TW201940553A - Photosensitive resin composition - Google Patents

Abstract

To provide a photosensitive resin composition which is suitable as a pixel barrier material and a material for forming a patterned insulating film that is used for liquid crystal display elements, organic EL display elements and the like, and which is able to maintain a good image even after curing and is capable of forming an image of a cured film having high lypophilicity on a substrate without requiring oxygen plasma processing or the like, while having high oil repellency even after UV ozone processing. [Solution] A thermally curable photosensitive resin composition which contains component (A), component (B), solvent (C) and component (D) described below. (A): a polysiloxane having the following groups (A1) and (A2) (A1): an organic group having a fluorine atom (A2): an organic group having a thermally crosslinkable group (B): an alkali-soluble resin (C): a solvent (D): a sensitizing agent.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition and a cured film obtained therefrom.
More specifically, it 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 suitable for use as an interlayer insulation film in liquid crystal displays or EL displays, a light-shielding material corresponding to an inkjet method, or a partition wall material.

In recent years, the manufacturing steps of display elements such as thin-film transistor (TFT) liquid crystal display elements and organic EL (electroluminescent) elements have also been actively reviewed using inkjet-based full-color display substrate manufacturing techniques. For example, regarding the production of color filters in liquid crystal display elements, for the conventional printing method, electrodeposition method, dyeing method, or pigment dispersion method, there is a proposal to define a pixel compartment (hereinafter referred to as a partition) that is previously patterned. A wall is formed by a photosensitive resin layer that blocks light, and a color filter that drips ink droplets in an area surrounded by the partition wall and a method for manufacturing the same (Patent Document 1) and the like. In addition, a method is also proposed in which an organic EL display element is prepared with a partition wall in advance, and an ink that becomes a light-emitting layer is dropped to produce an organic EL display element (Patent Document 2).
However, when the ink droplet is dropped to the area surrounded by the partition wall by the inkjet method, in order to prevent the ink droplet from overflowing to the adjacent pixel beyond the partition wall, the substrate must be ink-repellent (hydrophilic, lipophilic). The surface of the partition wall must be water-repellent and oil-repellent.

In order to achieve the above-mentioned object, it is proposed to use a continuous plasma treatment or UV ozone treatment such as an oxygen gas plasma treatment and a fluorine gas plasma treatment to make the substrate hydrophilic and to make the partition wall water-repellent (Patent Document 3) ). In addition, proposals have been made to add a fluorine-based surfactant or a fluorine-based polymer to a photosensitive organic thin film (Patent Document 4). However, it is not only the photosensitivity, but also the photosensitivity, including coating properties, that should be considered. There are many points, and because of the UV ozone treatment during the hydrophilic treatment of the substrate, the water repellency of the surface is reduced, so it is not practical.

In addition, conventionally, as a liquid-repellent partition wall, as a negative type, there is Japanese Patent Application Laid-Open No. 2015-172742 (Patent Document 5). As a positive type, there is Japanese Patent Application Laid-Open No. 2012-220860 (Patent Document 6).

[Prior technical literature]
[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-187111
[Patent Document 2] Japanese Unexamined Patent Publication No. 11-54270
[Patent Document 3] Japanese Patent Laid-Open No. 2000-353594
[Patent Document 4] Japanese Patent Application Laid-Open No. 10-197715
[Patent Document 5] Japanese Patent Laid-Open No. 2015-172742
[Patent Document 6] Japanese Patent Application Publication No. 2012-220860

[Problems to be Solved by the Invention]

The present invention has been made in view of the above circumstances, and the problem to be solved is to form a liquid crystal display element, an organic EL display element, and the like. Even after UV ozone treatment, it has high water repellency and high water repellency on the surface of the cured film. Oil-repellent, hardened film image with high lyophilicity to substrate even without plasma treatment or UV ozone treatment. In particular, in the production of a substrate using inkjet, an image of a cured film that prevents ink droplets from overflowing the partition wall and overflowing to adjacent pixels is formed.

[Means to solve the problem]

As a result of careful review in order to achieve the above-mentioned object, the inventors have found that a hardened film is formed from a composition containing a polysiloxane containing an organic group containing a fluorine atom and an organic group containing a thermally crosslinkable group, After the UV ozone treatment, the liquid-repellent property can be efficiently provided on the surface of the film, and even if the plasma treatment or the UV ozone treatment is not performed, the substrate can be effectively provided with high lyophilicity, and the present invention has been completed.

That is, the present invention relates to the following.
A heat-curable photosensitive resin composition comprising the following (A) component, (B) component, (C) solvent, and (D) component,
(A) Ingredient: Polysiloxane having the following groups (A1) and (A2)
(A1) an organic group having a fluorine atom
(A2) Organic group having a thermally crosslinkable group
(B) Ingredient: Alkali soluble resin
(C) solvents,
(D) component: Photosensitizer.
2. The photosensitive resin composition according to the above 1, wherein the organic group (A2) having a thermally crosslinkable group is an organic group having an epoxy group.
3. The photosensitive resin composition according to 1 or 2 above, which satisfies at least any one of the following (Z1) to (Z4),
(Z1): a crosslinking agent further containing (E) component,
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinkable group, or further has a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amine group, and an amine group,
(Z3): the component (D) is a photo radical generator, and further contains a compound having (F) a component having two or more ethylenic double bonds,
(Z4): The compound (D) is a photoacid generator, and further contains a compound (G) having two or more functional groups that form a covalent bond with an acid generated by the (D) component.
4. The photosensitive resin composition according to the above 1 or 2, wherein the component (D) is a quinonediazide compound.
5. The photosensitive resin composition according to the above 3, wherein the component (D) is a quinonediazide compound and satisfies any one of the above (Z1) and (Z2).
6. The photosensitive resin composition according to any one of the above 1 to 5, wherein the component (A) further has a phenyl group.
7. The photosensitive resin composition according to the above 6, wherein the number average molecular weight of the polysiloxane of the component (A) is 1,000 to 100,000 in terms of polystyrene.
8. The photosensitive resin composition according to any one of 1 to 7 above, wherein the number average molecular weight of the alkali-soluble resin of the component (B) is 2,000 to 50,000 in terms of polystyrene.
9. The photosensitive resin composition according to any one of 1 to 8 above, which contains 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B).
10. The photosensitive resin composition according to any one of the above 1 to 9, wherein the (D) component is 5 to 100 parts by mass with respect to 100 parts by mass of the total of the (A) component and the (B) component.
11. The photosensitive resin composition according to any one of the above 3 to 10, wherein the (E) component is 1 to 50 parts by mass with respect to 100 parts by mass of the total of the (A) component and the (B) component.
12. A cured film obtained by using the photosensitive resin composition according to any one of 1 to 11 above.
13. A display element comprising the cured film according to 12 above.
14. A display element having the cured film as described in 12 above as a partition wall for image formation.

[Inventive effect]

The photosensitive resin composition of the present invention is formed to have a high oil-repellency on the surface of the cured film even after UV ozone treatment, and has a high lyophilicity to the substrate even without plasma treatment or UV ozone treatment. Image of hardened film.

[Form of Implementing Invention]

The photosensitive resin composition of this invention is a photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component.
(A) Ingredient: Polysiloxane having the following groups (A1) and (A2)
(A1) an organic group having a fluorine atom
(A2) Organic group having a thermally crosslinkable group
(B) Ingredient: Alkali soluble resin
(C) solvents,
(D) component: Photosensitizer.

The photosensitive resin composition of the present invention preferably satisfies at least any one of the following (Z1) to (Z4).
(Z1): a cross-linking agent further containing (E) component,
(Z2): The alkali-soluble resin of the component (B) further has a self-crosslinkable group, or a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amine group, and an amine group,
(Z3): the component (D) is a photo-radical generator, and further contains (F) a compound having two or more ethylenic double bonds,
(Z4): A compound in which the component (D) is a photoacid generator, and further contains (G) a component having two or more functional groups that form a covalent bond with an acid generated by the component (D).

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

The details of each component are described below.

＜ (A) component ＞
The polysiloxane (A) used in the present invention is a polysiloxane having the following groups (A1) and (A2).
(A1) an organic group having a fluorine atom
(A2) Organic group having a thermally crosslinkable group

(A1) An organic group having a fluorine atom is an organic group bonded to a silicon atom of a polysiloxane backbone, and an organic group partially or entirely substituted with a fluorine atom. The organic group having a fluorine atom is not particularly limited as long as the effect of the present invention is not impaired, as long as it has a fluorine atom. Particularly, an alkyl group having a hydrogen atom partially or completely substituted with a fluorine atom, or an alkyl group containing an ether bond partially or completely substituted with a fluorine atom is preferred. In this case, the number of fluorine atoms in the organic group is not particularly limited. More preferred is a perfluoroalkyl group, and even more preferred is an organic group represented by the formula (1).

(k represents an integer from 0 to 12.)

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

The organic group having a fluorine atom of the polysiloxane (A), from the viewpoint of having both liquid repellency, film hardness, and solvent resistance, is one to one of all silicon atoms of the polysiloxane (A). Mol is preferably 0.05 to 0.5 mole, and still more preferably 0.1 to 0.4 mole.

(A2) The thermally crosslinkable group in the organic group having a thermally crosslinkable group is not particularly limited as long as it is a group that forms a covalent bond by heating, and examples include vinyl, epoxy, amine, and mercapto , Blocked isocyanate group, or isocyanate group.
When the thermally crosslinkable group is an epoxy group, the organic group having an epoxy group includes glycidyloxy group, 3,4-epoxycyclohexylmethyl group, and the like.
The organic group having a thermally crosslinkable group of the polysiloxane (A), compared with the all-silicone possessed by the polysiloxane (A), from the viewpoints of both liquid-repellency and film hardness and solvent resistance. One mole of atom is preferably 0.2 to 0.95 mole, and still more preferably 0.3 to 0.8 mole.

The polysiloxane (A) of the present invention is not an organic group (A1) having a fluorine atom, or an organic group (A2) having a thermally crosslinkable group, but other organic groups may be bonded to the polymer. The silicon atom of the siloxane backbone. The other organic group is an organic group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, which does not have a fluorine atom.

Examples of such an organic group having no fluorine atom include a saturated hydrocarbon group having a linear or branched structure; an aromatic group having a benzene ring; an organic group such as an amino group, a urea group, or a vinyl group; or an ether having an ether group. Organic groups such as bonds or ester bonds.
Specific examples of these include methyl, ethyl, propyl, butyl, pentyl, heptyl, octyl, dodecyl, cetyl, octadecyl, and cyclohexyl , Phenyl, vinyl, γ-aminopropyl, γ-methacryloxypropyl and the like.

In the present invention, the amount of the organic group having no fluorine atom in the polysiloxane (A) is not particularly limited as long as the effect of the present invention is not impaired, but it is relative to the total amount of the polysiloxane (A). 1 mole of silicon atom, preferably 0.01 to 0.75 mole. In this range, a film having a contact angle of an organic solvent of 50 degrees or more can be easily obtained, and a homogeneous solution of polysiloxane (A) can be easily obtained.

(A) The number average molecular weight of the component polysiloxane is in the range of 1,000 to 100,000. If the number average molecular weight is more than 100,000, the workability may be deteriorated. If the number average molecular weight is less than 1,000, the workability may be too small. During development, a considerable amount of the exposed portion film is reduced, and the liquid repellency may be insufficient. situation.

The method for obtaining such a polysiloxane (A) is not particularly limited, but an alkoxysilane represented by the following formula (2), an alkoxysilane having an epoxy group, and other organic groups having an organic group as desired Polysiloxanes obtained by polycondensation of alkoxysilanes are 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 organic group having a fluorine atom described above.

In Formula (2), R ² and R ³ each independently represent a hydrocarbon group having 1 to 5 carbon atoms, and particularly preferably a saturated hydrocarbon group. Among these, lower alkyl groups such as methyl, ethyl, propyl, and butyl are preferable because they can be obtained as commercially available products. When a plurality of alkoxysilanes represented by formula (2) are used, their R ² and R ³ may be the same or different from each other.

In the present invention, among the alkoxysilanes represented by formula (2), R ¹ is preferably an alkoxysilane represented by an organic group represented by formula (1).

(k represents an integer from 0 to 12.)

Specific examples of such alkoxysilanes in which R ¹ is an organic group represented by formula (1) include trifluoropropyltrimethoxysilane, trifluoropropyltriethoxysilane, and trifluorooctyltrimethoxy Trisilane, tridecylfluorooctyltriethoxysilane, heptafluorodecyltrimethoxysilane, heptafluorodecyltriethoxysilane, 2- (perfluorohexyl) ethyltrimethoxysilane, and the like.

In the present invention, at least one of the alkoxysilanes represented by the formula (2) may be used, and plural kinds may be used if necessary.

The alkoxysilane having an organic group containing 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 the formula (3), R ⁴ is an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amine group, a mercapto group, a blocked isocyanate group, an isocyanate group, a methacryl group, an acryl group, or a urea group. . Among them, an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amine group, a methacryl group, an acryl group, or a ureido group is preferred from the viewpoint of ease of acquisition. More preferably, it is an organic group having 2 to 12 carbon atoms having an epoxy group, a methacryl group, an acryl group or a urea group.
More specifically, an organic group having 2 to 12 carbon atoms having a glycidyloxy 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 them, 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, and dimethoxymethyl Vinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltri (2-methoxyethoxy) silane, m-styrylethyltriethoxysilane, p-benzene Vinylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyltriethoxysilane, 3- (N-styrylmethyl-2-amine Ethylethylamino) propyltrimethoxysilane, diethoxy (3-glycidoxypropyl) methylsilane, 3-glycidoxypropyl (dimethoxy) methylsilane, 3 -Glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 2- (3,4 -Epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, 3- (2-aminoethylamino) propyldi Methoxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane , 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyldiethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-amino Propyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3-mercaptopropyl (dimethoxy) methylsilane, (3-mercaptopropyl) triethoxy Silane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilyl) propyl isocyanate, 3- (triethoxysilyl) propylmethacrylate, 3- (trimethoxyl Silyl) propylmethacrylate, 3- (triethoxysilyl) propylacrylate, 3- (trimethoxysilyl) propylacrylate, 2- (triethoxysilyl) Ethyl methacrylate, 2- (trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethyl acrylate, 2- (trimethoxysilyl) ethyl acrylate Esters, (triethoxysilyl) methacrylate, (trimethoxysilyl) methacrylate, (triethoxysilyl) methacrylate, (trimethoxysilyl) ) Methacrylate, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyl Tripropoxysilane, (R) -N-1-phenylethyl-N'-triethoxysilylpropylurea, (R) -N-1-phenylethyl-N'-trimethoxy Silylpropylurea, 1- [3- (trimethoxysilyl) propyl] urea and the like.
In addition, 3-glycidyloxypropyl (dimethoxy) methylsilane, 3-glycidyloxypropyl (diethoxy) methylsilane, 3-glycidyl Glyceryloxypropyltrimethoxysilane or 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane is preferred.

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

Examples of the alkoxysilane having another organic group 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 represents 0, 1, or 2.)

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

In the formula (4), when p = 0, the alkoxysilane represented by the formula (4) represents a tetraalkoxysilane. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetrabutoxysilane, and the like, and they are easily available as commercially available products.

In the formula (4), when p = 1 to 3, the alkoxysilane type R ⁷ represented by the formula (4) is a hydrogen atom or a carbon number without a fluorine atom of 1 to 20, preferably 1 to 10 An organic group and an alkoxysilane having 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 having no 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 amine group, a urea group, or a vinyl group, 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 preferred that R ⁸ is the same. However, in the present invention, R ⁸ may be the same or different from each other. When p = 1 to 3 in the formula (4), specific examples of the alkoxysilane are shown below.
Examples thereof include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxy Silane, propyltriethoxysilane, butyltrimethoxysilane, butyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, heptyltrimethoxysilane, heptyltrimethoxysilane Ethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, cetyltrimethoxysilane, cetyl Alkyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, etc. alkyltrialkoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane , Benzyltrimethoxysilane, benzyltriethoxysilane, and other alkoxy groups such as trialkoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, etc. Silane, cyclohexyltriethoxysilane, cyclohexyltrimethoxysilane, allyltriethoxysilane, allyl Methoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltri (2-methoxyethyl (Oxy) silane, m-styrylethyltriethoxysilane, p-styrylethyltriethoxysilane, m-styrylmethyltriethoxysilane, p-styrylmethyl Triethoxysilane, 3- (N-styrylmethyl-2-aminoethylamino) propyltrimethoxysilane, 3- (2-aminoethylamino) propyldimethyl Oxymethylsilane, 3- (2-aminoethylamino) propyltriethoxysilane, 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyl Methyl diethoxymethylsilane, 3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, trimethoxy [3- (phenylamino) propyl] silane, 3 -Mercaptopropyl (dimethoxy) methylsilane, (3-mercaptopropyl) triethoxysilane, (3-mercaptopropyl) trimethoxysilane, 3- (triethoxysilane) propane Isocyanate, 3- (triethoxysilyl) propylmethacrylate, 3- (trimethoxysilyl) propylmethacrylate , 3- (triethoxysilyl) propyl acrylate, 3- (trimethoxysilyl) propyl acrylate, 2- (triethoxysilyl) ethyl methacrylate, 2- ( (Trimethoxysilyl) ethyl methacrylate, 2- (triethoxysilyl) ethylacrylate, 2- (trimethoxysilyl) ethylacrylate, (triethoxysilyl) Methyl methacrylate, (trimethoxysilyl) methacrylate, (triethoxysilyl) methacrylate, (trimethoxysilyl) methacrylate, γ-urea Propyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltripropoxysilane, (R) -N-1-phenylethyl-N'-triethoxy Silylpropylurea, (R) -N-1-phenylethyl-N'-trimethoxysilylpropylurea, 1- [3- (trimethoxysilyl) propyl] urea, and the like.

The polysiloxane (A) used in the present invention preferably contains 5 to 50 mole% of the alkoxysilane represented by the formula (2) in peralkoxysilane, and more preferably in the former alkoxysilane It is obtained by polycondensing the alkoxysilane represented by the formula (3) in an amount of 10 to 95 mol%, and the remainder is the alkoxysilane represented by the formula (4).

If the liquid repellency and solvent resistance of the film are considered, the content of the alkoxysilane represented by formula (2) is more preferably 10 to 40 mole%. The amount of the alkoxysilane represented by the formula (3) is preferably 30 to 80 mole% of the total alkoxysilane.

When the alkoxysilane represented by the formula (4) is contained, the amount is preferably 5 to 60 mole% of the total alkoxysilane.

Examples of the method for obtaining the polysiloxane (A) include, for example, an alkoxysilane represented by the formula (2), an alkoxysilane represented by the formula (3), and an alkoxy group represented by the formula (4) when necessary. A method of performing thermal polycondensation of silane and an organic solvent in the presence of an aqueous solution of tetraethylammonium hydroxide. Specifically, a method in which an aqueous tetraethylammonium hydroxide solution is added to an organic solvent in advance as a solution of the aqueous tetraethylammonium hydroxide solution, and the above-mentioned various alkoxysilanes are mixed while the solution is heated.
The above-mentioned tetraethylammonium hydroxide aqueous solution is present in an amount of 1 mol relative to the total alkoxy group amount of the alkoxysilane used, and is preferably 0.01 to 0.2 mol. The above heating can be performed at a liquid temperature of preferably 0 to 100 ° C, and to avoid evaporation and volatilization of the liquid, etc., it is preferably performed under reflux in a container provided with a return tube for several tens of minutes to ten hours.

When a plurality of types of alkoxysilanes are used, a mixture of alkoxysilanes may be mixed in advance and mixed, or a plurality of types of alkoxysilanes may be sequentially mixed.
When the alkoxysilane is subjected to polycondensation, the concentration of the total silicon atoms of the alkoxysilane to be converted into an oxide (hereinafter referred to as the concentration of SiO ₂ conversion) is 40% by mass or less, particularly preferably 10 to 30% by mass. The range is heated. By selecting an arbitrary concentration in 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 in the polycondensation of an alkoxysilane is required to dissolve the alkoxysilane represented by the formula (2) and the alkoxysilane represented by the formula (3). The alkoxysilane represented by the above formula (4) is not particularly limited, but a solvent (C) is preferably used. Among these, alcohols are produced by the polycondensation reaction of alkoxysilanes, so alcohols or organic solvents having good compatibility with alcohols can be used.

Specific examples of the polymerization solvent include alcohols such as methanol, ethanol, propanol, n-butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Glycol ethers such as diethyl ether and ethers such as tetrahydrofuran.
In the present invention, a plurality of the organic solvents may be mixed and used.

In the present invention, the solution of the specific polysiloxane obtained by the foregoing method may be directly used in the photosensitive resin composition of the present invention. If necessary, the solution of the specific polysiloxane obtained by the foregoing method may be concentrated, or a solvent may be added. It may be diluted or used in place of another solvent.

The solvent (also referred to as an additive solvent) used when adding the aforementioned solvent for dilution may be a solvent used in the polycondensation reaction or other solvents. The added solvent is not particularly limited as long as the specific polysiloxane is uniformly dissolved, and one or two or more kinds can be arbitrarily selected and used. Examples of such additional solvents include solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, methyl acetate, ethyl acetate, and ethyl lactate, in addition to the solvents used in the aforementioned polycondensation reaction. Ester solvents.

In the present invention, when a polymer other than the specific polysiloxane is used in the photosensitive resin composition, the specific polysiloxane is distilled off under normal pressure or reduced pressure before mixing the polymer other than the specific polysiloxane. Alcohols produced by polycondensation of alkanes are preferred.

＜ (B) component ＞
The component (B) of the present invention is a resin having an alkali-soluble group. Examples of the alkali-soluble group include a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, a fluorenimine group, a sulfonium group, phosphoric acid, boric acid, an active methylene group, and an active methine group.

The so-called active methylene refers to a group in which methylene (-CH _2- ) has a carbonyl group at an adjacent position and has reactivity with a nucleophile. In the present invention, the active methine refers to a structure in which one hydrogen atom of a methylene group is substituted with an alkyl group in the active methylene group and has reactivity with a nucleophile.

The active methylene group and the active methine group are more preferably a group represented by the following formula (b1).

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

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

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

Examples of the base represented by the formula (b1) include the following structures. In the structural formula, a dotted line indicates a bonding bond.

Among the alkali-soluble groups, an alkali-soluble resin having at least one organic group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group and having a number average molecular weight of 2,000 to 50,000 is preferred.

The alkali-soluble resin of the component (B) may be an alkali-soluble resin having such a structure, and the type of the skeleton and side chains of the main chain of the polymer constituting the resin is not particularly limited.

However, the average molecular weight of the alkali-soluble resin coefficient of the component (B) is in the range of 2,000 to 50,000. If the number-average molecular weight exceeds 50,000, it will be too large, which will easily cause development residues, and the sensitivity will be greatly reduced. On the other hand, if the number-average molecular weight is less than 2,000, which is too small, a large amount of film will be generated in the exposed portion during development It may become insufficiently hardened.

Examples of the alkali-soluble resin of the component (B) include an acrylic resin, a polyhydroxystyrene resin, a polyimide precursor, and a polyimide.

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

That is, the above-mentioned specific copolymer is 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 hydroxyl group, and a monomer selected from the monomers copolymerizable with these monomers A copolymer in which at least one monomer of a population is an essential constituent unit, and whose number average molecular weight is 2,000 to 50,000. If the number average molecular weight is more than 50,000, a residue may be generated.

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

Specific examples of the above-mentioned monomers are listed below, but are not limited thereto.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (propenyloxy) ethyl) phthalate, and mono- (2- (methacryloxy) ) Ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and the like.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, and N- (hydroxyphenyl) maleam. Amine, 4-hydroxyphenyl methacrylate, etc.

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

(B) 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 of the component is that of the alkali-soluble acrylic polymer of the component (B) Among all the monomers used in manufacturing, 10 to 90 mol% is preferred, 5 to 60 mol% is more preferred, and 5 to 30 mol% is most preferred. When the unsaturated carboxylic acid and / or phenolic hydroxy derivative is less than 10% by weight, the polymer has insufficient alkali solubility.

The alkali-soluble resin of the component (B) of the present invention can further copolymerize a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of stabilizing the pattern shape after curing.

Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, and 2,3-dihydroxypropyl acrylic acid. Ester, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate Esters, 5-propenyloxy-6-hydroxynorbornene-2-carboxylic acid-6-lactone, and the like.

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

From the viewpoint of increasing the Tg of the copolymer, the alkali-soluble resin of the component (B) of the present invention can further copolymerize the N-substituted maleimide compound.

N-substituted maleimide compounds Maleimide compounds include, for example, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N -Cyclohexylmaleimide and the like. From the viewpoint of transparency, those who do not have an aromatic ring are preferred. From the viewpoint of developability, transparency, and heat resistance, those with an alicyclic skeleton are more preferred, and the most preferred is cyclohexylmaleimide.

(B) The ratio of N-substituted maleimide in the production of the alkali-soluble acrylic polymer of the component is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, and most preferably 20 to 40% by weight. %. When the N-substituted maleimide is less than 10% by weight, the Tg of the copolymer is reduced, and the heat resistance may be poor. When it is 60% by weight or more, transparency may be reduced.

When the photosensitive resin composition of the present invention satisfies the requirement (Z2), the alkali-soluble resin (B) used in the present invention further has a self-crosslinking group, or has Copolymers in which at least one of the groups in the group reacts (hereinafter also referred to as a crosslinkable group) are preferred.

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

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

The content when the resin of the component (B) contains the self-crosslinkable group or the crosslinkable group is the repeating unit per unit of the resin of the (B) component, preferably 0.1 to 0.9, from the developability and the resistance From the viewpoint of solvent properties, it is more preferably 0.1 to 0.8.

(B) The alkali-soluble resin having a component further has a member selected from the group consisting of N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, oxetanyl, vinyl, and blocked isocyanate groups. Repeating of at least one type of crosslinkable group such as N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, vinyl, blocked isocyanate, etc. For the unit, for example, if the copolymerization has radical polymerizability and has a crosslinkable group selected from an epoxy group, an oxetanyl group, a vinyl group, a blocked isocyanate group, and the like, an N-alkoxymethyl group, The unsaturated compound may be at least one kind of self-crosslinkable group such as N-hydroxymethyl group and alkoxysilyl group.

Unsaturated compounds having radical polymerizability and having an N-alkoxymethyl group include N-butoxymethacrylamide, N-isobutoxymethacrylamide, and N-methoxy Methacrylamide, N-methoxymethylmethacrylamide, N-hydroxymethacrylamide and the like.

Examples of the monomer having a radical polymerizable property and further having a hydroxymethyl amidino group include N-hydroxymethacrylamide and N-hydroxymethylmethacrylamine.

Monomers having radical polymerizability and further having an alkoxysilyl group include 3-propenyloxytrimethoxysilane, 3-propenyloxytriethoxysilane, and 3-methacrylicyloxy Trimethoxysilane, 3-methacryloxytriethoxysilane, etc.

Unsaturated compounds having radical polymerizability and further having an epoxy group, for example, glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, and α-n-propyl glycidyl acrylate , Α-n-butyl glycidyl acrylate, -3,4-epoxybutyl acrylate, -3,4-epoxybutyl methacrylate, -6,7-epoxyheptyl acrylate, -6,7-epoxyheptyl methacrylate, α-ethylhexyl-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like. Among these, glycidyl methacrylate, -6,7-epoxyheptyl methacrylate, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3,4-epoxy cyclohexyl methacrylate and the like. These can be used alone or in combination.

Examples of the unsaturated compound having radical polymerizability and further having an oxetanyl group include a (meth) acrylate having an oxetanyl group. Among such monomers, preferred are 3- (methacryloxymethyl) oxetane, 3- (propenyloxymethyl) oxetane, and 3- ( Methacryloxymethyl) -3-ethyl-oxetane, 3- (propylenepyroxymethyl) -3-ethyl-oxetane, 3- (methacryl (Oxymethyl) -2-trifluoromethyloxetane, 3- (propenyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloxy) (Methyl) -2-phenyl-oxetane, 3- (propenyloxymethyl) -2-phenyl-oxetane, 2- (methacryloxymethyl) oxy Heterocyclobutane, 2- (propenyloxymethyl) oxetane, 2- (methacryloxymethyl) -4-trifluoromethyloxetane, 2- (propylene (Methoxymethyl) -4-trifluoromethyloxetane, preferably 3- (methacryloxymethyl) -3-ethyl-oxetane, 3- ( Propylene methoxymethyl) -3-ethyl-oxetane and the like.

Monomers having radical polymerizability and further having a vinyl group include 2- (2-vinyloxyethoxy) ethyl acrylate, 2- (2-vinyloxyethoxy) ethyl methacrylate, and the like .

Monomers having radical polymerization and further having a blocked isocyanate group include 2- (0- (1'-methylpropylamino) carboxyamino) ethyl methacrylate and 2- (methacrylic acid) 3,5-dimethylpyrazolyl) carbonylamino) ethyl and the like.

When the photosensitive resin composition of the present invention satisfies (Z1), it is preferably 10 to 70% by weight, and particularly preferably 20 to 60% by weight, based on the total of all repeating units of the alkali-soluble resin (B). It has free-radical polymerizability and is selected from N-alkoxymethyl, N-hydroxymethyl, silyl group, epoxy, oxetanyl, vinyl, and blocking At least one of a crosslinkable group such as an isocyanate group and a self-crosslinkable group such as N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, vinyl, blocked isocyanate, and the like A constituent unit derived from an unsaturated compound. When the constituent unit is less than 10% by weight, the heat resistance or surface hardness of the obtained cured film tends to decrease. On the other hand, when the amount of the constituent unit exceeds 70% by weight, the stability of the radiation-sensitive resin composition is stable. Reduced tendency.

In the present invention, the acrylic polymer of the component (B) may be a copolymer formed by using a monomer other than the monomers (hereinafter referred to as other monomers) as a constituent unit. The other monomers may be copolymerized with at least one selected from the group consisting of a monomer having a carboxyl group and a monomer having a phenolic hydroxyl group, as long as the component (B) is not impaired. The characteristics are not particularly limited. Specific examples of such monomers include acrylate compounds, methacrylate compounds, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds.
Specific examples of the other monomers are given below, but are not limited thereto.

Examples of the acrylate compound include methacrylate, ethacrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methacrylate, and phenyl acrylate , Glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxy Ethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl 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 2- (propenyloxy) ethyl ester, poly (ethylene glycol) ether acrylate, and the like.

Examples of the methacrylate compound include methmethacrylate, ethylmethacrylate, isopropylmethacrylate, benzylmethacrylate, naphthylmethacrylate, and anthrylmethyl Acrylate, anthryl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate Ester, tert-butyl methacrylate, cyclohexyl methacrylate, isofluorenyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2- Ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl Methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl Methyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloxy) ethyl, poly ( Glycol) ethyl ether methacrylate and the like.

Examples of the acrylamide compound include N-methacrylamide, N-methacrylamide, N, N-dimethylacrylamide, and N, N-dimethylmethacrylamine , N-methoxymethacrylamide, N-methoxymethacrylamide, N-butoxymethacrylamide, N-butoxymethylmethacrylamine, and the like.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, and 3-vinyl-7- Oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide, etc.

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

In the production of the component-soluble alkali-soluble acrylic polymer, the ratio of the other monomers 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 is more than 80% by weight, the relative essential components are reduced, and it becomes difficult to sufficiently obtain the effects of the present invention.

The method for obtaining the alkali-soluble acrylic polymer of the component (B) used in the present invention is not particularly limited. For example, the method has a property selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a carboxylic acid or a phenolic hydroxyl group generated by the action of heat or acid. Monomers grouped by at least one group, monomers having a hydroxyalkyl group, and optionally having a member selected from the group consisting of N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, and oxygen Crosslinkable groups such as heterocycloalkyl, vinyl, and blocked isocyanate groups, and N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, vinyl, and blocked isocyanate groups A monomer having at least one kind of self-crosslinkable group, a copolymerizable monomer other than the above if desired, and a solvent in which a desired polymerization initiator coexists, by using a temperature of 50 to 110 ° C. It was obtained by polymerization. In this case, the solvent used is not particularly limited as long as it dissolves the monomer constituting the alkali-soluble acrylic polymer and the acrylic polymer having a specific functional group. Specific examples include the solvents described in the (C) solvent described later.

The acrylic polymer having a specific functional group thus obtained is usually in a solution state dissolved in a solvent.

In addition, the solution of the specific copolymer obtained as described above is put into agitation with diethyl ether or water to reprecipitate, and the resulting precipitate is filtered, washed, and then under normal pressure or reduced pressure by normal temperature or heating. When dried, it becomes a powder of a specific copolymer. By this operation, a polymerization initiator or an unreacted monomer coexisting with the specific copolymer can be removed, and as a result, a powder of the specific copolymer after purification can be obtained. When sufficient purification cannot be performed in one operation, the obtained powder may be redissolved in a solvent, and the above operation may be repeated.
In the present invention, a powder of the specific copolymer described above may be used as it is, or the powder may be redissolved in a solvent (C) described later and used in a solution state.

In addition, as the alkali-soluble resin of the component (B), polyimide precursors such as polyamidic acid, polyamidate, a part of polyimidized polyamidic acid, and polyfluorene containing a carboxylic acid group can be used. Polyimide, such as imine, can be used without particular limitation if it is alkali-soluble.

The polyamidoacid of the polyamidoimine precursor is generally obtained by polycondensing (a) a tetracarboxylic dianhydride compound and (b) a diamine compound.

The (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 3,3', 4 , 4'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylphosphonium tetracarboxylic acid Aromatic tetracarboxylic dianhydrides such as dianhydride, such as 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane tetra Carboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, alicyclic tetracarboxylic acid A dianhydride, such as an aliphatic tetracarboxylic dianhydride of 1,2,3,4-butanetetracarboxylic dianhydride.
These can be used singly or in combination of two or more kinds.

The diamine compound (b) is not particularly limited, and examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, and 4,6 -Diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-terephthalic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4- Amino-3,5-dicarboxyphenyl) ether, bis (4-amino-3-carboxyphenyl) fluorene, bis (4-amino-3,5-dicarboxyphenyl) fluorene, 4,4 '-Diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-di Amino-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] fluorene, bis [4- (4-amino-3-carboxyphenoxy) Phenyl) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoropropane, 2,4-diaminophenol, 3,5-diamine Phenol, 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) fluorene, bis ( 4-amino-3-hydroxyphenyl) fluorene, bis (4-amino-3,5-dihydroxyphenyl) fluorene, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoro Propane, 2,2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4 '-Diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-di Amino-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] fluorene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2 -Diamine compounds with phenolic hydroxyl groups such as bis [4- (3-amino-4-hydroxyphenoxy) phenyl] hexafluoropropane, 1,3-diamino-4-mercaptobenzene, 1,3 -Diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl) ether, 2,2-bis (3-amino-4 -Mercaptophenyl) hexafluoropropane Diamine compounds having a thiophenol group, such as alkane, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diamine group Benzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, 4,4'-diamine Diamine compounds having a sulfonic acid group such as -3,3'-dimethylbiphenyl-6,6'-disulfonic acid. 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-benzidine, m-benzidine, 3,3 ', 5,5'-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenylbenzene (Oxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diamine Diphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aniline) hexafluoropropane, 2,2-bis (3-aniline) hexafluoropropane, 2, 2-bis (3-amino-4-methylfluorenyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene , Bis [4- (4-aminophenoxy) phenyl] fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- ( Diamine compounds such as 4-aminophenoxy) phenyl] hexafluoropropane and 2,2'-bis (trifluoromethyl) benzidine.
These can be used singly or in combination of two or more kinds.

When the polyamidic acid used in the present invention is manufactured from (a) a tetracarboxylic dianhydride compound and (b) a diamine compound, the blending ratio of the two compounds, that is, the total mole number of the (b) diamine compound / (a) The total mole number of the tetracarboxylic dianhydride compound is preferably 0.7 to 1.2. As with the normal polycondensation reaction, the closer this Mohr ratio is to 1, the greater the degree of polymerization of the polyamino acid produced and the more the molecular weight increases.

In addition, when polymerization is performed excessively using a diamine compound, a terminal amine group can be protected by reacting a carboxylic anhydride with respect to the terminal amine group of the remaining polyamic acid.
Examples of such carboxylic anhydride include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalenedicarboxylic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-di Carboxylic anhydride, itaconic anhydride, tetrahydrophthalic anhydride, etc.

In the production of polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound can be selected from any temperature of -20 to 150 ° C, preferably -5 to 100 ° C. In order to obtain a high molecular weight polyamic acid, the reaction temperature can be appropriately selected from a range of a reaction temperature of 5 ° C to 40 ° C and a reaction time of 1 to 48 hours. In order to obtain a low molecular weight and high storage stability, the reaction temperature is preferably 40 ° C to 90 ° C and the reaction time is more than 10 hours when the partially fluorinated polyamidized acid is used.
In addition, the reaction temperature when the terminal amine group is protected with an acid anhydride can be selected from -20 to 150 ° C, preferably any temperature from -5 to 100 ° C.

The reaction of the diamine compound and the tetracarboxylic dianhydride compound can be performed in a solvent. Examples of solvents that can be used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, and N-methylcaprolactone. Amine, dimethyl sulfene, tetramethyl urea, pyridine, dimethyl fluorene, hexamethyl fluorene, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, 3 -Methyl methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, 2 -Ethyl 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 monoethyl ether Methyl ether acetate, carbitol acetate, ethyl lysone acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, and the like. These can be used alone or in combination. Moreover, even if it is a solvent which does not dissolve a polyamic acid, as long as the polyamic acid produced by a polymerization reaction does not precipitate, you may mix and use with the said solvent.

The polyamine-containing solution thus obtained can be directly used for preparing a negative photosensitive resin composition. In addition, the polyamidic acid can be used in the form of a single solvent, such as water, methanol, or ethanol, to separate the precipitate and recover it.

In addition, as the component (B), an arbitrary polyimide may be used. The polyfluorene imine used in the present invention refers to a polyfluorine imine precursor such as the polyphosphoric acid, which is chemically or thermally subjected to 50% or more of fluorimide.

The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from a carboxyl group and a phenolic hydroxyl group in order to provide alkali solubility.
As a method for introducing a carboxyl group or a phenolic hydroxyl group into the polyimide, for example, a method using a monomer having a carboxyl group or a phenolic hydroxyl group, a method of blocking an amine terminal with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, or A method in which a polyimide precursor such as polyamidic acid is fluorinated, and the fluorinated ratio is 99% or less.

This polyfluorene imine can be obtained by synthesizing a polyfluorene imine precursor such as the polyphosphonium acid, and then performing chemical hydrazone or thermal hydrazone.
As a method of chemical fluorene imidization, a method of adding excess acetic anhydride and pyridine to a polyfluorene imine precursor solution and reacting the reaction at room temperature to 100 ° C can be generally used. In addition, as the method of the thermal ammonium imidization, a method of heating the polyimide precursor solution at a temperature of 180 ° C to 250 ° C while dehydrating is generally used.

As the alkali-soluble resin of the component (B), a phenol novolac resin can be used.

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

In the present invention, the alkali-soluble resin of the component (B) may be a mixture of a plurality of alkali-soluble resins.

The ratio of (A) component and (B) component is 0.1-20 mass parts with respect to 100 mass parts of (B) component.

＜ (C) Solvent ＞
The (C) solvent used in the present invention dissolves (A) component, (B) component, and (D) component, (E) component, (F) component, and (G) component described later as necessary, and dissolves as desired The component (H) mentioned later, other additives, and the like are added, and in the case of a solvent having such a dissolving energy, the type, structure, and the like are not particularly limited.

Examples of such (C) solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl lysin acetate, ethyl lysin acetate, diethylene glycol monomethyl ether, and diethylene glycol monomethyl ether. Ethylene 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-butane Ketone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl Ethyl ethoxylate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionate Ethyl acetate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide , N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used singly or in combination of two or more kinds.
Among these solvents (C), propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol propyl ether, and propylene glycol propyl ether are more preferable from the viewpoints of good coating properties and high safety. Acetate, ethyl lactate, butyl lactate and the like. These solvents are generally used as solvents for photoresist materials.

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

(D-1) A 1,2-quinonediazide compound is a compound having either a hydroxyl group or an amine group, or both a hydroxyl group and an amine group, and these hydroxy or amine groups (having a hydroxyl group and an amine group) can be used. Among the two, their total amount) is preferably 10 to 100 mole%, particularly preferably 20 to 95 mole% for esterification with 1,2-quinonediazidesulfonic acid, Or amidine compounds.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, and ethyl gallate. Ester, 1,3,3-tris (4-hydroxyphenyl) butane, 4,4-bisphenol A (isopropylidene diphenol), 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxyphenylphosphonium, 4,4-hexafluorobisphenol A, 4,4 ', 4' '-trihydroxyphenylethane, 1, 1,1-trihydroxyphenylethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylene] bisphenol, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'- Phenol compounds such as tetrahydroxybenzophenone, 2,2 ', 3,4,4'-pentahydroxybenzophenone, 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 Aliphatic alcohols such as alcohols, 2-butoxypropanol, ethyl lactate, butyl lactate and the like.

The amine group-containing compound includes aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, and o-phenylenediamine. , Anilines such as m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, and aminocyclohexane.

Examples of the compound having both a hydroxyl group and an amino group include o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, and 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 Aminophenols such as 5-hydroxyphenyl) propane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, 2-aminoethanol, 3-amino Alkanolamines such as propanol 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 when the compound having a quinonediazide group is contained in the component (D-1) is relative to the content of the components (A) and (B). The total amount is 100 parts by mass, preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass. If it is less than 5 parts by mass, the difference in the dissolution rate of the developing solution between the exposed portion and the unexposed portion of the positive-type photosensitive resin composition becomes small, and patterning due to development may become difficult. If it exceeds 100 parts by mass, the 1,2-quinonediazide compound is not sufficiently decomposed due to short-time exposure, so the sensitivity may be reduced, or the (D-1) component may absorb light and harden. When the transparency of the film is reduced.

(D-2) The photo radical generator is not particularly limited as long as it is a radical that is generated by exposure. Specific examples include benzophenone, michelone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, Aromatic ketones such as 2-ethylanthraquinone, phenanthrene, benzoin methyl ether, benzoin ether, benzoin ether, benzoin ether, methyl benzoin, ethyl benzoin, etc. Benzoin, 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (m-methoxyphenyl) Imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer , 2,4,5-triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (m-methylphenyl) imidazole dimer, 2-benzyl-2-di Methylamino-1- (4-morpholinylphenyl) -butanone, 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl- 5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadioxane Halomethyloxadiazole compounds such as azole, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -S-triazine, 2-triazine Chloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2- (naphthalene-1-yl) -4,6-bis-trichloromethyl-S-triazine , 2- (4-ethoxy-naphthalen-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-butoxy-naphthalene-1-yl) -4 Halomethyl-S-triazine compounds such as 1,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1,2-diphenylethane-1 ketone, 2 -Methyl-1- [4- (methylthio) phenyl] -2-morpholinylacetone, 1,2-benzyl-2-dimethylamino-1- (4-morpholinylbenzene ) -Butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenylethylenedione, benzamylbenzoic acid, methyl benzamylbenzoate, 4-benzylamyl-4 '-Methyldiphenylsulfide, benzylmethylacetal, dimethylaminobenzoate, p-dimethylaminobenzoate, 2-n-butoxyethyl- 4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 1- (4-phenylthiophenyl) -1,2-octanedione (Octanedione) -2- (O-benzylidene oxime), ethyl ketone, 1- [9-ethyl-6- (2-methyl Benzamyl) -9H-carbazol-3-yl] -1- (O-ethylammonium oxime), 4-benzylmethyl-methyldiphenyl sulfide, 1-hydroxyl -Cyclohexyl-phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethyl Amine) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone, α-dimethoxy-α-benzene Acetophenone, phenylbis (2,4,6-trimethylbenzyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzyl) phosphine oxide, 2-methyl Phenyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-acetone and the like.
The above-mentioned photopolymerization initiator can be easily obtained as a commercial product, and specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880. , IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (above manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (Stock system), 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 (the above are manufactured by Midori Chemical Co., Ltd.) and the like.
These photo radical generators may be used alone or in combination of two or more kinds.

The content when the photosensitive resin composition of the present invention contains the component (D-2) is 100 parts by mass with respect to the component (A), preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably It is 1 to 15 parts by mass. When this ratio is too small, the exposed portion becomes insufficiently hardened, and a pattern cannot be formed, or even if a pattern can be formed, it may become a film with low reliability. Moreover, when this ratio is too large, the transmittance of a coating film may fall, or the development failure of an unexposed part may arise.

The photoacid generator of (D-3) is not specifically limited as long as it is a compound which generates an acid by photodecomposition during ultraviolet irradiation. Examples of the acid generated when the photoacid generator undergoes photodecomposition 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-di Toluene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-Perfluorooctanesulfonic acid, Perfluoro (2-ethoxyethane) sulfonic acid, Pentafluoroethanesulfonic acid, Nine A sulfonic acid such as fluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, or a hydrate or a salt thereof.

Examples of the photoacid generator include a diazomethane compound, an onium salt compound, a sulfonimide compound, a difluorene compound, a sulfonic acid derivative compound, a nitrobenzyl compound, and benzoin p-toluenesulfonic acid ester. Compounds, iron arene complexes, halogen-containing triazine compounds, acetophenone derivative compounds, and cyano-containing oxime sulfonate compounds. There is no particular limitation on the conventionally known or conventionally used photoacid generators, and they can be used in the present invention. Moreover, in this invention, the photo-acid generator of a component (D) may be used individually by 1 type, and may be used in combination of 2 or more type. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

-

The content when the photosensitive resin composition of this embodiment contains the component (D-3) is 100 parts by mass with respect to the total of the components (A) and (B), preferably 0.01 to 20 parts by mass, and more preferably It is 0.1 to 10 parts by mass, and more preferably 0.5 to 8 parts by mass. When the content of the (D-3) component is 0.01 parts by mass or more, sufficient thermosetting properties and solvent resistance can be provided. However, when the content is more than 20 parts by mass, the unexposed portion may be poorly developed, and the storage stability of the composition may be reduced.

＜ (E) component ＞
(E) A component is a crosslinking agent, and when the photosensitive resin composition of this invention satisfies the requirement (Z1), it is introduce | transduced into a composition. More specifically, a compound having a structure capable of thermally reacting with a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B) to form a crosslinked structure. Specific examples are given below, but are not limited to these. The thermal crosslinking agent is, for example, selected from (E1) a crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl, or (E2) selected from a crosslinkable compound represented by formula (5) Those are better. These crosslinking agents can be used alone or in combination of two or more.

(E1) A crosslinkable compound having two or more substituents selected from the group consisting of alkoxymethyl and hydroxymethyl is a component that undergoes a cross-linking reaction by a dehydration condensation reaction when exposed to a high temperature during heat curing. Examples of such compounds include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast-based compounds.

Specific examples of the alkoxymethylated glycoluril include, for example, 1,3,4,6-tetra (methoxymethyl) glycol, and 1,3,4,6-tetra (butoxymethyl) Glycoluril, 1,3,4,6-tetra (hydroxymethyl) glycol, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetra (butoxymethyl) urea, 1,1,3,3-tetra (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methyl (Oxymethyl) -4,5-dimethoxy-2-imidazolinone and the like. Examples of commercially available products include compounds such as glycourea compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) made by Mitsui Cytec, and methylated urea resins (trade names: UFR (registered trademark)). 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock) urea / formaldehyde resin (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, same as P-955, same N) and so on.

Specific examples of the alkoxymethylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. Commercial products include Mitsui Cytec (trade name) (trade name: Cymel (registered trademark) 1123), (share) Sanwa chemical system (trade name: Nikalac (registered trademark) BX-4000, same as BX-37, same as BL -60, same as BX-55H) and so on.

Specific examples of the alkoxymethylated melamine include hexamethoxymethyl melamine and the like. Commercially available products include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, same 301, same 303, and 350) made by Mitsui Cytec (stock), butoxymethyl-type melamine compounds (commercial products) Name: Mycoat (registered trademark) 506, same as 508), methoxymethyl melamine compound (trade name: Nikalac (registered trademark) MW-30, same MW-22, same MW-11, same MW) manufactured by Sanwa Chemical -100LM, same as MS-001, same as MX-002, same as MX-730, same as MX-750, same as MX-035), butoxymethyl melamine compound (trade name: Nikalac (registered trademark) MX-45, Same as MX-410, same as MX-302).

Moreover, it may be a compound obtained by condensing such a melamine compound, a urea compound, a glycoluril compound, and a benzoguanamine compound in which the hydrogen atom of the amine group is substituted with a methylol group or an alkoxymethyl group. Examples thereof include high-molecular-weight compounds produced from melamine compounds and benzoguanamine compounds described in US Pat. No. 6,233,310. The commercial product of the aforementioned melamine compound may include a trade name: Cymel (registered trademark) 303 (manufactured by Mitsui Cytec), and the commercial product of the aforementioned benzoguanamine compound may include a trade name: Cymel (registered trademark) 1123 (Mitsui Cytec (shares) system) and so on.

Specific examples of the phenolic plastic compound include 2,6-bis (hydroxymethyl) phenol, 2,6-bis (hydroxymethyl) cresol, and 2,6-bis (hydroxymethyl) -4-methyl Oxyphenol, 3,3 ', 5,5'-tetrakis (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methyl) Benzyl alcohol), 4,4 '-(1-methylethylene) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6- Hydroxymethylphenol], 4,4 '-(1-methylethylene) 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-methyl Oxy-5-methylbenzyl alcohol), 4,4 '-(1-methylethylene) bis [2-methyl-6-methoxymethylphenol], 4,4'-methylene Bis [2-methyl-6-methoxymethylphenol], 4,4 '-(1-methylethylene) bis [2,6-bis (methoxymethyl) phenol], 4, 4'-methylenebis [2,6-bis (methoxymethyl) phenol] and the like. Available as commercially available products. Specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (the above are Asahi Machinery Industry (stock) system) and so on.

In addition, as the (E1) component, N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, and N-butoxymethyl can also be used. A polymer produced from acrylamide compound or methacrylamide compound substituted with hydroxymethyl or alkoxymethyl, such as methacrylamide.

Examples of such a polymer include poly (N-butoxymethacrylamide), a copolymer of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacrylamide and Copolymer of methyl methacrylate, copolymer of N-ethoxymethylmethacrylamide and benzylmethacrylate, and N-butoxymethacrylamide and benzylmethacrylic acid Copolymers of esters and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of this polymer is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

The photosensitive resin composition of the present invention may contain a crosslinkable compound represented by formula (5) as a component (E2).

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

The component (E2) is not particularly limited as long as it is a compound having a cycloalkane oxide structure represented by formula (5). Specific examples thereof include the following formulas E2-1 and E2-2, or commercially available products shown below.

Commercially available products include EPOLEAD GT-401, same GT-403, same GT-301, same GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (DAICEL Chemical Industry Co., Ltd. product name), and Denacol of alicyclic epoxy resin. EX-252 (Nagasechemtex (stock) trade name), CY175, CY177, CY179 (above the trade name of CIBA-GEIGY AG), araldite CY-182, the same CY-192, the same CY-184 (the above is CIBA-GEIGY AG product name), EPICLON 200, same as 400 (the above is the DIC (stock) product name), Epikote 871, the same as 872 (the above is the petrochemical Shell Epoxy (stock) product name), ED-5661, ED-5662 (The above is a Celanese coating (trade name) product name) and the like. These crosslinkable compounds can be used alone or in combination of two or more kinds.

Among these, from the viewpoints of step resistance such as heat resistance, solvent resistance, and long-term firing resistance, and transparency, the formulae C1 and C2 having an epoxycyclohexane structure are preferred. Compound, EPOLEAD GT-401, same as GT-403, same as GT-301, same as GT-302, CELLOXIDE 2021, CELLOXIDE 3000.

In addition, the E component may use a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) with a component (B) other than the component (E1) and the component (E2) as shown in FIG. Constructed compounds. Specific examples include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl. Glyceryl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl -2,4-hexanediol, N, N, N ', N',-tetraglycidyl-m-xylylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) ) Cyclohexane, and epoxy compounds such as N, N, N ', N',-tetraglycidyl-4, 4'-diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF 1540 (above It is an isocyanurate-modified polyisocyanate, manufactured by Degussa Japan (stock), Takenate (registered trademark) B-882N, and the same as Takenate B-7075 (the above are isocyanurate-type modified polyisocyanates, Mitsui Chemicals ( ) And other isocyanate compounds.

As the E component, a polymer having a structure capable of forming a crosslinked structure by thermally reacting with a thermally reactive site (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B) can be used. Specifically, for example, glycidyl methacrylate, 3,4-epoxycyclohexylmethmethacrylate, 3,4-epoxycyclohexylmethmethacrylate and the like are used. Polymers made of epoxy-based compounds, polymers made of compounds with alkoxysilyl groups such as 3-methacryloxypropyltrimethoxysilane, and 2-isocyanatoethyl Isocyanate (Karenz MOI [registered trademark], manufactured by Showa Denko), 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko), etc. Compounds, or 2- (0- [1'-methylpropyleneamino] carboxyamino) ethyl methacrylate (karenz MOI-BM [registered trademark], manufactured by Showa Denko Corporation), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (karenz MOI-BP [registered trademark], manufactured by Showa Denko Corporation) and the like having a blocked isocyanate group (blocked isocyanate group). These compounds can be used alone or in combination to make polymers, and can also be used in combination with other compounds to make polymers.

(B) When the component has a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a fluorenylamino group, and an amine group, it has two or more hydroxy, carboxyl, sulfonylamino, and amine groups. The compound represented by the group can be used as the component (E).

These crosslinkable compounds can be used individually or in combination of 2 or more types.

The content when the (E) component is selected as the crosslinking agent in the photosensitive resin composition of the present invention is 1 to 50 parts by mass relative to 100 parts by mass of the total of the (A) component and the (B) component, and more preferably 1 to 40 parts by mass, more preferably 1 to 30 parts by mass. When the content of the cross-linkable compound is small, the cross-linking density formed by the cross-linkable compound is insufficient, so it is impossible to improve the heat resistance, solvent resistance, and resistance to long-term firing after pattern formation. And other effects. On the other hand, when it exceeds 50 parts by mass, a non-crosslinked crosslinkable compound is present, and the heat resistance, solvent resistance, and resistance to long-term firing after pattern formation are reduced. Furthermore, the photosensitive resin When the storage stability of the composition is deteriorated.

＜ (F) component ＞
(F) A component is a compound which has two or more ethylenic polymerizable groups. The term "compound having two or more ethylenic polymerizable groups" means a compound having two or more polymerizable groups in one molecule and their polymerizable groups at the molecular ends, so-called their polymerizability The group means at least one type of polymerizable group selected from the group consisting of an acrylate group, a methacrylate group, a vinyl group, and an allyl group.
The compound of the component (F) having two or more ethylenic polymerizable groups has a good compatibility with each component in the solution of the negative photosensitive resin composition of the present invention, and does not affect the developability. In view of this, compounds having a molecular weight (weight average molecular weight when the compound is a polymer) of 1,000 or less are preferred.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol Triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylolmethane tetraacrylate Ester, tetramethylolmethane tetramethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,3,5-tripropenylhexahydro-S-triazine , 1,3,5-trimethacrylfluorenylhexahydro-S-triazine, tris (hydroxyethylpropenyl) isocyanurate, tris (hydroxyethylmethacryl) isocyanurate Acid ester, tripropenylacetal, trimethacrylacetal, formalin, 1,6-hexanediol acrylate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, new Pentylene glycol dimethacrylate, ethylene diethylene glycol Diacrylate, ethylene glycol dimethacrylate, 2-hydroxypropylene glycol diacrylate, 2-hydroxypropylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropyl Propylene glycol diacrylate, isopropyl glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N, N'-bis (acrylfluorenyl) cysteine, N, N '-Bis (methacrylfluorenyl) cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate Ester, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol 茀 diacrylate, bisphenoxyethanol 茀Dimethacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate, and the like.

The above-mentioned polyfunctional acrylate compound can be easily obtained as a commercially available product. Specific examples thereof include KYARAD T-1420, the same DPHA, the same DPHA-2C, the same D-310, the same D-330, the same DPCA-20, and the same DPCA. -30, same as DPCA-60, same as DPCA-120, same as DN-0075, same as DN-2475, same as R-526, same as NPGDA, same as PEG400DA, same as MANDA, same as R-167, same as HX-220, same as HX620, Same as R-551, same as R-712, same as R-604, same as R-684, same as GPO-303, same as TMPTA, same as THE-330, same as TPA-320, same as TPA-330, same as PET-30, same as RP -1040 (above are made by Nippon Kayaku Co., Ltd.), AronixM-210, same M-240, same M-6200, same M-309, same M-400, same M-402, same M-405, same M -450, same M-7100, same M-8030, same M-8060, same M-1310, same M-1600, same M-1960, same M-8100, same M-8530, same M-8560, same M -9050 (the above is made by East Asia Synthesis), Viscoat295, same 300, same 360, same GPT, same 3PA, same 400, same 260, same 312, and 335HP , 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 ( The above is the new Nakamura Chemical Industry Co., Ltd.).
These compounds having two or more ethylenic polymerizable groups may be used singly or in combination of two or more kinds.

The content when the photosensitive resin composition of the present invention contains the (F) component is 100 parts by mass relative to the total of the (A) component and the (B) component, preferably 5 to 100 parts by mass, and more preferably 10 to 80 Mass parts, particularly preferably 20 to 70 mass parts. When the ratio is too small, the exposed portion is insufficiently hardened to form a pattern, or even if a pattern can be formed, it may become a film with low reliability. In addition, if the ratio is too large, the coating film after pre-baking may become sticky, or the unexposed part may be poorly dissolved during development.

＜ (G) component ＞
The (G) component used for the photosensitive resin composition of this invention is a compound which has two or more functional groups which form a covalent bond by an acid. Examples of such a functional group that forms a covalent bond with an acid include an epoxy group and a methylol group.

Examples of the compound having two or more epoxy groups include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, and 1,2-epoxy. -4- (epoxyethyl) cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-diglycidylphenyl glycidyl ether, 1,1,3 -Tris [p- (2,3-epoxypropoxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N -Diglycidylaniline), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, trimethylolethane triglycidyl ether, bisphenol-A- Diglycidyl ether, and pentaerythritol polyglycidyl ether.

Moreover, the compound which has two or more epoxy groups is easy to obtain. Commercially available compounds can also be used. The following are specific examples (trade names), but are not limited to these: YH-434, YH434L (made by Tohto Kasei Co., Ltd.) and other epoxy resins with amine groups; EPOLEAD GT-401, same as GT-403, Same as GT-301, Same as GT-302, CELLOXIDE 2021, CELLOXIDE 3000 (made by DAICEL Chemical Industry Co., Ltd.) and other epoxy resins with epoxy cyclohexane structure; Epikote 1001, same 1002, same 1003, same 1004, same 1007, the same as 1009, the same as 1010, the same as 828 (the above is the oiled Shell Epoxy (stock) (now Japan Epoxy resin (stock))) and other bisphenol A type epoxy resin; Epikote 807 (oiled Shell Epoxy (stock) (Now Japan Epoxy resin (stock))) and other bisphenol F-type epoxy resins; Epikote 152, same as 154 (the above is made of oiled Shell Epoxy (stock) (now Japan Epoxy resin (stock))), EPPN201, same Phenol novolac epoxy resin such as 202 (above manufactured by Nippon Kayaku Co., Ltd.), etc .; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above are made in Japan) Cresol novolac epoxy resin; Epikote 180S75 (petrochemical Shell Epoxy (stock) (now Japan Epoxy resin)); Denacol EX-252 (nagase chemtex (stock)), CY175, CY 177, CY179, araldite CY-182, same as CY-192, same as CY-184 (above, manufactured by CIBA-GEIGY AG), EPICLON200, same as 400 (above are made by Dainippon Ink Chemical Industry (stock)), Epikote871, same as 872 ( The above are alicyclic epoxy resins such as oiled Shell Epoxy (stock) (currently made by Japan Epoxy resin), ED-5661, ED-5662 (the above are made by Celanese coating), and Denacol EX- 611, same EX-612, same EX-614, same EX-622, same EX-411, same EX-512, same EX-522, same EX-421, same EX-313, same EX-314, same EX- Aliphatic polyglycidyl ether such as 321 (produced by nagase chemtex).

As the compound having two or more epoxy groups, a polymer having an epoxy group can be used.
The polymer having an epoxy group can be produced, for example, by addition polymerization using an addition polymerizable monomer having an epoxy group. For example, polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate Additive polymer such as copolymer or polycondensation polymer such as epoxy novolac.

Or the polymer having an epoxy group can be produced by reacting a polymer compound having a hydroxyl group with a compound having an epoxy group, such as epichlorohydrin, glycidyl p-toluenesulfonate, and the like.

The weight average molecular weight of this 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 kinds.

Examples of the compound having two or more hydroxymethyl groups include 1,3,4,6-tetrakis (methoxymethyl) glycol urea, and 1,3,4,6-tetrakis (butoxymethyl) glycol. Urea, 1,3,4,6-tetra (hydroxymethyl) glycolurea, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetra (butoxymethyl) urea, 1 , 1,3,3-tetra (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxy) Methyl) -4,5-dimethoxy-2-imidazolinone and the like. Examples of commercially available products include compounds such as glycourea compounds (trade names: Cymel (registered trademark) 1170, Powderlink (registered trademark) 1174) made by Mitsui Cytec, and methylated urea resins (trade names: UFR (registered trademark)). 65), butylated urea resin (trade name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC (stock) urea / formaldehyde resin (high condensation type, trade name: BECKAMINE (registered trademark) J-300S, same as P-955, same as N), tetramethoxymethylbenzoguanamine and the like. Commercial products include Mitsui Cytec (trade name) (trade name: Cymel (registered trademark) 1123), (share) Sanwa chemical system (trade name: Nikalac (registered trademark) BX-4000, same as BX-37, same as BL -60, same as BX-55H), hexamethoxymethyl melamine, etc. Commercially available products include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, same 301, same 303, and 350) made by Mitsui Cytec (stock), butoxymethyl-type melamine compounds (commercial products) Name: Mycoat (registered trademark) 506, same as 508), methoxymethyl melamine compound made by Sanwa Chemical (trade name: Nikalac (registered trademark) MW-30, same MW-22, same MW-11, same MS -001, same as MX-002, same as MX-730, same as MX-750, same as MX-035), butoxymethyl melamine compound (trade name: Nikalac (registered trademark) MX-45, same as MX-410, Same as MX-302).

As the compound having two or more methylol groups, a polymer having methylol groups can be used.

Examples of the polymer having two or more methylol groups include N-hydroxymethyl (meth) acrylamide, N-methoxymethyl (meth) acrylamide, and N-ethoxymethyl. (Meth) acrylamide, N-butoxymethyl (meth) acrylamide, and other methacrylamide compounds or methacrylamide compounds substituted with hydroxymethyl or alkoxymethyl Of polymers.

Specific examples of such a polymer include poly (N-butoxymethacrylamide), a copolymer of N-butoxymethacrylamide and styrene, and N-hydroxymethylmethacryl Copolymer of fluorene and methmethacrylate, copolymer of N-ethoxymethylmethacrylamide and benzyl methacrylate, and N-butoxymethacrylamide and benzyl Copolymers of methacrylate and 2-hydroxypropyl methacrylate, etc. The weight average molecular weight of this polymer is 1,000 to 200,000, more preferably 3,000 to 150,000, and still more preferably 3,000 to 50,000.

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

When the photosensitive resin composition of the present invention contains the (G) component, the content of the compound having two or more functional groups forming a covalent bond with an acid is based on a total of 100 masses of the (A) component and the (B) component. It is preferably 5 to 200 parts by mass, and more preferably 50 to 150 parts by mass. When the ratio is too small, the photocurability of the negative photosensitive resin composition may be reduced. When the ratio is too large, the developability of the unexposed portion may be reduced, which may cause a residual film or residue.

＜ Other additives ＞
In addition, as long as the photosensitive resin composition of the present invention does not impair the effects of the present invention, it may contain a rheology modifier, a pigment, a dye, a storage stabilizer, a defoaming agent, an adhesion promoter, or a polyphenol, if necessary. Dissolving accelerators such as polycarboxylic acids.

<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 may further contain cross-linking of the (E) component if necessary. Agent, compound of component (F) having two or more polymerizable groups, compound of component (G) having two or more functional groups that form a covalent bond with an acid, and one or more of other additives组合 物。 Composition.
(A) Ingredient: Polysiloxane having the following groups (A1) and (A2)
(A1) an organic group having a fluorine atom
(A2) Organic group having a thermally crosslinkable group
(B) Ingredient: Alkali soluble resin
(C) solvents,
(D) component: Photosensitizer.

Among these, the preferable examples of the photosensitive resin composition of this invention are as follows.
[1]: A photosensitive resin composition containing 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B). These components are dissolved in the solvent (C).
[2]: Photosensitivity that contains 0.1 to 20 parts by mass of the (A) component and 5 to 100 parts by mass of the (D) component with respect to 100 parts by mass of the (B) component Resin composition.
[3]: Photosensitivity of (B) component (B), containing 0.1 to 20 parts by mass of (A) component, and 5 to 100 parts by mass of (D) component. The resin composition is a photosensitive resin composition further containing 1 to 50 parts by mass of a crosslinking agent of the component (E) based on 100 parts by mass of the total of the components (A) and (B).

The proportion of 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 a solvent, and is, for example, 1 to 80% by mass, and, for example, 5 to 60% by mass, or 10 to 50% by mass. Here, the solid content means the latter (C) solvent is removed from all the components of the photosensitive resin composition.

The method for preparing the photosensitive resin composition of the present invention is not particularly limited. Examples of the method for preparing the photosensitive resin composition include dissolving the component (A) (specific polymer) in the solvent (C), and mixing this solution in a specific ratio ( B) Alkali-soluble resin of component, Photosensitizer of component (D), Crosslinking agent of component (E) if necessary, Compound of component (F) having two or more polymerizable groups, (G) Component of having A method of forming two or more compounds having a functional group covalently bonded by an acid to form a homogeneous solution, or a method of mixing other additives when necessary at an appropriate stage of the preparation method.

When preparing the photosensitive resin composition of the present invention, the solution of the copolymer obtained by the polymerization reaction in the solvent (C) can be used directly. At this time, the solution of the component (A) is added in the same manner as above (B ) Component, (D) component, (E) component, (F) component, (G) component, etc., when forming a uniform solution, the solvent (C) can be further added for the purpose of concentration adjustment. At this time, the (C) solvent used in the formation of the specific copolymer and the (C) solvent used for the concentration adjustment during the preparation of the photosensitive resin composition may be the same or different.

In addition, the prepared solution of the photosensitive resin composition is preferably used after filtration using a filter having a pore size of about 0.2 μm or the like.

＜ Coated film and hardened film ＞
The photosensitive resin composition of the present invention is applied to a semiconductor substrate (for example, silicon by spin coating, flow coating, roll coating, slit coating, slit subsequent spin coating, inkjet coating, or the like). / Silicon dioxide coated substrate, silicon nitride substrate, substrate coated with metal (such as aluminum, molybdenum, chromium, etc., glass substrate, quartz substrate, ITO substrate, etc.), and then prepared with a hot plate or oven, etc. When dried, a coating film can be formed. Then, this coating film is subjected to a heat treatment to form a photosensitive resin film.

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

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

On the coating film obtained above, a mask having a specific pattern is installed, and light such as ultraviolet rays is irradiated, and development is performed with an alkali developing solution. The material composition rinses either the exposed portion or the unexposed portion, and the remaining pattern is The shaped film may be heated at 80 ° C. to 140 ° C. for 0.5 to 10 minutes as necessary to obtain a sharp relief pattern on the end surface.

Examples of usable alkaline developing solutions include aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline. Aqueous solutions of quaternary ammonium hydroxide, aqueous amines such as ethanolamine, propylamine, and ethylenediamine. In addition, a surfactant may be added to these developers.

Among the above, an aqueous solution of tetraethylammonium hydroxide of 0.1 to 2.58% by mass is generally used as a photoresist developing solution. In the photosensitive resin composition of the present invention, this alkaline developing solution is also used, which does not cause problems such as swelling. , Can develop well.

As the development method, any method such as a liquid holding method, a dipping method, or a shaking dipping method can be used. The development time at this time is usually 15 to 180 seconds.

After development, the photosensitive resin film is washed with flowing water, for example, for 20 to 120 seconds, and then compressed air or compressed nitrogen is used, or spin drying is performed to remove moisture from the substrate to obtain a pattern. Of the film.

Next, by forming a film on this pattern, post-baking is performed for thermal curing. Specifically, by using a hot plate, an oven, or the like, heat resistance, transparency, flatness, low water absorption, A film having excellent chemical resistance and the like, and having a good uneven pattern.

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

Then, by this subsequent baking, a desired cured film having a good pattern shape can be obtained.

As described above, with the photosensitive resin composition of the present invention, it is possible to form a coating film with high storage stability, sufficiently high sensitivity, and a small reduction in the film of the unexposed portion during development, with a fine pattern.

[Example]

The following examples illustrate the present invention in more detail, but the present invention is not limited to these examples. The measurement of the number average molecular weight and the weight average molecular weight is as follows.

[Measurement of number average molecular weight and weight average molecular weight]
Using a GPC device (Shodex column KF-804L and 803L) manufactured by Shimadzu Corporation, the elution solvent tetrahydrofuran was flowed through the column (column temperature 40 ° C) at a flow rate of 1 ml / min to measure the dissolution according to the following synthesis example. Number average molecular weight and weight average molecular weight of the copolymer. The number average molecular weight (hereinafter referred to as Mn) and weight average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

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: Compound synthesized by the condensation reaction of 1 mol of 4-hydroxyphenyl methacrylate and 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride
CHMI: N-cyclohexylmaleimide
TMSSMA: Methacryloxypropyltris (trimethylsilyloxy) silane
PFHMA: 2- (perfluorohexyl) ethyl methacrylate
MAA: methacrylic acid
AIBN: α, α'-azobisisobutyronitrile
QD: by 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene and 1,2-naphthoquinone-2-diazide-5-sulfofluorene Compound synthesized by condensation reaction of 2mol of chlorine
GT-401: Butane tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) modified ε-caprolactone
P2: a styrene polymer mixed with 85% of hydroxystyrene and 15% of styrene and 70% of hydroxystyrene and 30% of styrene
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: ion exchange resin made by organo
I907: 2-methylfluorene 1- [4- (methylthio) phenyl] -2-morpholinylpropanefluorene 1 ketone (IRGACURE 907, manufactured by BASF)
DEAB: 4,4'-bis (diethylamino) benzophenone
DPHA: Dipentaerythritol hexaacrylate
8KQ: 8KQ-2001 (Dacheng Fine Chemical Co., Ltd. alkali-soluble UV-curable acrylic resin) (P8)
PGME: propylene glycol monomethyl ether
PGMEA: propylene glycol monomethyl ether acetate
CHN: cyclohexanone
THF: tetrahydrofuran

<Synthesis example 1>
MAA 70.00g, HEMA 218.75g, HPMA 43.75g, MMA 192 ･ 50g, CHMI 350.00g, AIBN 56.00g were dissolved in PGME 1396.50g, and reacted at 90 ° C for 20 hours to obtain an acrylic polymer solution (solid Component concentration: 40% by mass) (P1). Mn of the obtained acrylic polymer was 2,800 and Mw was 4,900.

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

<Synthesis example 3>
2.34 g of PFHTMOS, 4.45 g of KBM-403, 0.21 g of 35% by weight TEAH, and 0.68 g of water were dissolved in 9.21 g of THF and stirred at 40 ° C. for 4 hours. Next, 0.68 g of 15 JWET washed with THF was added and stirred at 25 ° C. for 1 hour. Next, the unnecessary 15 JWET was filtered to obtain a siloxane polymer solution (P4). The siloxane polymer obtained had a Mn of 2,400 and a 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% by weight TEAH, and 0.68 g of water were dissolved in 9.21 g of THF and stirred at 40 ° C for 4 hours. Next, 0.48 g of 15 JWET washed with THF was added and stirred at 25 ° C. for 1 hour. Next, the unnecessary 15JWET was filtered to obtain a siloxane polymer solution (P5). The siloxane polymer obtained had a Mn of 1,900 and a Mw of 2,400.

<Synthesis example 5>
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 were dissolved in 51.3 g of CHN and stirred at 110 ° C for 20 hours to obtain an acrylic polymer solution ( (Solid content concentration: 20% by mass) (P6). Mn of the obtained acrylic polymer was 7,200 and Mw was 11,000.

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

<Examples 1 to 5 and Comparative Examples 1 to 4>
According to the composition shown in Table 1 below, (A) component solution, (B) component solution, (D) component, (E) component, (F) component are dissolved in (C) solvent at a specific ratio, and The photosensitive resin composition of each Example and each comparative example was prepared by stirring at room temperature for 3 hours to form a uniform solution.

[Evaluation of contact angle: Examples 1 to 3 and Comparative Examples 1 to 3]
After the photosensitive resin composition was coated on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a film 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 ultrapure water for 30 seconds. Next, this coating film was heated at 230 ° C. for 30 minutes to perform post-baking to form a cured film having a film thickness of 1.0 μm. The contact angle of methyl benzoate on this cured film was measured using Drop Master made by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2.

[Evaluation of contact angle: Example 4, Example 5, and Comparative Example 4]
After the photosensitive resin composition was applied on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. Next, this coating film was heated at 230 ° C. for 30 minutes to perform post-baking to form a cured film having a film thickness of 1.0 μm. The contact angle of methyl benzoate on this cured film was measured using Drop Master made by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2.

[Evaluation of UV ozone treatment resistance: Examples 1 to 3 and Comparative Examples 1 to 3]
After the photosensitive resin composition was coated on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a film 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 ultrapure water for 30 seconds. Next, this coating film was heated at 230 ° C. for 30 minutes to perform post-baking to form a cured film having a film thickness of 1.0 μm. This cured film was UV-312 manufactured by Technovision and washed with ozone for 10 minutes. The contact angle of methyl benzoate on the ozone-washed film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2. The difference between the post-baking and the UV ozone treatment was within 20 °, which was evaluated as good.

[Evaluation of UV ozone treatment resistance: Example 4, Example 5, and Comparative Example 4]
After the photosensitive resin composition was applied on a silicon wafer using a spin coater, pre-baking was performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. This coating film was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds, and then washed with ultrapure water for 30 seconds. Next, this coating film was heated at 230 ° C. for 30 minutes to perform post-baking to form a cured film having a film thickness of 1.0 μm. This cured film was UV-312 manufactured by Technovision and washed with ozone for 10 minutes. The contact angle of methyl benzoate on the ozone-washed film was measured using Drop Master manufactured by Kyowa Interface Science Co., Ltd. The obtained results are shown in Table 2. The difference between the post-baking and the UV ozone treatment was within 20 °, which was evaluated as good.

[Evaluation of wettability: Examples 1 to 3 and Comparative Examples 1 to 3]
After the photosensitive resin composition was applied on ITO-glass using a spin coater, pre-baking was performed on a hot plate at a temperature of 80 ° C. for 120 seconds to form a coating film having a film thickness of 1.2 μm. For this coating film, a rectangular pattern-shaped mask having a length of 50 μm and a width of 100 μm was passed through an ultraviolet irradiation device PLA-600FA made by Canon Corporation to irradiate ultraviolet rays with a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time. Then, it was immersed in a 2.38% by mass TMAH aqueous solution for 60 seconds for development, and then rinsed with ultrapure water for 30 seconds. Next, this coating film formed with a rectangular pattern was heated at 230 ° C. for 30 minutes to perform post-baking to harden it. On the rectangular opening of the obtained cured film, a solution of about 20 pl was ejected with a driving waveform: A, a repetition frequency: 1 kHz, and a driving voltage: 4 V by using Inkjet Designer made by Cluster Technology. Spit out the solution using methyl benzoate. The obtained results are shown in Table 3.

[Evaluation of wettability: Example 4, Example 5 and Comparative Example 4]
After the photosensitive resin composition was applied onto the ITO-glass using a spin coater, pre-baking was performed on a hot plate at a temperature of 100 ° C for 120 seconds to form a coating film having a film thickness of 1.2 μm. For this coating film, a rectangular pattern-shaped mask having a length of 50 μm and a width of 100 μm was passed through an ultraviolet irradiation device PLA-600FA made by Canon Corporation to irradiate ultraviolet rays with a light intensity of 5.5 mW / cm ² at 365 nm for a certain period of time. Then, it was immersed in a 0.4 mass% TMAH aqueous solution for 60 seconds for development, and then rinsed with ultrapure water for 30 seconds. Next, this coating film formed with a rectangular pattern was heated at 230 ° C. for 30 minutes to perform post-baking to harden it. On the rectangular opening of the obtained cured film, a solution of about 20 pl was ejected with a driving waveform: A, a repetition frequency: 1 kHz, and a driving voltage: 4 V by using Inkjet Designer made by Cluster Technology. Spit out the solution using methyl benzoate. The obtained results are shown in Table 3.

＜ Evaluation criteria of wettability ＞
○: The solution was completely wet and diffused in the rectangular opening.
×: In the rectangular opening, a portion where the solution was not wet and diffused was observed.

As shown in Table 2, in Comparative Examples 2, Examples 1 to 5, even after UV ozone treatment, a high contact angle was shown. On the other hand, in Comparative Examples 1, 3, and 4, the contact angle after UV ozone treatment was greatly reduced, and sufficient liquid repellency of methyl benzoate could not be obtained.

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

Claims (14)

A heat-curable photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component, (A) Ingredient: Polysiloxane having the following groups (A1) and (A2) (A1) an organic group having a fluorine atom (A2) Organic group having a thermally crosslinkable group (B) Ingredient: Alkali soluble resin (C) solvents, (D) component: Photosensitizer. The photosensitive resin composition according to claim 1, wherein the organic group (A2) having a thermally crosslinkable group is an organic group having an epoxy group. If the photosensitive resin composition of claim 1 or claim 2 satisfies at least one of the following (Z1) to (Z4), (Z1): a crosslinking agent further containing (E) component, (Z2): The alkali-soluble resin of the component (B) further has a self-crosslinkable group, or further has a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a amine group, and an amine group, (Z3): the component (D) is a photo radical generator, and further contains a compound having (F) a component having two or more ethylenic double bonds, (Z4): The compound (D) is a photoacid generator, and further contains a compound (G) having two or more functional groups that form a covalent bond with an acid generated by the (D) component. The photosensitive resin composition according to claim 1 or claim 2, wherein the component (D) is a quinonediazide compound. The photosensitive resin composition according to claim 3, wherein the component (D) is a quinonediazide compound and satisfies any one of (Z1) and (Z2) described above. The photosensitive resin composition according to any one of claims 1 to 5, wherein the component (A) further has a phenyl group. The photosensitive resin composition according to claim 6, wherein the number average molecular weight of the polysiloxane of the component (A) is 1,000 to 100,000 in terms of polystyrene. The photosensitive resin composition according to any one of claims 1 to 7, wherein the number average molecular weight of the alkali-soluble resin of the component (B) is 2,000 to 50,000 in terms of polystyrene. The photosensitive resin composition according to any one of claims 1 to 8, which contains 0.1 to 20 parts by mass of the component (A) with respect to 100 parts by mass of the component (B). The photosensitive resin composition according to any one of claims 1 to 9, wherein the (D) component is 5 to 100 parts by mass with respect to 100 parts by mass of the total of the component (A) and the component (B). The photosensitive resin composition according to any one of claims 3 to 10, wherein the (E) component is 1 to 50 parts by mass with respect to 100 parts by mass of the total of the components (A) and (B). A cured film obtained by using the photosensitive resin composition according to any one of claims 1 to 11. A display element having a cured film as claimed in claim 12. A display element having a cured film as claimed in claim 12 as a partition wall for image formation.