JP7406181B2 - Photosensitive resin composition - Google Patents

Description

The present invention relates to a photosensitive resin composition and a cured film obtained therefrom.
More specifically, the present invention relates to a photosensitive resin composition capable of forming an image having high water repellency and oil repellency on the surface of a cured film, a cured film thereof, and various materials using the cured film. This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in liquid crystal displays and EL displays, and as light-shielding materials and barrier rib materials compatible with inkjet systems.

2. Description of the Related Art In recent years, full-color display substrate manufacturing technology using inkjet has been actively studied in the manufacturing process of display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements. For example, in the production of color filters for liquid crystal display elements, in contrast to conventional printing, electrodeposition, dyeing, or pigment dispersion methods, sections defining pre-patterned pixels (hereinafter referred to as banks) are blocked from light. A color filter and a method for manufacturing the same (Patent Document 1) have been proposed, in which the color filter is formed of a photosensitive resin layer and ink droplets are dropped in an area surrounded by the banks. Furthermore, a method has been proposed (Patent Document 2) in which a bank is prepared in advance for an organic EL display element, and ink that becomes a light emitting layer is similarly dropped onto the bank to produce an organic EL display element.
However, when using the inkjet method to drop ink droplets into an area surrounded by banks, the substrate must have ink-philic properties (hydrophilicity, lipophilicity) to prevent ink droplets from overflowing beyond the bank and into neighboring pixels. In addition, the bank surface must be water and oil repellent.

In order to achieve the above objective, it is possible to make the substrate hydrophilic and the bank water repellent by continuous plasma treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment and UV ozone treatment. It has been proposed (Patent Document 3). In addition, a proposal has been made to incorporate a fluorine-based surfactant or a fluorine-based polymer into a photosensitive organic thin film (Patent Document 4), but consideration must be given to not only photosensitivity but also coating properties, such as compatibility and amount Not only is there a lot to be done, but the UV ozone treatment during hydrophilic treatment of the substrate reduces the water repellency of the surface, making it impractical.

On the other hand, conventionally, as a negative type liquid-repellent bank, there is JP-A No. 2015-172742 (Patent Document 5). Further, as a positive type, there is Japanese Patent Application Laid-Open No. 2012-220860 (Patent Document 6).

Japanese Patent Application Publication No. 2000-187111 Japanese Patent Application Publication No. 11-54270 Japanese Patent Application Publication No. 2000-353594 Japanese Unexamined Patent Publication No. 10-197715 Japanese Patent Application Publication No. 2015-172742 JP2012-220860A

The present invention was made in view of the above circumstances, and the problem to be solved is that the cured film surface even after UV ozone treatment is used in liquid crystal display elements, organic EL display elements, etc. The object of the present invention is to form an image of a cured film having high water repellency and high oil repellency, and having high lyophilicity on a substrate without plasma treatment or UV ozone treatment. In particular, the purpose of this invention is to form an image of a cured film that can prevent ink droplets from overflowing beyond a bank into an adjacent pixel when manufacturing a substrate using inkjet.

As a result of intensive studies to achieve the above object, the present inventors discovered that by forming a cured film from a composition containing a polysiloxane having an organic group having a fluorine atom and an organic group having a thermally crosslinkable group. They discovered that it is possible to efficiently impart liquid repellency to the membrane surface even after UV ozone treatment, and to efficiently impart high lyophilicity to the substrate without plasma treatment or UV ozone treatment, and have completed the present invention. .

That is, the present invention relates to the following.
1. A thermosetting photosensitive resin composition containing the following components (A), (B), (C) and (D).
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having a fluorine atom (A2) Organic group having a thermally crosslinkable group (B) Component: Alkali-soluble resin (C) Solvent ,
(D) Component: Photosensitizer.
2. (A2) The photosensitive resin composition as described in 1 above, wherein the organic group having a thermally crosslinkable group is an organic group having an epoxy group.
3. The photosensitive resin composition as described in 1 or 2 above, which satisfies at least one of the following (Z1) to (Z4).
(Z1): further contains a crosslinking agent as component (E),
(Z2): The alkali-soluble resin of component (B) further has a self-crosslinking group, or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. It also has.
(Z3): Component (D) is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as component (F).
(Z4): Component (D) is a photoacid generator, and further contains a compound having two or more functional groups that form a covalent bond with the acid that is component (G).
4. 3. The photosensitive resin composition as described in 1 or 2 above, wherein component (D) is a quinonediazide compound.
5. 3. The photosensitive resin composition as described in 3 above, wherein component (D) is a quinonediazide compound and satisfies either (Z1) or (Z2) above.
6. 6. The photosensitive resin composition according to any one of 1 to 5 above, wherein component (A) further contains a phenyl group.
7. 7. The photosensitive resin composition as described in 6 above, wherein the polysiloxane component (A) has a number average molecular weight of 1,000 to 100,000 in terms of polystyrene.
8. 8. The type photosensitive resin composition according to any one of 1 to 7 above, wherein the alkali-soluble resin as the component (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene.
9. 9. The type photosensitive resin composition as described in any one of 1 to 8 above, which contains 0.1 to 20 parts by mass of component (A) per 100 parts by mass of component (B).
10. Photosensitivity according to any one of claims 1 to 9, characterized in that component (D) is present in an amount of 5 to 100 parts by mass based on a total of 100 parts by mass of components (A) and (B). Resin composition.
11. The photosensitive resin according to any one of items 3 to 10 above, wherein the component (E) is 1 to 50 parts by mass based on a total of 100 parts by mass of the components (A) and (B). Composition.
12. A cured film obtained using the photosensitive resin composition according to any one of 1 to 11 above.
13. 13. A display element having the cured film according to 12 above.
14. 13. A display element having the cured film described in 12 above as a partition wall for image formation.

The photosensitive resin composition of the present invention has high oil repellency on the surface of the cured film even after UV ozone treatment, and has high lyophilicity to the substrate even without plasma treatment or UV ozone treatment. The purpose is to form an image of the film.

The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following components (A), (B), (C) solvent, and (D).
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having a fluorine atom (A2) Organic group having a thermally crosslinkable group (B) Component: Alkali-soluble resin;
(C) solvent;
(D) Component: Photosensitizer.

It is preferable that the photosensitive resin composition of the present invention further satisfies at least one of the following (Z1) to (Z4).
(Z1): further contains a crosslinking agent as component (E),
(Z2): The alkali-soluble resin of component (B) further has a self-crosslinking group, or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. It also has.
(Z3): Component (D) is a photoradical generator, and further contains a compound having two or more ethylenic polymerizable groups as component (F).
(Z4): Component (D) is a photoacid generator, and further contains a compound having two or more functional groups that form a covalent bond with the acid that is component (G).

The photosensitive resin composition of the present invention is preferably a positive photosensitive resin composition in which component (D) is a quinonediazide compound.

The details of each component will be explained below.
<(A) component>
The polysiloxane (A) used in the present invention is a polysiloxane having the following groups (A1) and (A2).
(A1) Organic group having a fluorine atom (A2) Organic group having a thermally crosslinkable group

（ｋは０～１２の整数を表す。）(A1) The fluorine atom-containing organic group is an organic group bonded to the silicon atom of the polysiloxane main chain, and is partially or completely substituted with a fluorine atom. The organic group having a fluorine atom is not particularly limited as long as it does not impair the effects of the present invention. Particularly preferred are alkyl groups in which some or all of the hydrogen atoms are substituted with fluorine atoms, and alkyl groups containing an ether bond in which some or all of the hydrogen atoms are substituted with fluorine atoms. At that time, the number of fluorine atoms that this organic group has is also not particularly limited. More preferred is a perfluoroalkyl group, and even more preferred is an organic group represented by formula (1).

(k represents an integer from 0 to 12.)

Specific examples of the organic group represented by formula (1) include trifluoropropyl group, tridecafluorooctyl group, heptadecafluorodecyl group, 2,2,2-trifluoroethyl group, 2,2,3 , 3,3-pentafluoropropyl group, 2-(perfluorobutyl)ethyl group, 2-(perfluorohexyl)ethyl group, 2-(perfluorooctyl)ethyl group, 2-(perfluorodecyl)ethyl group, Examples include 2-(perfluoro-3-methylbutyl)ethyl group, 2-(perfluoro-5-methylhexyl)ethyl group, and 2-(perfluoro-7-methyloctyl)ethyl group. In the present invention, the organic group having a fluorine atom contained in the polysiloxane (A) may be a single type or a plurality of types.

The organic group having a fluorine atom in the polysiloxane (A) is 0.05% per mole of all silicon atoms in the polysiloxane (A) from the viewpoint of achieving both liquid repellency, film hardness, and solvent resistance. ~0.5 mol is preferred, and 0.1 ~ 0.4 mol is more preferred.

(A2) The thermally crosslinkable group in the organic group having a thermally crosslinkable group is not particularly limited as long as it forms a covalent bond by heating, but examples include vinyl group, epoxy group, amino group, mercapto group, block Examples thereof include an isocyanate group and an isocyanate group.
Further, when the thermally crosslinkable group is an epoxy group, examples of the organic group having an epoxy group include a glycidyloxy group and a 3,4-epoxycyclohexylmethyl group.
From the viewpoint of achieving both liquid repellency, film hardness, and solvent resistance, the organic group having a thermally crosslinkable group in polysiloxane (A) is 0 per mole of all silicon atoms contained in polysiloxane (A). 0.2 to 0.95 mol is preferable, and 0.3 to 0.8 mol is more preferable.

In addition, the polysiloxane (A) of the present invention is not (A1) an organic group having a fluorine atom, (A2) is not an organic group having a thermally crosslinkable group, and other organic groups are silicon atoms in the polysiloxane main chain. may be combined with The other organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and does not have a fluorine atom.

Examples of such an organic group without a fluorine atom include a saturated hydrocarbon group having a linear or branched structure; an aromatic group having a benzene ring; an organic group having an amino group, a ureido group, or a vinyl group; Alternatively, an organic group having an ether bond or an ester bond may be mentioned.
Specific examples of these include methyl group, ethyl group, propyl group, butyl group, pentyl group, heptyl group, octyl group, dodecyl group, hexadecyl group, octadecyl group, cyclohexyl group, phenyl group, vinyl group, γ -aminopropyl group, γ-methacryloxypropyl group, etc.

In the present invention, the amount of organic groups that do not have fluorine atoms in polysiloxane (A) is not particularly limited as long as it does not impair the effects of the present invention. On the other hand, it is preferably 0.01 to 0.75 mol. In the case of such a range, a film having a contact angle of 50 degrees or more with the organic solvent is easily obtained, and a homogeneous solution of polysiloxane (A) is easily obtained.

The polysiloxane of component (A) has a number average molecular weight within the range of 1,000 to 100,000. If the number average molecular weight is too high (more than 100,000), handling properties may deteriorate; if the number average molecular weight is too small (less than 1,000), the film in the exposed area may be damaged during development. A considerable amount of loss may occur, resulting in insufficient liquid repellency.

（式中、Ｒ^１はフッ素原子を有する有機基であり、Ｒ^２およびＲ^３はそれぞれ独立に炭素数１～５の炭化水素基を表し、ｍは０または１を表す。）The method for obtaining such polysiloxane (A) is not particularly limited, but an alkoxysilane represented by the following formula (2), an alkoxysilane having an epoxy group, and optionally an alkoxysilane having other organic groups are used. Polysiloxane obtained by polycondensation is preferred.

(In the formula, R ¹ is an organic group having a fluorine atom, R ² and R ³ each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and m represents 0 or 1.)

Here, R ¹ in formula (2) represents the above-mentioned organic group having a fluorine atom.

Furthermore, in formula (2), R ² and R ³ each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and a saturated hydrocarbon group is particularly preferred. Among these, lower alkyl groups such as methyl, ethyl, propyl, and butyl groups are preferred because they are readily available as commercial products. When a plurality of alkoxysilanes represented by formula (2) are used, their R ² and R ³ may be the same or different.

（ｋは０～１２の整数を表す。）In the present invention, among alkoxysilanes represented by formula (2), alkoxysilanes in which R ¹ is an organic group represented by formula (1) are preferred.

(k represents an integer from 0 to 12.)

Specific examples of alkoxysilanes in which R ¹ is an organic group represented by formula (1) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane. Examples include fluorooctyltriethoxysilane, heptadecafluorodecyltrimethoxysilane, heptadecafluorodecyltriethoxysilane, and 2-(perfluorohexyl)ethyltrimethoxysilane.

In the present invention, at least one type of alkoxysilane represented by formula (2) may be used, but a plurality of types may be used as necessary.

（式中、Ｒ^４は熱架橋性基を有する有機基であり、Ｒ^５およびＲ^６はそれぞれ独立に炭素数１～５の炭化水素基を表し、ｎは０または１を表す。）The alkoxysilane having an organic group having a thermally crosslinkable group is an alkoxysilane represented by the following formula (3).

(In the formula, R ⁴ is an organic group having a thermally crosslinkable group, R ⁵ and R ⁶ each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and n represents 0 or 1.)

In formula (3), R ⁴ is an organic group having 2 to 12 carbon atoms and having a vinyl group, an epoxy group, an amino group, a mercapto group, a blocked isocyanate group, an isocyanate group, a methacrylic group, an acrylic group, or a ureido group. Among these, organic groups having 2 to 12 carbon atoms and having a vinyl group, an epoxy group, an amino group, a methacrylic group, an acrylic group, or a ureido group are preferred from the viewpoint of easy availability. More preferably, it is an organic group having 2 to 12 carbon atoms and having an epoxy group, methacrylic group, acrylic group, or ureido group.
More specifically, an organic group having 2 to 12 carbon atoms and having a glycidoxy group or a 3,4-epoxycyclohexylmethyl group is preferred.

In formula (3), R ⁵ and R ⁶ are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Among these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferred.

Specific examples of the specific alkoxysilane represented by formula (3) include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, and vinyltris(2-methoxyethoxysilane). ) Silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3-(N-styrylmethyl-2-aminoethylamino)propyl Trimethoxysilane, diethoxy(3-glycidyloxypropyl)methylsilane, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxy Silane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-epoxycyclohexyl)ethyltriethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane -aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3-(phenylamino)propyl]silane, 3-mercaptopropyl(dimethoxy)methylsilane, (3-mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, 3-(triethoxysilyl)propylisocyanate, 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3-(triethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 2-(triethoxysilyl)ethyl methacrylate, 2-(trimethoxysilyl)ethyl methacrylate, 2-(triethoxysilyl)ethyl acrylate, 2-(trimethoxysilyl)ethyl acrylate, (triethoxysilyl)methyl methacrylate, (trimethoxysilyl)methyl methacrylate, (triethoxysilyl) ) Methyl acrylate, (trimethoxysilyl)methyl acrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'- Examples include triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxysilylpropylurea, and 1-[3-(trimethoxysilyl)propyl]urea.
Furthermore, 3-glycidyloxypropyl(dimethoxy)methylsilane, 3-glycidyloxypropyl(diethoxy)methylsilane, 3-glycidyloxypropyltrimethoxysilane or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, which undergoes a crosslinking reaction due to heat. It is also preferred to use silane.

In this case, a plurality of types of alkoxysilanes having an organic group having a thermally crosslinkable group may be used.

（Ｒ^７は、水素原子、又はフッ素原子を有しない炭素数１～２０の有機基であり、Ｒ^８は、それぞれ炭素数１～５の炭化水素基であり、ｐは０、１または２を表す。）Examples of alkoxysilanes having other organic groups include alkoxysilanes represented by formula (4).

(R ⁷ is a hydrogen atom or an organic group having 1 to 20 carbon atoms without a fluorine atom, R ⁸ is a hydrocarbon group having 1 to 5 carbon atoms, and p is 0, 1 or 2. represent.)

In formula (4), R ⁸ represents a hydrocarbon group, and is preferably a saturated hydrocarbon group having 1 to 5 carbon atoms, since the smaller the number of carbon atoms, the higher the reactivity. More preferred are methyl group, ethyl group, propyl group, and butyl group.

When p=0 in formula (4), the alkoxysilane represented by formula (4) represents tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane, which are easily available as commercial products.

In the case of p=an integer of 1 to 3 in formula (4), the alkoxysilane represented by formula (4) has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, and R ⁷ does not have a hydrogen atom or a fluorine atom. It is an alkoxysilane having an organic group and an alkoxy group. In the present invention, R ⁷ may be the same or different.

Examples of the organic group having 1 to 20 carbon atoms and not having a fluorine atom include a saturated hydrocarbon group having a linear or branched structure, an aromatic group having a benzene ring, an organic group having an amino group, a ureido group, a vinyl group, etc. , or an organic group having an ether bond or an ester bond.

R ⁸ in formula (4) is a hydrocarbon group having 1 to 5 carbon atoms. When p is 1 or 2, it is generally preferable that R ⁸ are the same, but in the present invention, R ⁸ may be the same or different. Specific examples of alkoxysilanes in which p in formula (4) is an integer of 1 to 3 are shown below.
For example, tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, Pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxy Silane, octadecyltrimethoxysilane, alkyltrialkoxysilane such as octadecyltriethoxysilane, trialkoxysilane with an aromatic group such as phenyltrimethoxysilane, phenyltriethoxysilane, benzyltrimethoxysilane and benzyltriethoxysilane, dimethyldimethoxysilane Silane, dialkoxysilane such as dimethyldiethoxysilane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, Vinyltris(2-methoxyethoxy)silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3-(N-styrylmethyl-2 -aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyldimethoxymethylsilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxy Silane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy[3-(phenylamino)propyl]silane, 3-mercaptopropyl(dimethoxy)methylsilane, (3 -Mercaptopropyl)triethoxysilane, (3-mercaptopropyl)trimethoxysilane, 3-(triethoxysilyl)propyl isocyanate, 3-(triethoxysilyl)propyl methacrylate, 3-(trimethoxysilyl)propyl methacrylate, 3- (Triethoxysilyl)propyl acrylate, 3-(trimethoxysilyl)propyl acrylate, 2-(triethoxysilyl)ethyl methacrylate, 2-(trimethoxysilyl)ethyl methacrylate, 2-(triethoxysilyl)ethyl acrylate, 2- (Trimethoxysilyl)ethyl acrylate, (triethoxysilyl)methyl methacrylate, (trimethoxysilyl)methyl methacrylate, (triethoxysilyl)methyl acrylate, (trimethoxysilyl)methyl acrylate, γ-ureidopropyltriethoxysilane, γ- ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R)-N-1-phenylethyl-N'-triethoxysilylpropylurea, (R)-N-1-phenylethyl-N'-trimethoxy Examples include silylpropylurea, 1-[3-(trimethoxysilyl)propyl]urea, and the like.

The polysiloxane (A) used in the present invention preferably contains an alkoxysilane represented by formula (2) in an amount of 5 to 50 mol% based on the total alkoxysilane, and an alkoxysilane represented by formula (3) as a pre-alkoxysilane. It is preferably contained in an amount of 10 to 95 mol %, with the remainder obtained by polycondensing an alkoxysilane represented by the above formula (4).

Considering the liquid repellency and solvent resistance of the coating, the content of the alkoxysilane represented by formula (2) is more preferably 10 to 40 mol%. The amount of alkoxysilane represented by formula (3) is preferably 30 to 80 mol% of the total alkoxysilane.

Further, when the alkoxysilane represented by the above formula (4) is contained, the amount thereof is preferably 5 to 60 mol% based on the total alkoxysilane.

As a method for obtaining polysiloxane (A), for example, an alkoxysilane represented by the formula (2), an alkoxysilane represented by the formula (3), and an alkoxysilane represented by the above formula (4) as necessary. A method of polycondensing silane and an organic solvent by heating them in the presence of an aqueous tetraethylammonium hydroxide solution can be mentioned. Specifically, this method involves adding an aqueous tetraethylammonium hydroxide solution to an organic solvent in advance to form a solution of the aqueous tetraethylammonium hydroxide solution, and then mixing the various alkoxysilanes described above while heating the solution.
The amount of the tetraethylammonium hydroxide aqueous solution present is preferably 0.01 to 0.2 mol per 1 mol of the total amount of alkoxy groups contained in the alkoxysilane used. The above heating can be carried out at a liquid temperature of preferably 0 to 100°C, and preferably under reflux for several minutes in a container equipped with a reflux tube to prevent evaporation or volatilization of the liquid. ~Continues for over ten hours.

When using multiple types of alkoxysilanes, the alkoxysilanes may be mixed in advance as a mixture, or multiple types of alkoxysilanes may be mixed one after another.
When polycondensing alkoxysilane, the concentration of all silicon atoms in the charged alkoxysilane converted into oxides (hereinafter referred to as SiO ₂ equivalent concentration) is 40% by mass or less, particularly preferably 10 to 30% by mass. %. By selecting an arbitrary concentration within this concentration range, gel formation can be suppressed and a homogeneous polysiloxane-containing solution can be obtained.

The organic solvent (hereinafter also referred to as a polymerization solvent) used when polycondensing alkoxysilane is an alkoxysilane represented by formula (2), an alkoxysilane represented by formula (3), and an alkoxysilane represented by formula (3). Although the solvent is not particularly limited as long as it dissolves the alkoxysilane represented by the above formula (4), it is preferable to use the solvent (C). Among these, since alcohol is produced by the polycondensation reaction of alkoxysilane, alcohols and organic solvents having good compatibility with alcohols are used.

Specific examples of the above polymerization solvent include alcohols such as methanol, ethanol, propanol, and n-butanol, glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether, and tetrahydrofuran. Examples include ether.
In the present invention, a mixture of two or more of the above organic solvents may be used.

In the present invention, the solution of the specific polysiloxane obtained by the above method may be used as it is in the photosensitive resin composition of the present invention, or if necessary, the solution of the specific polysiloxane obtained by the above method may be used as is. It can also be used by concentrating it, diluting it by adding a solvent, or replacing it with another solvent.

The solvent used when diluting by adding the solvent (also referred to as added solvent) may be a solvent used in a polycondensation reaction or another solvent. The additive solvent is not particularly limited as long as the specific polysiloxane is uniformly dissolved therein, and one or more types can be arbitrarily selected and used. Examples of such additional solvents include, in addition to the solvent used in the polycondensation reaction, ketone solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, and ester solvents such as methyl acetate, ethyl acetate, or ethyl lactate.

Furthermore, in the present invention, when a polymer other than the specific polysiloxane is used in the photosensitive resin composition, before mixing the polymer other than the specific polysiloxane, It is preferable to distill off the alcohol under normal pressure or reduced pressure.

<(B) component>
Component (B) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxy group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid, a boronic acid, and an active methylene group and an active methine group.

An active methylene group refers to a methylene group (-CH ₂ -) having a carbonyl group at an adjacent position and having reactivity with a nucleophilic reagent. Furthermore, in the present invention, the active methine group refers to the active methylene group having a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group, and has reactivity with nucleophilic reagents.

（式（ｂ１）中、Ｒはアルキル基、アルコキシ基又はフェニル基を表し、破線は結合手を表す。）As the active methylene group and the active methine group, a group represented by the following formula (b1) is more preferable.

(In formula (b1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the broken line represents a bond.)

In the above formula (b1), examples of the alkyl group represented by R include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.
Examples of such alkyl groups include methyl, ethyl, n-propyl, and i-propyl groups.
Among these, methyl, ethyl, n-propyl and the like are preferred.

In the above formula (b1), the alkoxy group represented by R includes, for example, an alkoxy group having 1 to 20 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is preferable.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, and t-butoxy groups.
Among them, methoxy group, ethoxy group, n-propoxy group, etc. are preferred.

Examples of the group represented by the above formula (b1) include the following structures. In addition, in the structural formula, a broken line represents a bond.

Among the above alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxy group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000. It is preferable that there be.

The alkali-soluble resin of the component (B) may be any alkali-soluble resin having such a structure, and there are no particular limitations on the main chain skeleton and the type of side chains of the polymer constituting the resin.

However, the alkali-soluble resin of component (B) has a number average molecular weight within the range of 2,000 to 50,000. If the number average molecular weight is too high (more than 50,000), development residues are likely to be generated and the sensitivity will be greatly reduced, while if the number average molecular weight is too small (less than 2,000), development will be difficult. In this case, a considerable amount of film loss may occur in the exposed areas, resulting in insufficient curing.

Examples of the alkali-soluble resin of component (B) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

Further, in the present invention, an alkali-soluble resin made of a copolymer (hereinafter referred to as a specific copolymer) obtained by polymerizing a plurality of types of monomers can also be used as the component (B). In this case, the alkali-soluble resin of component (B) may be a blend of multiple types of specific copolymers.

That is, the above-mentioned specific copolymer comprises a monomer exhibiting alkali solubility, that is, a monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group, and a monomer copolymerizable with these monomers. It is a copolymer formed with at least one selected monomer as an essential structural unit, and has a number average molecular weight of 2,000 to 50,000. If the number average molecular weight is more than 50,000, a residue may be produced.

The above-mentioned "monomer having at least one selected from the group consisting of a carboxyl group and a phenolic hydroxy group" includes a monomer having a carboxyl group and a monomer having a phenolic hydroxy group. These monomers are not limited to those having one carboxyl group or phenolic hydroxy group, but may have a plurality of them.

Specific examples of the above monomers will be listed below, but the invention is not limited thereto.
Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono-(2-(acryloyloxy)ethyl) phthalate, mono-(2-(methacryloyloxy)ethyl) phthalate, N-(carboxyphenyl) ) maleimide, N-(carboxyphenyl)methacrylamide, N-(carboxyphenyl)acrylamide, and the like.

Examples of the monomer having a phenolic hydroxy group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenylmethacrylate.

Examples of the monomer having an imide group include maleimide and the like.

The ratio of the unsaturated carboxylic acid derivative and/or phenolic hydroxyl group to the monomer having a polymerizable unsaturated group in the production of the alkali-soluble acrylic polymer as the component (B) is as follows: Of all the monomers used, it is preferably 10 to 90 mol%, more preferably 5 to 60 mol%, and most preferably 5 to 30 mol%. When the unsaturated carboxylic acid and/or phenolic hydroxy group derivative is less than 10% by weight, the alkali solubility of the polymer is insufficient.

The alkali-soluble resin which is the component (B) of the present invention may further be copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group in order to further stabilize the pattern shape after curing.

Examples of monomers having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, Examples include 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone.

The ratio of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group in the production of the alkali-soluble acrylic polymer as component (B) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably is 20 to 40% by weight. If the monomer having a hydroxyalkyl group and a polymerizable unsaturated group is less than 10% by weight, the effect of stabilizing the pattern shape of the copolymer may not be obtained. If the amount is 60% by weight or more, the alkali-soluble groups in component (B) may be insufficient, and properties such as developability may deteriorate.

The alkali-soluble resin which is component (B) of the present invention may further be copolymerized with an N-substituted maleimide compound from the viewpoint of increasing the Tg of the copolymer.

N-Substituted Maleimide Compounds Examples of maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the viewpoint of transparency, those having no aromatic ring are preferred, and from the viewpoint of developability, transparency, and heat resistance, those having an alicyclic skeleton are more preferred, and among them, cyclohexylmaleimide is the most preferred.

The proportion of N-substituted maleimide in the production of the alkali-soluble acrylic polymer of component (B) is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably 20 to 40% by weight. If the N-substituted maleimide content is less than 10% by weight, the copolymer may have a low Tg and poor heat resistance. If the content is 60% by weight or more, transparency may decrease.

When the photosensitive resin composition of the present invention satisfies requirement (Z2), the alkali-soluble resin (B) used in the present invention further has a self-crosslinking group, or contains a hydroxy group, a carboxyl group, an amide group, and Preferably, the copolymer further has a group (hereinafter also referred to as a crosslinkable group) that reacts with at least one group selected from the group consisting of amino groups.

Examples of the self-crosslinking group include N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, oxetane group, vinyl group, and blocked isocyanate group.

Examples of the crosslinkable group include N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, and the like.

When such a self-crosslinkable group or a crosslinkable group is contained in the resin of the component (B), the content is preferably 0.1 to 0.9 per repeating unit in the resin of the (B) component. Preferably, from the viewpoint of developability and solvent resistance, the number is more preferably 0.1 to 0.8.

The alkali-soluble resin of component (B) further contains a crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a blocked isocyanate group, and an N-alkoxymethyl group. , N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, etc., for example, if the repeating unit has at least one type of self-crosslinking group such as N-hydroxymethyl group, alkoxysilyl group, epoxy group, vinyl group, blocked isocyanate group, etc. an unsaturated compound having at least one type selected from crosslinkable groups such as oxetane groups, vinyl groups, blocked isocyanate groups, and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, and alkoxysilyl groups. What is necessary is to copolymerize.

Examples of unsaturated compounds having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-methylolacrylamide. etc.

Examples of the monomer having radical polymerizability and further having a hydroxymethylamide group include N-hydroxymethylacrylamide, N-hydroxymethylmethacrylamide, and the like.

Examples of monomers having radical polymerizability and an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane. Can be mentioned.

Examples of unsaturated compounds having radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propylacrylate glycidyl, α-n-butyl acrylate. Glycidyl, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate-6, Examples include 7-epoxyheptyl, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, and p-vinylbenzylglycidyl ether. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. Preferably used. These may be used alone or in combination.

Examples of the unsaturated compound having radical polymerizability and further having an oxetane group include (meth)acrylic acid ester having an oxetane group. Among such monomers are 3-(methacryloyloxymethyl)oxetane, 3-(acryloyloxymethyl)oxetane, 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3- Ethyl-oxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxetane, 3-(methacryloyloxymethyl)-2-phenyl-oxetane, 3- (acryloyloxymethyl)-2-phenyl-oxetane, 2-(methacryloyloxymethyl)oxetane, 2-(acryloyloxymethyl)oxetane, 2-(methacryloyloxymethyl)-4-trifluoromethyloxetane, 2-(acryloyloxy methyl)-4-trifluoromethyloxetane is preferred, and 3-(methacryloyloxymethyl)-3-ethyl-oxetane, 3-(acryloyloxymethyl)-3-ethyl-oxetane, and the like are preferably used.

Examples of monomers having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of monomers that have radical polymerizability and further have a blocked isocyanate group include 2-(0-(1'-methylpropylideneamino)carboxyamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl) methacrylate. carbonylamino)ethyl and the like.

When the photosensitive resin composition of the present invention satisfies (Z1), it has radical polymerizability and contains an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a block An inorganic compound having at least one group selected from a crosslinkable group such as an isocyanate group and a self-crosslinkable group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group. The content of structural units derived from saturated compounds is preferably 10 to 70% by weight, particularly preferably 20 to 60% by weight, based on the total of all repeating units possessed by the alkali-soluble resin (B). If the amount of this structural unit is less than 10% by weight, the heat resistance and surface hardness of the resulting cured film tends to decrease, while if the amount of this structural unit exceeds 70% by weight, the storage of the radiation-sensitive resin composition Stability tends to decrease.

Furthermore, in the present invention, the acrylic polymer of component (B) may be a copolymer formed using monomers other than the above-mentioned monomers (hereinafter referred to as other monomers) as constituent units. Specifically, the other monomers may be any monomer as long as it is copolymerizable with at least one selected from the group consisting of the monomers having a carboxyl group and the monomers having a phenolic hydroxy group, and has the characteristics of component (B). There is no particular limitation as long as it does not cause any damage. Specific examples of such monomers include acrylic ester compounds, methacrylic ester compounds, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds.
Specific examples of the other monomers will be listed below, but the invention is not limited to these.

Examples of the acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2- Trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy Butyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, caprolactone Examples include 2-(acryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether acrylate, and the like.

Examples of the methacrylic acid ester compounds include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2- Trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxy Butyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, Examples include diethylene glycol monomethacrylate, caprolactone 2-(methacryloyloxy)ethyl ester, poly(ethylene glycol)ethyl ether methacrylate, and the like.

Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-butoxy. Examples include methylacrylamide, N-butoxymethylmethacrylamide, and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinylnaphthalene, vinylanthracene, vinylcarbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo[4.1.0]heptane, 1,2 -epoxy-5-hexene, 1,7-octadiene monoepoxide, and the like.

Examples of the styrene compound include styrene having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

In the production of the alkali-soluble acrylic polymer that is component (B), the ratio of the other monomers mentioned above is preferably 80% by weight or less, more preferably 50% by weight or less, and still more preferably 20% by weight or less. . If it exceeds 80% by weight, the essential components will be relatively reduced, making it difficult to obtain the full effect of the present invention.

The method for obtaining the alkali-soluble acrylic polymer, which is component (B) used in the present invention, is not particularly limited. A monomer having at least one selected from the group consisting of groups that form, a monomer having a hydroxyalkyl group, optionally an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and Contains at least one group selected from crosslinkable groups such as blocked isocyanate groups and self-crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and blocked isocyanate groups. It is obtained by carrying out a polymerization reaction at a temperature of 50 to 110° C. in a solvent in which monomers, optionally other copolymerizable monomers, and optionally a polymerization initiator are present. At that time, the solvent used is not particularly limited as long as it dissolves the monomers constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include the solvents described in (C) Solvent described below.

The acrylic polymer having a specific functional group obtained in this manner is usually in the form of a solution dissolved in a solvent.

In addition, the solution of the specific copolymer obtained as described above is poured into diethyl ether, water, etc. under stirring to cause reprecipitation, and the resulting precipitate is filtered and washed, and then under normal pressure or reduced pressure. By drying at room temperature or by heating, powder of the specific copolymer can be obtained. By such an operation, the polymerization initiator and unreacted monomer coexisting with the specific copolymer can be removed, and as a result, purified powder of the specific copolymer can be obtained. If sufficient purification cannot be achieved in one operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.
In the present invention, the powder of the above-mentioned specific copolymer may be used as it is, or the powder may be redissolved in, for example, the solvent (C) described later and used in the form of a solution.

In addition, as the alkali-soluble resin of component (B), polyimide precursors such as polyamic acid, polyamic acid ester, partially imidized polyamic acid, etc., and polyimides such as polyimide containing carboxylic acid groups can also be used. As long as it is soluble, it can be used without particular limitation on its type.

The polyamic acid, which is a polyimide precursor, can generally be obtained by polycondensing (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.

The above (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3' , 4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride Aromatic tetracarboxylic acids such as 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2, 3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexane tetra Carboxylic dianhydrides, cycloaliphatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, 1,2,3, Mention may be made of aliphatic tetracarboxylic dianhydrides such as 4-butanetetracarboxylic dianhydride.
These compounds may be used alone or in combination of two or more.

Further, the diamine compound (b) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1 , 3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl) ether, bis(4-amino-3,5-dicarboxyphenyl) ether, Bis(4-amino-3-carboxyphenyl)sulfone, bis(4-amino-3,5-dicarboxyphenyl)sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'- Diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino -3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4- Amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2 , 5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3-amino-4-hydroxyphenyl) ether, bis(4-amino-3-hydroxyphenyl) ether, bis(4- Amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl) Methane, bis(3-amino-4-hydroxyphenyl)sulfone, bis(4-amino-3-hydroxyphenyl)sulfone, bis(4-amino-3,5-dihydroxyphenyl)sulfone, 2,2-bis(3 -Amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoro Propane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis (4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfone, bis[4 -(3-amino-4-hydroxyphenoxy)phenyl]propane, 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane and other diamine compounds having a phenolic hydroxy group, 1, 3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis(4-amino-3-mercaptophenyl)ether, 2,2-bis( Diamine compounds having a thiophenol group such as 3-amino-4-mercaptophenyl)hexafluoropropane, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diamino Benzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, 4,4'-diamino-3,3'-dimethyl Examples include diamine compounds having a sulfonic acid group such as biphenyl-6,6'-disulfonic acid. Also, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4, 4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o- Tolidine, m-tolidine, 3,3',5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl] Propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4- Diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4 -tolyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2 -Diamines such as bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine Compounds can be mentioned.
These compounds may be used alone or in combination of two or more.

When the polyamic acid used in the present invention is produced from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the blending ratio of both compounds, i.e. (b) total number of moles of diamine compound/(a) The total number of moles of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. As in normal polycondensation reactions, the closer this molar ratio is to 1, the higher the degree of polymerization of the produced polyamic acid and the higher the molecular weight.

Furthermore, when polymerization is performed using an excessive amount of a diamine compound, the terminal amino groups of the remaining polyamic acid can be protected by reacting the terminal amino groups with a carboxylic acid anhydride.
Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, and methyl-5-norbornene-2,3-dicarboxylic acid. Examples include anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

In the production of polyamic acid, the reaction temperature for the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from any temperature from -20 to 150°C, preferably from -5 to 100°C. In order to obtain a high molecular weight polyamic acid, the reaction temperature is suitably selected within the range of 5°C to 40°C and the reaction time is within the range of 1 to 48 hours. In order to obtain a partially imidized polyamic acid having a low molecular weight and high storage stability, it is more preferable to select a reaction temperature from 40°C to 90°C and a reaction time of 10 hours or more.
Further, the reaction temperature when protecting the terminal amino group with an acid anhydride can be selected from any temperature from -20 to 150°C, preferably from -5 to 100°C.

The reaction between the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Solvents that can be used in this case include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, Hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, 3 - Ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol Monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone, Examples include methyl isobutyl ketone and 2-heptanone. These may be used alone or in combination. Furthermore, even a solvent that does not dissolve polyamic acid may be mixed with the above solvent and used as long as the polyamic acid produced by the polymerization reaction does not precipitate.

The solution containing polyamic acid thus obtained can be used as it is for preparing a negative photosensitive resin composition. Alternatively, the polyamic acid can be isolated by precipitation in a poor solvent such as water, methanol, or ethanol, and then recovered and used.

Further, as the component (B), any polyimide can be used. The polyimide used in the present invention is one obtained by chemically or thermally imidizing a polyimide precursor such as the above-mentioned polyamic acid by 50% or more.

The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxy group in order to impart alkali solubility.
The method for introducing a carboxyl group or a phenolic hydroxy group into polyimide includes a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of capping the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxy group, Alternatively, a method may be used in which the imidization rate is reduced to 99% or less when imidizing a polyimide precursor such as polyamic acid.

Such a polyimide can be obtained by synthesizing a polyimide precursor such as the above-mentioned polyamic acid, followed by chemical imidization or thermal imidization.
As a method for chemical imidization, a method is generally used in which excess acetic anhydride and pyridine are added to a polyimide precursor solution and the mixture is reacted at room temperature to 100°C. Further, as a method for thermal imidization, a method is generally used in which a polyimide precursor solution is heated at a temperature of 180° C. to 250° C. while being dehydrated.

Further, as the alkali-soluble resin of component (B), a phenol novolak resin can be further used.

Further, as the alkali-soluble resin of component (B), polyester polycarboxylic acid can also be used. Polyester polycarboxylic acid can be obtained from acid dianhydride and diol by the method described in WO2009/051186.
Examples of the acid dianhydride include the above-mentioned (a) tetracarboxylic dianhydride.
Examples of diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol, hydrogenated bisphenol A, and hydrogenated bisphenol F. , 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol and other alicyclic diols, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol Examples include aliphatic diols such as.

Moreover, in the present invention, the alkali-soluble resin of component (B) may be a mixture of multiple types of alkali-soluble resins.

The ratio of component (A) to component (B) is 0.1 to 20 parts by mass of component (A) per 100 parts by mass of component (B).

<(C) Solvent>
The (C) solvent used in the present invention dissolves the (A) component, the (B) component, and optionally the below-mentioned (D) component, (E) component, (F) component, and (G) component, In addition, the solvent dissolves the component (H) described below and other additives that are added as desired, and the type and structure thereof are not particularly limited as long as they have such a dissolving ability.

Examples of such solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol. Monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-hydroxypropion ethyl acid, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion Ethyl acid, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, etc. can be mentioned.

These solvents can be used alone or in combination of two or more.
Among these (C) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, etc. have good coating properties and are safe. This is preferable from the viewpoint of high These solvents are commonly used as solvents for photoresist materials.

<(D) component>
Examples of the photosensitizer as component (D) include (D-1) a 1,2-quinonediazide compound, (D-2) a photoradical generator, and (D-3) a photoacid generator.

(D-1) The 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amino group, or both a hydroxyl group and an amino group, , preferably 10 to 100 mol%, particularly preferably 20 to 95 mol% of the total amount) is esterified or amidated with 1,2-quinonediazide sulfonic acid. I can do it.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallic acid, ethyl gallic acid, 1,3,3-tris(4-hydroxyphenyl) Butane, 4,4-isopropridendiphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4- Hexafluoroisopropylidene diphenol, 4,4',4''-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxy) phenyl)-1-methylethyl]phenyl]ethylidene]bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,4 , 4'-tetrahydroxybenzophenone, 2,2',3,4,4'-pentahydroxybenzophenone, phenolic compounds such as 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, ethanol, 2-propanol , 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, butyl lactate, and other aliphatic alcohols I can list several types.

In addition, the compounds containing the amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine. , 4,4'-diaminophenylmethane, anilines such as 4,4'-diaminodiphenyl ether, and aminocyclohexane.

Furthermore, examples of compounds containing both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4''-hydroxytriphenylmethane, 4-amino-4',4''-dihydroxytriphenylmethane, bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis (4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, 2,2-bis(4-amino-3-carboxy Examples include aminophenols such as -5-hydroxyphenyl)hexafluoropropane, and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention is a positive photosensitive resin composition, the content of the compound having a quinonediazide group as component (D-1) is as follows: component (A) and component (B). The amount is preferably 5 to 100 parts by weight, more preferably 8 to 50 parts by weight, and still more preferably 10 to 40 parts by weight. When the amount is less than 5 parts by mass, the difference in dissolution rate in the developer between the exposed area and the unexposed area of the positive photosensitive resin composition becomes small, and patterning by development may be difficult. In addition, if it exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be sufficiently decomposed by short exposure, resulting in a decrease in sensitivity, or the component (D-1) may absorb light, causing the cured film to deteriorate. Transparency may be reduced.

(D-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure to light. Specific examples include aromatic ketones such as benzophenone, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone, and phenanthrene, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoin phenyl ether, benzoin such as methylbenzoin and ethylbenzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di( m-methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2, 4,5-triarylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimer, 2-benzyl-2-dimethylamino-1-(4-morpho) linophenyl)-butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanostyryl)-1,3,4-oxadiazole, 2 -Halomethyloxadiazole compounds such as trichloromethyl-5-(p-methoxystyryl)-1,3,4-oxadiazole, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-S- Triazine, 2,4-bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl- S-triazine, 2-(naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2-(4-ethoxy-naphth-1-yl)-4,6-bis-trichloromethyl- S-triazine, halomethyl-S-triazine compounds such as 2-(4-butoxy-naphth-1-yl)-4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2- Diphenylethan-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone -1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-Butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1-(4-phenylthiophenyl)-1,2-octane Dione-2-(O-benzoyloxime), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 4-benzoyl -Methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-(dimethylamino)-2 -[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzoyl)phos Examples include fin oxide, diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, and the like.
The above photopolymerization initiators are easily available as commercial products, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, and IRGA CURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 2 50 (manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ ( The above are manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114 , TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (manufactured by Midori Kagaku Co., Ltd.).
These photoradical generators can be used alone or in combination of two or more.

When component (D-2) is contained in the photosensitive resin composition of the present invention, the content is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass based on 100 parts by mass of component (A). is 0.5 to 20 parts by weight, particularly preferably 1 to 15 parts by weight. If this ratio is too small, the exposed portions may be insufficiently cured, resulting in failure to form a pattern, or even if pattern formation is possible, the film may have low reliability. Furthermore, if this ratio is excessive, the transmittance of the coating film may decrease or poor development may occur in unexposed areas.

The photoacid generator (D-3) is not particularly limited as long as it is a compound that photodecomposes and generates an acid when irradiated with ultraviolet rays. Examples of acids generated when photoacid generators are photodecomposed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p- Toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzene Sulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, etc. Examples include acids or hydrates and salts thereof.

Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, halogen-containing triazine compounds, and acetophenone derivative compounds. and cyano group-containing oxime sulfonate compounds. Any conventionally known or conventionally used photoacid generator can be applied in the present invention without particular limitation. In the present invention, the photoacid generator (D) component may be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

When component (D-3) is contained in the photosensitive resin composition of the present embodiment, the content is preferably 0.01 parts by mass based on a total of 100 parts by mass of components (A) and (B). parts to 20 parts by weight, more preferably 0.1 parts to 10 parts by weight, even more preferably 0.5 parts to 8 parts by weight. By setting the content of component (D-3) to 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be imparted. However, if the amount is more than 20 parts by mass, unexposed areas may develop poorly or the storage stability of the composition may deteriorate.

<(E) component>
Component (E) is a crosslinking agent, and is introduced into the photosensitive resin composition of the present invention when it satisfies requirement (Z1). More specifically, it is a compound having a structure capable of forming a bridged structure through a thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxyl group) of component (B). Specific examples will be given below, but the invention is not limited to these. The thermal crosslinking agent is, for example, one selected from (E1) a crosslinkable compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group, and (E2) a crosslinkable compound represented by formula (5). preferable. These crosslinking agents can be used alone or in combination of two or more.

When the crosslinkable compound having two or more substituents selected from the alkoxymethyl group and hydroxymethyl group of component (E1) is exposed to high temperatures during thermosetting, the crosslinking reaction proceeds through a dehydration condensation reaction. . Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast compounds.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 , 6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include compounds such as glycoluril compounds (product names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and methylated urea resins (product name: UFR (registered trademark) 65). ), butylated urea resin (product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by DIC Corporation (high condensation type, product name: Beckamine ( Examples include registered trademarks) J-300S, P-955, N), etc.

Specific examples of alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine. Commercially available products include Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, and BL-). 60, BX-55H), etc.

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine and the like. Commercially available products include methoxymethyl type melamine compounds (trade name: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark)) manufactured by Mitsui Cytec Co., Ltd. ) 506, 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical (trade name: Nikalak (registered trademark) MW-30, Nikalak MW-22, Nikalak MW-11, Nikalak MW-100LM, MS-001, Nikalak (registered trademark) MX-002, MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nikalac (registered trademark) MX-45, MX-410, MX-302), etc. Can be mentioned.

It may also be a compound obtained by condensing a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amino group is substituted with a methylol group or an alkoxymethyl group. Examples include high molecular weight compounds made from melamine and benzoguanamine compounds as described in US Pat. No. 6,323,310. Examples of commercial products of the melamine compound include the trade name Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercial products of the benzoguanamine compound include the trade name Cymel (registered trademark) 1123 (trade name). (manufactured by Mitsui Cytec Co., Ltd.), etc.

Specific examples of phenoplast compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3 , 3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzenemethanol), 4,4'-(1-methyl ethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6- bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxymethyl)phenol], 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2 , 6-bis(methoxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(methoxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-methoxy-5 -methylbenzene methanol), 4,4'-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4'-methylenebis[2-methyl-6-methoxymethylphenol], 4, Examples include 4'-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol] and 4,4'-methylenebis[2,6-bis(methoxymethyl)phenol]. It is also available as a commercial product, and specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA ( As mentioned above, examples include those manufactured by Asahi Yokuzai Kogyo Co., Ltd.).

Furthermore, as the component (E1), an acrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, or Polymers made using methacrylamide compounds can also be used.

Such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-ethoxymethyl. Examples include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is from 1,000 to 50,000, preferably from 1,500 to 20,000, more preferably from 2,000 to 10,000.

（式中、ｋは２～１０の整数、ｍは０～４の整数を示し、Ｒ^１１はｋ価の有機基を表す）Further, the photosensitive resin composition of the present invention can contain a crosslinkable compound represented by formula (5) as component (E2).

(In the formula, k represents an integer of 2 to 10, m represents an integer of 0 to 4, and R ¹¹ represents a k-valent organic group)

Component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by formula (5). Specific examples thereof include the following formulas E2-1 and E2-2, and the commercial products shown below.

Commercially available products include Epolead GT-401, Epolead GT-403, Epolead GT-301, Epolead GT-302, Celloxide 2021, Celloxide 3000 (product name manufactured by Daicel Chemical Industries, Ltd.), and Denacol, an alicyclic epoxy resin. EX-252 (trade name manufactured by Nagase Chemtechs Co., Ltd.), CY175, CY177, CY179 (trade name manufactured by CIBA-GEIGY A.G.), Araldite CY-182, CY-192, CY-184 ( CIBA-GEIGY A.G (product name), Epiclon 200, 400 (product name from DIC Corporation), Epicort 871, 872 (product name from Yuka Shell Epoxy Co., Ltd.), Examples include ED-5661 and ED-5662 (trade names manufactured by Celanese Coating Co., Ltd.). Moreover, these crosslinkable compounds can be used alone or in combination of two or more types.

Among these, compounds represented by formula C1 and formula C2, Epolead GT-401, which have a cyclohexene oxide structure from the viewpoint of heat resistance, solvent resistance, process resistance such as long-term baking resistance, and transparency, Preferably, the same GT-403, the same GT-301, the same GT-302, Celoxide 2021, and Celoxide 3000.

In addition, as component E, a cross-linking structure is formed by a thermal reaction with a thermally reactive site (for example, a carboxyl group and/or a phenolic hydroxyl group) of component (B) other than those shown as components (E1) and (E2). Compounds that can be formed can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexane Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N', -tetraglycidyl-m-xylene diamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and N,N,N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, etc. Epoxy compounds, VESTANAT B1358/100, VESTAGON BF 1540 (all are isocyanurate-type modified polyisocyanates, manufactured by Degussa Japan Co., Ltd.), Takenate (registered trademark) B-882N, Takenate B-7075 (all are isocyanurate-type modified polyisocyanates) Examples include isocyanate compounds such as polyisocyanate (manufactured by Mitsui Chemicals, Inc.).

Furthermore, as component E, it is possible to use a polymer having two or more structures that can form a cross-linked structure by thermal reaction with the heat-reactive moieties (for example, carboxyl groups and/or phenolic hydroxyl groups) of component (B). can. Specifically, for example, polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxy Polymers produced using compounds having alkoxysilyl groups such as silane, 2-isocyanatoethyl methacrylate (Karens MOI [registered trademark], manufactured by Showa Denko K.K.), 2-isocyanatoethyl acrylate (Karens AOI [registered trademark], manufactured by Showa Denko KK), 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate (Karens MOI-BM [registered trademark], Showa Denko Co., Ltd.), 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karens MOI-BP [registered trademark], Showa Denko Co., Ltd.), etc., which have a blocked isocyanate group. Polymers produced using the compounds are included. These compounds may be used alone or in combination to produce a polymer, or may be used in combination with other compounds to produce a polymer.

When component (B) has a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group, a hydroxy group, a carboxyl group, an amide group, A compound having two or more groups represented by amino groups can be used as the component (E).

These crosslinking compounds can be used alone or in combination of two or more.

When component (E) is selected as the crosslinking agent in the photosensitive resin composition of the present invention, the content is preferably 1 to 50 parts by mass, based on 100 parts by mass of the total of components (A) and (B). The amount is 1 to 40 parts by weight, more preferably 1 to 30 parts by weight. If the content of the crosslinkable compound is small, the density of the crosslinks formed by the crosslinkable compound is not sufficient, so it has the effect of improving heat resistance, solvent resistance, resistance to long firing, etc. after pattern formation. may not be obtained. On the other hand, if it exceeds 50 parts by mass, uncrosslinked crosslinkable compounds will be present, and the heat resistance after pattern formation, solvent resistance, resistance to long-term baking, etc. will decrease, and the photosensitive resin composition Storage stability may deteriorate.

<(F) component>
Component (F) is a compound having two or more ethylenic polymerizable groups. The compound having two or more ethylenic polymerizable groups as used herein means a compound that has two or more polymerizable groups in one molecule, and those polymerizable groups are located at the end of the molecule. , those polymerizable groups mean at least one type of polymerizable group selected from the group consisting of acrylate groups, methacrylate groups, vinyl groups, and allyl groups.
This component (F), a compound having two or more ethylenic polymerizable groups, has good compatibility with each component in the solution of the negative photosensitive resin composition of the present invention, and has no effect on developability. From the viewpoint of not giving any adverse effects, a compound having a molecular weight (weight average molecular weight when the compound is a polymer) of 1,000 or less is preferable.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, and pentaerythritol triacrylate. Erythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5-trimethacryloylhexahydro-S-triazine, tris(hydroxyethyl acryloyl) isocyanurate, tris(hydroxyethyl methacryloyl) isocyanurate, triacryloyl Formal, trimethacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate Acrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl ) Cysteine, N,N'-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate , bisphenol S dimethacrylate, bisphenoxyethanol fluorene acrylate, bisphenoxyethanol fluorene methacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate, and the like.

The above polyfunctional acrylate compounds are easily available as commercial products, and specific examples thereof include KYARAD T-1420, KYARAD DPHA, KYARAD DPHA-2C, KYARAD D-310, KYARAD D-330, and KYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075, DN-2475, R-526, NPGDA, PEG400DA, MANDA, R-167, HX -220, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, M-240, M-6200, M-309, M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530, M-8560, M-9050 (manufactured by Toagosei Co., Ltd.), Viscoat 295, 300, 360, GPT, 3PA, 400, 260, 312, 335HP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD -TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900 , BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.).
These compounds having two or more heavy ethylenic groups can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains component (F), the content is preferably 5 to 100 parts by mass based on 100 parts by mass of the total of components (A) and (B). , more preferably 10 to 80 parts by weight, particularly preferably 20 to 70 parts by weight. If this ratio is too small, the exposed portions will be insufficiently cured, and pattern formation may not be possible, or even if pattern formation is possible, the film may have low reliability. Furthermore, if this ratio is excessive, tackiness may occur in the coating film after prebaking, or unexposed areas may become poorly dissolved during development.

<(G) component>
Component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups that form a covalent bond with an acid. Examples of functional groups that form covalent bonds with acids include epoxy groups and methylol groups.

Examples of compounds having two or more epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diglycidyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, and glycerol. Triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidyl phenylglycidyl ether, 1,1,3-tris[p-(2,3-epoxypropoxy)phenyl]propane, diglycidyl 1,2-cyclohexanedicarboxylate Ester, 4,4'-methylenebis(N,N-diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A-diglycidyl ether, and pentaerythritol polyglycidyl ether.

Furthermore, as the compound having two or more epoxy groups, commercially available compounds may be used because they are easily available. Specific examples (product names) are listed below, but are not limited to: epoxy resins with amino groups such as YH-434 and YH434L (manufactured by Toto Kasei Co., Ltd.); Epoxy resins having a cyclohexene oxide structure such as GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); Epicoat 1001, 1002, 1003, 1004, Bisphenol A epoxy resins such as 1007, 1009, 1010, and 828 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.); Epicote 807 (manufactured by Yuka Shell Epoxy Co., Ltd.) Bisphenol F-type epoxy resins such as (manufactured by Japan Epoxy Resins Co., Ltd.); EPPN 201, Epikot 154 (all manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resins Co., Ltd.)); Phenol novolak type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.); Cresol novolak type epoxy resins such as Epikote 180S75 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resins Co., Ltd.)); Denacol EX-252 (manufactured by Nagase ChemteX Co., Ltd.), CY175, CY177 , CY179, Araldite CY-182, CY-192, CY-184 (all manufactured by CIBA-GEIGY A.G.), Epicron 200, 400 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.), Epicort 871 , 872 (manufactured by Yuka Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)), ED-5661, ED-5662 (manufactured by Celanese Coating Co., Ltd.), and other alicyclic epoxy resins. Denacol EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314 , aliphatic polyglycidyl ether such as EX-321 (manufactured by Nagase ChemteX Co., Ltd.).

Further, as the compound having two or more epoxy groups, a polymer having epoxy groups can also be used.
The above polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. Examples include addition polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, copolymers of glycidyl methacrylate, styrene and 2-hydroxyethyl methacrylate, and condensation polymers such as epoxy novolak. .

Alternatively, the above-mentioned polymer having an epoxy group can also be produced by reacting a polymer compound having a hydroxy group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.

The weight average molecular weight of such a polymer is, for example, 300 to 20,000.

These compounds having two or more epoxy groups can be used alone or in combination of two or more.

Examples of compounds having two or more methylol groups include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4 , 6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl) Examples include urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolinone. Commercially available products include compounds such as glycoluril compounds (product names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., and methylated urea resins (product name: UFR (registered trademark) 65). ), butylated urea resin (product name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), urea/formaldehyde resin manufactured by DIC Corporation (high condensation type, product name: Beckamine ( Examples include registered trademarks) J-300S, P-955, N), and tetramethoxymethylbenzoguanamine. Commercially available products include Mitsui Cytec Co., Ltd. (product name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (product names: Nikalac (registered trademark) BX-4000, BX-37, and BL-). 60, BX-55H), hexamethoxymethylmelamine, and the like. Commercially available products include methoxymethyl type melamine compounds (trade name: Cymel (registered trademark) 300, Cymel 301, Cymel 303, Cymel 350), butoxymethyl type melamine compounds (trade name: Mycoat (registered trademark)) manufactured by Mitsui Cytec Co., Ltd. ) 506, 508), methoxymethyl type melamine compounds manufactured by Sanwa Chemical (trade name: Nikalak (registered trademark) MW-30, Nikalak MW-22, Nikalak MW-11, Nikalak MS-001, Nikalak MX-002, Nikalak (registered trademark) MX-730, MX-750, MX-035), butoxymethyl type melamine compounds (trade name: Nikalac (registered trademark) MX-45, MX-410, MX-302).

Further, as the compound having two or more methylol groups, a polymer having methylol groups can also be used.

Examples of polymers having two or more methylol groups include hydroxyl groups such as N-hydroxymethyl (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, and N-butoxymethyl (meth)acrylamide. Mention may be made of polymers produced using acrylamide or methacrylamide compounds substituted with methyl or alkoxymethyl groups.

Specific examples of such polymers include, for example, poly(N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methyl methacrylate, and N-butoxymethylacrylamide. Examples include a copolymer of -ethoxymethylmethacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such a polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, still more preferably 3,000 to 50,000.

These compounds having two or more methylol groups can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention contains a compound having two or more functional groups that form a covalent bond with the acid of component (G), the content is 100% in total of components (A) and (B). It is preferably 5 to 200 parts by weight, more preferably 50 to 150 parts by weight. If this ratio is too small, the photocurability of the negative photosensitive resin composition may decrease; on the other hand, if it is too large, the developability of unexposed areas will decrease, resulting in residual film and residue. It may be the cause.

<Other additives>
Furthermore, the photosensitive resin composition of the present invention may optionally contain rheology modifiers, pigments, dyes, storage stabilizers, antifoaming agents, adhesion promoters, or polyvalent additives, as long as the effects of the present invention are not impaired. It may contain a solubility promoter such as phenol and polyhydric carboxylic acid.

<Photosensitive resin composition>
The photosensitive resin composition of the present invention is a photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component, and optionally (E) component. Further, one or more of the crosslinking agent, (F) a compound having two or more polymerizable groups, (G) a compound having two or more functional groups that form a covalent bond with an acid, and other additives. It is a composition that can contain.
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having a fluorine atom (A2) Organic group having a thermally crosslinkable group (B) Component: Alkali-soluble resin (C) Solvent ,
(D) Component: Photosensitizer.

Among them, preferred examples of the photosensitive resin composition of the present invention are as follows.
[1]: A photosensitive resin composition containing 0.1 to 20 parts by mass of component (A) per 100 parts by mass of component (B), and these components are dissolved in a solvent (C).
[2]: Contains 0.1 to 20 parts by mass of component (A) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (B), and these components are dissolved in the solvent (C). photosensitive resin composition.
[3]: Contains 0.1 to 20 parts by mass of component (A) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (B), and these components are dissolved in the solvent (C). The photosensitive resin composition further contains 1 to 50 parts by mass of a crosslinking agent as component (E) based on 100 parts by mass of the total of components (A) and (B). Composition.

The solid content in the photosensitive resin composition of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, but is, for example, 1 to 80% by mass, and is, for example, 5 to 80% by mass. 60% by weight, or 10 to 50% by weight. Here, the solid content refers to all the components of the photosensitive resin composition excluding the (C) solvent.

The method for preparing the photosensitive resin composition of the present invention is not particularly limited, but for example, component (A) (specific polymer) is dissolved in (C) solvent, and (B) is added to this solution. Alkali-soluble resin (component), photosensitizer (component (D)), crosslinking agent (component (E) if necessary), compound having two or more polymerizable groups (component (F)), and covalent bonding by acid (component (G)) A method in which compounds having two or more functional groups forming One method is to do so.

In preparing the photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the (C) solvent can be used as it is. Similarly, when adding component (B), component (D), and if necessary component (E), component (F), component (G), etc. to make a uniform solution, add (C) for the purpose of concentration adjustment. ) Additional solvent may be added. At this time, the (C) solvent used in the process of forming the specific copolymer and the (C) solvent used for concentration adjustment during the preparation of the photosensitive resin composition may be the same or different. Good too.

Therefore, it is preferable that the prepared solution of the photosensitive resin composition is used after being filtered using a filter having a pore size of about 0.2 μm.

<Coating film and cured film>
The photosensitive resin composition of the present invention can be applied to semiconductor substrates (e.g. silicon/silicon dioxide coated substrates, silicon nitride substrates, metal (e.g. aluminum, molybdenum, chromium) coated substrates, glass substrates, quartz substrates, ITO substrates). etc.) by spin coating, flow coating, roll coating, slit coating, spin coating following slit coating, inkjet coating, etc., and then pre-drying on a hot plate or oven to form a coating film. can do. Thereafter, a photosensitive resin film is formed by heat-treating this coating film.

As conditions for this heat treatment, for example, a heating temperature and heating time appropriately selected from a temperature range of 70° C. to 160° C. and a time range of 0.3 to 60 minutes are adopted. The heating temperature and heating time are preferably 80°C to 140°C and 0.5 to 10 minutes.

Further, the thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 to 30 μm, further, for example, 0.2 to 10 μm, and further, for example, 0.3 to 8 μm.

A mask with a predetermined pattern is attached to the coating film obtained above, irradiation with light such as ultraviolet rays, and development with an alkaline developer results in either exposed or unexposed areas depending on the material composition. By heating the washed out and remaining patterned film at 80° C. to 140° C. for 0.5 to 10 minutes, a relief pattern with sharp end faces can be obtained.

Examples of alkaline developers that can be used include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline Examples include alkaline aqueous solutions such as quaternary ammonium aqueous solutions and amine aqueous solutions such as ethanolamine, propylamine, and ethylenediamine. Furthermore, surfactants and the like can also be added to these developers.

Among the above, an aqueous solution of 0.1 to 2.58% by mass of tetraethylammonium hydroxide is generally used as a developer for photoresists, and this alkaline developer is also used in the photosensitive resin composition of the present invention. , development can be performed satisfactorily without causing problems such as swelling.

Moreover, as a developing method, any of the liquid piling method, dipping method, rocking immersion method, etc. can be used. The developing time at that time is usually 15 to 180 seconds.

After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by spinning to remove moisture on the substrate, and then pattern formation. A film is obtained.

Subsequently, the pattern-formed film is post-baked for thermosetting, specifically by heating using a hot plate, oven, etc., to improve heat resistance, transparency, and flattening properties. , a film with excellent low water absorption, chemical resistance, etc., and a good relief pattern can be obtained.

Post-baking is generally performed at a heating temperature selected from the range of 140°C to 270°C for 5 to 30 minutes when on a hot plate, and for 30 to 90 minutes when in an oven. This method is adopted.

By such post-baking, it is possible to obtain a cured film having a desirable pattern shape.

As described above, the photosensitive resin composition of the present invention has high storage stability, has sufficiently high sensitivity, and has very little film loss in unexposed areas during development, and can produce coating films with fine patterns. can be formed.

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. Note that the number average molecular weight and weight average molecular weight are measured as follows.
[Measurement of number average molecular weight and weight average molecular weight]
The number average molecular weight and weight average molecular weight of the copolymer obtained according to the following synthesis example were measured using a Shimadzu GPC device (Shodex columns KF-804L and 803L), and the elution solvent tetrahydrofuran was added to the column at a flow rate of 1 ml/min. (Column temperature: 40°C) The measurement was carried out under the conditions of elution by flowing. The following number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in polystyrene equivalent values.

The meanings of the abbreviations used in the following examples are as follows.
MMA: Methyl methacrylate HEMA: 2-hydroxyethyl methacrylate HPMA: 4-hydroxyphenyl methacrylate HPMA-QD: Condensation reaction between 1 mol of 4-hydroxyphenyl methacrylate and 1.1 mol of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride Compound synthesized by CHMI: N-cyclohexylmaleimide TMSSMA: methacryloxypropyl tris(trimethylsiloxy)silane PFHMA: 2-(perfluorohexyl)ethyl methacrylate MAA: methacrylic acid AIBN: α,α'-azobisisobutyronitrile QD: Synthesized by a condensation reaction between 1 mol of α, α, α'-tris(4-hydroxyphenyl)-1-ethyl-4-isopropylbenzene and 2 mol of 1,2-naphthoquinone-2-diazido-5-sulfonyl chloride. Compound GT-401: Butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone P2: Polymer of 85% hydroxystyrene and 15% styrene, and polymer of 70% hydroxystyrene and 30% styrene. Styrene polymer PFHTMOS: 2-(perfluorohexyl)ethyltrimethoxysilane KBM-503: 3-methacryloxypropyltrimethoxysilane KBM-403: 3-glycidoxypropyltrimethoxysilane KBM- 303: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane 35wt% TEAH: 35wt% tetraethylammonium hydroxide aqueous solution PTMOS: Phenyltrimethoxysilane 15JWET: Organo ion exchange resin I907: 2-methyl-1-[4 -(Methylthio)phenyl]-2-morpholinopropan-1-one (IRGACURE 907, manufactured by BASF)
DEAB: 4,4'-bis(diethylamino)benzophenone DPHA: Dipentaerythritol hexaacrylate 8KQ: 8KQ-2001 (Alkali-soluble UV-curable acrylic resin manufactured by Taisei Fine Chemical Co., Ltd.) (P8)
PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate CHN: Cyclohexanone THF: Tetrahydrofuran

<Synthesis example 1>
70.00 g of MAA, 218.75 g of HEMA, 43.75 g of HPMA, 192.50 g of MMA, 350.00 g of CHMI, and 56.00 g of AIBN were dissolved in 1396.50 g of PGME and reacted at 90°C for 20 hours to obtain acrylic polymer. A combined solution (solid content concentration 40% by mass) was obtained (P1). The obtained acrylic polymer had Mn of 2,800 and Mw of 4,900.

<Synthesis example 2>
2.34 g of PFHTMOS, 4.93 g of KBM-303, 0.21 g of 35 wt% TEAH, and 0.68 g of water were dissolved in 9.79 g of THF and stirred at 40° C. for 4 hours. Subsequently, 0.73 g of 15JWET washed with THF was added, and the mixture was stirred at 25° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P3). The obtained siloxane polymer had Mn of 1,900 and Mw of 2,200.

<Synthesis example 3>
2.34 g of PFHTMOS, 4.45 g of KBM-403, 0.21 g of 35 wt% TEAH, and 0.68 g of water were dissolved in 9.21 g of THF and stirred at 40° C. for 4 hours. Subsequently, 0.68 g of 15JWET washed with THF was added, and the mixture was stirred at 25° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P4). The obtained siloxane polymer had Mn of 2,400 and Mw of 2,900.

<Synthesis example 4>
2.34 g of PFHTMOS, 2.46 g of KBM-303, 1.98 g of PTMOS, 0.21 g of 35 wt% TEAH, and 0.68 g of water were dissolved in 9.21 g of THF and stirred at 40° C. for 4 hours. Subsequently, 0.48 g of 15JWET washed with THF was added, and the mixture was stirred at 25° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P5). The obtained siloxane polymer had Mn of 1,900 and Mw of 2,400.

<Synthesis example 5>
By dissolving 2.50 g of HPMA-QD, 2.58 g of TMSSMA, 5.26 g of PFHMA, 0.70 g of MAA, 1.46 g of CHMI, and 0.33 g of AIBN in 51.3 g of CHN and stirring at 110 ° C. for 20 hours. An acrylic polymer solution (solid content concentration 20% by mass) was obtained (P6). The obtained acrylic polymer had Mn of 7,200 and Mw of 11,000.

<Synthesis example 6>
2.34 g of PFHTMOS, 4.97 g of KBM-503, 0.21 g of 35 wt% TEAH, and 0.68 g of water were dissolved in 9.83 g of THF and stirred at 40° C. for 4 hours. Subsequently, 0.73 g of 15JWET washed with THF was added, and the mixture was stirred at 25° C. for 1 hour. Next, the waste 15JWET was filtered to obtain a siloxane polymer solution (P7). The obtained siloxane polymer had Mn of 2,000 and Mw of 2,100.

<Examples 1 to 5 and Comparative Examples 1 to 4>
According to the composition shown in the following Table 1, (A) component solution, (B) component solution, (D) component, (E) component, and (F) component are dissolved in (C) solvent at predetermined ratios, The photosensitive resin compositions of each Example and each Comparative Example were prepared by stirring at room temperature for 3 hours to obtain a uniform solution.

[Evaluation of contact angle: Examples 1 to 3 and Comparative Examples 1 to 3]
After applying the photosensitive resin composition onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 80° C. for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (hereinafter referred to as TMAH) for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to form a cured film with a thickness of 1.0 μm. The contact angle of methyl benzoate on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.
[Evaluation of contact angle: Example 4, Example 5, and Comparative Example 4]
After applying the photosensitive resin composition onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to form a cured film with a thickness of 1.0 μm. The contact angle of methyl benzoate on this cured film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2.

[Evaluation of UV ozone treatment resistance: Examples 1 to 3 and Comparative Examples 1 to 3]
After applying the photosensitive resin composition onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 80° C. for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was immersed in a 2.38% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to form a cured film with a thickness of 1.0 μm. This cured film was cleaned with ozone for 10 minutes using UV-312 manufactured by Techno Vision Co., Ltd. The contact angle of methyl benzoate on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2. It is considered good if the difference after post-baking and after UV ozone treatment is within 20°.
[Evaluation of UV ozone treatment resistance: Example 4, Example 5, and Comparative Example 4]
After applying the photosensitive resin composition onto a silicon wafer using a spin coater, it was prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was immersed in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, this coating film was post-baked by heating it at a temperature of 230° C. for 30 minutes to form a cured film with a thickness of 1.0 μm. This cured film was cleaned with ozone for 10 minutes using UV-312 manufactured by Techno Vision Co., Ltd. The contact angle of methyl benzoate on the ozone-cleaned membrane was measured using a Drop Master manufactured by Kyowa Interface Science Co., Ltd. The results obtained are shown in Table 2. It is considered good if the difference after post-baking and after UV ozone treatment is within 20°.

[Evaluation of wettability: Examples 1 to 3 and Comparative Examples 1 to 3]
The photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 80° C. for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays at a light intensity of 5.5 mW/cm ² at 365 nm for a certain period of time using a UV irradiation device PLA-600FA manufactured by Canon Inc. through a mask with a rectangular pattern having a length of 50 μm and a width of 100 μm. Thereafter, the film was developed by immersing it in a 2.38% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, the coating film on which the rectangular pattern was formed was post-baked and cured by heating at a temperature of 230° C. for 30 minutes. Approximately 20 pl of the solution was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. at a driving waveform of A, a repetition frequency of 1 kHz, and a driving voltage of 4 V. Methyl benzoate was used as the discharge solution. The results obtained are shown in Table 3.
[Evaluation of wettability: Example 4, Example 5, and Comparative Example 4]
The photosensitive resin composition was applied onto ITO-glass using a spin coater, and then prebaked on a hot plate at a temperature of 100° C. for 120 seconds to form a coating film with a thickness of 1.2 μm. This coating film was irradiated with ultraviolet rays at a light intensity of 5.5 mW/cm ² at 365 nm for a certain period of time using a UV irradiation device PLA-600FA manufactured by Canon Inc. through a mask with a rectangular pattern having a length of 50 μm and a width of 100 μm. Thereafter, the film was developed by immersing it in a 0.4% by mass TMAH aqueous solution for 60 seconds, and then washed with running ultrapure water for 30 seconds. Next, the coating film on which the rectangular pattern was formed was post-baked and cured by heating at a temperature of 230° C. for 30 minutes. Approximately 20 pl of the solution was discharged onto the rectangular opening of the obtained cured film using an Inkjet Designer manufactured by Cluster Technology Co., Ltd. at a driving waveform of A, a repetition frequency of 1 kHz, and a driving voltage of 4 V. Methyl benzoate was used as the discharge solution. The results obtained are shown in Table 3.

<Wettability evaluation criteria>
○: The solution completely wets and spreads in the rectangular opening.
×: A portion where the solution does not wet and spread is observed in the rectangular opening.

As shown in Table 2, Comparative Example 2 and Examples 1 to 5 exhibited high contact angles even after UV ozone treatment. On the other hand, in Comparative Examples 1, 3, and 4, the contact angle decreased significantly after UV ozone treatment, and sufficient liquid repellency for methyl benzoate was not obtained.

As shown in Table 3, in Comparative Example 1 and Examples 1 to 5, the wettability of the rectangular opening was good. On the other hand, in Comparative Examples 2 to 4, sufficient wettability could not be confirmed.

Claims (12)

A thermosetting photosensitive resin composition containing the following components (A), (B), (C) solvent, and (D).
(A) Component: Polysiloxane having the following groups (A1) and (A2) (A1) Organic group having a fluorine atom (A2) Organic group having an epoxy group (B) Component: Acrylic resin, polyhydroxystyrene resin , an alkali-soluble resin (C) solvent that is a polyimide precursor or polyimide,
Component (D): quinonediazide compound . The photosensitive resin composition according to claim 1, wherein component (B) is an acrylic resin or a polyhydroxystyrene resin. The photosensitive resin composition according to claim 1 or 2, which satisfies at least one of the following (Z1) and (Z2) .
(Z1): further contains a crosslinking agent as component (E),
(Z2): The alkali-soluble resin of component (B) further has a self-crosslinking group, or a group that reacts with at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group, and an amino group. It also has . The photosensitive resin composition according to claim 1, wherein component (A) further has a phenyl group. 2. The photosensitive resin composition according to claim 1, wherein the polysiloxane as component (A) has a number average molecular weight of 1,000 to 100,000 in terms of polystyrene. 6. The photosensitive resin composition according to claim 1 , wherein the alkali-soluble resin as component (B) has a number average molecular weight of 2,000 to 50,000 in terms of polystyrene. The photosensitive resin composition according to any one of claims 1 to 6 , which contains 0.1 to 20 parts by mass of component (A) per 100 parts by mass of component (B). Photosensitivity according to any one of claims 1 to 7 , characterized in that component (D) is present in an amount of 5 to 100 parts by mass based on a total of 100 parts by mass of components (A) and (B). Resin composition. Photosensitivity according to any one of claims 3 to 8 , characterized in that the component (E) is 1 to 50 parts by mass with respect to a total of 100 parts by mass of the components (A) and (B). Resin composition. A cured film obtained using the photosensitive resin composition according to any one of claims 1 to 9 . A display element comprising the cured film according to claim 10 . A display element comprising the cured film according to claim 10 as an image forming partition.