TW202244092A - Alkali-soluble resin, photosensitive resin composition, cured product, and image display device - Google Patents

Abstract

A purpose of the present invention is to provide: an alkali-soluble resin able to form a cured film having excellent development adhesiveness and resolution even if the film is thick; and a photosensitive resin composition that contains the alkali-soluble resin. Another purpose of the present invention is to provide a photosensitive resin composition which, in addition to the characteristics mentioned above, can be developed in a short time even if a weakly alkaline developing solution is used. This alkali-soluble resin contains one or more types of repeating unit X represented by general formula (1). (In the formula, R1 is hydrogen or a methyl group, R2 is a linking group having one or more carbon atoms, R3 is an organic group which is represented by general formula (2) and bonds to a carbon atom in the linking group, and R4 is a hydroxyl group or organic group which bonds to a carbon atom in the linking group.) (In the formula, R5 is an organic group which includes a heteroatom and which has 3-8 carbon atoms in the main structure, or an organic group which includes a carboxyl group and which has 2-7 carbon atoms in the main structure.).

Description

Alkali-soluble resin, photosensitive resin composition, cured product, and image display device

The invention relates to an alkali-soluble resin, a photosensitive resin composition, a cured product, and an image display device.

In liquid crystal display elements, photo spacers are used to maintain the thickness of the liquid crystal layer sandwiched between the color filter side substrate and the thin film transistor (TFT) side substrate.

A photo-spacer is generally formed by coating a photosensitive resin composition on a substrate, exposing it to light passing through a photomask having a specific fine pattern after drying, and developing it.

In recent years, along with the high functionality of image display devices such as liquid crystal display devices (such as 3D stereoscopic vision, widening viewing angle, etc.), thicker film thickness (10 μm or more) of photo-spacers is required.

For example, the object of Patent Document 1 is to provide a negative-type photosensitive resin composition capable of forming a fine photo-spacer with excellent development adhesion and resolution and a good shape even when processing a thick film with a film thickness of 10 μm or more. A negative-type photosensitive resin composition is proposed, which contains (A) an alkali-soluble resin, (B) a photoradical polymerization initiator, and (C) a photopolymerizable monomer, and the above-mentioned (C) photopolymerizable monomer contains (C-1) a photopolymerizable monomer having an isocyanuric acid skeleton, and (C-2) a photopolymerizable monomer having a fennel skeleton.

Furthermore, the object of Patent Document 2 is to provide a photosensitive resin composition capable of forming a gap of 10 μm or more, having good adhesion to the substrate, and ensuring transparency after exposure. A photosensitive resin composition, which is used as a spacer forming material, is proposed, comprising (A) component: binder polymer, (B) component: photopolymerizable compound, (C) component: photopolymerization initiator, and ( D) Component: a hydrogen donor containing a mercapto group, and the above-mentioned (B) photopolymerizable compound includes a photopolymerizable compound having an ethylenically unsaturated group and an isocyanuric acid ring structure. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2019-124929 [Patent Document 2] International Publication No. 2013/115262

[Problem to be Solved by the Invention]

However, the photosensitive resin composition described in Patent Document 1 or 2 has room for improvement in image development adhesiveness and resolution when the photo-spacer is thickened. Also, from an environmental point of view, there is a need for a photosensitive resin composition that can be developed using a relatively dilute weak alkaline aqueous solution, but when the photosensitive resin composition described in Patent Document 1 or 2 is developed using a weak alkaline aqueous solution, There are concerns about longer developing time and lower productivity.

An object of the present invention is to provide an alkali-soluble resin capable of forming a cured film excellent in development adhesion and resolution even when the film is thickened, and a photosensitive resin composition containing the above-mentioned alkali-soluble resin. Moreover, the objective of this invention is providing the photosensitive resin composition which can develop in a short time even when using weak alkaline developing solution, in addition to having the said characteristic. Furthermore, an object of the present invention is to provide a cured product obtained from the above-mentioned photosensitive resin composition, and an image display device including the above-mentioned cured product. [Technical means to solve the problem]

As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention found that the above-mentioned object can be achieved by using the following alkali-soluble resin and a photosensitive resin composition containing the alkali-soluble resin, and completed the present invention.

（式中，R ¹為氫或甲基，R ²為碳數為1以上之連結基，R ³為鍵結於上述連結基之碳原子之由下述通式（2）所表示之有機基，R ⁴為鍵結於上述連結基之碳原子之羥基或有機基）

（式中，R ⁵為母體之碳數為3～8且包含雜原子之有機基、或母體之碳數為2～7且具有羧基之有機基） The present invention relates to an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin A") comprising one or more repeating structural units X represented by the following general formula (1).

(In the formula, R1 is hydrogen or ^a methyl group, R2 is a linking group with a carbon number of ¹ or more, and ^R3 is an organic group represented by the following general formula (2) bonded to the carbon atom of the linking group , R ⁴ is a hydroxyl group or an organic group bonded to the carbon atom of the above linking group)

(In the ^formula , R5 is an organic group whose parent has 3-8 carbon atoms and contains heteroatoms, or an organic group whose parent has 2-7 carbon atoms and has a carboxyl group)

（式中，R ¹為氫或甲基，R ²為碳數為1以上之連結基，R ^3'為鍵結於上述連結基之碳原子之由下述通式（2'）所表示之有機基，R ⁴為鍵結於上述連結基之碳原子之羥基或有機基）

（式中，R ^5'為母體之碳數為2～7之烴基、母體之碳數為3～8且包含雜原子之有機基、或母體之碳數為2～7且具有羧基之有機基） Also, the present invention relates to an alkali-soluble resin (hereinafter also referred to as "alkali-soluble resin B"), which includes one or more repeating structural units X' represented by the following general formula (1'), but does not include the following: A repeating structural unit of a branched side chain having 2 to 3 ends each terminated with a radically polymerizable substituent.

(In the formula, R ¹ is hydrogen or methyl, R ² is a linking group with a carbon number of 1 or more, and R ^3' is a carbon atom bonded to the above linking group represented by the following general formula (2') Organic group, ^R4 is a hydroxyl group or an organic group bonded to the carbon atom of the above linking group)

(wherein, R ^5' is a hydrocarbon group whose parent body has 2 to 7 carbon atoms, an organic group whose parent body has 3 to 8 carbon atoms and contains heteroatoms, or an organic group whose parent body has 2 to 7 carbon atoms and has a carboxyl group )

In the above-mentioned alkali-soluble resin A or B, it is preferable that the linking group of the above ^- mentioned R2 is a hydrocarbon group with a parent body having 1 to 10 carbon atoms, or an organic group with a parent body having 1 to 10 carbon atoms and containing heteroatoms.

In the above-mentioned alkali-soluble resin A or B, it is preferable that the organic group of the above ^- mentioned R4 is selected from the group consisting of acryloxy, methacryloxy, acyloxy, amidooxy, alkoxy, aryloxy , amine group, and an organic group with more than one functional group in the group consisting of nitrogen-containing heterocyclic rings.

In addition, in the above-mentioned alkali-soluble resin A or B, it is preferable that the linking group of the above ^- mentioned R2 is a hydrocarbon group whose parent body has 1 to 7 carbon atoms, or an organic group whose parent body has 1 to 7 carbon atoms and contains heteroatoms, and The above-mentioned R ⁴ is a hydroxyl group, an acryloxy group, or a methacryloxy group bonded to a carbon atom of the linking group of the above-mentioned R ² .

（式中，R ⁶及R ⁷分別獨立地為母體之碳數為1～6之烴基，R ⁶及R ⁷之母體之合計碳數為3～8）

（式中，R ⁸為氫或甲基，R ⁹為母體之碳數為1～5之烴基、或母體之碳數為1～5且包含雜原子之有機基） In addition, in the above-mentioned alkali-soluble resin A or B, it is preferable that the linking group of the above ^- mentioned R2 is a hydrocarbon group whose parent body has 1 to 7 carbon atoms, or an organic group whose parent body has 1 to 7 carbon atoms and contains heteroatoms. R ⁵ or the above R ^5' is an organic group represented by the following general formula (3), and the above R ⁴ is a hydroxyl group, acryloxy group, methacryl group bonded to the carbon atom of the linking group of the above R ² an acyloxy group, or an organic group represented by the following general formula (4).

(In the formula, R ⁶ and R ⁷ are independently a hydrocarbon group whose parent body has 1 to 6 carbon atoms, and the total carbon number of the parent body of R ⁶ and R ⁷ is 3 to 8)

(In the formula, R ⁸ is hydrogen or methyl, R ⁹ is a hydrocarbon group whose parent has 1 to 5 carbons, or an organic group whose parent has 1 to 5 carbons and contains heteroatoms)

In the above-mentioned alkali-soluble resin A or B, the content of the above-mentioned repeating structural unit X or X' is preferably 5 to 50 mol% in all repeating structural units.

The above-mentioned alkali-soluble resin A or B preferably has an acid value of 20 to 120 mgKOH/g.

The above-mentioned alkali-soluble resin A or B preferably has a weight average molecular weight of 5,000 to 40,000.

The photosensitive resin composition of the present invention contains at least the above-mentioned alkali-soluble resin A and/or B, a polymerizable monomer, and a photopolymerization initiator.

The cured product of the present invention is obtained from the above photosensitive resin composition.

The cured product is preferably an optical spacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material.

Also, the present invention relates to an image display device including the above-mentioned cured product. [Effect of Invention]

The main feature of the alkali-soluble resin A or B of the present invention is that it has the following structure: it contains more than one repeating structural unit X or X' represented by the above-mentioned general formula (1) or (1'), and the above-mentioned repeating structural unit X or X In ', the length of the side chain is not less than a certain length, and there is a carboxyl group at the end of the side chain. The alkali-soluble resin A or B of this invention can obtain the cured film excellent in image development adhesiveness and resolution even when it thickens a film by having the structure of this characteristic. In addition, the alkali-soluble resin A or B of the present invention has a hydroxyl group or an organic group bonded to the carbon atom of the linking group R ² , so it can further have characteristics derived from these groups. Also, since the photosensitive resin composition comprising the alkali-soluble resin A and/or B of the present invention can be developed in a short time even when using a weakly alkaline developing solution, it can improve the hardness of cured products such as photo-spacers. productive. In particular, when the above-mentioned R ⁴ is an organic group, the alkali-soluble resin A or B of the present invention has a branched side chain structure, so even when the film is thickened, it can obtain excellent adhesiveness and resolution for development. hardened film. The reason for this is not bound by theory, but it is believed that the carboxyl group at the end tends to face the direction opposite to the main chain because the above-mentioned R ³ or R ^3' is relatively long (more atoms) , so the number of carboxyl groups that can participate in the close contact with the substrate increases. Furthermore, the reason is considered to be that when the above-mentioned R ⁴ is an organic group, the side chain of the alkali-soluble resin A or B has a branched structure, so the carboxyl group at the end of the above-mentioned R ³ or R ^3' is more likely to be oriented opposite to the main chain In this direction, the number of carboxyl groups that can participate in the close contact with the substrate increases.

（式中，R ¹為氫或甲基，R ²為碳數為1以上之連結基，R ³為鍵結於上述連結基之碳原子之由下述通式（2）所表示之有機基，R ⁴為鍵結於上述連結基之碳原子之羥基或有機基）

（式中，R ⁵為母體之碳數為3～8且包含雜原子之有機基、或母體之碳數為2～7且具有羧基之有機基） The alkali-soluble resin A of the present invention contains one or more repeating structural units X represented by the following general formula (1).

(In the formula, R1 is hydrogen or ^a methyl group, R2 is a linking group with a carbon number of ¹ or more, and ^R3 is an organic group represented by the following general formula (2) bonded to the carbon atom of the linking group , R ⁴ is a hydroxyl group or an organic group bonded to the carbon atom of the above linking group)

(In the ^formula , R5 is an organic group whose parent has 3-8 carbon atoms and contains heteroatoms, or an organic group whose parent has 2-7 carbon atoms and has a carboxyl group)

（式中，R ¹為氫或甲基，R ²為碳數為1以上之連結基，R ^3'為鍵結於上述連結基之碳原子之由下述通式（2'）所表示之有機基，R ⁴為鍵結於上述連結基之碳原子之羥基或有機基）

（式中，R ^5'為母體之碳數為2～7之烴基、母體之碳數為3～8且包含雜原子之有機基、或母體之碳數為2～7且具有羧基之有機基） Also, the alkali-soluble resin B of the present invention includes one or more repeating structural units X' represented by the following general formula (1'), but does not include repeating structural units having branched side chains having each 2 to 3 ends ending in radically polymerizable substituents.

(In the formula, R ¹ is hydrogen or methyl, R ² is a linking group with a carbon number of 1 or more, and R ^3' is a carbon atom bonded to the above linking group represented by the following general formula (2') Organic group, ^R4 is a hydroxyl group or an organic group bonded to the carbon atom of the above linking group)

(wherein, R ^5' is a hydrocarbon group whose parent body has 2 to 7 carbon atoms, an organic group whose parent body has 3 to 8 carbon atoms and contains heteroatoms, or an organic group whose parent body has 2 to 7 carbon atoms and has a carboxyl group )

In the present invention, (meth)acrylic means propylene or methacrylic, (meth)acryl means acryl or methacryl, (meth)acrylic means acrylic or methacrylic, ( Meth)acrylate means acrylate or methacrylate. In addition, in the present invention, the carbon number of the matrix refers to the carbon number of the group serving as the main skeleton other than the substituent.

In the above-mentioned general formula (1) or (1'), the above-mentioned R ² is a linking group with a carbon number of 1 or more, which is not particularly limited, as long as the above-mentioned R ³ and the above-mentioned R ⁴ , or the above-mentioned R ^3' and The above-mentioned R ⁴ is linked to the oxygen atom of the ester bond and has a carbon number of 1 or more. Examples of the linking group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridged rings and condensed rings), aromatic Hydrocarbon groups, organic groups in which part of the carbon atoms constituting the above-mentioned hydrocarbon groups are replaced by heteroatoms (such as oxygen atoms, nitrogen atoms, and sulfur atoms, etc.), and organic groups in which two or more of these are bonded together. Moreover, the above-mentioned hydrocarbon group or the above-mentioned organic group may have various substituents (such as halogen, hydroxyl, carboxyl, amino, alkyl, alkenyl, alkoxy, and aryl, etc.) or functional groups (such as ester bonds, amide groups, etc.) bond, ether bond, thioether bond, and urethane bond, etc.).

The above-mentioned linking group is preferably a hydrocarbon group whose parent body has 1 to 10 carbon atoms, or an organic group whose parent body has 1 to 10 carbon atoms and contains heteroatoms (such as oxygen atoms, nitrogen atoms, and sulfur atoms, etc.). Moreover, the above-mentioned linking group is more preferably a hydrocarbon group with a parent body having 1 to 7 carbon atoms, or an organic group with a parent body having 1 to 7 carbon atoms and containing heteroatoms (such as oxygen atoms, nitrogen atoms, and sulfur atoms, etc.). Furthermore, when the above-mentioned linking group contains heteroatoms, the heteroatoms of the above-mentioned linking group exist in the above-mentioned general formula (1) or (1') in "except for the bond with the above-mentioned R ³ or R ^3' part", "a part other than the bonded part with the above ^- mentioned R4", and "a part other than the bonded part with the oxygen atom of the ester bond". Moreover, the above-mentioned linking group is further preferably a straight-chain or branched aliphatic saturated or unsaturated hydrocarbon group whose parent body has 2 to 7 carbon atoms, or an alicyclic saturated or unsaturated hydrocarbon group whose parent body has 3 to 7 carbon atoms. Hydrocarbyl, the carbon number of the parent is 4 to 7 and the hydrocarbon group formed by the bonding of methylene and alicyclic saturated or unsaturated hydrocarbon group, the carbon number of the parent is 5 to 7 and a straight-chain or branched aliphatic saturated Or a hydrocarbon group in which an unsaturated hydrocarbon group is bonded to an alicyclic saturated or unsaturated hydrocarbon group, or an organic group whose parent body has 2 to 7 carbon atoms and contains an ether bond.

In the above-mentioned general formula (1), the above-mentioned R ³ is an organic group represented by the above-mentioned general formula (2) that is bonded to the carbon atom of the linking group of the above-mentioned R ² . In the above-mentioned general formula (2), the above-mentioned R ⁵ is an organic group whose parent body has 3-8 carbon atoms and contains heteroatoms (such as oxygen atom, nitrogen atom, and sulfur atom, etc.), or the parent body has 2-7 carbon atoms. And an organic group with a carboxyl group. The above-mentioned R ⁵ is preferably an organic group with a parent having 2 to 7 carbon atoms and a carboxyl group. When the above-mentioned R ⁵ has a carboxyl group, the number of carboxyl groups is not particularly limited, but is preferably 1-2. The above-mentioned organic groups may have various substituents (such as halogen, hydroxyl, carboxyl, amino, alkyl, alkenyl, alkoxy, and aryl, etc.) or functional groups (such as ester bond, amide bond, ether bond, thioether bond, and urethane bond, etc.).

The organic group represented by the above general formula (2) is preferably any one of the following organic groups.

In the above-mentioned general formula (1'), the above-mentioned R ^3' is an organic group represented by the above-mentioned general formula (2') that is bonded to the carbon atom of the linking group of the above-mentioned R ² . In the above-mentioned general formula (2'), the above-mentioned R ^5' is a hydrocarbon group whose parent body has 2-7 carbon atoms, and the parent body has 3-8 carbon atoms and contains heteroatoms (such as oxygen atoms, nitrogen atoms, and sulfur atoms, etc.) The organic group, or the carbon number of the parent is 2 to 7 and has a carboxyl organic group. The above-mentioned R ^5' is preferably a hydrocarbon group whose parent body has 2 to 7 carbon atoms, or an organic group whose parent body has 2 to 7 carbon atoms and has a carboxyl group. When the above-mentioned R ^5' has a carboxyl group, the number of carboxyl groups is not particularly limited, but is preferably 1-2. Examples of the aforementioned hydrocarbon group include linear or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridging rings and condensed rings), aromatic hydrocarbon groups, and the like. A hydrocarbon group formed by bonding two or more types. The above-mentioned hydrocarbon groups or the above-mentioned organic groups may have various substituents (such as halogen groups, hydroxyl groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups, etc.) or functional groups (such as ester bonds, amide bonds, Ether bond, thioether bond, and urethane bond, etc.).

The organic group represented by the above general formula (2') is preferably any one of the following organic groups.

（式中，R ⁶及R ⁷分別獨立地為母體之碳數為1～6之烴基，R ⁶及R ⁷之母體之合計碳數為3～8） In addition, in the above-mentioned general formula (2) or (2'), it is preferable that the above-mentioned R ⁵ or R ^5' is an organic group represented by the following general formula (3).

(In the formula, R ⁶ and R ⁷ are independently a hydrocarbon group whose parent body has 1 to 6 carbon atoms, and the total carbon number of the parent body of R ⁶ and R ⁷ is 3 to 8)

As said hydrocarbon group, a linear or branched aliphatic saturated or unsaturated hydrocarbon group, an aromatic hydrocarbon group, an alicyclic saturated or unsaturated hydrocarbon group, etc. are mentioned. The above-mentioned hydrocarbon group may have various substituents (for example, a halogen group, a hydroxyl group, a carboxyl group, an amino group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, and the like).

As an example of the organic group represented by the said general formula (3), the following organic group is mentioned.

Preferably, the above-mentioned R ⁶ and R ⁷ are each independently a hydrocarbon group whose parent body has 1-5 carbon atoms, and the total carbon number of the parent body of R ⁶ and R ⁷ is 3-7.

The organic group represented by the above general formula (2) or (2') is preferably any one of the following organic groups.

In the above-mentioned general formula (1) or (1′), the above-mentioned R ⁴ is a hydroxyl group or an organic group bonded to a carbon atom of the linking group of the above-mentioned R ² . When the above-mentioned R ⁴ is a hydroxyl group, developability can be further improved. Also, when the above-mentioned R ⁴ is an organic group, properties derived from the organic group (such as developability, adhesiveness, and solubility, etc.) can be further imparted. The above-mentioned organic groups are not particularly limited, for example, straight-chain or branched aliphatic saturated or unsaturated hydrocarbon groups, alicyclic saturated or unsaturated hydrocarbon groups (including bridging rings, condensed rings), aromatic hydrocarbon groups . An organic group in which a part of the carbon atoms constituting the above-mentioned hydrocarbon group is replaced by a heteroatom (such as an oxygen atom, a nitrogen atom, and a sulfur atom, etc.), and an organic group in which two or more of these are bonded together, etc. Moreover, the above-mentioned hydrocarbon group or the above-mentioned organic group may have various substituents (such as halogen, hydroxyl, carboxyl, amino, alkyl, alkenyl, alkoxy, and aryl, etc.) or functional groups (such as ester bonds, amide groups, etc.) bond, ether bond, thioether bond, and urethane bond, etc.).

（式中，R ¹⁰及R ¹¹分別獨立地為段落[0039]所記載之有機基） ^The organic group of the above-mentioned R preferably comprises a group selected from acryloxy, methacryloxy, acyloxy, amidooxy, alkoxy, aryloxy, amino, and nitrogen-containing heterocycles. The organic group of one or more functional groups in the group is more preferably an acryloxy group, a methacryloxy group, or an organic group represented by any one of the following formulas.

(In the formula, R ¹⁰ and R ¹¹ are independently the organic groups described in paragraph [0039])

（式中，R ⁸為氫或甲基，R ⁹為母體之碳數為1～5之烴基、或母體之碳數為1～5且包含雜原子之有機基） Also, the above-mentioned R ⁴ is preferably a hydroxyl group bonded to a carbon atom of the linking group of the above-mentioned R ² , an acryloxy group, a methacryloxy group, or an organic group represented by the following general formula (4).

(In the formula, R ⁸ is hydrogen or methyl, R ⁹ is a hydrocarbon group whose parent has 1 to 5 carbons, or an organic group whose parent has 1 to 5 carbons and contains heteroatoms)

In the above-mentioned general formula (4), the above-mentioned R ⁹ is a hydrocarbon group whose parent body has 1 to 5 carbon atoms, or a hydrocarbon group whose parent body has 1 to 5 carbon atoms and contains heteroatoms (such as oxygen atoms, nitrogen atoms, and sulfur atoms, etc.) Organic based. Furthermore, when the above-mentioned organic group contains heteroatoms, the heteroatoms of the above-mentioned organic group exist in "parts other than the bonding part of the nitrogen atom bonded to the urethane" in the above-mentioned general formula (4). , and "parts other than the bonded part with the oxygen atom of (meth)acryloxy group". As said hydrocarbon group, a linear or branched aliphatic saturated or unsaturated hydrocarbon group is mentioned. The above-mentioned hydrocarbon groups or the above-mentioned organic groups may have various substituents (such as halogen groups, hydroxyl groups, carboxyl groups, amino groups, alkyl groups, alkenyl groups, alkoxy groups, and aryl groups, etc.) or functional groups (such as ester bonds, amide bonds, Ether bond, thioether bond, and urethane bond, etc.). The above-mentioned R ⁹ is preferably a hydrocarbon group whose parent has 1 to 5 carbon atoms, more preferably an ethylidene group or a propylidene group.

Examples of monomers that form the basis of repeating structural units other than the repeating structural unit X or X' constituting the above-mentioned alkali-soluble resin A or B include: (meth)acrylic acid, 2-(meth)acryl Carboxyl-containing monomers such as oxyethylsuccinic acid, maleic acid, and itaconic acid; carboxylic anhydride-containing monomers such as maleic anhydride and itaconic anhydride; methyl (meth)acrylate, ( Ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, benzyl (meth)acrylate, lauryl (meth)acrylate, hydroxyethyl (meth)acrylate, (meth)acrylate Alkyl (meth)acrylates such as hydroxypropyl acrylate, ethoxyethyl (meth)acrylate, and glycidyl (meth)acrylate; cyclohexyl (meth)acrylate, (meth)acrylate ) isocamphoryl acrylate, and alicyclic (meth)acrylates such as dicyclopentenyl (meth)acrylate, and the like. In addition, styrene, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, n-butylmaleimide, and n-butylmaleimide can be used. Diene imide, laurylmaleimide, polysiloxane-containing monomer, etc. are used as comonomers. These monomers may be used alone or in combination of two or more.

However, the above-mentioned alkali-soluble resin B does not contain a repeating structural unit (hereinafter also referred to as "repeating structural unit Y") having a branched side chain having 2 to 3 substituents each terminated with a radically polymerizable substituent. ends. The above-mentioned repeating structural unit Y is the monomer unit (1) described in International Publication No. 2018/169036. Specifically, each of the above-mentioned free radically polymerizable substituents is substituted on the hydrocarbon chain (L), for example, the hydrocarbon chain (L) is bonded to the main chain of the polymer, for example, via a -COO- group. The number of carbons constituting the hydrocarbon chain (L) is, for example, 3 to 5, 3 or 4, or 3. The above radical polymerizable substituent is, for example, a (meth)acryloyloxy group.

Alkali-soluble resin A or B of the present invention can be synthesized, for example, by the following method (1) or method (2): method (1) is to make carboxyl-containing compounds and "(meth)acrylic acid containing epoxy groups Polymers with epoxy groups in the side chains obtained by polymerizing ester monomer compositions are converted into side chains with hydroxyl groups, and then the carboxylic anhydride is reacted with the above hydroxyl groups; Compounds with saturated groups and carboxyl groups react with "polymers having epoxy groups in side chains obtained by polymerizing monomer compositions containing epoxy-containing (meth)acrylates" to convert them into hydroxyl and vinyl compounds. The side chain of the unsaturated group, and then react the compound with the functional group such as isocyanate group and the hydroxyl group to react with the above-mentioned hydroxyl group, and then make the compound having the "hydroxyl group, thiol group, and amino group, etc., react with the ethylenically unsaturated group "functional group and carboxyl" compound reacts with the above-mentioned ethylenically unsaturated group.

The above-mentioned alkali-soluble resin A or B may be a homopolymer composed of the above-mentioned repeating structural unit X or X', and may also be a random copolymer composed of the above-mentioned repeating structural unit X or X' and other repeating structural units. compounds, block copolymers, alternating copolymers, or periodic copolymers.

In the above-mentioned alkali-soluble resin A or B, the content of the above-mentioned repeating structural unit X or X' is not particularly limited, and it is based on the viewpoint of forming a cured film excellent in developing adhesion and resolution even in the case of thickening the film, and even if From the viewpoint of being able to develop in a short time when using a weak alkaline developing solution, it is preferably 5-50 mol%, more preferably 5-25 mol% in all repeating structural units.

The weight average molecular weight of the alkali-soluble resin A or B is not particularly limited, but is preferably 5,000-40,000, more preferably 5,000-20,000 from the viewpoint of sensitivity and developability. The above-mentioned weight average molecular weight is a value in terms of polystyrene measured using gel permeation chromatography (GPC), and is a value measured based on JIS 7252-4. The weight-average molecular weight described in the Examples described later is also a value obtained from the description in this section.

The acid value of the above-mentioned alkali-soluble resin A or B is not particularly limited, and it is preferably 20-120 mgKOH/g, more preferably from the viewpoint that it can be developed in a short time even when a weak alkaline developer is used. It is 20-80 mgKOH/g.

The photosensitive resin composition of the present invention contains at least the above-mentioned alkali-soluble resin A and/or B, a polymerizable monomer, and a photopolymerization initiator.

The content ratio of the above-mentioned alkali-soluble resin A and/or B to the content of all solids in the above-mentioned photosensitive resin composition (total in the case of combined use) is not particularly limited, and is based on the fact that even in the case of thickening the film From the viewpoint of forming a cured film with excellent adhesion and resolution, and from the viewpoint of being able to develop in a short time even when a weak alkaline developer is used, it is usually about 40 to 90% by mass, preferably 40 to 80% by mass, more preferably 50 to 70% by mass.

The aforementioned polymerizable monomers are not particularly limited, and examples include: nonylphenylcarbitol (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, 2-ethyl Monofunctional monomers such as hexyl carbitol (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and N-vinylpyrrolidone; divinylbenzene, diallyl phthalate, and Diallyl benzene phosphonate and other polyfunctional aromatic vinyl monomers; (2) ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, trimethylolpropane Di(meth)acrylate, trimethylolpropane tri(meth)acrylate, neopentylthritol di(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra (Meth)acrylates, diperythritol di(meth)acrylates, diperythritol tri(meth)acrylates, diperythritol tetra(meth)acrylates, diperythritol tetra(meth)acrylates, Multi-functional (meth)acrylates such as alcohol penta(meth)acrylate, dipenteoerythritol hexa(meth)acrylate, and tri(meth)acrylate of ginseng (hydroxyethyl)isocyanurate and other multifunctional monomers. These polymerizable monomers may be used alone or in combination of two or more.

The content of the above-mentioned polymerizable monomer is not particularly limited, and from the viewpoint of sufficiently obtaining the effects of the present invention, it is preferably 30 parts by mass relative to 100 parts by mass of the above-mentioned alkali-soluble resin A and/or B (total when used in combination). -100 mass parts, More preferably, it is 40-80 mass parts, More preferably, it is 50-70 mass parts.

、2,4-二異丙基9-氧硫

、2-氯9-氧硫

等9-氧硫

類；苯乙酮二甲基縮酮、二苯乙二酮二甲基縮酮等縮酮類；二苯甲酮等二苯甲酮類；2-甲基-1-[4-(甲硫基)苯基]-2-

啉基-丙烷-1-酮或2-苄基-2-二甲胺基-1-(4-

啉基苯基)-丁酮-1；醯基氧化膦類及

酮類等。該等光聚合起始劑可單獨使用，亦可併用兩種以上。The above-mentioned photopolymerization initiator is not particularly limited, for example, benzoin, benzoin methyl ether, benzoin ether and other benzoin and its alkyl ethers; acetophenone, 2,2-dimethoxy-2-phenyl Acetophenones such as acetophenone and 1,1-dichloroacetophenone; anthraquinones such as 2-methylanthraquinone, 2-amylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone Class; 2,4-dimethyl 9-oxosulfur

, 2,4-Diisopropyl 9-oxosulfur

, 2-chloro 9-oxysulfur

9-oxosulfur

ketals such as acetophenone dimethyl ketal and diphenyl ketone dimethyl ketal; benzophenones such as benzophenone; 2-methyl-1-[4-(methylsulfide Base) phenyl] -2-

Linyl-propan-1-one or 2-benzyl-2-dimethylamino-1-(4-

Linylphenyl)-butanone-1; Acylphosphine oxides and

Ketones etc. These photopolymerization initiators may be used alone or in combination of two or more.

The content of the above-mentioned photopolymerization initiator is not particularly limited, but it is preferably 0.1 to 5 parts by mass, more preferably 0.2-4 mass parts, More preferably, it is 0.5-3 mass parts.

A photopolymerization start aid may also be added to the above-mentioned photosensitive resin composition. Examples of photopolymerization initiation aids include: 1,3,5-paraffin(3-mercaptopropionyloxyethyl)isocyanurate, 1,3,5-paraffin(3-mercapto Trifunctional thiol compounds such as butoxyethyl) ester (manufactured by Showa Denko, Karenz MT (registered trademark) NR1), trimethylolpropane (3-mercaptopropionate); -Mercaptopropionate), neopentylthritol tetrakis (3-mercaptobutyrate) (manufactured by Showa Denko, Karenz MT (registered trademark) PEI) and other tetrafunctional thiol compounds; propionate) and other polyfunctional thiols such as hexafunctional thiol compounds. These photopolymerization start aids may be used individually, and may use 2 or more types together.

A thermal polymerization initiator can also be added to the said photosensitive resin composition. Examples of thermal polymerization initiators include cumene hydroperoxide, dicumyl peroxide, di-tert-butyl peroxide, lauryl peroxide, benzoyl peroxide, and cumene peroxide. Organic peroxides such as tert-butyl carbonate, tert-butyl peroxide (2-ethylhexanoate), tertiary pentyl peroxide; 2,2'-azobis (isobutyronitrile), 1,1'-azobis (cyclohexanecarbonitrile) (1,1'-azobis (cyclohexanecarbonitrile)), 2,2'- azobis (2,4-dimethylvaleronitrile ), 2,2'-azobis(2-methylpropionate) dimethyl ester and other azo compounds, etc. These thermal polymerization initiators may be used alone or in combination of two or more.

Radical polymerizable oligomers such as unsaturated polyesters, epoxy acrylates, urethane acrylates, and polyester acrylates; hardening resins such as epoxy resins may also be added to the photosensitive resin composition.

烷、乙二醇二甲醚、二乙二醇二甲醚等醚類；丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮類；乙酸乙酯、乙酸丁酯、丙二醇單甲醚乙酸酯、乙酸3-甲氧基丁酯等酯類；甲醇、乙醇、異丙醇、正丁醇、乙二醇單甲醚、丙二醇單甲醚等醇類；甲苯、二甲苯、乙基苯等芳香族烴類；氯仿、二甲基亞碸等。該等溶劑可單獨使用，亦可併用兩種以上。再者，溶劑之含量根據使用該組成物時之最佳黏度適當地設定即可。The above-mentioned photosensitive resin composition may also contain a solvent. As a solvent, for example, tetrahydrofuran, di

Alkanes, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and other ethers; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones; ethyl acetate, butyl acetate, Propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate and other esters; methanol, ethanol, isopropanol, n-butanol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether and other alcohols; toluene, di Aromatic hydrocarbons such as toluene and ethylbenzene; Chloroform, dimethyl sulfide, etc. These solvents may be used alone or in combination of two or more. Furthermore, the content of the solvent may be appropriately set according to the optimum viscosity when using the composition.

The above-mentioned photosensitive resin composition may also contain fillers such as aluminum hydroxide, talc, clay, barium sulfate, dyes, pigments, defoamers, coupling agents, leveling agents, sensitizers, etc. within the range that does not impair the effects of the present invention. Known additives such as additives, mold release agents, lubricants, plasticizers, antioxidants, ultraviolet absorbers, flame retardants, polymerization inhibitors, tackifiers, and dispersants.

The cured product of the present invention can be obtained by curing the aforementioned photosensitive resin composition. As a method for producing the above-mentioned cured product, for example, the method of injecting the above-mentioned photosensitive resin composition into a molding die (resin mold), or coating the above-mentioned photosensitive resin composition on a base material (substrate) or various functional layer, formed into a desired shape, and then irradiated with light (such as ultraviolet rays) to harden the above-mentioned photosensitive resin composition. Curing conditions are appropriately adjusted according to the above-mentioned photosensitive resin composition used.

The cured product described above can be suitably used as a photo-spacer, partition wall material, lens material, interlayer insulating film material, protective film material, optical waveguide material, or planarizing film material, especially as a photo-spacer.

The method of forming the photo-spacer is not particularly limited. For example, the above-mentioned photosensitive resin composition can be coated on a substrate such as glass or transparent plastic film, dried to form a coating film, and then formed by photolithography. . In the photolithography method, for example, a photomask is placed on the coating film, and ultraviolet rays are irradiated to harden the coating film, and an alkaline solution is spread on the coating film after ultraviolet irradiation to dissolve and remove the unexposed part, and the remaining The exposed portion was washed with water and developed to form a photo-spacer. Thereafter, post-baking may be performed.

By using the photosensitive resin composition of the present invention, it is possible to manufacture a photo-spacer with a film thickness of 10 μm or more, 20 μm or more, 30 μm or more, and furthermore, 50 μm or more with high development adhesion and high resolution. Moreover, by using the photosensitive resin composition of this invention, the photo-spacer whose aspect ratio is 4.0 or more can be manufactured. Moreover, since the photosensitive resin composition of this invention can develop in a short time even when using weak alkaline developing solution, it can manufacture a photo-spacer with good productivity. [Example]

Hereinafter, although an Example is given and demonstrated to this invention, this invention is not limited by these Examples at all.

向具備加熱冷卻/攪拌裝置、回流冷凝管、及氮氣導入管之玻璃製燒瓶加入甲基丙烯酸環氧丙酯100 g、及丙二醇單甲醚乙酸酯212 g。用氮氣置換系統內之氣相部分，然後添加2,2'-偶氮雙(2,4-二甲基戊腈)17 g，於80℃進行加熱，於同一溫度反應8小時。向所獲得之溶液進而添加丙烯酸53.2 g、三苯基膦1.0 g、對苯二酚0.02 g、及丙二醇單甲醚乙酸酯6.0 g，於100℃反應16小時。反應後，向反應溶液進而添加琥珀酸酐3.7 g、及丙二醇單甲醚乙酸酯13.0 g，於65℃反應6小時，從而獲得包含45質量%鹼可溶性樹脂1之溶液。藉由GPC進行分子量測定，結果鹼可溶性樹脂1之重量平均分子量（Mw）為7,000。再者，分子量之測定係藉由凝膠滲透層析儀（東曹公司製造，產品編號：HLC-8120，管柱：G-5000HXL及G-3000HXL兩者連結，檢測器：RI，流動相：四氫呋喃）進行。以下亦以相同之方法測定重量平均分子量。又，鹼可溶性樹脂1之酸值為21 mgKOH/g。 [Synthesis Example 1] Synthesis of Alkali-Soluble Resin 1 Alkali-soluble resin 1 including the following repeating structural units A and X1 was synthesized by the following production method.

100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were charged into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube. After substituting the gas phase portion in the system with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80° C., and reacted at the same temperature for 8 hours. 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and it was made to react at 100 degreeC for 16 hours. After the reaction, 3.7 g of succinic anhydride and 13.0 g of propylene glycol monomethyl ether acetate were further added to the reaction solution, and reacted at 65° C. for 6 hours to obtain a solution containing 45% by mass of the alkali-soluble resin 1 . As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 1 was 7,000. Furthermore, the determination of the molecular weight is carried out by gel permeation chromatography (manufactured by Tosoh Corporation, product number: HLC-8120, column: G-5000HXL and G-3000HXL, detector: RI, mobile phase: THF). The weight average molecular weight is also measured by the same method below. Moreover, the acid value of the alkali-soluble resin 1 was 21 mgKOH/g.

[Synthesis Example 2] Synthesis of Alkali-Soluble Resin 2 Except that the addition amount of succinic anhydride added to the reaction solution was changed to 11.0 g, and the addition amount of propylene glycol monomethyl ether acetate was changed to 22.0 g, a compound containing 45% by mass of alkali-soluble Solution of Resin 2. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 2 was 7,000. In addition, the acid value of the alkali-soluble resin 2 was 54 mgKOH/g.

[Synthesis Example 3] Synthesis of Alkali-Soluble Resin 3 Except that the addition amount of succinic anhydride added to the reaction solution was changed to 18.5 g, and the addition amount of propylene glycol monomethyl ether acetate was changed to 31.0 g, a compound containing 45% by mass of alkali-soluble Solution of Resin 3. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 3 was 7,000. Moreover, the acid value of the alkali-soluble resin 3 was 66 mgKOH/g.

向具備加熱冷卻/攪拌裝置、回流冷凝管、及氮氣導入管之玻璃制燒瓶加入甲基丙烯酸環氧丙酯100 g、及丙二醇單甲醚乙酸酯150 g。用氮氣置換系統內之氣相部分，然後添加2,2'-偶氮雙(2,4-二甲基戊腈)5.2 g，於80℃進行加熱，於同一溫度反應8小時。向所獲得之溶液進而添加丙烯酸53.2 g、三苯基膦2.0 g、對苯二酚0.02 g、及丙二醇單甲醚乙酸酯1.0 g，於100℃反應7小時。反應後，向反應溶液進而添加琥珀酸酐11 g、及丙二醇單甲醚乙酸酯9.3 g，於65℃反應6小時，從而獲得包含52質量%鹼可溶性樹脂4之溶液。藉由GPC進行分子量測定，結果鹼可溶性樹脂4之重量平均分子量（Mw）為13,000。又，鹼可溶性樹脂4之酸值為51 mgKOH/g。 [Synthesis Example 4] Synthesis of Alkali-Soluble Resin 4 Alkali-soluble resin 4 including the following repeating structural units A and X1 was synthesized by the following production method.

100 g of glycidyl methacrylate and 150 g of propylene glycol monomethyl ether acetate were charged into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube. After substituting the gas phase in the system with nitrogen, 5.2 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80° C., and reacted at the same temperature for 8 hours. 53.2 g of acrylic acid, 2.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 1.0 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and it was made to react at 100 degreeC for 7 hours. After the reaction, 11 g of succinic anhydride and 9.3 g of propylene glycol monomethyl ether acetate were further added to the reaction solution, and reacted at 65° C. for 6 hours to obtain a solution containing 52% by mass of alkali-soluble resin 4 . As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 4 was 13,000. In addition, the acid value of the alkali-soluble resin 4 was 51 mgKOH/g.

向具備加熱冷卻/攪拌裝置、回流冷凝管、及氮氣導入管之玻璃制燒瓶加入甲基丙烯酸環氧丙酯100 g、及丙二醇單甲醚乙酸酯160 g。用氮氣置換系統內之氣相部分，然後添加2,2'-偶氮雙(2,4-二甲基戊腈)7.5 g，於80℃進行加熱，於同一溫度反應8小時。向所獲得之溶液進而添加丙烯酸53.2 g、三苯基膦0.3 g、及對苯二酚0.02 g，於100℃反應15小時。反應後，向反應溶液進而添加甲基丙烯酸2-異氰酸基乙酯（昭和電工公司製造，Karenz MOI）87 g、對苯二酚0.01 g、及N,N'-二甲基苄胺0.1 g，於65℃反應15小時。反應後，向反應溶液進而添加巰基乙酸26.0 g、丙二醇單甲醚乙酸酯50 g、對苯二酚0.003 g、對甲氧基苯酚（p-methoxyphenol）0.5 g、及N,N'-二甲基苄胺0.5 g，於70℃反應20小時，從而獲得包含50質量%鹼可溶性樹脂5之溶液。藉由GPC進行分子量測定，結果鹼可溶性樹脂5之重量平均分子量（Mw）為28,000。又，鹼可溶性樹脂5之酸值為59 mgKOH/g。 [Synthesis Example 5] Synthesis of Alkali-Soluble Resin 5 Alkali-soluble resin 5 including the following repeating structural units A, B, and X2 was synthesized by the following production method.

100 g of glycidyl methacrylate and 160 g of propylene glycol monomethyl ether acetate were charged into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube. After substituting the gas phase in the system with nitrogen, 7.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80° C., and reacted at the same temperature for 8 hours. 53.2 g of acrylic acid, 0.3 g of triphenylphosphine, and 0.02 g of hydroquinone were further added to the obtained solution, and it was made to react at 100 degreeC for 15 hours. After the reaction, 87 g of 2-isocyanatoethyl methacrylate (manufactured by Showa Denko, Karenz MOI), 0.01 g of hydroquinone, and 0.1 g of N,N'-dimethylbenzylamine were further added to the reaction solution. g, reacted at 65°C for 15 hours. After the reaction, 26.0 g of thioglycolic acid, 50 g of propylene glycol monomethyl ether acetate, 0.003 g of hydroquinone, 0.5 g of p-methoxyphenol, and N,N'-dimethoxyphenol were further added to the reaction solution. 0.5 g of methylbenzylamine was reacted at 70° C. for 20 hours to obtain a solution containing 50 mass % of alkali-soluble resin 5 . As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 5 was 28,000. Moreover, the acid value of the alkali-soluble resin 5 was 59 mgKOH/g.

向具備加熱冷卻/攪拌裝置、回流冷凝管、及氮氣導入管之玻璃製燒瓶加入甲基丙烯酸環氧丙酯100 g、及丙二醇單甲醚乙酸酯212 g。用氮氣置換系統內之氣相部分，然後添加2,2'-偶氮雙(2,4-二甲基戊腈)17 g，於80℃進行加熱，於同一溫度反應8小時。向所獲得之溶液進而添加丙烯酸53.2 g、三苯基膦1.0 g、對苯二酚0.02 g、及丙二醇單甲醚乙酸酯6.0 g，於100℃反應16小時。反應後，向反應溶液進而添加5-降莰烯-2,3-二羧酸酐18.2 g、及丙二醇單甲醚乙酸酯31.0 g，於65℃反應19小時，從而獲得包含45質量%鹼可溶性樹脂6之溶液。藉由GPC進行分子量測定，結果鹼可溶性樹脂6之重量平均分子量（Mw）為8,000。又，鹼可溶性樹脂6之酸值為58 mgKOH/g。 [Synthesis Example 6] Synthesis of Alkali-Soluble Resin 6 Alkali-soluble resin 6 comprising the following repeating structural units A and X3 was synthesized by the following production method.

100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were charged into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube. After substituting the gas phase portion in the system with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80° C., and reacted at the same temperature for 8 hours. 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and it was made to react at 100 degreeC for 16 hours. After the reaction, 18.2 g of 5-norbornene-2,3-dicarboxylic anhydride and 31.0 g of propylene glycol monomethyl ether acetate were further added to the reaction solution, and reacted at 65° C. for 19 hours to obtain an alkali-soluble compound containing 45% by mass. Solution of Resin 6. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 6 was 8,000. Moreover, the acid value of alkali-soluble resin 6 was 58 mgKOH/g.

[Synthesis Example 7] Synthesis of Alkali-Soluble Resin 7 Put 25.0 g of methacrylic acid, 12.8 g of methyl methacrylate, 20.2 g of dicyclopentyl methacrylate, and propylene glycol monomethyl ether into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube After adding 94.6 g of acetate, 6.4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and it was made to react at 80 degreeC under nitrogen atmosphere for 8 hours. 12.3 g of glycidyl methacrylate, 0.2 g of hydroquinone, and 2.5 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and reacted at 100° C. for 19 hours to obtain an alkali-soluble resin containing 45 mass % 7 solution. As a result of molecular weight measurement by GPC, the weight average molecular weight (Mw) of alkali-soluble resin 7 was 11,800. In addition, the acid value of the alkali-soluble resin 7 was 107 mgKOH/g.

[Synthesis Example 8] Synthesis of Alkali-Soluble Resin 8 Add 25.0 g of methacrylic acid, 22.6 g of methyl methacrylate, 18.4 g of butyl methacrylate, and propylene glycol monomethyl ether acetic acid into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube After adding 99.0 g of ester, 5.6 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and it was made to react at 80 degreeC under nitrogen atmosphere for 8 hours. 18.4 g of glycidyl methacrylate, 0.2 g of hydroquinone, and 4.3 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and reacted at 100° C. for 19 hours to obtain an alkali-soluble compound containing 45% by mass. Solution of Resin 8. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 8 was 10,800. In addition, the acid value of alkali-soluble resin 8 was 106 mgKOH/g.

[Synthesis Example 9] Synthesis of Alkali-Soluble Resin 9 100 g of glycidyl methacrylate and 212 g of propylene glycol monomethyl ether acetate were charged into a glass flask equipped with a heating/cooling/stirring device, a reflux condenser, and a nitrogen introduction tube. After substituting the gas phase portion in the system with nitrogen, 17 g of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, heated at 80° C., and reacted at the same temperature for 8 hours. 53.2 g of acrylic acid, 1.0 g of triphenylphosphine, 0.02 g of hydroquinone, and 6.0 g of propylene glycol monomethyl ether acetate were further added to the obtained solution, and reacted at 100° C. for 12 hours to obtain a base containing 44% by mass. Solution of soluble resin 9. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 9 was 9,000. In addition, the acid value of alkali-soluble resin 9 was 12 mgKOH/g.

[Synthesis Example 10] Synthesis of Alkali-Soluble Resin 10 Add 14.2 g of 1,2,4-benzenetricarboxylic anhydride instead of 18.2 g of 5-norbornene-2,3-dicarboxylic anhydride, change the amount of propylene glycol monomethyl ether acetate from 31.0 g to 26.2 g, and Other than that, the solution containing the alkali-soluble resin 10 of 45 mass % was obtained by the manufacturing method similar to the synthesis example 6. As a result of measuring the molecular weight by GPC, the weight average molecular weight (Mw) of the alkali-soluble resin 10 was 16,000. Moreover, the acid value of the alkali-soluble resin 10 was 62 mgKOH/g.

Examples 1-7, and Comparative Examples 1-3 [Preparation of photosensitive resin composition] 100 parts by mass of the above solution containing 45% by mass of alkali-soluble resin 1, 60 parts by mass of diperythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA), and a photopolymerization initiator (manufactured by LAMBSON, SPEEDCURE TPO) were mixed. ) 1.6 parts by mass, photopolymerization initiator (BASF Japan Co., Ltd., Irgacure OXE01) 1.0 parts by mass, and surfactant (manufactured by BYK, BYK-307) 0.2 parts by mass, the solid content in the prepared composition was 50 % of the photosensitive resin composition (embodiment 1). The solid matter in the composition was prepared in the same manner as above, except that 100 parts by mass of each of the above-mentioned solutions containing 2 to 10 mass % of the above-mentioned alkali-soluble resin was used instead of 100 parts by mass of the above-mentioned solution containing 45 mass % of alkali-soluble resin 1 50% photosensitive resin composition (Examples 2-7 and Comparative Examples 1-3).

[Evaluation of developability] Using a spin coater, the photosensitive resin compositions prepared in Examples 1 to 7 and Comparative Examples 1 to 3 were coated on glass substrates of 10 cm x 10 cm square to form For a coating film with a film thickness of 30 μm, heat the coating film on a hot plate at 90°C for 2 minutes to completely remove the solvent. Thereafter, the obtained coating film was subjected to alkaline development using a 0.3% Na ₂ CO ₃ aqueous solution, and the time taken for the coating film to be dissolved and removed was regarded as the shortest developing time to evaluate developability. It is considered that the smaller this value is, the more excellent the developability is. Grades are assigned based on the following criteria. A: The shortest developing time is within 60 seconds B: The shortest developing time exceeds 60 seconds and is within 80 seconds C: The shortest developing time exceeds 80 seconds and is within 100 seconds F: The shortest developing time exceeds 100 seconds

[Production of Photo-Spacer] Using a spin coater, adjust the rotation speed of the spin coater so that the height of the photo-spacer after formation becomes 30 μm. Prepared in Examples 1-7 and Comparative Examples 1-3 Each photosensitive resin composition was coated on each glass substrate of 10 cm×10 cm square to form a coating film respectively, and each coating film was heated on a heating plate at 100°C for 2 minutes to completely remove the solvent. Thereafter, each of the obtained coating films was passed through a photomask for forming a photo-spacer having 100 openings per 1 cm ² with a gradation of 1 μm in the range of 4 to 30 μm in diameter. 100 mJ/cm ² is irradiated with the light of the ultra-high pressure mercury lamp (the illuminance is 21 mW/cm ² in terms of i-line conversion). Furthermore, exposure was performed with a "gap between the mask and substrate (exposure gap)" of 100 μm. Thereafter, alkaline development was performed using a 0.3% Na ₂ CO ₃ aqueous solution. The developing time is 1.5 times of the shortest developing time measured by the above-mentioned method. After washing with water, post-baking was performed at 230° C. for 30 minutes to form a photo-spacer.

[Evaluation of developer adhesion] In the photo-spacer formed by the above method, the line width of the smallest pattern formed without being removed by development was evaluated as development adhesion. It is considered that the smaller this value is, the more excellent the image development adhesiveness is. Grades are assigned based on the following criteria. A: The smallest pattern is less than 15 μm B: The minimum pattern is more than 15 μm and less than 20 μm C: Minimum pattern is 20 μm or more F: Unable to develop

[Table 1] Alkali soluble resin Minimum developing time Developing Adhesiveness type Content of repeating structural unit X or X' (mole %) Weight average molecular weight Acid value (mgKOH/g) Example 1 1 5 7,000 twenty one B (70s) A (10 μm) Example 2 2 15 7,000 54 A (50s) A (8 μm) Example 3 3 25 7,000 66 B (70s) A (10 μm) Example 4 4 15 13,000 51 A (50s) A (8 μm) Example 5 5 40 28,000 59 B (70s) A (12 μm) Example 6 6 15 8,000 58 A (60s) A (8 μm) Example 7 10 10 16,000 62 B (80s) B (15 μm) Comparative example 1 7 0 11,800 107 F (230s) C (20μm) Comparative example 2 8 0 10,800 106 F (180s) C (20μm) Comparative example 3 9 0 9,000 12 F (>>400s) f

According to the results in Table 1, it can be seen that in the case of using a weakly alkaline developing solution when forming a thick film pattern with a pattern height of about 30 μm, compared with the photosensitive resin compositions of Comparative Examples 1 to 3, Examples 1 to 3 are more effective. The photosensitive resin composition of 7 can be developed in a short time, and can form a cured film with excellent adhesiveness after development. [Industrial availability]

The alkali-soluble resin of the present invention and the photosensitive resin composition containing the alkali-soluble resin can be suitably used as a photo-spacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planar The raw material of chemical film material.

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Claims (14)

An alkali-soluble resin comprising one or more repeating structural units X represented by the following general formula (1),

(In the formula, R1 is hydrogen or ^a methyl group, R2 is a linking group with a carbon number of ¹ or more, and ^R3 is an organic group represented by the following general formula (2) bonded to the carbon atom of the linking group , R ⁴ is a hydroxyl group or an organic group bonded to the carbon atom of the above linking group),

(In the formula, R ⁵ is an organic group whose parent has 3 to 8 carbon atoms and contains a heteroatom, or an organic group whose parent has 2 to 7 carbon atoms and has a carboxyl group). An alkali-soluble resin comprising one or more repeating structural units X' represented by the following general formula (1'), but excluding repeating structural units having branched side chains each having a free radical 2 to 3 ends of the end of the polymerizable substituent,

(In the formula, R ¹ is hydrogen or methyl, R ² is a linking group with a carbon number of 1 or more, and R ^3' is a carbon atom bonded to the above linking group represented by the following general formula (2') An organic group, R4 is a hydroxyl group or an organic group bonded to the carbon atom of the above ^- mentioned linking group),

(wherein, R ^5' is a hydrocarbon group whose parent body has 2 to 7 carbon atoms, an organic group whose parent body has 3 to 8 carbon atoms and contains heteroatoms, or an organic group whose parent body has 2 to 7 carbon atoms and has a carboxyl group ). The alkali-soluble resin according to claim 1 or ² , wherein the above-mentioned linking group of R2 is a hydrocarbon group whose parent body has 1 to 10 carbon atoms, or an organic group whose parent body has 1 to 10 carbon atoms and contains heteroatoms. The alkali-soluble resin according to any one of claim items 1 to ³ , wherein the organic group of the above-mentioned R4 is selected from the group consisting of acryloxy, methacryloxy, acyloxy, amidooxy, alkoxy An organic group with more than one functional group in the group consisting of aryloxy group, amine group, and nitrogen-containing heterocyclic ring. The alkali-soluble resin as claimed in claim 1 or ² , wherein the linking group of the above-mentioned R2 is a hydrocarbon group with a carbon number of 1 to 7 in the parent body, or an organic group with a carbon number in the parent body of 1 to 7 and containing heteroatoms, and the above-mentioned R ⁴ is a hydroxyl group, acryloxy group, or methacryloxy group bonded to the carbon atom of the linking group of R ² . The alkali-soluble resin according to claim ¹ , wherein the linking group of the above-mentioned R2 is a hydrocarbon group with a parent carbon number of 1-7, or an organic group with a parent carbon number of 1-7 and containing heteroatoms, and the above ^- mentioned R5 is An organic group represented by the following general formula ( ³ ), and the above-mentioned R4 is a hydroxyl group, an acryloxy group, a methacryloxy group bonded to the carbon atom of the linking group of the above ^- mentioned R2, or the following The organic group represented by the general formula (4),

(In the formula, R ⁶ and R ⁷ are independently a hydrocarbon group whose parent body has 1 to 6 carbon atoms, and the total carbon number of the parent body of R ⁶ and R ⁷ is 3 to 8),

(wherein, R ⁸ is hydrogen or methyl, and R ⁹ is a hydrocarbon group whose parent has 1 to 5 carbons, or an organic group whose parent has 1 to 5 carbons and contains heteroatoms). The alkali-soluble resin of claim 2, wherein the linking group of the above-mentioned R ² is a hydrocarbon group with a carbon number of 1 to 7 as a parent, or an organic group with a carbon number of 1 to 7 and containing heteroatoms, and the above R ^5' is an organic group represented by the following general formula ( ³ ), and the above-mentioned R4 is a hydroxyl group, an acryloxyl group, a methacryloxyl group that is bonded to the carbon atom of the linking group of the above ^- mentioned R2, or the following The organic group represented by general formula (4),

(In the formula, R ⁶ and R ⁷ are independently a hydrocarbon group whose parent body has 1 to 6 carbon atoms, and the total carbon number of the parent body of R ⁶ and R ⁷ is 3 to 8),

(wherein, R ⁸ is hydrogen or methyl, and R ⁹ is a hydrocarbon group whose parent has 1 to 5 carbons, or an organic group whose parent has 1 to 5 carbons and contains heteroatoms). The alkali-soluble resin according to any one of claims 1 to 7, wherein the content of the repeating structural unit X or X' is 5-50 mol% in all repeating structural units. The alkali-soluble resin according to any one of claims 1 to 8, wherein the acid value of the above-mentioned alkali-soluble resin is 20-120 mgKOH/g. The alkali-soluble resin according to any one of claims 1 to 9, wherein the weight average molecular weight of the above-mentioned alkali-soluble resin is 5,000-40,000. A photosensitive resin composition comprising at least the alkali-soluble resin according to any one of claims 1 to 10, a polymerizable monomer, and a photopolymerization initiator. A hardened product obtained from the photosensitive resin composition of claim 11. The cured product according to claim 12, wherein the cured product is a photospacer, a partition wall material, a lens material, an interlayer insulating film material, a protective film material, an optical waveguide material, or a planarizing film material. An image display device comprising the cured product of claim 12 or 13.