-, m-, p-) cresol novolac-type epoxy compounds, phenol aralkyl-type epoxy compounds, containing naphthalene Skeleton phenol novolac compound (such as NC-7000L, manufactured by Nippon Kayaku Co., Ltd.), biphenyl type epoxy compound (such as jERYX4000, manufactured by Mitsubishi Chemical Corporation, "jER" is a registered trademark of the same company), Phenol novolac compound containing biphenyl skeleton (such as NC-3000, manufactured by Nippon Kayaku Co., Ltd.), naphthol aralkyl type epoxy Compounds, trisphenol methane type epoxy compounds (for example, EPPN-501H, manufactured by Nippon Kayaku Co., Ltd.), tetraphenol ethane type epoxy compounds, and the like.

Among these, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, biphenyl type epoxy compounds, and biphenyl type epoxy compounds are preferable from the viewpoint of suppressing cracking or peeling during bending. The phenyl-skeleton phenol novolak compound is more preferably a biphenyl-type epoxy compound and a biphenyl-skeleton-containing phenol novolak compound.

(E) The weight average molecular weight (Mw) of a component becomes like this. Preferably it is 200-20,000, More preferably, it is 500-15,000, More preferably, it is 1,000-10,000. (E) The higher the Mw of the component, the softer the cured film is, and it is less likely to cause cracks or peeling when bending, and the lower the Mw, the more the developability improves. From the viewpoint of achieving such a balance, the above-mentioned range is preferable.

The epoxy equivalent weight (EEW) of the component (E) is preferably from 100 g/eq to 10,000 g/eq, more preferably from 110 g/eq to 7,500 g/eq, and more preferably from 150 g/eq to 5,000 g/eq the following. (E) The larger the EEW of the component, the lower the developability due to the reaction with the (A) component can be suppressed, and the smaller the EEW, the lower the molecular weight of the epoxy compound and improve the developability. In addition, the smaller the EEW of the component (E), the higher the reactivity, and uneven curing due to remaining unreacted sites is less likely to remain in the cured film. Therefore, it is not easy to reduce the toughness caused by uneven hardening, and it is even less likely to generate cracks or peeling off. From the viewpoint of achieving such a balance, the above-mentioned range is preferable.

In addition, in this specification, the epoxy group equivalent of (E) component can be calculated|required by titrating with 1/10N-perchloric acid solution using the potentiometric titration apparatus "COM-1600" (made by Hiranuma Sangyo Co., Ltd.).

In the component (E), the number of benzene rings relative to the epoxy group (number of benzene rings/epoxy group) is preferably 1.1 to 50, more preferably 1.1 to 45, still more preferably 1.3 to 45, particularly preferably 1.9 to 35. The number of benzene rings mentioned here is, for example, 2 for naphthalene ring, 2 for biphenyl ring, 3 for anthracene ring, and 4 for bisphenol fluorine ring. If the number of benzene rings/epoxy groups is 1.0 or more, the number of aromatic rings derived from the (E) component will increase, which can improve the toughness of the cured film, prevent cracking or peeling when bending, or improve the toughness of the cured film. softness. On the other hand, when the number of benzene rings/the number of epoxy groups is 50 or less, the number of epoxy groups increases, and the component (E) tends to undergo a curing reaction, thereby sufficiently improving the flexibility of the cured film.

Here, the number of benzene rings/the number of epoxy groups can be calculated from the epoxy group equivalent based on the ratio relationship between the number of benzene rings/the number of epoxy groups and the epoxy group equivalent in consideration of the repeating unit of the epoxy compound. That is, the number of benzene rings or epoxy groups will change due to the respective chemical structures or repeating unit numbers of epoxy compounds, but the relationship between the epoxy group equivalents can be grasped in advance by applying certain repeating units. The number of benzene rings/the number of epoxy groups can be calculated according to the measured value of epoxy group equivalent. Here, compounds represented by the following chemical formulas (i) to (vii) are shown as specific examples thereof, but epoxy compounds other than these can also be obtained in the same manner.

˙Bisphenol peroxide type epoxy compound

In the case of the above formula (i), the number of benzene rings/the number of epoxy groups=(4m ₁ +4)/2, for example, 4 when m ₁ =1. At this time, the epoxy group equivalent was 435. Similarly, when m ₁ =2, the number of benzene rings/epoxy group is 6, and the epoxy group equivalent is 638. From this relationship, it can be seen that (number of benzene rings/number of epoxy groups)=(((epoxy group equivalent)-28)/102. The number of benzene rings/the number of epoxy groups can be calculated from the epoxy group equivalent by using this conversion formula.

˙1,6-Naphthalene diol aralkyl type epoxy compound

In the case of the above formula (ii), the number of benzene rings/the number of epoxy groups=(3m ₂ +2)/(2m ₂ +2), for example, when m ₂ =1, it is 1.25. At this time, the epoxy group equivalent was 162. Similarly, when m ₂ =2, the number of benzene rings/glycidyl group was 1.33, and the epoxy group equivalent was 170. From this relationship, it can be seen that (number of benzene rings/number of epoxy groups)=(((epoxy group equivalent)-34)/102.

˙1-Naphthol aralkyl epoxy compound

In the case of the above formula (iii), the number of benzene rings/the number of epoxy groups=(3m ₃ +2)/(m ₃ +1), for example, when m ₃ =1, it is 2.5. At this time, the epoxy group equivalent was 252. Similarly, when m ₃ =2, the number of benzene rings/epoxy group is 2.67, and the epoxy group equivalent is 269. From this relationship, it can be seen that (number of benzene rings/number of epoxy groups)=((equivalent weight of epoxy groups)+3)/102.

˙Phenol novolac type epoxy compound

In the case of the above formula (iv), the number of benzene rings/the number of epoxy groups=(m ₄ +2)/(m ₄ +2), and (the number of benzene rings/the number of epoxy groups)=1 regardless of the epoxy group equivalent.

˙Multifunctional epoxy resin containing biphenyl skeleton

In the case of the above formula (v), the number of benzene rings/the number of epoxy groups=(3m ₅ +1)/(m ₅ +1), for example, 2 when m ₅ =1. At this time, the epoxy group equivalent was 239. Similarly, when m ₅ =2, the number of benzene rings/epoxy group is 2.33, and the epoxy group equivalent is 269. From this relationship, it can be seen that (number of benzene rings/number of epoxy groups)=((epoxy group equivalent)-61)/89.

˙Multifunctional epoxy resin containing bisphenol A skeleton

In the case of the above formula (vi), the number of benzene rings/the number of epoxy groups=(2m ₆ +2)/2, for example, 2 when m ₆ =1. At this time, the epoxy group equivalent was 312. Similarly, when m ₆ =2, the number of benzene rings/epoxy group is 3, and the epoxy group equivalent is 455. From this relationship, it can be seen that (number of benzene rings/number of epoxy groups)=(((epoxy group equivalent)-28)/142.

˙Multifunctional epoxy resin containing biphenyl skeleton

In the case of the above formula (vii), the number of benzene rings/the number of epoxy groups=(4m ₇ +2)/(2m ₇ +2), for example, when m ₇ =1, it is 1.5. At this time, the epoxy group equivalent was 194. Similarly, when m ₇ =2, the number of benzene rings/epoxy group is 1.67, and the epoxy group equivalent is 209. From this relationship, it can be seen that (number of benzene rings/number of epoxy groups)=((epoxy group equivalent)-60)/89.

The content of the component (E) is preferably from 0.4% by mass to 40% by mass, more preferably from 1% by mass to 20% by mass, more preferably from 2% by mass to 15% by mass, based on the total mass of the solid content . The more the content of the component (E) is, the more remarkable the property improvement effect of adding the component (E) (especially the effect of improving the developability and adhesiveness and preventing cracks and peeling during bending) is more remarkable. Moreover, favorable developability can be maintained by the content of (E) component not being excessive. From the viewpoint of achieving such a balance, the above-mentioned range is preferable.

When using (E) component, a hardening|curing agent and a hardening accelerator can be used together.

Examples of hardeners include amine compounds that accelerate the curing of epoxy resins, polycarboxylic acid compounds and their anhydrides, phenol resins, amine resins, dicyandiamine, Lewis acid complexes, and the like.

Examples of hardening accelerators include tertiary amines, quaternary ammonium salts, tertiary phosphines, quaternary phosphonium salts, boric acid esters, Lewis acids, organometallic compounds, imidazoles, etc., which accelerate the hardening of epoxy resins.

Moreover, (E) component, a hardening|curing agent, and a hardening accelerator can be used individually by 1 type or in combination of 2 or more types.

The photosensitive resin composition may also contain (F) coupling agent and (G) surfactant.

(F) Examples of components (coupling agents) include 3-(glycidoxy)propyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-isocyanatopropyltriethyl Oxysilane, and 3-ureidopropyltriethoxysilane, etc.

(G) Examples of the component (surfactant) include fluorine-based surfactants, silicone-based surfactants, and the like.

The photosensitive resin composition contains (H) a solvent.

Examples of (H) components include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol; terpenes such as α- or β-terpineol; acetone, methyl ethyl ketone, cyclic Ketones such as hexanone and N-methyl-2-pyrrolidone; aromatic hydrocarbons such as toluene, xylene and tetramethylbenzene; methyl cellosolve, ethyl cellosolve, methyl cellosolve, etc. Carbitol (methyl carbitol), ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol Glycol ethers such as monomethyl ether and triethylene glycol monoethyl ether; Ethyl acetate, butyl acetate, cellothreoacetate, ethyl cellothreoacetate, butyl cellothreonate Acetate esters, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. (H) The component can be used individually by 1 type or in combination of 2 or more types.

The content of the component (H) varies depending on the target viscosity, but is preferably 30% by mass or more and 90% by mass or less with respect to the total mass of the photosensitive resin composition. If the content of the component (H) is 30% by mass or more, the viscosity of the photosensitive resin composition on the substrate can be easily applied, and if it is 90% by mass or less, the time required to coat the photosensitive resin composition on the substrate can be shortened. The time required for subsequent drying (adjusted as solid content).

In addition to these components, the photosensitive resin composition may contain additives such as other resin components, polymerization inhibitors and antioxidants, fillers, ultraviolet absorbers, and rheology modifiers.

Examples of other resin components include vinyl resins, polyester resins, polyamide resins, polyimide resins, polyurethane resins, polyether resins, and melamine resins.

Examples of thermal polymerization inhibitors and antioxidants include, for example, hydroquinone, hydroquinone monomethyl ether, pyrogallol, tert-butylcatechol, phenthiazine, hindered phenolic compounds, and the like.

Examples of fillers include glass fiber, silica, mica, alumina, and the like.

Examples of ultraviolet absorbers include benzotriazole compounds, benzophenone compounds, triazine compounds, and the like.

The photosensitive resin composition can be obtained by mixing the above-mentioned components.

Coating the photosensitive resin composition on the above-mentioned flexible substrate to form a coating film, selectively exposing and curing the above-mentioned coating film position, developing and forming a pattern on the coating film hardened by the above-mentioned exposure, and then forming the above-mentioned pattern The coated film is baked (post-hardened), thereby forming the above-mentioned substrate with a cured film.

Coating of the photosensitive resin composition can be performed by a known coating method. Examples of the above-mentioned coating method include using a known solution dipping method, spray method, roll coater, flat coater, The method of slit coater or rotary machine, etc. By these methods, the above-mentioned photosensitive resin composition can be applied to a desired thickness.

The coating film thus formed is preferably dried before exposure. Drying of the coating film can be performed by a known drying method. Examples of the above-mentioned drying method include heating by an oven, a hot air blower, a hot plate, an infrared heater, etc., vacuum drying, and combinations thereof. The heating temperature and heating time during drying can be appropriately selected according to the solvent used, for example, it is preferably carried out at 60 to 110° C. for 1 to 5 minutes.

The above-mentioned exposure can be performed by a method in which a part of the above-mentioned coating film is irradiated with radiation through a photomask. A part corresponding to the pattern of the coating film can be photocured by this exposure.

A well-known one can be used for the said photomask. Examples of masks include multi-tone masks such as halftone masks and gray tone masks. The gray tone mask is formed on a light-transmitting substrate with a light-shielding portion and a diffraction grating. In the diffraction grating, the intervals between slits, dots, nets and other light-transmitting areas are below the resolution limit of the light used for exposure, and the light transmittance is controlled by this structure. A half-tone mask is formed on a light-transmitting substrate with a light-shielding portion and a half-transmission portion. The transmittance of the light used for exposure is controlled by the half-transmission part.

The exposure apparatus used for exposure and its exposure irradiation conditions can be appropriately selected. Examples of irradiated radiation include visible rays, ultraviolet rays, deep ultraviolet rays, electron rays, and X-rays. Ultraviolet rays are preferable among the above-mentioned radiations. Also, a known exposure device (ultrahigh pressure mercury lamp, high pressure mercury lamp, metal halide lamp, extreme ultraviolet lamp, etc.) can be used as the device for irradiating radiation. Also, the wavelength of the radiation to be irradiated is preferably not less than 250 nm and not more than 400 nm. The amount of radiation exposure is preferably not less than 25 mJ/cm ² and not more than 3000 mJ/cm ² .

After the exposure, the coating film irradiated with radiation is subjected to alkaline development, and the coating film of the unexposed part is removed.

Examples of the developing method of the coating film include a shower developing method, a spray developing method, a immersion (dip) developing method, and a liquid-covered developing method. Moreover, the above-mentioned image development can be performed using a commercially available developing machine, an ultrasonic cleaner, etc.

Examples of a developer suitable for development include aqueous solutions of carbonates of alkali metals or alkaline earth metals, aqueous solutions of hydroxides of alkali metals, and the like. Among them, it is preferable to use a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonates such as sodium carbonate, potassium carbonate, and lithium carbonate at a temperature of 23 to 28°C. Moreover, a commercially available developing machine, an ultrasonic cleaner, etc. can be used for an image development process.

Thereafter, the exposed portion (coating film) after development is heat-treated and fully cured (post-baking).

The method of heating the exposed part (coating film) after development can be performed by a known method (heating by an oven, a hot air blower, a hot plate, an infrared heater, etc., vacuum drying, or a combination thereof). The heating temperature is not particularly limited as long as it is a temperature at which the coating film is fully cured (post-baked). The heating temperature is preferably at a temperature of 60 to 250° C. for 20 to 60 minutes.

After heating and hardening, the coating film (cured film) can be cleaned with short-wavelength radiation to remove organic pollutants on the surface of the coating film.

The above-mentioned cleaning can be performed by, for example, a method of irradiating ultraviolet rays having wavelengths of 184.9 nm and 253.7 nm with a low-pressure mercury lamp. The irradiation dose at this time may be 1000mJ.

Various functional layers such as a black matrix, a color filter, a light-shielding film, a protective film, and a wavelength conversion layer for a display device can be used for the above-mentioned substrate with a cured film. The light source of the display device is a well-known light source such as an organic electroluminescent (EL) light source and a laser light emitting diode (LED) light source. Can. In addition, the display device may have a configuration in which a wavelength conversion layer containing quantum dots or a phosphor compound is disposed between the light source and the above-mentioned substrate with a cured film. The above-mentioned substrate with a hardened film can also have good flexibility and resistance especially when it is formed as a thick film with a film thickness of 2 μm or more, so it can be arranged sideways with respect to the LED light source in an LED display with this film thickness. It is also used as a light-shielding film for suppressing lateral light leakage.

(Example)

Embodiments of the present invention will be specifically described below based on examples, but the present invention is not limited thereto.

First, the synthesis examples of the unsaturated group-containing alkali-soluble resin of the (A) component and the epoxy resin of the (E) component will be described, but the evaluation of the resins in these synthesis examples is performed in the following manner unless otherwise specified.

Also, when the same model is used for various measurement devices, the device manufacturer's name is omitted from the second occurrence. In addition, in the examples, the glass substrates used for the production of the substrates with cured resin films for measurement were all subjected to the same treatment and used. In addition, when the first decimal place of the content of each component is 0, descriptions below the decimal point are omitted.

[Solid content concentration]

Impregnate 1 g of the resin solution obtained in the synthesis example into a glass filter [weight: W ₀ (g)] and weigh [W ₁ (g)], borrow the weight [W ₂ (g)] after heating at 160°C for 2 hours Seek from the following formula.

Solid content concentration (weight %)=100×(W ₂ -W ₀ )/(W ₁ -W ₀ ).

[Epoxy equivalent]

Dissolve the resin solution in dioxane, add tetraethylammonium bromide acetic acid solution, and use the potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.) to titrate with 1/10N-perchloric acid solution to obtain .

[acid value]

The acid value was determined by dissolving the resin solution in dioxane and titrating with a 1/10 N-KOH aqueous solution using a potentiometric titration device "COM-1600" (manufactured by Hiranuma Sangyo Co., Ltd.).

[molecular weight]

The molecular weight is based on gel permeation chromatography (GPC) "HLC-8220GPC" (manufactured by TOSOH Co., Ltd., solvent: tetrahydrofuran, column: TSKgelSuper H-2000 (2 tubes) + TSKgelSuper H-3000 (1 tube) + TSKgelSuper H-4000 (1) + TSKgelSuper H-5000 (1) (TOSOH Co., Ltd.), temperature: 40 ° C, speed: 0.6ml/min), and standard polystyrene (TOSOH Co., Ltd. Weight average molecular weight (Mw) converted from PS-Oligomer Kit).

[Acrylic acid equivalent]

Acrylic equivalent weight is found by dividing the molecular weight by the number of acrylic functional groups.

The abbreviations used in the following synthesis examples and the like are as follows.

AA: Acrylic.

BPFE: Bisphenol fluorine-type epoxy compound (reaction product of 9,9-bis(4-hydroxyphenyl) fluorine and chloromethyloxirane).

BPDA: 3,3',4,4'-biphenyltetracarboxylic dianhydride.

THPA: Tetrahydrophthalic anhydride.

TEAB: Tetraethylammonium bromide.

PGMEA: Propylene Glycol Monomethyl Ether Acetate.

[Synthesis Example 1]

Add BPFE (114.4g, 0.23 mol), AA (33.2g, 0.46 mol), PGMEA (157.0g) and TEAB (0.48g) into a 500ml four-necked flask with a reflux cooler, and stir at 100 to 105°C for 20 hour response. Then add BPDA (35.3g, 0.12 mol) and THPA (18.3g, 0.12 mol) in the flask, and stir for 6 hours at 120 to 125°C to obtain the alkali-soluble resin (A) containing polymerizable unsaturated groups- 1. The solid content concentration of the obtained resin solution was 55.8% by mass, the acid value (solid content conversion) was 100 mgKOH/g, and the Mw analyzed by GPC was 3600.

[Synthesis Example 2]

Add 4,4'-dihydroxybiphenyl (77.5g), diethylene glycol dimethyl ether (97.9g), 4,4'-bischloromethylbiphenyl (52.3g) to a 1000ml 4-neck flask , the temperature was raised to 160°C while stirring under a nitrogen flow, and the reaction was carried out for 10 hours. Then, 48% potassium hydroxide solution (3 g) was added, and the reaction was carried out at 130° C. for 3 hours. After the reaction, a large amount of pure water was dropped and recovered by reprecipitation to obtain a pale yellow resin (110 g). Epichlorohydrin (518g) was added to 110g of obtained resin, and it melt|dissolved. Then, 49% sodium hydroxide aqueous solution (67.4 g) was added dropwise at 70° C. under reduced pressure for 4 hours. During the dropping, the water distilled off by reflux and epichlorohydrin were separated in a separation tank, and the epichlorohydrin was returned to to the reaction vessel, and the reaction was carried out by removing water from the system. After completion|finish of reaction, the salt which produced|generated was removed by filtration, and after washing with water further, epichlorohydrin was distilled off, and epoxy resin (E)-3 (108g) was obtained. The epoxy group equivalent weight of the obtained solid resin was 230, and the Mw was 1800.

The photosensitive resin composition was prepared with the compounding quantity (unit: mass %) recorded in Table 1 and Table 2. The compounding components used in Table 1 and Table 2 are as follows.

(Alkali-soluble resins containing unsaturated groups)

(A)-1: The resin solution obtained in the synthesis example 1 (55.8 mass % of solid content concentration).

(A)-2: An acid-modified epoxy acrylate resin solution (KAYARAD ZCR-1797, manufactured by Nippon Kayaku Co., Ltd., solid content concentration 60.0% by mass) containing biphenyl in the main skeleton.

(A)-3: Acid-modified epoxy acrylate resin solution (KAYARAD ZAR-2000, manufactured by Nippon Kayaku Co., Ltd., solid content concentration 60.0% by mass) containing bisphenol A group in the main skeleton.

((B) Photopolymerizable compound having at least 2 ethylenically unsaturated bonds).

(B): A mixture of diperythritol pentaacrylate and hexaacrylate (DPHA, manufactured by Nippon Kayaku Co., Ltd.).

((C) Photopolymerizable initiator)

(C): Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)( IrgacureOXE02, manufactured by BASF Corporation).

((D) Shading material dispersion)

(D)-1: Propylene glycol 1-monomethyl ether-2-acetate solvent dispersion (24% by mass) of 20% by mass of carbon black pigment and 4% by mass of polymer dispersant.

(D)-2: Propylene glycol 1-monomethyl ether-2-acetate solvent dispersion (solid content concentration: 24 mass %) of 20 mass % of bisbenzofuranone pigment and 4 mass % of polymer dispersant.

((E) epoxy resin)

(E)-1: Multifunctional epoxy resin containing biphenyl skeleton (NC-3000H, epoxy group equivalent weight: 280 to 300, number of benzene rings relative to the number of epoxy groups: 2.5 to 2.7, Nippon Kayaku Co., Ltd. system).

(E)-2: Multifunctional epoxy resin containing bisphenol A skeleton (JER1010, epoxy group equivalent weight 3000 to 5000, Mw6000 to 10000, number of benzene rings relative to epoxy group number: 21 to 35, Mitsubishi Chemical Co., Ltd. limited company).

(E)-3: Epoxy resin described in Synthesis Example 2 (epoxy group equivalent: 230, Mw1800, number of benzene rings relative to the number of epoxy groups: 1.9).

((F) Couplant)

(F): 50% alcohol solution of the active ingredient of 3-ureidopropyltrialkoxysilane (KBE-585, manufactured by Shin-Etsu Chemical Co., Ltd.).

((G)surfactant)

(G): Fluorine-based surfactant (Megafac RS-72-A, manufactured by DIC Corporation).

((H) solvent)

(H)-1: Propylene glycol 1-monomethyl ether 2-acetate (made by Tokyo Chemical Industry Co., Ltd.).

(H)-2: cyclohexanone (made by Tokyo Chemical Industry Co., Ltd.).

[Table 1]

[Table 2]

[evaluate]

[Preparation of cured film for property evaluation]

The photosensitive resin compositions shown in Table 1 and Table 2 were previously irradiated with ultraviolet rays by a low-pressure mercury lamp in such a way that the cumulative illuminance at a wavelength of 254nm became 500mJ/ ^cm2 , and the glass substrate "Eagle XG" ( (manufactured by Corning Incorporated) (hereinafter referred to as "glass substrate") was coated with a spin coater to form a specific film thickness after heating and hardening, and prebaked at 90° C. for 2 minutes using a hot plate to produce a coating film.

Next, cover the above coating film with a negative photomask, and irradiate 100 mJ/cm ² of ultraviolet rays with an ultra-high pressure mercury lamp with an i-line illumination intensity of 30 mW/cm ² to carry out photohardening reaction.

Then, the above-mentioned cured film that was exposed was developed at 23°C, 0.04% potassium hydroxide solution, and a shower pressure of 1kgf/ ^cm2 . After 30 seconds from the development time (membrane rupture time = BT) when the pattern began to appear, 5kgf /cm ² spray water wash, remove the unexposed part of the above-mentioned cured film and form a cured film pattern on the glass substrate, use a hot air dryer to 230 ° C for 30 minutes for formal hardening (post-baking), and obtain Examples 1 to 17 Substrate with hardened film.

The cured films obtained by curing the photosensitive resin compositions of Examples 1 to 17 obtained above evaluated the following items, and the results are shown in Table 2.

<Shading property>

A cured film having a film thickness of 1 μm was prepared, and the shading (optical density OD) was measured using a desktop penetration densitometer (X-Rite 361T, manufactured by X-Rite Corporation).

<Thick film forming ability>

A cured film was prepared by changing the film thickness, and the occurrence of wrinkles on the film surface of the cured film was visually confirmed. At this time, it was judged as ◯ when no wrinkles occurred even when the film thickness was 5 μm or more, and it was judged as × when wrinkles occurred when the film thickness was 5 μm or less.

<Pore resolution in thick film>

When the film thickness after main curing was fixed at 7 μm, it was developed and it was checked with a microscope (XD-1000, manufactured by Nikon Corporation) whether or not the openings had a quadrangular shape. At this time, when the opening size of the negative mask corresponding to the opening is less than 100 μm, it is judged as ○, when it is 100 to 200 μm, it is judged as △, and when it is more than 200 μm, it is judged as ×.

<Edge Clearance of Hole in Thick Film>

A microscope (XD-1000, manufactured by Nikon Corporation) was used to check whether the four sides of the aforementioned hole pattern with a size of 100 μm or less had residues or defects impairing linearity such as edge protrusions and flanges. At this time, when there is no defect at all and the edge gap is good, it is judged as ○, when defects are observed on one to two sides of the four sides, it is judged as △, and when defects are observed on all four sides, it is judged as ×.

<Adhesion to substrate>

Adhesion (cross-cut method) evaluation according to JIS K 5600 Part 5, Section 6 was performed using a glass substrate with a cured film having a film thickness of 7 μm after main curing. As a result, when the classification of adhesiveness was 4 to 5B, it was judged as ◯, when it was 2 to 4B, it was judged as Δ, and when it was less than 2B, it was judged as x.

<flexibility>

The base material was changed to Kapton 100H (a polyimide-based film with a film thickness of 25 μm, manufactured by Toray DuPont Co., Ltd.), and a cured film with a film thickness of 7 μm was formed according to the above-mentioned film-forming conditions. The film was processed into a long strip with a width of 1 cm and a length of 12 cm having an opening of 50 μm×50 μm obtained by development in advance, and one end of the short side was fixed to a SUS circle with a diameter of 40 mm, 30 mm, and 10 mm by tape. The cylinder was wound around the cylinder so that the cured film of the substrate with the cured film was pulled out, and this operation was repeated 100 times.

After the operation, check with a microscope (XD-1000, manufactured by Nikon Corporation) whether there are defects such as cracks and peeling in the four corners of the pattern at the opening size of the negative mask corresponding to 50 μm×50 μm or in the cured film. Among them, the range of 1200 μm×1200 μm was observed, 16 opening patterns were randomly selected, and those who observed the aforementioned defects were counted.

Here, when there is no defect at all, it is judged as ⊚, when there are 0 to 3 places, it is judged as ○, when there are 3 to 8 places, it is judged as △, and when there are 8 or more places, it is judged as ×.

The evaluation results are shown in Table 3 and Table 4.

[table 3]

[Table 4]

From the results of Examples 1 to 17 above, it can be seen that by using the photosensitive resin composition of the present invention, it is possible to produce a black matrix having the same light-shielding property as that used in color filters, A cured film that provides plate-making properties and flex resistance. Therefore, the cured film of the present invention is suitably used as a light-shielding layer for flexible displays.

(Industrial Utilization)

According to the photosensitive resin composition of the present invention, it is possible to obtain a substrate with a cured film that can be patterned by photolithography and is excellent in flexibility under a light-shielding material. For example, a light-shielding layer in a movable display device in which the substrate is curved can be used. In particular, it is excellent in adhesion to the substrate and crack resistance of the cured film, and is suitable for use in flexible devices typified by organic EL displays and LED displays.

Claims (15)

A substrate with a hardened film, comprising a flexible substrate that can be repeatedly bent and deformed to return to its original shape, and a cured film formed on the surface of the flexible substrate, wherein, The aforementioned cured film is a cured film of a photosensitive resin composition having a film thickness of 1 to 30 μm, and the photosensitive resin composition includes an alkali-soluble resin containing an unsaturated group. The substrate with a cured film according to claim 1, wherein when the cured film is bent to a radius of curvature of 50 mm, the cured film does not crack or peel off. The substrate with a cured film according to claim 1 or 2, wherein the optical density (OD value) of the cured film is 0.1 to 4.0/μm. A photosensitive resin composition, which is used to manufacture the substrate with a hardened film as described in any one of claims 1 to 3, Further, (A) an unsaturated group-containing alkali-soluble resin having an aromatic skeleton is included in the main chain. The photosensitive resin composition according to claim 4, wherein (A) the alkali-soluble resin containing an unsaturated group has a bisphenol skeleton, a fenene group or a novolak skeleton in the main chain. The photosensitive resin composition as described in Claim 5, wherein the aforementioned bisphenol skeleton contains a structure derived from bisphenol A or bisphenol F, The aforementioned fennelyl is bisphenol fennelyl, biscresol fennelyl or bisnaphthyl fennelyl, The aforementioned novolak skeleton contains a group selected from the group consisting of a phenol novolac structure, a cresol novolac structure, a trimethylphenol novolac structure, a biphenol novolak structure, a naphthol novolak structure, and a naphthol aralkyl structure. The novolac structure. The photosensitive resin composition as described in Claim 4 or 5, which contains: (B) a photopolymerizable compound having at least 2 ethylenically unsaturated bonds; (C) photopolymerization initiator; (D) shades; and (E) Epoxy resin. The photosensitive resin composition according to Claim 7, wherein the aforementioned component (E) is: a weight average molecular weight (Mw) of 200 to 20,000, and an epoxy equivalent weight (EEW) of 100 g/eq to 10,000 g/eq of epoxy resin. The photosensitive resin composition according to claim 7, wherein the aforementioned component (E) has an aromatic skeleton in the main chain. The photosensitive resin composition according to claim 7, wherein the content of the above-mentioned (E) component is 0.4% by mass or more and 40% by mass or less with respect to the total mass of the solid content. The photosensitive resin composition according to Claim 7, wherein the total amount of the content of the aforementioned component (A) and the content of the aforementioned component (B) is 4% by mass or more and 93% by mass or less with respect to the total mass of the solid content , The blending ratio of the aforementioned (A) component to the aforementioned (B) component is 10/90 to 90/10 in terms of mass ratio (A)/(B), The content of the above-mentioned (E) component is 0.4 mass % or more and 40 mass % or less with respect to the total mass of solid content. A method for manufacturing a substrate with a hardened film, comprising the following steps: Coating the photosensitive resin composition as described in claim 7 on a flexible substrate that can be repeatedly bent and deformed to return to its original shape to form a coating film; A step of position-selectively exposing the aforementioned coating film; A step of developing the above-mentioned exposed coating film to form a pattern; and The step of baking the aforementioned patterned coating film. A display device comprising a substrate with a cured film manufactured from the substrate with a cured film according to any one of Claims 1 to 3. The display device according to claim 13, which has an organic electroluminescence (EL) light source or a laser light emitting diode (LED) light source. The display device according to claim 14, which is provided with a wavelength conversion layer containing quantum dots or phosphor compounds.