KR20190133786A - Photosensitive resin composition - Google Patents

Abstract

[PROBLEMS] Used for liquid crystal display devices, organic EL display devices, and the like, a good image is maintained even after curing, and has a high liquid repellency on the surface of the cured film even when plasma treatment or UV ozone treatment is not performed. It provides the photosensitive resin composition which can form the image of the cured film which has a high lyophilic property.
[Solution] A thermosetting photosensitive resin composition containing (A) component, (B) component and (C) solvent and (D) component and at least one of (A) component and (B) component having an amide group. . (A) component: The polymer (A1) liquid repellent group (A2) which has following group (A1) and (A2) At least 1 group chosen from the group which consists of a carboxyl group and an amide group, (B) component: The group which consists of a carboxyl group and an amide group Alkali-soluble resin which has at least 1 group chosen from (C) solvent, (D) component: Photosensitive 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 the photosensitive resin composition which can form an image which has high liquid repellency on the cured film surface, its cured film, and various materials using this cured film. This photosensitive resin composition is especially suitable for use as a light shielding material or a partition material corresponding to an interlayer insulating film and an inkjet method in a liquid crystal display or an EL display.

BACKGROUND ART In recent years, full-color display substrate manufacturing technology using inkjet has been actively studied in the manufacturing process of display devices such as thin film transistor (TFT) type liquid crystal display devices and organic EL (electroluminescent) devices. For example, in manufacturing a color filter in a liquid crystal display device, in the conventional printing method, electrodeposition method, dyeing method or pigment dispersion method, a section (also referred to as a bank) for defining a patterned pixel in advance is used. A color filter, a manufacturing method thereof (Patent Document 1), and the like, which are formed of a photosensitive resin layer to be blocked and drop ink drops in an area surrounded by the bank, have been proposed. Moreover, also in organic electroluminescent display element, the bank is produced beforehand, and the method (patent document 2) which manufactures an organic electroluminescence display by dropping the ink used as a light emitting layer similarly is proposed.

However, when ink droplets are dropped in an area surrounded by a bank by the inkjet method, in order to prevent the ink droplets from spilling over the bank to neighboring pixels, the substrate is made to have ink ink (hydrophilicity) and water repellency on the surface of the bank. It is necessary to have.

In order to achieve the above object, it has been proposed that continuous plasma (ozone) treatment such as oxygen gas plasma treatment and fluorine gas plasma treatment can make the substrate hydrophilic and the bank can have water repellency (patent document). 3) The process is complicated. In addition, proposals have been made in which a fluorinated surfactant or a fluorinated polymer is added to the photosensitive organic thin film to impart water repellency and oil repellency (Patent Document 4). There are many points to consider including not only photosensitivity but also coating properties such as compatibility and addition amount, Since the surface water repellency falls by UV ozone treatment at the time of hydrophilic treatment of the board | substrate mentioned above, it was not practical.

On the other hand, Japanese Patent Application Laid-Open No. 2015-172742 (Patent Document 5) is conventionally used as a liquid repellent bank. Moreover, as a positive type, there is Unexamined-Japanese-Patent No. 2012-220860 (patent document 6).

Japanese Patent Application Laid-Open No. 2000-187111 Japanese Patent Laid-Open No. H11-54270 Japanese Patent Publication No. 2000-353594 Japanese Patent Application Laid-Open No. H10-197715 Japanese Patent Application Laid-Open No. 2015-172742 Japanese Patent Publication No. 2012-220860

The present invention has been made in view of the above circumstances, and the problem to be solved is used in liquid crystal display devices, organic EL display devices and the like, and has high liquid repellency on the surface of the cured film even without plasma treatment or UV ozone treatment. Moreover, there are few residues and it forms an image of the cured film which has high lyophilic property to a board | substrate. In particular, in fabrication of a substrate using an inkjet, an image of a cured film capable of preventing a situation where ink droplets spill over a bank and neighboring pixels is prevented.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to achieve the said objective, in the composition containing the polymer which is a liquid repellent component, and the polymer which has alkali-soluble group, the said polymer forms a cured film from the composition which has a specific substituent, The present inventors have found that liquid solution can be efficiently provided, thereby completing the present invention.

That is, this invention relates to the following.

1. The thermosetting photosensitive resin composition containing the following (A) component, (B) component, (C) solvent, and (D) component, and at least one of (A) component and (B) component has an amide group.

(A) component: The polymer which has the following groups (A1) and (A2)

(A1) liquid-repellent group

(A2) at least one group selected from the group consisting of carboxyl groups and amide groups

(B) component: Alkali-soluble resin which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group.

(C) a solvent,

(D) component: Photosensitive agent.

2. The photosensitive resin composition as described in said 1. which satisfy | fills at least any one of following (Z1)-(Z4).

(Z1): It further contains a crosslinking agent as (E) component,

(Z2): Alkali-soluble resin of (B) component further has a self-crosslinkable group, or further has group which reacts with at least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, and an amino group. .

(Z3): (D) A component is an optical radical generating agent and contains the compound which has two or more ethylenic polymerizable groups as (F) component further.

(Z4): The component (D) is a photoacid generator, and further contains a compound having two or more functional groups which form a covalent bond with an acid as the component (G).

3. Photosensitive resin composition as described in said 1. whose (D) component is a quinonediazide compound.

4. Photosensitive resin composition of said 2. whose (D) component is a quinonediazide compound and satisfy | fills any one of said (Z1) and (Z2).

5. Said (A1) liquid-repellent group of (A) component is at least 1 group chosen from the fluoroalkyl group, the polyfluoroether group, the silyl ether group, and the polysiloxane group of 2-11 carbon atoms, The said 1.-4. The photosensitive resin composition in any one of.

6. The photosensitive resin composition in any one of said 1.-5 whose polymer of (A) component is an acrylic polymer.

7. Photosensitive resin composition as described in said 6. whose polymer of (A) component is acrylic polymer which has number average molecular weight of 2,000-100,000 in polystyrene conversion.

8. Type-sensitive photosensitive resin composition in any one of said 1.-7 whose alkali-soluble resin of (B) component has the number average molecular weight of 2,000-50,000 in polystyrene conversion.

9. (B) It contains 0.1-20 mass parts of (A) component with respect to 100 mass parts of components, The said photosensitive resin composition in any one of said 1.-8.

10. It contains 1-50 mass parts of (E) component with respect to a total of 100 mass parts of (A) component and (B) component, The photosensitive resin composition in any one of said 2.-9. .

11. Cured film obtained using the photosensitive resin composition in any one of said 1.-10.

12. A display element having the cured film described in 11. above.

13. A display element having the cured film described in 11. above as an image forming partition.

The photosensitive resin composition of this invention can provide liquid repellency to a film surface efficiently, and can form the cured film which does not impair the wettability of the pattern opening part at the time of image development.

MEANS TO SOLVE THE PROBLEM This invention discovers that the wettability (liquidity) of an opening improves by employ | adopting the structure which has a specific substituent (amide group) in at least one of (A) component which is a liquid repellent component, and (B) component which is alkali-soluble resin. Thus, the present invention was completed. In forming a bank having high liquid repellency on a base layer (substrate or organic cured film) that is inherently lyophilic, if the liquid repellent material remains on the base layer, there is a fear that the lyophilic property of the underlayer is impaired. The present inventors have found for the first time that by presenting an amide group, it is possible to prevent the remaining of the liquid-repellent material on the surface of the underlying layer, which may occur during development, thereby impairing the hydrophilicity of the underlying layer. Without this, it is possible to select a material composition with higher liquid repellency.

The photosensitive resin composition of this invention contains (A) component, (B) component, (C) solvent, and (D) component, and at least one of (A) component and (B) component has a amide group, thermosetting Possible photosensitive resin composition.

(A) component: the polymer which has the following group (A1) and (A2),

(A1) liquid-repellent group

(A2) at least one group selected from the group consisting of carboxyl groups and amide groups

(B) component: Alkali-soluble resin which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group;

(C) a solvent,

(D) component: Photosensitive agent.

Meanwhile, the amide group, -CONH ₂ group is especially preferred.

It is preferable that the photosensitive resin composition of this invention further satisfy | fills the requirement of at least any one of the following (Z1)-(Z4).

(Z1): It further contains a crosslinking agent as (E) component,

(Z2): Alkali-soluble resin of (B) component further has a self-crosslinkable group, or further has group which reacts with at least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, and an amino group. .

(Z3): (D) A component is an optical radical generating agent and contains the compound which has two or more ethylenic polymerizable groups as (F) component further.

(Z4): The component (D) is a photoacid generator, and further contains a compound having two or more functional groups which form a covalent bond with an acid as the component (G).

Among these, it is preferable that (D) component of the photosensitive resin composition of this invention is a quinonediazide compound, ie, it is a positive photosensitive resin composition.

Hereinafter, the detail of each component is demonstrated.

<(A) component>

(A) component is a polymer which has the following group (A1) and (A2).

(A1) liquid-repellent group

(A2) at least one group selected from the group consisting of carboxyl groups and amide groups

In the present invention, examples of the polymer include polyimide, polyamic acid, polyamide, polyurea, polyurethane, phenol resin, epoxy resin, polysiloxane, polyester, and acrylic polymer. An acrylic polymer is mentioned.

Here, the acrylic polymer is an acrylic monomer such as acrylic acid ester and / or methacrylic acid ester as a main monomer, and polymerizable unsaturated groups such as styrene and maleimide, ie, C = C double bonds are included in the structure as necessary. The polymer obtained using the monomer which has a polymeric group is shown.

As polyamic acid, polyimide, polyamide, and polyurea, polyamic acid obtained by reacting diamine with an acid dianhydride, polyimide obtained by imidating the polyamic acid, polyamide obtained by reacting diamine with dicarboxylic acid anhydride, and diamine The polyurea obtained by making it react with diisocyanate is mentioned, In this case, in the polymer of (A) component of this invention, in the combination of the said diamine and acid dianhydride, diamine and dicarboxylic acid anhydride, diamine and diisocyanate, At least one group having at least one (A1) liquid-repellent group (at least one group selected from the following fluoroalkyl group, polyfluoroether group, silyl ether group, and polysiloxane group), and the other group consisting of (A2) carboxyl group and amide group A combination of compounds having at least one group selected from, or at least one group (A1) and It becomes a polymer obtained from the combination of the compound which has both (A2) groups. Or as a polyamic acid, polyimide, polyamide, and polyurea, the polyamic acid which made diamine react with the acid dianhydride, the polyimide obtained by imidating this polyamic acid, the polyamide obtained by making diamine react with dicarboxylic acid anhydride, And resin obtained by combining the compound which has group of (A1), and the compound which has group of (A2) with respect to any one of polyurea obtained by making diamine react with diisocyanate, respectively.

As a polyurethane, it is the diol which has (A1) liquid-repellent group (at least 1 sort (s) of group chosen from the fluoroalkyl group, polyfluoroether group, silyl ether group, and polysiloxane group mentioned later), for example, (A2) Polyurethane obtained by making diol which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group, or diol which has both (A1) group and (A2) group react with diisocyanate is mentioned. Or resin obtained by combining the compound which has group of (A1), and the compound which has group of (A2) with respect to the polyurethane obtained by making arbitrary diol and diisocyanate react.

As a phenol resin, For example, the phenol which has a (A1) liquid-repellent group (at least 1 sort (s) of group chosen from the fluoroalkyl group, polyfluoroether group, silyl ether group, and polysiloxane group mentioned later), (A2) The novolak resin obtained by superposing | polymerizing the phenol which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group, or the phenol which has both of said (A1) group and (A2) group with formaldehyde is mentioned. Or resin obtained by combining the compound which has group of (A1), and the compound which has group of (A2) with respect to arbitrary novolak resin is mentioned.

As an epoxy resin, it is an epoxy resin obtained by making bisphenol A and / or bisphenol F react with the diglycidyl ether of this bisphenol A and / or bisphenol F, for example, and in said combination, one is (A1) At least one selected from the group consisting of (A2) carboxyl groups and amide groups, having a liquid-repellent group (at least one group selected from fluoroalkyl groups, polyfluoroether groups, silyl ether groups, and polysiloxane groups described later); Epoxy resin which has a group or one or both has both of said (A1) group and (A2) group is mentioned. Alternatively, a compound having a group of (A1) or a compound having a group of (A2) is bonded to an epoxy resin obtained by reacting bisphenol A and / or bisphenol F with diglycidyl ether of bisphenol A and / or bisphenol F. The resin obtained by making it stand can be mentioned.

Examples of polysiloxanes include, for example, trialkoxysilanes having a (A1) liquid-repellent group (at least one group selected from a fluoroalkyl group, a polyfluoroether group, a silyl ether group, and a polysiloxane group described later). Silane monomer mixture comprising an alkoxysilane and a trialkoxysilane and / or dialkoxysilane having at least one group selected from the group consisting of (A2) carboxyl groups and amide groups, or the (A1) and (A2) groups The polymer obtained by superposing | polymerizing the silane monomer mixture containing a trialkoxysilane and / or a dialkoxysilane which have both are mentioned. Or resin obtained by combining the compound which has group of (A1), and the compound which has group of (A2) with respect to arbitrary polysiloxane is mentioned.

As polyester, For example, at least 1 sort (s) chosen from dicarboxylic acid or tetracarboxylic dianhydride, and (A1) liquid-repellent group (fluoroalkyl group, polyfluoroether group, silyl ether group, and polysiloxane group mentioned later). Polyester obtained by making the diol which has the group) react is mentioned. Or resin obtained by combining the compound which has group of (A1), and the compound which has group of (A2) with respect to arbitrary polyester is mentioned.

<(A1) introduction of liquid repellent group>

Examples of the liquid-repellent group include at least one group selected from a fluoroalkyl group having 2 to 11 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group.

<< liquid repellent group: The fluoroalkyl group of 2-11 carbon atoms >>

It is preferable that it is C2-C11 fluoroalkyl group of the said fluoroalkyl group, Preferably, it is a C4-C10 fluoroalkyl group.

Examples of such fluoroalkyl groups include 2,2,2-trifluoroethyl group, 2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group and 3-perfluorobutyl 2-hydroxypropyl group, 2- (perfluorohexyl) ethyl group, 3-perfluorohexyl-2-hydroxypropyl group, 2- (perfluorooctyl) ethyl group, 3-perfluorooctyl-2 -Hydroxypropyl group, 2- (perfluorodecyl) ethyl group, 2- (perfluoro-3-methylbutyl) ethyl group, 3- (perfluoro-3-methylbutyl) -2-hydroxypropyl group, 2- (perfluoro-5-methylhexyl) ethyl group, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl group, 2- (perfluoro-7-methyloctyl) ethyl group, and 2 -(Perfluoro-7-methyloctyl) -2-hydroxypropyl group etc. are mentioned.

What is necessary is just to copolymerize the monomer which has a C2-C11 fluoroalkyl group in order to introduce the C2-C11 fluoroalkyl group into the polymer which is (A) component of this invention.

Specific examples of the monomer having a fluoroalkyl group having 2 to 11 carbon atoms in the case where the component (A) is an acrylic polymer include 2,2,2-trifluoroethyl acrylate and 2,2,2- Trifluoroethyl methacrylate, 2,2,3,3,3-pentafluoropropyl acrylate, 2,2,3,3,3-pentafluoropropyl methacrylate, 2- (perfluorobutyl ) Ethylacrylate, 2- (perfluorobutyl) ethylmethacrylate, 3-perfluorobutyl-2-hydroxypropylacrylate, 3-perfluorobutyl-2-hydroxypropylmethacrylate, 2 -(Perfluorohexyl) ethyl acrylate, 2- (perfluorohexyl) ethyl methacrylate, 3-perfluorohexyl-2-hydroxypropyl acrylate, 3-perfluorohexyl-2-hydroxy Propyl methacrylate, 2- (perfluorooctyl) ethylacrylate, 2- (perfluorooctyl) ethyl methacrylate, 3-perfluoroocta 2-hydroxypropyl acrylate, 3-perfluorooctyl-2-hydroxypropyl methacrylate, 2- (perfluorodecyl) ethyl acrylate, 2- (perfluorodecyl) ethyl methacrylate, 2- (perfluoro-3-methylbutyl) ethylacrylate, 2- (perfluoro-3-methylbutyl) ethylmethacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxy Propylacrylate, 3- (perfluoro-3-methylbutyl) -2-hydroxypropylmethacrylate, 2- (perfluoro-5-methylhexyl) ethylacrylate, 2- (perfluoro-5 -Methylhexyl) ethyl methacrylate, 2- (perfluoro-5-methylhexyl) -2-hydroxypropyl acrylate, 2- (perfluoro-5-methylhexyl) -2-hydroxypropylmethacryl Late, 2- (perfluoro-7-methyloctyl) ethylacrylate, 2- (perfluoro-7-methyloctyl) ethylmethacrylate, 2- (perfluoro-7-methyloctyl) -2- Hydroxypropylacrylate Bit, and 2, and the like (perfluoro-7-methyl-octyl) -2-hydroxypropyl methacrylate.

<< liquid repellent group: polyfluoroether group >>

As said polyfluoroether group, Rf group (a) which consists of a polyfluoroether structure represented by following formula (1) is mentioned.

-(XO) _n -Y ... Equation 1

In Formula 1, X is a C1-C10 divalent saturated hydrocarbon group or a C1-C10 fluorine-substituted divalent saturated hydrocarbon group, and represents the same group or different group for every unit enclosed by n. Y is a hydrogen atom (unless fluorine is bonded to a carbon atom adjacent to an oxygen atom adjacent to Y), a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a fluorine substituted at 1 to 20 carbon atoms Monovalent saturated hydrocarbon group is shown. n represents the integer of 2-50. However, the total number of fluorine atoms in Formula 1 is two or more.

As an aspect of X and Y in Formula 1, Preferably, X is an alkylene group of 1-10 carbon atoms or 1-10 carbon atoms which are all fluorine-substituted except one hydrogen atom couple | bonded with a carbon atom. Is a fully fluorinated alkylene group, wherein each unit bound with n represents the same group or a different group, and Y represents an alkyl group having 1 to 20 carbon atoms or carbon atoms, all of which is fluorine-substituted except one hydrogen atom bonded to a carbon atom The thing which shows 1-20 fully fluorinated alkyl group is mentioned, respectively.

As an aspect of X and Y in Formula 1, More preferably, X is a C1-C10 fully fluorinated (perfluorinated) alkylene group, and represents the same group or different group for every unit of n group. And Y represent a fully fluorinated (perfluorinated) alkyl group having 1 to 20 carbon atoms.

In Formula 1, n represents the integer of 2-50. 2-30 are preferable and, as for n, 2-15 are more preferable. If n is two or more, liquid repellency is favorable. When N is 50 or less, the polymer which is (A) component is a monomer which has Rf group (a), the monomer which has at least 1 group chosen from the group which consists of a (A2) carboxyl group and an amide group, and if necessary, Rf group (a When synthesize | combined by copolymerization with the monomer and other monomer which have a liquid repellent group other than), compatibility of a monomer becomes favorable.

Moreover, 2-50 are preferable and, as for the total number of carbon atoms in the Rf group (a) which consists of a polyfluoroether structure represented by Formula 1, 2-30 are more preferable. By making the carbon atom number in Rf group (a) into the said range, the polymer which is (A) component shows the effect which provides favorable liquid repellency. In addition, the polymer which is (A) component is a monomer which has a monomer which has Rf group (a), and the monomer which has at least 1 group chosen from the group which consists of (A2) carboxyl group and an amide group, and if necessary, other than Rf group (a) When synthesize | combining by copolymerization with the monomer and other monomer which have a liquid group, compatibility of a monomer becomes favorable.

Specific examples of X include -CF _2- , -CF ₂ CF _2- , -CF ₂ CF ₂ CF _2- , -CF ₂ CF (CF ₃ )-, -CF ₂ CF ₂ CF ₂ CF ₂ -,- CF ₂ CF ₂ CF (CF ₃ ) — and CF ₂ CF (CF ₃ ) CF ₂ —.

Specific examples of Y include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CHF ₂ ,-(CF ₂ ) ₂ CF ₃ ,-(CF ₂ ) ₃ CF ₃ ,-(CF ₂ ) ₄ CF ₃ , -(CF ₂ ) ₅ CF ₃ ,-(CF ₂ ) ₆ CF ₃ ,-(CF ₂ ) ₇ CF ₃ ,-(CF ₂ ) ₈ CF ₃ ,-(CF ₂ ) ₉ CF ₃ , and (CF ₂ ) ₁₁ CF ₃ ,-(CF ₂ ) ₁₅ CF ₃ .

As a preferable aspect of the Rf group (a) which consists of a polyfluoroether structure represented by Formula 1, the Rf group (a) represented by Formula 2 is mentioned.

-C _p-1 F _{2 (p-1)} -O- (C _p F _2p -O) _n-1 -C _q F _{2q + 1} Equation 2

In Formula 2, p represents the integer of 2 or 3, is the same group for every unit enclosed by n, q is the integer of 1-20, n represents the integer of 2-50.

As Rf group (a) represented by Formula 2, specifically,

CF ₂ O (CF ₂ CF ₂ O) _n-1 CF ₃ (n is 2 to 9),

-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₆ F ₁₃ (n is 2 to 6),

-CF (CF ₃ ) O (CF ₂ CF (CF ₃ ) O) _n-1 C ₃ F ₇ (n is 2 to 6)

It is mentioned preferably from the point of the ease of synthesis.

Rf group (a) in the polymer which is (A) component may be all the same, and may differ.

<< liquid-repellent group: silyl ether group >>

The silyl ether group means a group in which the hydroxy group of the alcohol is protected by a trialkylsilyl group, and is preferably a group represented by the following formula.

-X ⁴ -Si (O-SiX ¹ X ² X ³ ) ₃

(Wherein, X ¹ , X ² , X ³ each independently represent an alkyl group having 1 to 3 carbon atoms, and X ⁴ represents an alkylene group having 1 to 6 carbon atoms.)

What is necessary is just to copolymerize the monomer which has a silyl ether group in order to introduce a silyl ether group into the polymer which is (A) component of this invention.

Examples of the monomer having a silyl ether group in the case where the component (A) is an acrylic polymer include methacryloxypropyl tris (trimethylsiloxy) silane and acryloxypropyl tris (trimethylsiloxy) silane.

<< liquid-repellent group: polysiloxane group >>

As said polysiloxane group, group (a) which has the polysiloxane structure represented by Formula (3) is mentioned. Hereinafter, group (a) which has a polysiloxane structure represented by Formula 3 is called pSi group (a).

-(SiR ¹ R ² -O) _r -SiR ¹ R ² R ³ Equation 3

(However, R ¹ , R ² independently represent hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, and r represents an integer of 1 to 200.).

R ¹ and R ² independently represent hydrogen, an alkyl group, a cycloalkyl group or an aryl group and may be the same or different for each siloxy unit (SiR ¹ R ² -O). Since the polymer which is (A) component shows favorable liquid repellency, it is preferable that R <^1> , R <^2> is a hydrogen atom, a methyl group, or a phenyl group independently, Furthermore, R <^1> , R <^2> of all the siloxy units It is preferable that is a methyl group. In addition, the organic group of R <^3> may contain nitrogen atom, oxygen atom, etc.

As a method of introducing the pSi group (a) into the polymer as the component (A), a method of copolymerizing a monomer having a pSi group (a), various kinds of reacting a compound having a pSi group (a) with a polymer having a reaction site The modification method, the method of using the polymerization initiator which has pSi group (a), etc. are mentioned.

a monomer having a group pSi (a) there may be mentioned _{CH 2 = CHCOO (pSi),} CH 2 = C (CH 3) COO (pSi). Provided that pSi represents a pSi group (a). The monomer which has a pSi group (a) may be used independently and may use 2 or more types together.

As various modification methods for making the compound which has a pSi group (a) react with the polymer which has a reaction site, the following method is mentioned, for example.

A method of copolymerizing a monomer having an epoxy group in advance and then reacting a compound having a carboxyl group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having an epoxy group in advance and then reacting a compound having an amino group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having an epoxy group in advance and then reacting a compound having a mercapto group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having an amino group in advance, and then reacting a compound having a carboxyl group at one end and a pSi group (a) at one end.

A method of copolymerizing a monomer having an amino group in advance and then reacting a compound having an epoxy group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having a carboxyl group in advance and then reacting a compound having an epoxy group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having a carboxyl group in advance and then reacting a compound having an amino group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having a carboxyl group in advance and then reacting a compound having a silyl chloride group at one end and a pSi group (a) at one end. A method of copolymerizing a monomer having a hydroxy group in advance and then reacting a compound having a silyl chloride group at one end and a PSi group (a) at one end.

As the polymerization initiator having a pSi group (a), a group having a divalent polysiloxane structure may be included in the initiator molecule main chain, or a group having a monovalent polysiloxane structure may be included in the terminal or side chain of the initiator molecule. As an initiator in which the group which has a bivalent polysiloxane structure is contained in an initiator molecule main chain, the compound etc. which have the group which has a bivalent polysiloxane structure, and an azo group alternately are mentioned. As a commercial item, VPS-1001 and VPS-0501 (above, Wako Pure Chemical Co., Ltd. (present: Fujifilm Wako Pure Chemical Co., Ltd. product)) are mentioned.

Introduction of at least one group selected from the group consisting of (A2) carboxyl groups and amide groups>

In order to introduce at least one group selected from the group consisting of the (A2) carboxyl group and the amide group into the polymer which is the component (A) of the present invention, a monomer having at least one group selected from the group consisting of the (A2) carboxyl group and the amide group may be copolymerized. do.

As a monomer which has a carboxyl group in the case where (A) component is an acrylic polymer, acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, mono- ( 2- (methacryloyloxy) ethyl) phthalate, N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, etc. are mentioned.

As a monomer which has an amide group in the case where (A) component is an acrylic polymer, For example, acrylamide, methacrylamide, N-methyl acrylamide, N, N- dimethyl acrylamide, N, N-diethyl Acrylamide etc. are mentioned, These can be used individually or in combination of 2 or more types. Among these, methacrylamide is preferable.

As a manufacturing method of the polymer of the said (A) component in the case where (A) component is an acrylic polymer, the monomer which has a liquid repellent group, for example, the monomer which has a C2-C11 fluoroalkyl group, polyfluoro Polymerizing at least 1 sort (s) of the monomer which has a roether group, the monomer which has a silyl ether group, and the polysiloxane group, the monomer which has at least 1 group chosen from a carboxyl group, an amide group, and the other monomer copolymerizable other than the above as needed. It is obtained by superposing | polymerizing in the solvent in presence of initiator at the temperature of 50-110 degreeC. At this time, the solvent used will not be specifically limited if the monomer which comprises the acrylic polymer of (A) component, and the acrylic polymer of (A) component are melt | dissolved. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.

Specific examples of the other monomers include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, and phenyl methacrylate. Acrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydro Furfuryl methacrylate, 3-methoxybutyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate , Anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxy triethylene glycol acrylate, 2-ethoxy ethyl acrylate, 2-amino methyl acrylate, Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl -8-tricyclodecylacrylate, 3-trimethoxysilylpropylacrylate, 3-triethoxysilylpropylacrylate, 3-trimethoxysilylpropylmethacrylate, 3-triethoxysilylpropylmethacrylate , N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxy Lofilacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl meth Acrylate, glycerin monomethacrylate, diethylene glycol monoacrylate, diethylene glycol monomethacrylate, caprolactone 2- (acryloyloxy) ethyl ester, caprolactone 2- (methacryloyloxy) ethyl ester , Poly (ethylene glycol) acrylate, poly (propylene glycol) acrylate, poly (ethylene glycol) ethyl ether acrylate, poly (ethylene glycol) ethyl ether methacrylate, 5-acryloyloxy-6-hydroxynovo Nene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p- Hydroxystyrene, N-hydroxy Nylmaleimide, N-hydroxyphenylacrylamide, N-hydroxyphenyl methacrylamide, p-hydroxyphenyl acrylate, p-hydroxyphenyl methacrylate, aminoethyl acrylate, aminoethyl methacrylate, amino Propyl acrylate, aminopropyl methacrylate, styrene, vinyl naphthalene, vinyl anthracene, vinyl biphenyl, and the like.

The polymer of (A) component obtained in this way is a state of the solution melt | dissolved in the solvent normally. In this invention, the solution of the polymer of the obtained (A) component can also be used for preparation of the photosensitive resin composition mentioned later as it is.

In addition, the solution of the polymer of the component (A) obtained as described above is reprecipitated by stirring under distillation such as diethyl ether, water, and the like, and the resulting precipitate is filtered and washed, at room temperature or under reduced pressure. By drying, it can be set as the powder of the polymer of (A) component. By such operation, the polymerization initiator and unreacted monomer which coexist with the polymer of (A) component can be removed, As a result, the powder of the refined polymer of (A) component can be obtained. When it is not fully refined by one operation, the obtained powder may be dissolved again in a solvent and the above operation may be repeated.

In this invention, the powder of the polymer of the said (A) component can also be used as it is, or the powder can be melt | dissolved in the (C) solvent mentioned later, for example, and can also be used as a state of a solution.

In the polymer of the above-mentioned (A) component, it is preferable that it is 5-70 mass% with respect to all the repeating units, and, as for the introduction amount of (A1) liquid repellent group, it is more preferable that it is 10-60 mass%. When it is less than 5 mass%, the liquid repellency effect may not be exhibited. When it is over 70 mass%, problems, such as aggregation, may arise.

In the polymer of the component (A), the amount of at least one group selected from the group consisting of the (A2) carboxyl group and the amide group is preferably 5 to 60% by mass, and 5 to 40% by mass based on the total repeating units. It is more preferable that is. When it is less than 5 mass%, the effect of this invention may not be fully acquired. If it exceeds 60 mass%, the solubility with respect to a solvent and compatibility with another component may fall.

Moreover, it is preferable that the number average molecular weights of the polymer of the said (A) component are 2,000-100,000. More preferably, it is 3,000-50,000, More preferably, it is 4,000-10,000. If the number average molecular weight is greater than 100,000, residues may occur.

In addition, in this specification, a number average molecular weight and a weight average molecular weight show the value measured by polystyrene conversion by gel permeation chromatography (GPC).

In addition, in this invention, the polymer of (A) component may be a mixture of several types of specific copolymers.

<(B) component>

(B) component of this invention is alkali-soluble resin which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group. In order to provide alkali solubility, resin of (B) component contains alkali-soluble group, As this alkali-soluble group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, a phosphoric acid group, Boronic acid group, and an active methylene group and an active methine group are mentioned. On the other hand, the phenolic hydroxyl group and the carboxyl group are also alkali-soluble groups, and are also thermally reactive moieties (sites capable of forming a crosslinking structure with a crosslinking agent of (E) component) as described later.

In addition, if (B) component is alkali-soluble resin which has at least 1 group chosen from the group which consists of said carboxyl group and an amide group, another structure and the functional group contained will not be specifically limited. For example, when including the compound which has 2 or more functional groups which form a covalent bond by (G) acid mentioned later, (B) component does not need to have a reaction site with (G) component, and (G) In the case of having a reaction site with the component, the reaction site can form a covalent bond with the (G) component by the action of an acid, or a covalent bond with the (G) component by heating. If it is group, it will not specifically limit.

Herein, the active methylene group refers to one having a carbonyl group in an adjacent position among methylene groups (-CH _2- ) and having reactivity with a nucleophilic reagent. In addition, in the present invention, the active methine group means a structure in which one hydrogen atom of the methylene group is substituted with an alkyl group in the active methylene group and has reactivity with a nucleophilic reagent.

As an active methylene group and an active methine group, group represented by a following formula (b1) is more preferable.

[Formula 1]

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

In the formula (b1), examples of the alkyl group represented by R include an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 5 carbon atoms is preferable.

As such an alkyl group, a methyl group, an ethyl group, n-propyl group, i-propyl group, etc. are mentioned, for example.

Especially, a methyl group, an ethyl group, n-propyl group, etc. are preferable.

In said formula (b1), as an alkoxy group which R represents, alkoxy groups of 1 to 20 carbon atoms are mentioned, for example, and an alkoxy group of 1 to 5 carbon atoms is preferable.

As such alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group etc. are mentioned, for example. have.

Especially, a methoxy group, an ethoxy group, i-propoxy group, n-propoxy group, etc. are preferable.

As group represented by said formula (b1), the following structures etc. are mentioned, for example. In addition, in a structural formula, a broken line shows a bond number.

[Formula 2]

Among the alkali-soluble resins of the component (B), at least one group selected from the group consisting of a phenolic hydroxyl group and a carboxyl group as the alkali-soluble group, while having at least one group selected from the group consisting of a carboxyl group and an amide group It is preferable that it is alkali-soluble resin which has a number average molecular weight 2,000-50,000.

Alkali-soluble resin of the said (B) component should just be alkali-soluble resin which has such a structure, and it does not specifically limit with respect to the kind of backbone, side chain, etc. of the main chain of the polymer which comprises resin.

However, alkali-soluble resin of (B) component exists in the range of the number average molecular weight 2,000-50,000. If the number average molecular weight is more than 50,000, development residues tend to occur, and the sensitivity is greatly reduced. On the other hand, if the number average molecular weight is less than 2,000, a significant amount of film reduction occurs during development. There may be a case of hardening.

As alkali-soluble resin of (B) component, acrylic resin, polyhydroxy styrene resin, a polyimide precursor, a polyimide, etc. are mentioned, for example. Among these, acrylic resin (acryl polymer) is mentioned as preferable resin.

In addition, in this invention, alkali-soluble resin which consists of a copolymer obtained by superposing | polymerizing a some kind of monomer (henceforth a specific copolymer) can also be used as (B) component. In this case, the alkali-soluble resin of (B) component may be a blend of several types of specific copolymers.

That is, the said specific copolymer consists of a monomer which expresses alkali solubility, ie, a phenolic hydroxyl group and a carboxyl group as a suitable alkali-soluble group with the monomer which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group. A copolymer having a monomer having at least one group selected from the group and at least one monomer selected from the group of monomers copolymerizable with these monomers as essential structural units, the number average molecular weight 2,000 to 50,000. If the number average molecular weight is greater than 50,000, residues may occur.

In addition, the monomer which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group, and the monomer which expresses alkali solubility may be a monomer which has both a carboxyl group, and in that case, the monomer of the same kind may be sufficient as it.

Examples of the monomer having an amide group include acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N, N-diethylacrylamide, and the like. It can be used in combination of 2 or more type. Among these, methacrylamide is preferable.

Said "monomer which has at least 1 sort (s) chosen from the group which consists of a carboxyl group and a phenolic hydroxyl group" contains the monomer which has a carboxyl group, and the monomer which has a phenolic hydroxyl group. These monomers are not limited to having one carboxyl group or phenolic hydroxy group, and may have two or more.

Hereinafter, although the specific example of the said monomer is given, it is not limited to these.

Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono- (2- (acryloyloxy) ethyl) phthalate, and mono- (2- (methacryloyloxy) ethyl) phthalate. , N- (carboxyphenyl) maleimide, N- (carboxyphenyl) methacrylamide, N- (carboxyphenyl) acrylamide, and the like.

As a monomer which has a phenolic hydroxy group, For example, hydroxy styrene, N- (hydroxyphenyl) acrylamide, N- (hydroxyphenyl) methacrylamide, N- (hydroxyphenyl) maleimide, 4 -Hydroxyphenyl methacrylate, etc. are mentioned.

In the production of alkali-soluble resin (specific copolymer) of component (B), a monomer having at least one group selected from the group consisting of ratios of monomers expressing alkali solubility, for example, phenolic hydroxyl groups and carboxyl groups The ratio of is in all the monomers used for manufacture of alkali-soluble resin (specific copolymer) of (B) component, Preferably it is 5 mass% or more, More preferably, it is 10 mass% or more. When the monomer which expresses alkali solubility (monomer which has at least 1 sort (s) of group chosen from the group which consists of a phenolic hydroxyl group and a carboxyl group) is less than 5 mass%, alkali solubility of alkali-soluble resin (acryl polymer) is insufficient.

In alkali-soluble resin of (B) component, it is preferable that the introduction amount of the at least 1 group chosen from the group which consists of a carboxyl group and an amide group is 5-60 mass% with respect to all the repeating units, and it is 5-40 mass% More preferred. For example, in the production of a specific copolymer, the proportion of the monomer having at least one group selected from the group consisting of carboxyl groups and amide groups, relative to all monomers used in the production of the specific copolymer, is 5 to 60% by mass, for example. For example, it can be 5-40 mass%.

Since alkali-soluble resin which is (B) component of this invention stabilizes the pattern shape after hardening more, it is preferable to further copolymerize the monomer which has a hydroxyalkyl group and a polymerizable unsaturated group.

As a monomer which has a hydroxyalkyl group and a polymerizable unsaturated group, it is 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2, 3- dihydroxy propyl acryl, for example. Latex, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerin monomethacrylate, 5-acrylic Royloxy-6-hydroxy norbornene-2-carboxylic-6-lactone, and the like.

In manufacture of alkali-soluble resin (specific copolymer) of (B) component, the ratio when using the monomer which has a hydroxyalkyl group and a polymerizable unsaturated group is preferable with respect to all the monomers used for manufacture of a specific copolymer. Preferably it is 5-60 mass%, More preferably, it is 10-50 mass%, Most preferably, it is 20-40 mass%. When the monomer which has a hydroxyalkyl group and a polymerizable unsaturated group is less than 5 mass%, the stabilizing effect of the pattern shape of a copolymer may not be acquired. When it is 60 mass% or more, the ratio of the alkali-soluble group of (B) component may be insufficient, and characteristics, such as developability, may fall.

Alkali-soluble resin which is (B) component of this invention can also copolymerize N-substituted maleimide compound from the point which raises Tg of a copolymer.

As an N-substituted maleimide compound, N-methyl maleimide, N-ethyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example. The compound which does not have an aromatic ring from a viewpoint of transparency is preferable, It is more preferable to have an alicyclic skeleton from the point of developability, transparency, and heat resistance, Among these, cyclohexyl maleimide is the most preferable.

In manufacture of alkali-soluble resin (specific copolymer) of (B) component, the ratio at the time of using N-substituted maleimide is 5-60 mass% with respect to all the monomers used for manufacture of a specific copolymer. More preferably, it is 10-50 mass%. When N-substituted maleimide is less than 5 mass%, the Tg improvement effect of a copolymer may not be acquired. When it is 60 mass% or more, solubility to a solvent may fall.

In the case where 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-crosslinkable group or a hydroxyl group, a carboxyl group, an amide group and an amino group. It is preferable that it is a copolymer which further has group (henceforth a crosslinkable group) reacting with at least 1 group chosen from the group which consists of. For example, the requirement (Z2) can be satisfied by introducing a repeating unit having at least one group selected from the group consisting of the self-crosslinkable group and the crosslinkable group into the alkali-soluble resin (B).

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

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

Content in the case where such self-crosslinkable group or crosslinkable group is contained in alkali-soluble resin of (B) component has a self-crosslinkable group or a crosslinkable group based on the sum total of all the repeating units in resin of (B) component. Preferably a unit is 10-70 mass%, Especially preferably, it contains in the ratio of 20-60 mass%.

Alkali-soluble resin of (B) component further contains N-alkoxy methyl group, N-hydroxymethyl group, alkoxy silyl group, epoxy group, oxetanyl group, self-crosslinking groups, such as vinyl group and block isocyanate group, and N-alkoxy methyl group When it has a repeating unit which has at least 1 sort (s) chosen from crosslinkable groups, such as N-hydroxymethyl group, an alkoxy silyl group, an epoxy group, a vinyl group, and a block isocyanate group, it has radical polymerization property, for example, epoxy group, jade What is necessary is just to copolymerize the unsaturated compound (monomer) which has at least 1 sort (s) chosen from crosslinkable groups, such as a cetanyl group, a vinyl group, and a block isocyanate group, and self-crosslinkable groups, such as N-alkoxy methyl group, N-hydroxymethyl group, and alkoxy silyl group. .

As a monomer which has radical polymerization property and has N-alkoxy methyl group, N-butoxymethyl acrylamide, N-isobutoxymethyl acrylamide, N-methoxymethyl acrylamide, N-methoxymethyl methacrylamide, N -Methylol acrylamide etc. are mentioned.

N-hydroxymethyl acrylamide, N-hydroxymethyl methacrylamide, etc. are mentioned as a monomer which has radical polymerization property and has N-hydroxymethylamide group further.

As a monomer which has radical polymerization property and has an alkoxy silyl group, 3-acryloyloxy trimethoxysilane, 3-acryloyloxy triethoxysilane, 3-methacryloyloxy trimethoxysilane, 3-methacryloyloxy triethoxysilane etc. are mentioned.

As a monomer which has radical polymerization property and has an epoxy group further, For example, glycidyl acrylate, glycidyl methacrylate, the glycidyl (alpha)-ethyl acrylate, the glycidyl (alpha)-n-propyl acrylate, alpha- n-butyl glycidyl acrylate, acrylic acid-3,4-epoxybutyl, methacrylic acid-3,4-epoxybutyl, 3,4-epoxycyclohexyl methacrylate, acrylic acid-6,7-epoxyheptyl, methacryl Acids-6,7-epoxyheptyl, α-ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, and the like. Can be. Of these, methacrylic acid glycidyl, methacrylic acid-6,7-epoxyheptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, 3, 4-epoxycyclohexyl methacrylate etc. are used preferably. These are used individually or in combination.

As a monomer which has radical polymerization property and has an oxetanyl group further, the (meth) acrylic acid ester etc. which have an oxetanyl group are mentioned, for example. In addition, in this specification, the base material called "(meth) acrylic acid" shows both acrylic acid and methacrylic acid.

Among these monomers, 3- (methacryloyloxymethyl) oxetane, 3- (acryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (Acryloyloxymethyl) -3-ethyl-oxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (acryloyloxymethyl) -2-trifluoro Methyl oxetane, 3- (methacryloyloxymethyl) -2-phenyl-oxetane, 3- (acryloyloxymethyl) -2-phenyl-oxetane, 2- (methacryloyloxymethyl) jade Cetane, 2- (acryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, 2- (acryloyloxymethyl) -4-trifluoromethyl Oxetane is preferable and 3- (methacryloyloxymethyl) -3-ethyl-oxetane, 3- (acryloyloxymethyl) -3-ethyl-oxetane, etc. are used preferably.

As a monomer which has radical polymerization property and has a vinyl group further, 2- (2-vinyl oxyethoxy) ethyl acrylate, 2- (2-vinyl oxyethoxy) ethyl, etc. are mentioned.

As a monomer which has radical polymerization property and has a block isocyanate group further, methacrylic acid 2- (0- (1'-methylpropylidene amino) carboxyamino) ethyl, and methacrylic acid 2- (3,5-dimethylpyra Zolyl) carbonylamino) ethyl and the like.

When the photosensitive resin composition of this invention satisfy | fills (Z2), it has radical polymerization property, and it is N-alkoxy methyl group, N-hydroxymethyl group, alkoxy silyl group, an epoxy group, an oxetanyl group, a vinyl group, a block isocyanate group, etc. Structural units derived from monomers (unsaturated compounds) having at least one group selected from crosslinkable groups such as self-crosslinkable groups and N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and block isocyanate groups Is based on the sum total of all the repeating units which alkali-soluble resin (B) has, Preferably it is 10-70 mass%, Especially preferably, it contains 20-60 mass%. When this structural unit is less than 10 mass%, there exists a tendency for the heat resistance and surface hardness of the cured film obtained to fall, and when the quantity of this structural unit exceeds 70 mass%, the storage stability of the photosensitive resin composition tends to fall. There is this.

In addition, in this invention, alkali-soluble resin (specific copolymer, for example, an acrylic polymer) of (B) component is formed also as a structural unit also monomers (henceforth other monomer.) Other than the monomer mentioned above. It may be a copolymer. The other monomer may specifically be copolymerizable with at least 1 sort (s) chosen from the group which consists of the monomer which has the said carboxyl group, and the monomer which has a phenolic hydroxyl group, and unless it impairs the characteristic of (B) component, it will specifically limit It doesn't happen. As an example of such a monomer, an acrylic acid ester compound, a methacrylic acid ester compound, an N-substituted acrylamide compound, a maleimide, an acrylonitrile, a styrene compound, a vinyl compound, etc. are mentioned.

Hereinafter, although the specific example of this other monomer is given, it is not limited to these.

As said acrylic acid ester compound, methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycy Diacrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxy tree Ethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxy butyl acrylate, 2-methyl-2-adamantyl acrylate, γ-buty Rolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, di Ethylene, and the like glycol monoacrylate, lactone 2- (acryloyl-yloxy) caproic ester, and poly (ethylene glycol) ethyl ether acrylate.

As said methacrylic acid ester compound, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, for example. Acrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, iso Bonyl methacrylate, 2-methoxyethyl methacrylate, methoxy triethylene 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-tricyclo Decilme Acrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, caprolactone 2- (methacryloyloxy) ethyl ester, poly (ethylene glycol) ethyl ether methacrylate, etc. Can be mentioned.

As said N-substituted acrylamide compound, For example, N-methyl acrylamide, N-methyl methacrylamide, N, N- dimethyl acrylamide, N, N- dimethyl methacrylamide, N-methoxymethyl acryl Amide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, N-butoxymethylmethacrylamide, and the like.

As said styrene compound, styrene which does not have a hydroxyl group, for example, styrene, (alpha) -methylstyrene, chloro styrene, bromostyrene, etc. are mentioned.

As said vinyl compound, methylvinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [ 4.1.0] heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monoepoxide.

In manufacture of alkali-soluble resin (specific copolymer) which is (B) component, it is preferable that the ratio of the said other monomer is 80 mass% or less with respect to all the monomers used for manufacture of a specific copolymer, More preferably, it is 50 It is mass% or less, More preferably, it is 20 mass% or less. When it exceeds 80 mass%, since an essential component (essential monomer which comprises (B) component) reduces relatively, it becomes difficult to fully acquire the effect of this invention.

Although the method of obtaining alkali-soluble resin (specific copolymer) which is (B) component used for this invention is not specifically limited, For example, it has a group chosen from an amide group and a carboxyl group, and is a carboxyl group which is an alkali-soluble group, and phenolic hydride. Monomer which has at least 1 sort (s) of group chosen from a hydroxy group, etc., The monomer which has a hydroxyalkyl group, N-substituted maleimide compound as needed, and N-alkoxy methyl group, N-hydroxymethyl group, alkoxy silyl as needed. Selected from self-crosslinkable groups such as groups, epoxy groups, oxetanyl groups, vinyl groups and block isocyanate groups and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and block isocyanate groups Monomers having at least one group, copolymerizable monomers as necessary, polymerization initiators, etc., if necessary In the coexisting solvent, it is obtained by making a polymerization reaction at the temperature of 50-110 degreeC. At this time, the solvent used will not be specifically limited if it melt | dissolves the monomer and alkali-soluble resin (specific copolymer) which comprise alkali-soluble resin (specific copolymer). As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.

The alkali-soluble resin (specific copolymer) of (B) component obtained in this way is a state of the solution melt | dissolved in the solvent normally. In this invention, the solution of alkali-soluble resin (specific copolymer) of obtained (B) component can also be used for preparation of the photosensitive resin composition mentioned later as it is.

Furthermore, the solution of alkali-soluble resin (specific copolymer) of (B) component obtained as mentioned above is thrown in, stirring with diethyl ether, water, etc., and reprecipitated, and the produced precipitate is filtered and washed, and it is atmospheric pressure. Or it can be made into the powder of a specific copolymer by drying at normal temperature or heat under reduced pressure. By such operation, the polymerization initiator and unreacted monomer which coexist with a specific copolymer can be removed, As a result, the refined powder of the specific copolymer can be obtained. When it is not fully refined by one operation, the obtained powder may be dissolved again in a solvent and the above operation may be repeated.

In this invention, the powder of the said specific copolymer can be used as it is as alkali-soluble resin of (B) component, or it can also be melt | dissolved in the (C) solvent mentioned later, for example, and can be used as a state of a solution. have.

Moreover, as alkali-soluble resin of (B) component, polyimide precursors, such as polyamic acid, polyamic acid ester, and partially imidized polyamic acid, polyimide, such as a carboxylic acid group containing polyimide, can also be used, As long as they are alkali-soluble, they can be used, without restrict | limiting the kind in particular.

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

The (a) tetracarboxylic dianhydride compound is not particularly limited, and specific examples thereof 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'-diphenylsulfontetracarboxylic dianhydride Aromatic tetracarboxylic acid; 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, 3,4 Alicyclic tetracarboxylic dianhydrides such as dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride; And aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride.

These may be used individually by 1 type, or may be used in combination of 2 or more type of compound.

Moreover, the said (b) diamine compound also does not specifically limit, For example, 2, 4- diamino benzoic acid, 2, 5- diamino benzoic acid, 3, 5- diamino benzoic acid, 4, 6- diamino- 1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis (4-amino-3-carboxyphenyl) ether, bis (4-amino-3,5-dicarboxy Phenyl) ether, bis (4-amino-3-carboxyphenyl) sulfone, bis (4-amino-3,5-dicarboxyphenyl) sulfone, 4,4'-diamino-3,3'-dicarboxybiphenyl , 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxy ratio Phenyl, 1,4-bis (4-amino-3-carboxyphenoxy) benzene, 1,3-bis (4-amino-3-carboxyphenoxy) benzene, bis [4- (4-amino-3-carboxy Phenoxy) phenyl] sulfone, bis [4- (4-amino-3-carboxyphenoxy) phenyl] propane, 2,2-bis [4- (4-amino-3-carboxyphenoxy) phenyl] hexafluoro Propane etc. A diamine compound having a carboxyl group; 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4 -Hydroxyphenyl) ether, bis (4-amino-3-hydroxyphenyl) ether, bis (4-amino-3,5-dihydroxyphenyl) ether, bis (3-amino-4-hydroxyphenyl) Methane, bis (4-amino-3-hydroxyphenyl) methane, bis (4-amino-3,5-dihydroxyphenyl) methane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4 -Amino-3-hydroxyphenyl) sulfone, bis (4-amino-3,5-dihydroxyphenyl) sulfone, 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 2 , 2-bis (4-amino-3-hydroxyphenyl) hexafluoropropane, 2,2-bis (4-amino-3,5-dihydroxyphenyl) hexafluoropropane, 4,4'-dia Mino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-dia No-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino- 4-hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4 -(3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino- Diamine compounds having phenolic hydroxy groups such as 4-hydroxyphenoxy) phenyl] hexafluoropropane; 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1,4-diamino-2-mercaptobenzene, bis (4-amino-3-mercaptophenyl Diamine compounds having thiophenol groups such as) ether and 2,2-bis (3-amino-4-mercaptophenyl) hexafluoropropane; 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3-sulfonic acid Sulfonic acid groups such as ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid The diamine compound which has is mentioned. P-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis (2,6-ethylaniline), 4,4'-methylene-bis (2-isopropyl-6-methylaniline) , 4,4'-methylene-bis (2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4 -Phenylenediamine, o-tolidine, m-tolidine, 3,3 ', 5,5'-tetramethylbenzidine, bis [4- (3-aminophenoxy) phenyl] sulfone, 2,2-bis [ 4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (3-aminophenoxy) phenyl] hexafluoropropane, 4,4'-diamino-3,3'-dimethyldicy Clohexylmethane, 4,4'-diaminodiphenylether, 3,4-diaminodiphenylether, 4,4'-diaminodiphenylmethane, 2,2-bis (4-anilino) hexafluoro Propane, 2,2-bis (3-anilino) hexafluoropropane, 2,2-bis (3-amino-4-toluyl) hexafluoropropane, 1,4-bis (4-aminophenoxy) Benzene, 1,3-bis (4-aminophenoxy) benzene, bis [4- (4-aminophenoxy ) Phenyl] sulfone, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2 ' And diamine compounds such as -bis (trifluoromethyl) benzidine.

These may be used individually by 1 type, or may be used in combination of 2 or more type of compound.

When the polyamic acid used in the present invention is prepared from (a) tetracarboxylic dianhydride compound and (b) diamine compound, the compounding ratio of both compounds, i.e., the total moles of (b) diamine compound / (a) tetracarboxylic acid, It is preferable that the total mole number of anhydride compound is 0.7-1.2. As in the normal polycondensation reaction, the closer to 1 the molar ratio is, the higher the degree of polymerization of the resulting polyamic acid and the higher the molecular weight.

Moreover, when superposing | polymerizing using a diamine compound excessively, a carboxylic anhydride can also be made to react with the terminal amino group of the remaining polyamic acid, and can also protect a terminal amino group.

Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrogenated phthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride and tetrahydrophthalic acid. Anhydrides etc. are mentioned.

In the production of the polyamic acid, the reaction temperature of the reaction between the diamine compound and the tetracarboxylic dianhydride compound may 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, it selects suitably in the range of reaction temperature of 5 degreeC-40 degreeC, and reaction time of 1 to 48 hours. To obtain a low molecular weight, high storage stability and partially imidized polyamic acid, it is more preferable to select from a reaction temperature of 40 ° C to 90 ° C and a reaction time of 10 hours or more.

The reaction temperature in the case of protecting the terminal amino group with an acid anhydride can be selected from any temperature of -20 to 150 캜, preferably -5 to 100 캜.

Reaction of a diamine compound and a tetracarboxylic dianhydride compound can be performed in a solvent. Solvents that can be used at this time include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, N-methylcaprolactam, Dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate , Ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 2-ethoxypropionate, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Pylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellosolve acetate, cyclohexanone, methyl ethyl ketone And methyl isobutyl ketone, 2-heptanone, and the like. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt a polyamic acid, if it is a range in which the polyamic acid produced | generated by a polymerization reaction does not precipitate, you may mix and use it with the said solvent.

The solution containing the polyamic acid obtained in this way can be used as it is for preparation of the photosensitive resin composition. The polyamic acid may be precipitated and recovered in poor solvents such as water, methanol and ethanol to be recovered and used.

Moreover, arbitrary polyimide can also be used as (B) component. The polyimide used for this invention is what imidated 50% or more of polyimide precursors, such as said polyamic acid, chemically or thermally.

It is preferable that the polyimide used for the photosensitive resin composition of this invention has an amide group, and has group chosen from a carboxyl group and a phenolic hydroxyl group in order to provide alkali solubility.

As a method of introducing the amide group into the polyimide, a method using a monomer having an amide group, a method of sealing the amine end with an acid anhydride having an amide group, and the like are used.

The method of introducing a carboxyl group or a phenolic hydroxy group into a polyimide is a method using a monomer having a carboxyl group or a phenolic hydroxy group, a method of encapsulating the amine end with an acid anhydride having a carboxyl group or a phenolic hydroxyl group, or When imidating polyimide precursors, such as amic acid, the method of making imidation ratio 99% or less is used.

Such polyimide can be obtained by synthesize | combining polyimide precursors, such as polyamic acid mentioned above, and performing chemical imidation or thermal imidation.

Generally as a method of chemical imidation, an excess of acetic anhydride and pyridine is added to a polyimide precursor solution, and the method of making it react at 100 degreeC from room temperature is used. In addition, as a method of thermal imidation, generally the method of heating a polyimide precursor solution dehydrating at 180 degreeC-250 degreeC is used.

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

Moreover, polyester polycarboxylic acid can also be used as alkali-soluble resin of (B) component. Polyester polycarboxylic acid can be obtained from the acid dianhydride and diol by the method of international publication 2009/051186.

As said acid dianhydride, said (a) tetracarboxylic dianhydride is mentioned.

Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol and benzene-1,4-dimethanol; Alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; And aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

In addition, in this invention, the mixture of a plurality of types of alkali-soluble resin may be sufficient as alkali-soluble resin of (B) component.

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

<(C) solvent>

The (C) solvent used for this invention melt | dissolves (A) component, (B) component, (D) component, and (E) component mentioned later as needed, (F) component, and (G) component, and also It is a thing which melt | dissolves other additives etc. which are added as needed, and the kind, structure, etc. are not specifically limited, if it is a solvent which has such a dissolving ability.

Examples of such a solvent (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether, propylene glycol monopropyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone , 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxy Ethyl oxyacetate, 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-ethoxypropy Methyl acid, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like. Can be.

These solvents can be used individually by 1 type or in combination of 2 or more types.

Among these (C) solvents, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, propylene glycol monopropyl ether, propylene glycol monopropyl ether acetate, ethyl lactate, butyl lactate and the like have good coating properties. And from the viewpoint of high safety. These solvents are generally used as a solvent for photoresist materials.

<(D) component>

As a photosensitive agent which is (D) component, (D-1) 1,2-quinone diazide compound, (D-2) photoradical generator, and (D-3) photoacid generator are mentioned.

When (D-1) 1,2-quinone diazide compound is selected as a photosensitizer, the photosensitive resin composition of this invention becomes a positive photosensitive resin composition.

In addition, when (D-2) optical radical generating agent (photoinitiator) is selected as a photosensitizer, the compound which has 2 or more of ethylenically polymerizable bonds which are (F) component mentioned later is contained, In this case, this invention The photosensitive resin composition becomes a negative photosensitive resin composition.

In addition, when (D-3) photo-acid generator is selected as a photosensitizer, this invention contains the compound which has 2 or more functional groups which form a covalent bond with the acid which is (G) component mentioned later further, In this case, The photosensitive resin composition of this invention becomes a negative photosensitive resin composition.

<(D-1) 1,2-quinonediazide compound >>

(D-1) As a 1, 2- quinonediazide compound, the compound which has either a hydroxyl group or an amino group, and has both a hydroxyl group and an amino group is mentioned by these hydroxyl groups or amino groups (hydroxy group and amino group of In the case of having both, the compound is preferably 10 to 100 mol%, particularly preferably 20 to 95 mol%, esterified or amidated with 1,2-quinonediazidesulfonic acid. It is available.

Examples of the 1,2-quinonediazidesulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid and 1,2-naphthoquinone-2-diazide-4-sulfur. Phonic acid, 1,2-benzoquinone-2-diazide-4-sulfonic acid, etc. are mentioned, In reaction with the compound which has either one or both of the hydroxyl group or amino group mentioned above, this 1,2- Chlorides of quinonediazidesulfonic acid can be used.

Examples of the compound having a hydroxy group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris ( 4-hydroxyphenyl) butane, 4,4-isopropylidenediphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4 '-Dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4', 4 "-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4 '-[1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol (α, α, α'-tris (4-hydroxyphenyl) -1-ethyl 4,4 ', 4 "-(3-methyl-1-propaneyl-3-ylidene) trisphenol, 2,4-dihydroxybenzophenone, 2,3, 4-trihydroxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2 Phenolic compounds such as', 3,4,4'-pentahydroxybenzophenone and 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexanol Aliphatic alcohols such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate Can be mentioned.

Examples of the compound containing an amino group include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, anilines such as p-phenylenediamine, 4,4'-diaminodiphenylmethane and 4,4'-diaminodiphenyl ether; Aminocyclohexane etc. are mentioned.

Furthermore, as a compound containing both a hydroxyl group and an amino group, for example, o-aminophenol, m-aminophenol, p-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2, 4-diaminophenol, 4,4'-diamino-4 ”-hydroxytriphenylmethane, 4-amino-4 ', 4” -dihydroxytriphenylmethane, bis (4-amino-3-carboxy- 5-hydroxyphenyl) ether, bis (4-amino-3-carboxy-5-hydroxyphenyl) methane, 2,2-bis (4-amino-3-carboxy-5-hydroxyphenyl) propane, 2, Aminophenols such as 2-bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane; Alkanolamine, such as 2-amino ethanol, 3-amino propanol, and 4-amino cyclohexanol, etc. are mentioned.

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

When the photosensitive resin composition of this invention is a positive photosensitive resin composition, content in the case of containing the compound which has a quinone diazide group of (D-1) component is 100 mass in total of (A) component and (B) component. With respect to a part, Preferably it is 5-100 mass parts, More preferably, it is 8-50 mass parts, More preferably, it is 10-40 mass parts. When it is less than 5 mass parts, the difference in the dissolution rate with respect to the developing solution of the exposed part and unexposed part of positive type photosensitive resin composition may become difficult, and patterning by image development may be difficult. Moreover, when it exceeds 100 mass parts, since a 1, 2- quinonediazide compound will not fully decompose | disassemble by exposure in a short time, when a sensitivity will fall, (D-1) component will absorb light, and transparency of a cured film will fall. It may be made.

`` (D-2) Photoradical Generator ''

(D-2) An optical radical generating agent is mix | blended in this composition with the compound which has two or more ethylenic double bonds of (F) component mentioned later, when the photosensitive resin composition of this invention satisfy | fills requirement (Z3). do.

The radical radical generator (D-2) is not particularly limited as long as it generates radicals by exposure. Specific examples thereof include benzophenone, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4-methoxy-4'-dimethylaminobenzophenone, 2-ethylanthraquinone and phenanthrene. Aromatic ketones; Benzoin ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin phenyl ether; Benzoin such as methyl benzoin and ethyl benzoin; 2- (o-chlorophenyl) -4,5-phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o -Fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimida Sol dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone , 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2- Halomethyloxadiazole compounds such as trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole; 2,4-bis (trichloromethyl) -6-p-methoxystyryl-S-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3 -Butadienyl) -S-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-S-triazine, 2- (naphtho-1-yl) -4,6- Bis-trichloromethyl-S-triazine, 2- (4-ethoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2- (4-butoxy- Halomethyl-S-triazine-based compounds such as naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine; 2,2-dimethoxy-1,2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 1,2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, benzoyl benzoic acid, 4-benzoyl-4'- Methyldiphenylsulfide, benzyl methyl ketal, dimethylaminobenzoate, p-dimethylaminobenzoic acid isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-di Ethyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 1- (4-phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime), ethanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 4-benzoyl-methyldiphenylsulfide, 1-hydroxycyclohexyl -Phenyl ketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) Methyl] -1- [4- (4- Lepolyyl) phenyl] -1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl Phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone, and the like.

The above photo-radical generator (also called a photopolymerization initiator) can be easily obtained as a commercially available product, and specific examples thereof include, for example, IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, and 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 (or more, manufactured by BASF); KAYACURE® DETX-S, KAYACURE CTX, KAYACURE BMS, KAYACURE 2-EAQ (above, manufactured by Nippon Kayaku Co., Ltd.); TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ- 123, TAZ-140, TAZ-204 (above, Midori Chemical Co., Ltd. product), etc. are mentioned.

These photoradical generators may be used alone or in combination of two or more thereof.

Content in the case of containing (D-2) component in the photosensitive resin composition of this invention is 0.1-30 mass parts with respect to 100 mass parts which is the sum total of (A) component, (B) component, and (F) component mentioned later. It is preferable, More preferably, it is 1-15 mass parts. When this ratio is too small, an exposed part may be hardened | cured and it may become a film with low reliability, even if it does not form a pattern. In addition, when this ratio is excessive, the transmittance | permeability of a cured film may fall, or the developing defect of an unexposed part may arise.

`` (D-3) Mine Generator ''

(D-3) A photo-acid generator with the compound which has two or more functional groups which form a covalent bond with the acid of (G) component mentioned later, when the photosensitive resin composition of this invention satisfy | fills requirement (Z4). It is mix | blended in this composition.

The photo-acid generator of (D-3) is not particularly limited as long as it is a compound that generates an acid by photolysis upon ultraviolet irradiation. Examples of the acid generated when the photoacid generator is photolyzed include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentansulfonic acid, octanesulfonic acid, benzenesulfonic acid, and p-toluenesulfate. Phonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H-perfluorooctanesulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sul Sulfonic acids, such as phonic acid and dodecylbenzenesulfonic acid, its hydrate, salt, etc. are mentioned.

Examples of the photoacid generator include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfone compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzointosylate compounds, iron arene complexes, and halogen-containing triazines. A compound, an acetophenone derivative, a cyano group containing oxime sulfonate compound, etc. are mentioned. Conventionally known or conventionally used photoacid generators can be applied in the present invention without any particular limitation. In addition, in this invention, the photo-acid generator of (D-3) component may be used individually by 1 type, and may be used in combination of 2 or more type. As a specific example, the compound etc. which are represented by following formula [PAG-1]-a formula [PAG-41] are mentioned.

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

Content in the case of containing (D-3) component in the photosensitive resin composition of this embodiment is preferably with respect to a total of 100 mass parts of (A) component, (B) component, and (G) component mentioned later in total. 0.01 mass part-20 mass parts, More preferably, they are 0.1 mass part-10 mass parts, More preferably, they are 0.5 mass part-8 mass parts. By making content of (D-3) component into 0.01 mass part or more, sufficient thermosetting and solvent resistance can be provided. However, when more than 20 mass parts, unexposed part may become inferior in development, or the storage stability of a composition may fall.

<(E) component>

(E) A component is a crosslinking agent (crosslinkable compound), and is introduce | transduced in a composition, when the photosensitive resin composition of this invention meets requirement (Z1). More specifically, it is a compound which has a structure which can form a crosslinked structure by thermal reaction with the thermally reactive site | part (for example, a carboxyl group and / or phenolic hydroxyl group) which may exist in (B) component, Also called thermal crosslinking agent. Hereinafter, although a specific example is given, it is not limited to these.

As a thermal crosslinking agent, it is chosen from the crosslinkable compound which has 2 or more substituents chosen from (E1) alkoxymethyl group and the hydroxymethyl group, for example, or the crosslinkable compound represented by Formula (4) mentioned later (E2). It is preferable. These crosslinking agents can be used individually or in combination of 2 or more types.

<< crosslinkable compound which has 2 or more substituents chosen from (E1) alkoxymethyl group and the hydroxymethyl group >>

The crosslinking | crosslinked compound which has 2 or more substituents chosen from the alkoxy methyl group and the hydroxymethyl group of (E1) component is a compound in which a crosslinking reaction advances by dehydration condensation reaction, when exposed to the high temperature at the time of thermosetting. As such a compound, compounds, such as an alkoxy methylation glycoluril, an alkoxy methylation benzoguanamine, and an alkoxy methylation melamine, and a phenoplast type compound are mentioned, for example.

As a specific example of the alkoxy methylation glycoluril, For example, 1,3,4,6- tetrakis (methoxymethyl) glycoluril, 1,3,4,6- tetrakis (butoxymethyl) glycoluril, 1,3,4,6-tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1 , 3,3-tetrakis (methoxymethyl) urea, 1,3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, and 1,3-bis (methoxymethyl ) -4,5-dimethoxy-2-imidazolinone etc. are mentioned.

As a commercial item, compounds, such as a glycoluril compound (brand name: Cymel (trademark) 1170, Powder Link (trademark) 1174) by Mitsui Cytec Co., Ltd. (now: Allnex Corporation), methylated urea resin (brand name: UFR ( 65), Butylated Urea Resin (trade name: UFR® 300, U-VAN10S60, U-VAN10R, U-VAN11HV); Urea / formaldehyde-type resin (high condensation type, a brand name: beccarmin (trademark) J-300S, the said P-955, the same N) made by DIC Corporation, etc. are mentioned.

Specific examples of the alkoxy methylated benzoguanamine include tetramethoxymethylbenzoguanamine and the like. As a commercial item, Mitsui Cytec Co., Ltd. (present: Allnex Corporation) (brand name: Cymel (registered trademark) 1123), Sanwa Chemical Co., Ltd. (brand name: Nikarak (registered trademark) BX-4000, copper BX- 37, copper BL-60, copper BX-55H), and the like.

As a specific example of the alkoxy methylation melamine, hexamethoxy methyl melamine etc. are mentioned, for example. As a commercial item, a methoxymethyl type melamine compound (trade name: Cymel (registered trademark) 300, copper 301, copper 303, copper 350) made by Mitsui Cytec Co., Ltd. (present: Allnex Corporation), butoxymethyl type melamine compound ( Product name: My coat (trademark) 506, copper 508), methoxymethyl type melamine compound made by Sanwa Chemical Co., Ltd. (brand name: Nicarac (registered trademark) MW-30, copper MW-22, copper MW-11, copper MW-100LM, copper MS-001, copper MX-002, copper MX-730, copper MX-750, copper MX-035), butoxymethyl type melamine compound (brand name: Nicarac (registered trademark) MX-45, copper MX-410, MX-302) etc. are mentioned.

Moreover, the compound obtained by condensing the melamine compound, the urea compound, the glycoluril compound, and the benzoguanamine compound in which the hydrogen atom of such an amino group was substituted by the methylol group or the alkoxy methyl group may be sufficient. For example, a high molecular weight compound prepared from the melamine compound and the benzoguanamine compound described in US Pat. As a commercial item of the said melamine compound, a brand name: Cymel (registered trademark) 303 (made by Mitsui Cytec Co., Ltd. (present: Allnex Corporation)) etc. are mentioned, As a commercial item of the said benzoguanamine compound, Cymel (registered trademark) 1123 (Mitsui Cytec Co., Ltd. make (all: Nex Corporation)) etc. are mentioned.

As a specific example of a phenoplast type compound, 2, 6-bis (hydroxymethyl) phenol, 2, 6-bis (hydroxymethyl) cresol, 2, 6-bis (hydroxymethyl)- 4-methoxyphenol, 3,3 ', 5,5'-tetrakis (hydroxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-hydroxy-5-methylbenzene Methanol), 4,4 '-(1-methylethylidene) bis [2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis [2-methyl-6-hydroxymethylphenol], 4,4 '-(1-methylethylidene) bis [2,6-bis (hydroxymethyl) phenol], 4,4'-methylenebis [2,6-bis (hydroxymethyl) phenol], 2 , 6-bis (methoxymethyl) phenol, 2,6-bis (methoxymethyl) cresol, 2,6-bis (methoxymethyl) -4-methoxyphenol, 3,3 ', 5,5'- Tetrakis (methoxymethyl) biphenyl-4,4'-diol, 3,3'-methylenebis (2-methoxy-5-methylbenzenemethanol), 4,4 '-(1-methylethylidene) Bis [2-methyl-6-methoxymethylphenol], 4,4'-methylenebis [2-methyl-6-methoxy Tylphenol], 4,4 '-(1-methylethylidene) bis [2,6-bis (methoxymethyl) phenol], 4,4'-methylenebis [2,6-bis (methoxymethyl) Phenol] and the like. It can also be obtained as a commercial item, As a specific example, 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (above, Asahi Organic materials industry company make), etc. are mentioned.

Furthermore, as (E1) component, hydroxymethyl groups, such as N-hydroxymethyl acrylamide, N-methoxymethyl methacrylamide, N-ethoxymethyl acrylamide, and N-butoxymethyl methacrylamide, or an alkoxy methyl group The polymer manufactured using the acrylamide compound or methacrylamide compound substituted by the can also be used.

Examples of such polymers include poly (N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, and air of N-hydroxymethylmethacrylamide and methyl methacrylate. Copolymers, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, copolymers of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate, and the like. have. The weight average molecular weight of such a polymer is 1,000-50,000, Preferably it is 1,500-20,000, More preferably, it is 2,000-10,000.

<< crosslinkable compound represented by (E2) Formula (4) >>

Moreover, the photosensitive resin composition of this invention can contain the crosslinking | crosslinked compound represented by Formula (4) as (E2) component.

[Formula 10]

(In formula, k represents an integer of 2-10, m represents the integer of 0-4, R <^11> represents a k-valent organic group.)

(E2) A component will not be specifically limited if it is a compound which has a cycloalkene oxide structure represented by Formula (4). As the specific example, the compound represented by following formula E2-1 and formula E2-2, the commercial item shown below, etc. are mentioned.

[Formula 11]

[Formula 12]

As a commercial item, epoxide (registered trademark) GT-401, copper GT-403, copper GT-301, copper GT-302, Celoxide (registered trademark) 2021, Celoxide 2021P, Celoxide 3000 (Dai) Cell name), Denacol (registered trademark) EX-252 (trade name, manufactured by Nagase Chemtex Co., Ltd.), CY175, CY177, CY179 (above, CIBA-GEIGY AG (present: Huntsman Corp.) ), Araldite (registered trademark) CY-182, copper CY-192, copper CY-184 (above, CIBA-GEIGY AG (present: product made in Huntsman)), epiclon (registered trademark) 200, copper 400 (Above, DIC Corporation brand name), Epicoat (registered trademark) 871, copper 872 (above, Emulsion shell epoxy Co., Ltd. (prefecture: Mitsubishi Chemical Co., Ltd.) brand name, `` epi coat '' is a solution The trademark is a registered trademark of Research Netherlands Vesloten Vennootschap, ED-5661, ED-5662 (above, the product name of Cellanese Coating Co., Ltd.), etc. are mentioned. In addition, these crosslinkable compounds can be used individually or in combination of 2 or more types.

Among these, compounds represented by the formulas E2-1 and E2-2 and epoxides having a cyclohexene oxide structure from the viewpoints of process resistance, such as heat resistance, solvent resistance, and internal temporal resistance, and transparency ) GT-401, GT-403, GT-301, GT-302, Celoxide (registered trademark) 2021, Celoxide 2021P, and Celoxide 3000 are preferable.

Moreover, as E component, it heat-reacts with the thermally reactive site | part (for example, a carboxyl group and / or a phenolic hydroxyl group and an amide group) of (B) component other than what is shown as (E1) component and (E2) component. The compound which can form a crosslinked structure can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-di-risidylamino Epoxy compounds, such as methyl) cyclohexane, and N, N, N ', N'- tetraglycidyl-4, 4'- diamino diphenylmethane, VESTANAT® B1358 / 100, and VESTAGON® BF 1540 (above, isocyanurate-type modified polyisocyanate, product made by Degussa Japan), takeate (registered trademark) B-882N, copper takeate B-7075 (above, isocyanurate Type modified polyisocyanate, manufactured by Mitsui Chemical (Co., Ltd.)) and the like can be mentioned diisocyanate compounds such as.

In addition, (E) component has two structures which can form a crosslinked structure by thermal reaction with the thermally reactive site | part (for example, a carboxyl group and / or a phenolic hydroxyl group, and an amide group) of (B) component. The polymer which has the above can be used. Specifically, for example, a polymer produced using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloxypropyltrimethoxysilane, or the like Polymer produced using a compound having an alkoxysilyl group of 2-isocyanatoethyl methacrylate (Carens MOI [registered trademark], Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate Compound having an isocyanate group such as lens AOI (registered trademark) and Showa Denko Co., Ltd. or 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (Carens MOI-BM) Trademark, Showa Denko Co., Ltd., 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate (Carens MOI-BP [registered trademark], Showa Denko Co., Ltd.) The polymer etc. which are manufactured using the compound which has blocked isocyanate groups, such as ()) are mentioned. These compounds may be used alone or in combination of a plurality to produce a polymer, or may be combined with other compounds to produce a polymer.

When (B) component has group which reacts with at least 1 group chosen from the group which consists of group represented by a hydroxyl group, a carboxyl group, an amide group, and an amino group (when one of (Z2) requirements is satisfied), a hydroxyl group And a compound selected from the group consisting of groups represented by a carboxyl group, an amide group and an amino group, that is, a compound having two or more groups (B) and a thermally reactive group can be used as the component (E).

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

In the photosensitive resin composition of this invention, content when the mixture of the crosslinking agent of (E) component is selected is 1-50 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 1 It is -40 mass parts, More preferably, it is 1-30 mass parts. When the content of the crosslinking agent (crosslinkable compound) is small, the density of crosslinking formed by the crosslinkable compound is not sufficient, so that effects of improving heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation are not obtained. It may not. On the other hand, when it exceeds 50 mass parts, an uncrosslinked crosslinking | crosslinked compound exists, the heat resistance, solvent resistance, resistance to long-term baking after pattern formation, etc. fall, and also the storage stability of the photosensitive resin composition worsens. There is.

<(F) component>

(F) component is a compound which has 2 or more of ethylenic polymerizable groups (ethylenic double bond), and when the photosensitive resin composition of this invention satisfy | fills requirement (Z3), the above-mentioned (D-2) radical photoradical It is formulated with a generator. The compound which has two or more ethylenic polymerizable groups here means the compound which has two or more ethylenic polymerizable groups in one molecule, and these ethylenic polymerizable groups are in a molecule terminal. In addition, an ethylenic polymerizable group means at least 1 sort (s) of polymeric group chosen from the group which consists of an acrylate group, a methacrylate group, a vinyl group, and an allyl group.

In the solution of the photosensitive resin composition (negative photosensitive resin composition) of this invention, the compound which has two or more ethylenic polymerizable groups which are this (F) components has favorable compatibility with each component, and is also in developability. From the viewpoint of not affecting, a compound having a molecular weight of 1,000 or less in terms of molecular weight (when this compound is a polymer, refers to a weight average molecular weight).

As a specific example of such a compound, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate , Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, tetramethylol methane tetraacrylic Rate, tetramethylolmethanetetramethacrylate, trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, 1,3,5-triacryloylhexahydro-S-triazine, 1,3,5- Trimethacryloylhexahydro-S-triazine, Tris (Hydroxyethyl acryloyl) isocyanurate, tris (hydroxyethyl methacryloyl) isocyanurate, triacryloyl formal, trimethacryloyl formal, 1,6-hexanediol acryl Rate, 1,6-hexanediol methacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethanediol diacrylate, ethanediol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene Glycol dimethacrylate, N, N'-bis (acryloyl) cysteine, N, N'-bis (methacryloyl) cysteine, thiodiglycol diacrylate, thiodiglycol Dimethacrylate, Bisphenol A Diacrylate, Bisphenol A Dimethacrylate, Bisphenol F Diacrylate, Bisphenol F Dimethacrylate, Bisphenol S Diacrylate, Bisphenol S Dimethacrylate, Bisphenoxyethanol flu Orylene diacrylate, bisphenoxyethanol fluorene dimethacrylate, diallyl ether bisphenol A, o- diallyl bisphenol A, diallyl maleic acid, triallyl trimellitate, and the like.

The polyfunctional acrylate compound can be easily obtained as a commercially available product, and specific examples thereof include, for example, KAYARAD (registered trademark) T-1420, copper DPHA, copper DPHA-2C, copper D-310, copper D-330, East DPCA-20, East DPCA-30, East DPCA-60, East DPCA-120, East DN-0075, East DN-2475, East R-526, East NPGDA, East PEG400DA, East MANDA, East R -167, East HX-220, East HX620, East R-551, East R-712, East R-604, East R-684, East GPO-303, East TMPTA, East THE-330, East TPA-320, East TPA-330, copper PET-30, copper RP-1040 (above, made by Nippon Kayaku Co., Ltd.), aronix (registered trademark) M-210, copper M-240, copper M-6200, copper M-309, copper M-400, M-402, M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M M-8100, M-8530, M-8560, M-9050 (above, manufactured by Toa Synthetic Co., Ltd.), Biscot 295, Copper 300, Copper 360, Copper GPT, Copper 3PA, Copper 400, Copper 260 , East 312, East 335HP (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM -3LM-N, A-TMPT, AD-TMP, ATM-35E, A-TMMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE- 1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), etc. are mentioned.

The compound which has 2 or more of these ethylenic polymerizable groups can be used 1 type or in combination of 2 or more types.

It is preferable that content in the case of containing (F) component in the photosensitive resin composition of this invention is 5-200 mass parts with respect to 100 mass parts which is the sum total of (A) component and (B) component, More preferably, it is 10 It is -80 mass parts, Especially preferably, it is 20-100 mass parts. If this ratio is too small, there is a possibility that the exposed portion becomes insufficiently hardened, and even if the pattern is not formed, a film having low reliability is obtained. In addition, when this ratio is excessive, tack may generate | occur | produce in the coating film (photosensitive resin film) after prebaking, or the unexposed part may become insoluble at the time of image development.

<(G) component>

The (G) component used for the photosensitive resin composition of this invention is a compound which has 2 or more functional groups which form a covalent bond with an acid, and when the photosensitive resin composition of this invention meets requirement (Z4), it is said It is mix | blended with the (D-3) photo-acid generator mentioned. As a functional group which forms a covalent bond with such an acid, an epoxy group, a methylol group, etc. are mentioned.

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-diglycidylphenylglycidyl ether, 1,1,3-tris [p- (2,3-epoxypro Foxy) phenyl] propane, 1,2-cyclohexanedicarboxylic acid diglycidyl ester, 4,4'-methylenebis (N, N- diglycidylaniline), 3,4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylate, trimethylol ethane triglycidyl ether, bisphenol-A-diglycidyl ether, pentaerythritol polyglycidyl ether, etc. are mentioned.

Moreover, as a compound which has two or more epoxy groups, a commercially available compound can also be used from an easy point of acquisition. Although the specific example (brand name) is given to the following, it is not limited to these: Epoxy resin which has amino groups, such as YH-434 and YH434L (Toto Kasei Co., Ltd. (present: Shin-Nitetsu Chemical Co., Ltd. product)). ; Epolid (registered trademark) GT-401, copper GT-403, copper GT-301, copper GT-302, Celoxide (registered trademark) 2021, Celoxide 2021P, Celoxide 3000 (manufactured by Daicel) Epoxy resins having a cyclohexene oxide structure; Epicoat (registered trademark) 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, Emulsified Shell Epoxy Co., Ltd. (prefecture: Mitsubishi Chemical Co., Ltd. And bisphenol A epoxy resins such as resolution research, which is a registered trademark of Vesrotene Fuen Notebook, Netherlands; and bisphenols such as Epicoat 807 (emulsified Shell Epoxy Co., Ltd. (manufactured by Mitsubishi Chemical Co., Ltd.)) F-type epoxy resins; phenol novolacs such as epicoat 152, copper 154 (above, emulsion shell epoxy (manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201, copper 202 (above, Nippon Kayaku Co., Ltd.) Type epoxy resin; EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Emulsion Shell Epoxy Co., Ltd.) : Cresol novolac type epoxy resin such as Mitsubishi Chemical Co., Ltd .; Denacol (registered trademark) EX-252 (manufactured by Nagase ChemteX), CY175, CY177, CY179, Araldite (registered trademark) CY -182, East CY-192, East CY-184 CIBA-GEIGY AG (present: Huntsman Corporation), epiclon 200, copper 400 (more than, DIC Corporation made), epicoat 871, copper 872 (more, oil painting shell epoxy (present: Mitsubishi Chemical) Alicyclic epoxy resins, such as the following), ED-5661, ED-5662 (above, Celanese Coating Co., Ltd.), Denacol (registered trademark) EX-611, copper EX-612, copper EX- 614, East EX-622, East EX-411, East EX-512, East EX-522, East EX-421, East EX-313, East EX-314, East EX-321 (manufactured by Nagase Chemtex Co., Ltd.) Aliphatic polyglycidyl ether, such as these.

Moreover, the polymer which has an epoxy group can also be used as a compound which has two or more epoxy groups.

The polymer which has the said epoxy group can be manufactured by addition polymerization using the addition polymerization monomer which has an epoxy group, for example. As an example, addition polymerization of polyglycidyl acrylate, a copolymer of glycidyl methacrylate and ethyl methacrylate, a copolymer of glycidyl methacrylate and styrene and 2-hydroxyethyl methacrylate, and the like A polycondensation polymer, such as a polymer and an epoxy novolak, is mentioned.

Or the polymer which has the said epoxy group can also be manufactured by reaction with the high molecular compound which has a hydroxyl group, and the compound which has an epoxy group, such as epichlorohydrin and glycidyl tosylate.

As a weight average molecular weight of such a polymer, it is 300-20,000, for example.

The compound which has 2 or more of these epoxy groups can be used individually or in combination of 2 or more types.

As a compound which has two or more methylol groups, the crosslinking | crosslinked compound which has two or more substituents chosen from the above-mentioned (E1) alkoxy methyl group and the hydroxymethyl group is mentioned. That is, compounds, such as alkoxy methylation glycoluril, alkoxy methylation benzoguanamine, and alkoxy methylation melamine, and a phenoplast type compound are mentioned, A specific example of these is mentioned above (paragraph [0147]-[0152] ] Reference).

Moreover, as a compound which has two or more methylol groups, the polymer which has a methylol group can also be used, This polymer also the polymer mentioned in the above-mentioned (E1) component, ie, N-hydroxymethyl acrylamide, N- Polymers produced using acrylamide compounds or methacrylamide compounds substituted with hydroxymethyl groups or alkoxymethyl groups, such as methoxymethylmethacrylamide, N-ethoxymethylacrylamide and N-butoxymethylmethacrylamide These specific examples can also employ the above-described polymer and weight average molecular weight (see paragraphs [0153] to [0154]).

Content when the photosensitive resin composition of this invention contains the compound which has two or more functional groups which form a covalent bond with the acid of (G) component is 100 mass parts in total of (A) component and (B) component. It is preferable that it is 5-200 mass parts on the basis, More preferably, it is 50-150 mass parts. When this ratio is too small, the photocurability of the photosensitive resin composition (negative photosensitive resin composition) may fall, On the other hand, when it is excessive, developability of an unexposed part will fall and it will become a cause of a residual film or a residue. There is a case.

<Other additives>

Furthermore, the photosensitive resin composition of this invention dissolves a rheology modifier, a pigment, a dye, a storage stabilizer, an antifoamer, an adhesion promoter, or a polyhydric phenol, polyhydric carboxylic acid, etc. as needed, unless the effect of this invention is impaired. Accelerators and the like.

<Photosensitive resin composition>

The photosensitive resin composition of this invention contains (A) component, (B) component, (C) solvent, and (D) component, and at least one of (A) component and (B) component has a amide group, thermosetting It is a possible photosensitive resin composition, and if necessary, the functional group which forms a covalent bond with the crosslinking agent of (E) component, the compound which has two or more ethylenically polymerizable groups of (F) component, and the acid of (G) component It is a composition which can further contain 1 or more types of the compound which has two or more, and other additives.

(A) component: The polymer which has the following groups (A1) and (A2)

(A1) liquid-repellent group

(A2) at least one group selected from the group consisting of carboxyl groups and amide groups

(B) component: Alkali-soluble resin which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group.

(C) a solvent,

(D) component: Photosensitive agent.

Among these, the preferable example of the photosensitive resin composition of this invention is as follows.

[1]: Photosensitive resin composition in which 0.1-20 mass parts of (A) component and (D) component are contained with respect to 100 mass parts of (B) components, and these components melt | dissolved in (C) solvent.

[2]: 0.1 to 20 parts by mass of (A) component and 5 to 100 parts by mass of (D) component with respect to 100 parts by mass of component (B), and these components are dissolved in the solvent (C) as a photosensitive resin composition Furthermore, the photosensitive resin composition whose said (D) component is (D-1) component.

[3]: 0.1 to 20 parts by mass of component (A) and 5 to 100 parts by mass of (D) component with respect to 100 parts by mass of component (B), and these components are dissolved in the solvent (C) as a photosensitive resin composition Furthermore, as a photosensitive resin composition containing 1-50 mass parts of crosslinking agents which are (E) component with respect to 100 mass parts which are the sum total of (A) component and (B) component, Furthermore, said (D) component is (D-1 ) Photosensitive resin composition which is a component.

[4]: 5 to 200 parts by mass of (F) component with respect to 100 parts by mass of 0.1 to 20 parts by mass of (A) component, (A) component and (B) component relative to 100 parts by mass of component (B), (D) component containing 0.1-30 mass parts with respect to 100 mass parts which is the sum total of (A) component, (B) component, and (F) component, These are the photosensitive resin composition melt | dissolved in (C) solvent further Photosensitive resin composition whose (D) component is (D-2) component.

Although the ratio of solid content in the photosensitive resin composition of this invention is not specifically limited as long as each component is melt | dissolving uniformly in a solvent, For example, it is 1-80 mass%, For example, 5-60 mass %, Or 10-50 mass%. Here, solid content means what remove | eliminated the (C) solvent from the all components of the photosensitive resin composition.

Although the preparation method of the photosensitive resin composition of this invention is not specifically limited, As this preparation method, (A) component (polymer) is melt | dissolved in the (C) solvent and the alkali of (B) component is dissolved in this solution, for example. Functional group which forms covalent bond by soluble resin, the photosensitive agent of (D) component, the crosslinking agent of (E) component, the compound which has two or more ethylenically polymerizable groups of (F) component, and the acid of (G) component as needed. The method which mixes the compound which has two or more at a predetermined ratio, and makes it a uniform solution, or the method of adding and adding another additive further as needed in the suitable step of this preparation method is mentioned.

In preparation of the photosensitive resin composition of this invention, the solution of the polymer of (A) component obtained by the polymerization reaction in (C) solvent, and the solution of alkali-soluble resin of (B) component can be used as it is. In this case, (B) component (it may be a solution of (B) component), (D) component, (E) component, (F) component, ( When the G) component or the like is added to form a uniform solution, the (C) solvent may be further added for the purpose of concentration adjustment. At this time, the (C) solvent used in the formation process of the polymer of (A) component or alkali-soluble resin of (B) component, and (C) solvent used for density | concentration adjustment at the time of preparation of the photosensitive resin composition may be the same. It may be different.

Thus, it is preferable to use the prepared solution of the photosensitive resin composition after filtering using the filter etc. which have a pore diameter of about 0.2 micrometer.

<Film and Cured Film>

The photosensitive resin composition of the present invention may be a semiconductor substrate (for example, silicon / silicon dioxide coated substrate, silicon nitride substrate, metal such as aluminum, molybdenum, chromium coated substrate, glass substrate, quartz substrate, ITO substrate, etc.). ), The coating film can be formed by applying a rotary coating, a spilling coating, a roll coating, a slit coating, a slit followed by a rotary coating, an ink jet coating, or the like, followed by preliminary drying with a hot plate or an oven. Thereafter, the coating film is heated (prebaked) to form a photosensitive resin film.

As conditions of this heat processing, the heating temperature and heating time suitably selected from the range of the temperature of 70 degreeC-160 degreeC, and time 0.3 to 60 minutes are employ | adopted, for example. Heating temperature and a heat time become like this. Preferably they are 80 degreeC-140 degreeC, and 0.5 to 10 minutes.

In addition, the film thickness of the photosensitive resin film formed from the photosensitive resin composition is 0.1-30 micrometers, for example, 0.2-10 micrometers, Furthermore, it is 0.3-8 micrometers, for example.

By attaching a mask having a predetermined pattern onto the photosensitive resin film obtained above, irradiating light such as ultraviolet rays and developing with an alkali developer, either the exposed portion or the unexposed portion is washed and remains according to the material composition. If the patterned film | membrane is heated by 80 degreeC-140 degreeC for 0.5 to 10 minutes, the relief pattern which has a sharp cross section will be obtained.

Examples of the alkaline developer that may be used include, for example, aqueous solutions of alkali metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide and sodium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline (2-hydroxyethyltrimethylammonium aqueous solution). Alkaline aqueous solutions, such as aqueous solution of quaternary hydroxide ammonium hydroxide, such as an), amine aqueous solution, such as ethanolamine, propylamine, and ethylenediamine, are mentioned. Moreover, surfactant etc. can also be added to these developing solutions.

In the above, 0.1-2.58 mass% aqueous solution of tetraethylammonium hydroxide is generally used as a developing solution of a photoresist, and also in this photosensitive resin composition of this invention, a problem, such as swelling of a film, is used using this alkaline developing solution. It can be developed well without.

As the developing method, any of them can be used, such as a liquid method, a dipping method, and a rocking dipping method. The developing time at this time is 15 to 180 second normally.

After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, followed by air drying using compressed air or compressed nitrogen, or by spinning to remove moisture on the substrate and to obtain a patterned film. Lose.

Subsequently, post-baking is performed on the pattern forming film for thermal curing, and specifically, by heating using a hot plate, an oven, or the like, the heat resistance, transparency, planarization property, low water absorption, chemical resistance, etc. are excellent. A film having a good relief pattern is obtained.

The postbaking is generally employed at a heating temperature selected from the range of 140 ° C to 270 ° C for 5 to 30 minutes in the case of a hot plate and 30 to 90 minutes in the oven.

In this way, the cured film having the desired pattern shape can be obtained by such a post-baking.

As mentioned above, with the photosensitive resin composition of this invention, the cured film which has a high storage stability, is sufficiently high sensitivity, and the film reduction of an unexposed part at the time of image development is very small, and has a fine pattern can be formed.

On the other hand, the cured film obtained using the photosensitive resin composition of this invention, ie, the cured film which consists of thermosetting products of this photosensitive resin composition, is also a subject of this invention.

Example

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these Examples. In addition, the measurement of the molecular weight of a polymer is as follows.

[Measurement of Molecular Weight of Polymer]

The measurement of the molecular weight of the polymer was carried out under the following conditions using a GPC system manufactured by Japan Spectroscopy Co., Ltd. as a device, and Shodex (registered trademark) KF-804L and 803L as columns.

Column oven: 40 ℃

Flow rate: 1ml / min

Eluent: tetrahydrofuran

The meanings of the abbreviations used in the following examples are as follows.

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HPMA: 4-hydroxyphenyl methacrylate

CHMI: N-cyclohexylmaleimide

GMA: glycidyl methacrylate

PFHMA: 2- (perfluorohexyl) ethyl methacrylate

TMSSMA: methacryloxypropyl tris (trimethylsiloxy) silane

VN: 2-vinylnaphthalene

MAA: methacrylic acid

MAAm: methacrylamide

BMAA: N- (butoxymethyl) acrylamide

MOI-BM: Methacrylic acid 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl

AIBN: α, α'-azobisisobutyronitrile

QD1: Condensation of 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride Compound synthesized by reaction

QD2: Condensation of 1 mol of 4,4 ', 4 ”-(3-methyl-1-propaneyl-3-ylidene) trisphenol with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride Compound synthesized by reaction

GT-401: butane tetracarboxylic acid tetra (3,4-epoxycyclohexylmethyl) formula ε-caprolactone

CEL2021P: 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate

I907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one (IRGACURE 907, made by BASF)

DEAB: 4,4'-bis (diethylamino) benzophenone

DPHA: dipentaerythritol hexaacrylate

8KQ: 8KQ-2001 (Alkali-soluble UV curing type acrylic resin made by Taisei Fine Chemical Co., Ltd.)

PGME: Propylene Glycol Monomethyl Ether

PGMEA: propylene glycol monomethyl ether acetate

EL: ethyl lactate

Synthesis Example 1

6.86 g of VN, 3.14 g of MAA, and 0.50 g of AIBN were dissolved in 40.0 g of PGME, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 20% by mass) (P1). Mn of the obtained acrylic polymer was 4,200 and Mw was 8,100.

Synthesis Example 2

The acrylic polymer solution (solid content concentration 40 mass%) was obtained by melt | dissolving MAA 90.00g, HEMA 225.00g, HPMA 45.00g, MMA 180.00g, CHMI 360.00g, and AIBN57.60g in PGME1436.40g, and making it react at 80 degreeC for 20 hours. (P2). Mn of the obtained acrylic polymer was 3,100 and Mw was 6,100.

Synthesis Example 3

An acrylic polymer solution (solid content concentration of 30% by mass) was obtained by dissolving 3.00 g of MAAm, 3.00 g of HPMA, 4.00 g of CHMI, and 0.8 g of AIBN in 43.2 g of PGME, and reacting at 80 ° C for 20 hours (P3). Mn of the obtained acrylic polymer was 3,000 and Mw was 6,200.

Synthesis Example 4

5.50 g of HPMA, 4.50 g of GMA, and 0.50 g of AIBN were dissolved in 24.50 g of PGME, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P4). Mn of the obtained acrylic polymer was 6,900 and Mw was 23,000.

Synthesis Example 5

2.32 g of TMSSMA, 4.75 g of PFHMA, 1.92 g of MAAm, 1.00 g of HPMA, and 0.50 g of AIBN were dissolved in PGME 24.48 g, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P5). Mn of the obtained acrylic polymer was 3,500 and Mw was 6,700.

Synthesis Example 6

5.49 g of PFHMA, 0.73 g of MAAm, 2.26 g of HPMA, 1.52 g of CHMI, and 0.50 g of AIBN were dissolved in 24.50 g of PGME, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P6). Mn of the obtained acrylic polymer was 2,700 and Mw was 3,600.

Synthesis Example 7

5.00 g of PFHMA, 2.80 g of MOI-BM, 0.66 g of MAAm, 1.38 g of CHMI, and 0.49 g of AIBN were dissolved in 24.11 g of PGME and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P7). ). Mn of the obtained acrylic polymer was 5,800 and Mw was 7,600.

Synthesis Example 8

5.83 g of PFHMA, 1.36 g of MAA, 1.5 g of HPMA, 1.61 g of CHMI, and 0.50 g of AIBN were dissolved in 24.50 g of PGME, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P8). Mn of the obtained acrylic polymer was 4,100 and Mw was 5,200.

Synthesis Example 9

2.29 g of TMSSMA, 4.67 g of PFHMA, 0.47 g of MAA, 1.28 g of CHMA, 1.29 g of CHMI, and 0.50 g of AIBN were dissolved in 24.50 g of PGME and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass). (P9). Mn of the obtained acrylic polymer was 3,000 and Mw was 4,400.

Synthesis Example 10

5.00 g of PFHMA, 2.80 g of MOI-BM, 1.00 g of HEMA, 1.38 g of CHMI, and 0.51 g of AIBN were dissolved in 24.96 g of PGME and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P10). ). Mn of the obtained acrylic polymer was 5,600 and Mw was 6,900.

Synthesis Example 11

An acrylic polymer solution (solid content concentration of 30% by mass) was obtained by dissolving PFHMA 5.00g, BMAA 1.82g, HEMA 1.00g, CHMI 1.38g, and AIBN 0.46g in PGME 22.55g and reacting at 80 ° C for 20 hours (P11). Mn of the obtained acrylic polymer was 5,000 and Mw was 6,600.

<Examples 1 to 7> and <Comparative Examples 1 to 6>

Each component of (A)-(F) and a solvent are mixed with the composition shown in Table 1, and Examples 1-6 and a comparison are made by adjusting the addition amount of a solvent so that solid content concentration of a final composition may be 14 mass%-19 mass%. The negative photosensitive resin composition of Example 7 and the comparative example 6 was prepared by adjusting the addition amount of a solvent so that solid content concentration might be 20 mass% for the positive photosensitive resin composition of Examples 1-5, respectively.

In addition, the compounding quantity of Table 1 shall show the value at the time of solid content (excluding the solvent).

TABLE 1

[Evaluation of contact angle of evaluation 1 bank part]

After the photosensitive resin compositions of Examples and Comparative Examples were coated on a ITO-glass substrate by using a spin coater, prebaking was performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a photosensitive resin film having a film thickness of 1.2 μm. . In Example 7 and Comparative Example 6, the photosensitive resin film was irradiated with ultraviolet light having a light intensity of 2.6 mW / cm ² at 365 nm for a certain period of time by a Canon Co., Ltd. ultraviolet irradiation device PLA-600FA. Thereafter, the photosensitive resin film was immersed in 0.4% by mass or 2.38% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) solution for 60 seconds or 180 seconds, and then washed with ultrapure water for 30 seconds. Next, post-baking was performed by heating the photosensitive resin film after image development at the temperature of 230 degreeC for 30 minutes, and the cured film with a film thickness of 1.0 micrometer was formed.

The contact angle of the anisole on this cured film was measured using the contact angle gauge: Drop Master by Kyowa Interface Science Corporation.

The obtained results are shown in Table 2 together with the substrate preparation conditions (development conditions) in each example.

[Evaluation 2 Evaluation of contact angles of the exposure portions (Examples 1 to 6 and Comparative Examples 1 to 5) and the non-exposure portions (Example 7, Comparative Example 6) on the ITO substrate]

After the photosensitive resin compositions of Examples and Comparative Examples were coated on a ITO-glass substrate by using a spin coater, prebaking was performed on a hot plate at a temperature of 100 ° C. for 120 seconds to form a photosensitive resin film having a film thickness of 1.2 μm. . In Examples 1 to 6 and Comparative Examples 1 to 5, the photosensitive resin film was irradiated with ultraviolet light having a light intensity of 2.6 mW / cm ² at 365 nm for a certain period of time by a Canon Co., Ltd. ultraviolet irradiation device PLA-600FA. . Thereafter, the photosensitive resin film was immersed in 0.4% by mass or 2.38% by mass of tetramethylammonium hydroxide (hereinafter referred to as TMAH) solution for 60 seconds or 180 seconds, and then washed with ultrapure water for 30 seconds.

In Examples 1-7 and Comparative Examples 1-6, the photosensitive resin film was not seen on the board | substrate, and it confirmed that the film was removed by the developing process.

Subsequently, post-baking was performed by heating this board | substrate at the temperature of 230 degreeC for 30 minutes. The contact angle of the anisole of this board | substrate was measured using the contact angle gauge: Drop Master by Kyowa Interface Science Corporation.

The obtained results are shown in Table 2 together with the substrate preparation conditions (development conditions) in each example.

[Evaluation 3 Evaluation of Contact Angle of Exposed Part on Organic Cured Film]

As the base cured film material, 100 parts by mass of P1, 8 parts by mass of GT-401, 8 parts by mass of CEL2021P, R-30N (Megapak® R-30N, surfactant, manufactured by DIC Corporation) A PGMEA solution having a solid content concentration of 20% by mass containing 0.05 parts by mass was prepared. The base cured film material was applied onto a Si substrate using a spin coater, and then prebaked on a hot plate at a temperature of 100 ° C. for 120 seconds, followed by a post-baking by heating at a temperature of 230 ° C. for 30 minutes. A base cured film (referred to as an organic cured film) having a thickness of 0.6 µm was formed.

Substrate for contact angle evaluation by applying, exposing and developing the photosensitive resin compositions of Examples 3 and 4 and Comparative Examples 2 and 3 in the same manner as in Evaluation 2, using this substrate with a base cured film, and performing a post-baking. Was written. The contact angle of the anisole of this board | substrate was measured using the contact angle gauge: Drop Master by Kyowa Interface Science Corporation.

The obtained results are shown in Table 2 together with the substrate preparation conditions (development conditions) in each example.

TABLE 2

As shown in Table 2, Examples 1-4 using (A) component which has an amide group, and (B) component containing a carboxyl group all use the (B) component containing the same carboxyl group, except that an amide group Compared with Comparative Examples 1-3 using the (A) component which does not contain (and carboxyl group), the contact angle of the exposed part was small (evaluation 2), and it was a result with favorable lyophilic. In addition, in Examples 1-4, the contact angle in the unexposed part (bank part) was large large compared with the comparative examples 1-3, and the liquid repellency was favorable. On the other hand, in Examples 3 and 4, the contact angle was also small (evaluation 3) in the exposed portion on the organic cured film as compared with Comparative Examples 2 and 3, and the lyophilic result was good.

Moreover, in Examples 5 and 6 using the (B) component containing an amide group, compared with Comparative Examples 4 and 5 using the (B) component not containing an amide group, the lyophilic of the exposed part was good (evaluation 2), Moreover, the liquid repellency in the unexposed part (bank part) was also favorable (evaluation 3).

Furthermore, in Example 7, which was a negative material composition, the contact angle of the unexposed part was small compared with the comparative example 6 which is the same negative material composition, and the lyophilic property was favorable (evaluation 2), and also in the exposure part (bank part) The liquid repellency of was also good (evaluation 3).

Claims (13)

The thermosetting photosensitive resin composition containing (A) component, (B) component, (C) solvent, and (D) component, and at least one of (A) component and (B) component has an amide group.
(A) component: The polymer which has the following groups (A1) and (A2)
(A1) liquid-repellent group
(A2) at least one group selected from the group consisting of carboxyl groups and amide groups
(B) component: Alkali-soluble resin which has at least 1 group chosen from the group which consists of a carboxyl group and an amide group.
(C) a solvent,
(D) component: Photosensitive agent. The method of claim 1,
The photosensitive resin composition which satisfy | fills at least any one of following (Z1)-(Z4).
(Z1): It further contains a crosslinking agent as (E) component,
(Z2): Alkali-soluble resin of (B) component further has a self-crosslinkable group, or further has group which reacts with at least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, and an amino group. .
(Z3): (D) A component is an optical radical generating agent and contains the compound which has two or more ethylenic polymerizable groups as (F) component further.
(Z4): The component (D) is a photoacid generator, and further contains a compound having two or more functional groups which form covalent bonds with an acid generated from the component (D) as the component (G). The method according to claim 1 or 2,
The photosensitive resin composition whose (D) component is a quinonediazide compound. The method of claim 2,
The photosensitive resin composition whose (D) component is a quinonediazide compound and satisfy | fills any one of said (Z1) and (Z2). The method according to any one of claims 1 to 4,
The photosensitive resin composition of the said (A1) liquid repellent group of (A) component is at least 1 group chosen from the fluoroalkyl group of 2 to 11 carbon atoms, a polyfluoroether group, a silyl ether group, and a polysiloxane group. The method according to any one of claims 1 to 5,
The photosensitive resin composition whose polymer of (A) component is an acrylic polymer. The method of claim 6,
The photosensitive resin composition whose polymer of (A) component is an acrylic polymer which has the number average molecular weight of 2,000-100,000 in polystyrene conversion. The method according to any one of claims 1 to 7,
The photosensitive resin composition in which alkali-soluble resin of (B) component has a number average molecular weight of 2,000-50,000 in polystyrene conversion. The method according to any one of claims 1 to 8,
(B) 0.1-20 mass parts (A) component is contained with respect to 100 mass parts of components, The photosensitive resin composition characterized by the above-mentioned. The method according to any one of claims 2 to 9,
1-50 mass parts (E) component is contained with respect to a total of 100 mass parts of (A) component and (B) component, The photosensitive resin composition characterized by the above-mentioned. The cured film obtained using the photosensitive resin composition of any one of Claims 1-10. The display element which has a cured film of Claim 11. A display element having the cured film according to claim 11 as an image forming partition.