KR20190133776A - Photosensitive resin composition - Google Patents

Abstract

[Problem] Used in liquid crystal display device, organic EL display device, etc., it maintains a good image even after curing and has high water repellency and oil repellency on the surface of cured film even without plasma treatment or UV ozone treatment. It provides a photosensitive resin composition which is few and can form the image of the cured film which has high lyophilic property and high lipophilic property to a board | substrate.
[Solution] A thermosetting photosensitive resin composition containing the following (A) component, (B) component, (C) solvent and (D) component. (A) component: Polymer (A1) liquid-repellent group (A2) trialkoxy silyl group which has following group (A1) and (A2), (B) component: Alkali-soluble resin, (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 water repellency and oil 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 partition material corresponding to the interlayer insulating film and the inkjet method in a liquid crystal display or an EL display.

Full-color display substrate fabrication techniques using inkjet have also been actively studied in the manufacturing process of display elements such as thin film transistor (TFT) type liquid crystal display elements and organic EL (electroluminescent) elements. For example, in manufacturing a color filter in a liquid crystal display device, a section (hereinafter referred to as a bank) for defining a pixel patterned in advance with respect to a conventional printing method, electrodeposition method, dyeing method or pigment dispersion method is referred to as light. 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, the method which drips the ink used as a light emitting layer similarly, and produces the organic electroluminescence display element (patent document 2) is proposed.

However, in the case of dropping ink onto an area surrounded by a bank by the inkjet method, in order to prevent the ink droplets from overflowing the bank beyond the bank, the substrate has a hydrophilic property (hydrophilicity) and a water repellency on the surface of the bank. Needs to be.

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 provide hydrophilicity to the substrate and water repellency to the bank (patent document). 3) The process is complicated. In addition, proposals have been made in which a fluorine-based surfactant or a fluorine-based polymer is blended with the photosensitive organic thin film (Patent Document 4). UV ozone treatment at the time of treatment lowered the water repellency of the surface, which 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

SUMMARY OF THE INVENTION 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 water repellency and high oil repellency on the surface of the cured film even without plasma treatment or UV ozone treatment. In addition, there are few residues and it forms an image of the cured film which has a high lyophilic property and a high lipophilic 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 in which ink droplets overflow from a bank beyond a bank is prevented.

MEANS TO SOLVE THE PROBLEM The present inventors earnestly examined in order to achieve the said objective, As a result, at least 1 group selected from a fluoroalkyl group, a polyfluoroether group, a silyl ether group, and a polysiloxane group, and a trialkoxy silyl group of 3-10 carbon atoms are found. By forming a cured film from the composition containing the polymer which has, it discovered that water repellency and liquid repellency can be provided to a film surface efficiently, and completed this invention.

That is, this invention relates to the following.

1.The thermosetting photosensitive resin composition containing following (A) component, (B) component, (C) solvent, and (D) component.

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

(A1) liquid-repellent group

(A2) a trialkoxy silyl group,

(B) component: alkali-soluble resin,

(C) a solvent,

(D) component: Photosensitive agent.

2. Said photosensitive resin composition of 1 whose component (A) is a polymer which has the following (A3) further.

(A3): at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group.

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

(Z1): It further contains the crosslinking agent which is (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): The component (D) is an optical radical generating agent, and further contains a compound having two or more ethylenic double bonds as the component (F);

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

4. Photosensitive resin composition in any one of said 1-3 whose (D) component is a quinonediazide compound.

5. The photosensitive resin composition of said 3 whose (D) component is a quinonediazide compound and satisfy | fills any one of said (Z1) or (Z2).

6. The liquid-repellent group of component (A) is at least one group selected from fluoroalkyl group, polyfluoroether group, silyl ether group and polysiloxane group having 3 to 10 carbon atoms to any one of 1 to 5 above. The photosensitive resin composition described.

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

8. The photosensitive resin composition of said 7 whose number average molecular weights of the acrylic polymer of (A) component are 2,000-100,000 in polystyrene conversion.

9. Photosensitive resin composition in any one of said 1-8 whose number average molecular weights of alkali-soluble resin of (B) component are 2,000-50,000 in polystyrene conversion.

10. (B) 0.1 mass part-20 mass parts (A) component are contained with respect to 100 mass parts of components, The photosensitive resin composition in any one of said 1-9 characterized by the above-mentioned.

11. (E) component is 1 mass part-50 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, The photosensitive resin composition in any one of said 3-10 characterized by the above-mentioned.

12. The cured film which consists of thermosets of the photosensitive resin composition in any one of said 1-11.

13. The display element which has a cured film of 12.

14. A display element having the cured film according to 12 as an image forming partition.

The photosensitive resin composition of this invention can provide a water repellency and 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.

The photosensitive resin composition of this invention is a photosensitive resin composition containing following (A) component, (B) component, (C) solvent, and (D) component.

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

(A1) liquid-repellent group

(A2) a trialkoxy silyl group,

(B) component: alkali-soluble resin,

(C) a solvent,

(D) component: Photosensitive agent.

It is preferable that the photosensitive resin composition of this invention is a polymer in which (A) component further has the following (A3).

(A3): at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group.

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

(Z1): It further contains the crosslinking agent which is (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): The component (D) is an optical radical generating agent, and further contains a compound having two or more ethylenic polymerizable groups as the component (F);

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

It is preferable that the photosensitive resin composition of this invention is a positive photosensitive resin composition whose (D) component is a quinonediazide compound.

Hereinafter, the detail of each component is demonstrated.

<(A) component>

(A) A component is a polymer which has the following group (A1) and (A2), More preferably, it is a polymer which has (A3).

(A1) liquid-repellent group

(A2) trialkoxy silyl group

(A3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group

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, an acryl polymer represents the polymer obtained using the polymerizable unsaturated group, such as acrylic acid ester, methacrylic acid ester, styrene, and maleimide, ie, the monomer which has a C = C double bond in a structure.

Examples of the polyamic acid, polyimide, polyamide, and polyurea include polyamic acid obtained by reacting diamine with an acid dianhydride, polyimide obtained by imidating the polyamic acid, and polyamide or diamine obtained by reacting diamine with dicarboxylic acid anhydride. It is a polyurea obtained by reacting with diisocyanate, Furthermore, it has at least 1 type of monomer which has a fluoroalkyl group or a fluoroalkoxy group, and has at least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, and an amino group. The polymer obtained from the monomer mixture containing the monomer of 1 type and a trialkoxy silyl group is mentioned.

As a polyurethane, the polyurethane obtained by making the diol which has a fluoroalkyl group or a fluoroalkoxy group, and the diol which has an amino group react with diisocyanate is mentioned.

As a phenol resin, the phenol which has a fluoroalkyl group or a fluoroalkoxy group, and the novolak resin obtained by superposing | polymerizing formaldehyde is mentioned.

As an epoxy resin, the epoxy resin obtained by making bisphenol A and / or bisphenol F which have a fluoroalkyl group or a fluoroalkoxy group react with the diglycidyl ether of this bisphenol A and / or bisphenol F is mentioned.

As polysiloxane, the polymer obtained by superposing | polymerizing the silane monomer mixture containing the trialkoxysilane which has a fluoroalkyl group or the dialkoxysilane silane which has a fluoroalkyl group, and the trialkoxysilane which has an amino group, or the dialkoxysilane which has an amino group is mentioned. Can be.

As polyester, polyester obtained by making dicarboxylic acid or tetracarboxylic dianhydride, and diol which has a fluoroalkyl group or a fluoroalkoxy group react is mentioned.

<(A1) introduction of liquid repellent group>

As said liquid repellent group, at least 1 sort (s) of group chosen from the C3-C10 fluoroalkyl group, polyfluoroether group, silyl ether group, and polysiloxane group is mentioned, for example.

The number of carbon atoms of the fluoroalkyl group is 3 to 10, preferably, it is preferably a fluoroalkyl group having 4 to 10 carbon atoms.

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 C3-C10 fluoroalkyl group to introduce the C3-C10 fluoroalkyl group into the polymer which is (A) component of this invention.

Specific examples of the monomer having a fluoroalkyl group having 3 to 10 carbon atoms when 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.

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

-(XO) _n -Y ...

In Formula 1, X is a divalent saturated hydrocarbon group having 1 to 10 carbon atoms or a fluorinated divalent saturated hydrocarbon group having 1 to 10 carbon atoms, and represents the same group or a different group for each unit enclosed by n. , Hydrogen atom (unless fluorine atom is bonded to carbon atom adjacent to oxygen atom adjacent to Y), monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or fluorinated 1 having 1 to 20 carbon atoms A saturable hydrocarbon group is shown and n shows 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 a fluorinated alkylene group or perfluorinated C1-C10 by removing one C1-C10 hydrogen atom. As the alkylene group, each unit bound by n represents the same group or a different group, and Y represents a fluorinated alkyl group or a perfluorinated alkyl group having 1 to 20 carbon atoms by removing one hydrogen atom having 1 to 20 carbon atoms. It may be mentioned to indicate.

As an aspect of X and Y in Formula 1, More preferably, X is a perfluorinated alkylene group of 1 to 10 carbon atoms, and represents the same group or a different group for each unit of n, and Y represents The thing which represents a C1-C20 perfluorinated alkyl group is mentioned.

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 copolymerized with the monomer which has Rf group (a), the monomer which has a hydroxyl group, a carboxyl group, an amide group, an amino group, or a trialkoxy silyl group, or other monomer. In the case of synthesis | combination, the 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. In the said range, the polymer which is (A) component shows favorable liquid repellency. In addition, when synthesize | combining the polymer which is (A) component by copolymerization of the monomer which has a Rf group (a), the monomer which has a hydroxyl group, a carboxyl group, an amide group, an amino group, or a trialkoxy silyl group, or another monomer, , The compatibility of the monomer is good.

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.

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.

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) _n -SiR ¹ R ² R ³ Equation 3

(However, R ¹ , R ² independently represent a hydrogen, an alkyl group, a cycloalkyl group, or an aryl group, R ³ represents hydrogen or an organic group having 1 to 10 carbon atoms, and n 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. Since the polymer which is (A) component shows favorable liquid repellency, it is preferable that R <^1> , R <^2> is hydrogen, a methyl group, or a phenyl group, Furthermore, when R <^1> , R <^2> of all the siloxy units is a methyl group Is preferred. In addition, nitrogen atom, oxygen atom, etc. may be contained in R <^3> .

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 hydroxyl 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 Industries Ltd.) are mentioned.

<Introduction of (A2) trialkoxysilyl group>

What is necessary is just to copolymerize the monomer which has a (A2) trialkoxy silyl group in order to introduce (A2) trialkoxy silyl group into the polymer which is (A) component of this invention.

As a monomer which has the trialkoxy silyl group in the case where (A) component is an acrylic polymer, 3-trimethoxy silyl propyl acrylate, 3-triethoxy silyl propyl acrylate, 3-trimethoxy Silylpropyl methacrylate, 3-triethoxysilylpropyl methacrylate, and the like.

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 C3-C10 fluoroalkyl group, polyfluoro At least one of a monomer having a roether group, a monomer having a silyl ether group and a monomer having a polysiloxane group, a monomer having at least one group selected from the group consisting of a hydroxy group, a carboxyl group, an amide group and an amino group, a monomer having a trialkoxysilyl group And if necessary, monomers other than the above (also called other monomers A) are obtained by polymerizing at a temperature of 50 ° C to 110 ° C in a solvent in the presence of a polymerization initiator. At this time, the solvent used will not be specifically limited if the monomer which comprises an alkali-soluble polymer, and the polymer which has a specific functional group are melt | dissolved. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.

Specific examples of other monomers A include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, and phenyl. Methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetra Hydrofurfuryl 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 , Anthrylmethyl acrylate, phenyl acrylate, glycidyl acrylate, cyclohexyl acrylate, isobornyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminomethyl acrylate , Tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, γ-butyrolactone acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8- Ethyl-8-tricyclodecylacrylate, N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide, styrene, vinylnaphthalene, vinylanthracene, vinylbiphenyl, and the like. Can be.

The polymer which has a specific functional group obtained in this way is a state of the solution melt | dissolved in the solvent normally.

In addition, the solution of the specific copolymer obtained as described above is reprecipitated by stirring under diethyl ether, water, or the like, and the resulting precipitate is filtered and washed, and then dried under normal pressure or reduced pressure, and then dried under normal temperature or by heating. It can be set as the powder of a specific copolymer. 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 may be used as it is, or the powder may be redissolved in the solvent (C) mentioned later, for example, and may be used as a state of a solution.

Introduction of at least one group selected from the group consisting of (A3) hydroxy, carboxyl, amide and amino groups

To introduce at least one group selected from the group consisting of (A3) a hydroxy group, a carboxyl group, an amide group and an amino group into the polymer which is the component (A) of the present invention, a (A3) hydroxyl group, a carboxyl group, an amide group and an amino group What is necessary is just to copolymerize the monomer which has at least 1 group chosen from the group which consists of.

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 a hydroxy group in the case where (A) component is an acrylic polymer, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2 Hydroxypropyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropyl methacrylate, glycerin mono Methacrylate, 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-acryloyl jade -6-hydroxynorbornene-2-carboxylic-6-lactone, and 5-methacryloyloxy-6-hydroxynorbornene-2-carboxylic-6-lactone, p-hydroxystyrene, α-methyl-p-hydroxystyrene, N-hydroxyphenylmaleimide, N-hydroxyphenylacrylamide, N-hydroxyphenylmethacrylamide, p-hydroxyphenylacrylate, p-hydroxyphenylmethacryl The rate etc. are mentioned. Among these, the monomer chosen from 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate is preferable.

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 monomer which has an amino group in the case where (A) component is an acrylic polymer, aminoethyl acrylate, aminoethyl methacrylate, aminopropyl acrylate, aminopropyl methacrylate, etc. are mentioned, for example. These can be used individually or in combination of 2 or more types.

In the polymer of the component (A), the amount of the (A1) liquid-repellent group introduced is preferably 5 mol% to 60 mol%, more preferably 5 mol% to 40 mol% based on the total repeating units. When it is less than 5 mol%, the liquid repellency effect may not be exhibited. When it is over 60 mol%, problems, such as aggregation, may arise.

In the polymer of the component (A), the amount of the (A2) trialkoxysilyl group introduced is preferably 5 mol% to 70 mol%, more preferably 5 mol% to 50 mol% based on the total repeating units. . When it is less than 5 mol%, there may be a problem in heat resistance or solvent resistance of the resulting film. When it is over 70 mol%, it may affect developability.

In the polymer of component (A), the amount of at least one group selected from the group consisting of (A3) a hydroxy group, a carboxyl group, an amide group and an amino group is preferably 5 to 60 mol% based on the total repeating units. And it is more preferable that it is 5-40 mol%. When it is less than 5 mol%, there may be a problem in heat resistance or solvent resistance of the resulting film. When it exceeds 60 mol%, the repeating unit of liquid repellency becomes less.

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

<(B) component>

(B) component of this invention is resin which has alkali-soluble group. As an alkali-soluble group, a phenolic hydroxyl group, a carboxyl group, an acid anhydride group, an imide group, a sulfonyl group, phosphoric acid, boronic acid, an active methylene group, and an active methine group are mentioned, for example.

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 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, 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]

It is preferable that it is alkali-soluble resin which has at least 1 sort (s) of organic group chosen from the group which consists of a phenolic hydroxyl group and a carboxyl group among the said alkali-soluble group, and also has a number average molecular weight of 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.

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 is a monomer which shows alkali solubility, ie, the monomer which has at least 1 sort (s) chosen from the group which consists of a phenolic hydroxyl group and a carboxyl group, and at least selected from the group of monomer copolymerizable with these monomers. As a copolymer formed using one type of monomer as an essential structural unit, the number average molecular weight is 2,000-50,000. If the number average molecular weight is greater than 50,000, residues may occur.

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

The proportion of the unsaturated carboxylic acid derivative and / or the phenolic hydroxyl group and the polymerizable unsaturated group in the production of the alkali-soluble resin of the component (B) is in all monomers used for the production of the alkali-soluble resin of the component (B). , Preferably it is 5-90 mol%, More preferably, it is 10-60 mol%, Most preferably, it is 10-30 mol%. When the unsaturated carboxylic acid derivative is less than 5% by weight, the alkali solubility of the polymer is insufficient.

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.

The ratio of the monomer which has a hydroxyalkyl group and a polymerizable unsaturated group in manufacture of alkali-soluble resin of (B) component becomes like this. Preferably it is 10-60 mass%, More preferably, it is 5-50 mass%, Most preferably 20 To 40 mass%. When the monomer which has a hydroxyalkyl group and a polymerizable unsaturated group is less than 10 mass%, the stabilizing effect of the pattern shape of a copolymer may not be acquired. When it is 60 mass% or more, the alkali-soluble group of (B) component may run short and the characteristics, such as developability, may fall.

It is preferable that the alkali-soluble resin which is (B) component of this invention copolymerizes the N substituted maleimide compound further from the point which raises Tg of a copolymer.

N-substituted maleimide compound As a maleimide compound, N-methyl maleimide, N-ethyl maleimide, N-phenyl maleimide, N-cyclohexyl maleimide, etc. are mentioned, for example. It is preferable to have an aromatic ring from a viewpoint of transparency, 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.

The ratio of N-substituted maleimide in manufacture of alkali-soluble resin of (B) component becomes like this. Preferably it is 10-60 mass%, More preferably, it is 5-50 mass%, Most preferably, it is 20-40 mass%. . When N-substituted maleimide is less than 10 mass%, Tg of a copolymer may become low and heat resistance may be inferior. In the case of 60 mass% or more, transparency may fall.

When the photosensitive resin composition of this invention satisfy | fills requirement (Z2), alkali-soluble resin of (B) component used by this invention further has a self-crosslinkable group, or a hydroxyl group, a carboxyl group, an amide 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 an amino group.

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

It is preferable that content in the case of including this self-crosslinkable group or crosslinkable group in alkali-soluble resin of (B) component is 0.1-0.9 per 1 unit of repeating units in resin of (B) component, and developability and solvent resistance It is more preferable that it is 0.1-0.8 from a viewpoint of the.

Alkali-soluble resin of (B) component further contains N-alkoxy methyl group, N-hydroxymethyl group, alkoxy silyl group, epoxy group, oxetane group, vinyl crosslinking group, and self-crosslinking group, such as 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, oxetane What is necessary is just to copolymerize the unsaturated compound which has at least 1 sort (s) chosen from crosslinkable groups, such as group, a vinyl group, and a block isocyanate group, and self-crosslinkable groups, such as N-alkoxymethyl group, N-hydroxymethyl group, and alkoxy silyl group.

Examples of the unsaturated compound having radical polymerization property and having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, 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-hydroxymethyl 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 an unsaturated compound 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), Glycidyl n-butylacrylate, 3,4-epoxybutyl acrylate, methacrylic acid-3,4-epoxybutyl, acrylic acid-6,7-epoxyheptyl, methacrylic acid-6,7-epoxyheptyl, α -Ethylacrylic acid-6,7-epoxyheptyl, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, and the like. Can be mentioned. 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 an unsaturated compound which has radical polymerization property and has an oxetane group further, the (meth) acrylic acid ester etc. which have an oxetane group are mentioned, for example. 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.

Examples of the monomer having radical polymerization property and further having a vinyl group include acrylic acid 2- (2-vinyloxyethoxy) ethyl, methacrylic acid 2- (2-vinyloxyethoxy) ethyl and the like.

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 (Z1), it has radical polymerization property, such as N-alkoxy methyl group, N-hydroxymethyl group, alkoxy silyl group, an epoxy group, an oxetane group, a vinyl group, and a block isocyanate group, etc. A structural unit derived from an unsaturated compound having at least one group selected from a crosslinkable group such as a self-crosslinkable group and an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, a block isocyanate group, ( Based on the sum total of all the repeating units which the alkali-soluble resin of B) component has, Preferably it is 10 mass%-70 mass%, Especially preferably, it contains 20 mass%-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 a radiation sensitive resin composition falls. There is a tendency.

In addition, in this invention, the copolymer formed using the acrylic polymer of (B) component also as a structural unit also monomers (henceforth other monomer.) Other than the monomer mentioned above may be sufficient. 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, a maleimide, an acrylamide compound, an acrylonitrile, a styrene compound, a vinyl compound, etc. are mentioned.

Hereinafter, although the specific example of the said 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-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl 2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylic Sites, caprolactone 2- (acryloyloxy) ethyl ester, poly (ethylene glycol) and the like 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, and 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 acrylamide compound, for example, N-methyl acrylamide, N-methyl methacrylamide, N, N- dimethyl acrylamide, N, N- dimethyl methacrylamide, N-methoxymethyl acrylamide, N -Methoxymethyl methacrylamide, N-butoxymethylacrylamide, N-butoxymethyl methacrylamide, 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.

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

In manufacture of alkali-soluble resin which is (B) component, it is preferable that the ratio of the said other monomer is 80 mass% or less, More preferably, it is 50 mass% or less, More preferably, it is 20 mass% or less. When it exceeds 80 mass%, since an essential component becomes relatively small, it becomes difficult to fully acquire the effect of this invention.

Although the method of obtaining alkali-soluble resin which is (B) component used for this invention is not specifically limited, For example, a carboxylic group, a phenolic hydroxy group, and a carboxylic acid or phenolic hydroxy group by action of a heat or an acid are mentioned. Monomer which has at least 1 sort (s) chosen from the group which produces | generates, the monomer which has a hydroxyalkyl group, N-alkoxymethyl group, N-hydroxymethyl group, alkoxysilyl group, an epoxy group, an oxetane group, a vinyl group, and a block as needed Monomers having at least one group selected from self-crosslinkable groups such as isocyanate groups and crosslinkable groups such as N-alkoxymethyl groups, N-hydroxymethyl groups, alkoxysilyl groups, epoxy groups, vinyl groups, and block isocyanate groups, In the other copolymerizable monomer and the solvent which coexisted the polymerization initiator etc. as needed, under the temperature of 50 degreeC-110 degreeC By the polymerization reaction, it can be obtained. At this time, the solvent used will not be specifically limited if the monomer which comprises alkali-soluble resin, and the acrylic polymer which has a specific functional group are melt | dissolved. As a specific example, the solvent described in the (C) solvent mentioned later is mentioned.

The acrylic polymer which has a specific functional group obtained in this way is a state of the solution melt | dissolved in the solvent normally.

In addition, the solution of the specific copolymer obtained as described above is reprecipitated by stirring under diethyl ether, water, or the like, and the resulting precipitate is filtered and washed, and then dried under normal pressure or reduced pressure, and then dried under normal temperature or by heating. It can be set as the powder of a specific copolymer. 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 may be used as it is, or the powder may be redissolved in the solvent (C) mentioned later, for example, and may be used as a state of a solution.

Moreover, as alkali-soluble resin of (B) component, polyimide precursors, such as polyamic acid, polyamic acid ester, and some 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 acid Alicyclic tetracarboxylic dianhydrides such as dianhydrides, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydrides, 1,2,3,4-butanetetracarboxylic acids Aliphatic tetracarboxylic dianhydride such as anhydride Can be.

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, 2,4 -Diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis (3-amino-4-hydroxy Phenyl) 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'-diamino-3 , 3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4'-diami -3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis (3-amino-4-hydroxyphenoxy) benzene, 1,3-bis (3-amino-4 -Hydroxyphenoxy) benzene, 1,4-bis (4-amino-3-hydroxyphenoxy) benzene, 1,3-bis (4-amino-3-hydroxyphenoxy) benzene, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] sulfone, bis [4- (3-amino-4-hydroxyphenoxy) phenyl] propane, 2,2-bis [4- (3-amino-4 Diamine compounds having a phenolic hydroxy group such as -hydroxyphenoxy) phenyl] hexafluoropropane, 1,3-diamino-4-mercaptobenzene, 1,3-diamino-5-mercaptobenzene, 1, Having a thiophenol group, such as 4-diamino-2- mercaptobenzene, bis (4-amino-3- mercaptophenyl) ether, and 2, 2-bis (3-amino-4- mercaptophenyl) hexafluoro propane Diamine compound, 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis (4-aminobenzene-3 - Sulfonic acid groups such as sulfonic acid) 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 ranging from -20 ° C to 150 ° C, preferably from -5 ° C to 100 ° C. In order to obtain a high molecular weight polyamic acid, it selects suitably in the range of reaction temperature 5 degreeC-40 degreeC, and reaction time 1 hour-48 hours. It is more preferable to select from the reaction temperature of 40 degreeC-90 degreeC, and reaction time 10 hours or more in order to obtain the polyamic acid which has high storage stability at low molecular weight, and partially imidated.

In addition, the reaction temperature at the time of protecting a terminal amino group by an acid anhydride can select arbitrary temperature of -20 degreeC-150 degreeC, Preferably -5 degreeC-100 degreeC.

Reaction of a diamine compound and a tetracarboxylic dianhydride compound can be performed in a solvent. The solvent which can be used at this time is N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl Urea, pyridine, dimethylsulfone, hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, 3-methoxypropionic acid Ethyl, 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, propyl 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, Methyl isobutyl ketone, 2-heptanone, etc. are mentioned. These may be used alone or in combination. Furthermore, even if it is a solvent which does not melt a polyamic acid, it can also mix and use for the said solvent in the range which does not precipitate the polyamic acid produced | generated by a polymerization reaction.

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 group chosen from a carboxyl group and a phenolic hydroxyl group in order to provide alkali solubility.

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, the method which adds excess acetic anhydride and pyridine to a polyimide precursor solution, and makes it react at 100 degreeC from room temperature is used. Moreover, as a method of thermal imidation, the method of superheating, generally dehydrating a polyimide precursor solution 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 WO2009 / 051186.

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

Examples of the diols include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol and benzene-1,4-dimethanol, hydrogenated bisphenol A and hydrogenated bisphenol F. Alicyclic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexane Aliphatic diols, such as diol, etc. are mentioned.

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 mass part-20 mass parts with (A) component with respect to 100 mass parts of (B) component.

<(C) solvent>

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

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 propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3 -Methyl-2-pentanone, 2-pentanone, 2-heptanone, gamma -butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, hydroxyacetic acid Ethyl, 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, Methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

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 propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, and the like have good coating properties and safety. This is preferable from the viewpoint of high. 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.

(D-1) As a 1, 2- quinonediazide compound, it is a compound which has both a hydroxyl group and an amino group, and has both a hydroxyl group and an amino group, and when these hydroxyl groups or an amino group (both hydroxyl group and an amino group have both), Of the total amount of), preferably from 10 mol% to 100 mol%, particularly preferably from 20 mol% to 95 mol%, esterified or amidated with 1,2-quinonediazidesulfonic acid can be used. .

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 hydroxyl 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, 2,4-dihydroxybenzophenone, 2,3,4-trihydroxybenzo Phenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, 2,2', 3,4,4'-pentahydroxybenzophenone Phenolic compounds such as 2,5-bis (2-hydroxy-5-methylbenzyl) methyl, ethanol, 2-propanol, 4-butanol, cyclohexa 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, Aniline, such as p-phenylenediamine, 4,4'- diaminophenylmethane, 4,4'- diamino diphenyl ether, and aminocyclohexane 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, 2,2 Aminophenols such as -bis (4-amino-3-carboxy-5-hydroxyphenyl) hexafluoropropane, alkanolamines such as 2-aminoethanol, 3-aminopropanol and 4-aminocyclohexanol have.

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 quinonediazide group of (D-1) component is 100 mass parts in total of (A) component and (B) component. About 5 mass parts-100 mass parts, More preferably, they are 8 mass parts-50 mass parts, More preferably, they are 10 mass parts-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 does 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.

The radical radical generator (D-2) is not particularly limited as long as it generates radicals by exposure. As a specific example, for example, benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, 4-methoxy-4'- dimethylamino benzophenone, 2-ethyl anthraquinone, phenanthrene Benzoin ethers such as aromatic ketones such as aromatic ketones, benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, benzoin such as methyl benzoin and ethyl benzoin, and 2- (o-chlorophenyl) -4,5 -Phenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer, 2- (o-fluorophenyl) -4,5-diphenyl Imidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (m-methylphenyl) imidazole dimer, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 2-trichloromethyl-5-styryl- 1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxysty Lil) -1,3,4-oxadiazole Halomethyloxadiazole compound, 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, Halomethyl-S-triazine-based compounds such as 2- (4-butoxy-naphtho-1-yl) -4,6-bis-trichloromethyl-S-triazine, 2,2-dimethoxy-1, 2-diphenylethan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone, 1,2-benzyl-2-dimethylamino-1- (4- Morpholinophenyl) -butanone-1,1-hydroxy-cyclohexyl-phenylketone, benzyl, benzoyl benzoic acid, methyl benzoyl benzoate, 4-benzoyl-4'-methyldiphenylsulfide, benzyl methyl ketal, dimethylaminobenzo 8-P-dimethylaminobenzoate Isoamyl, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothioxanthone, 2,4-diethyl thioxanthone, 2,4-dimethyl thioxanthone, isopropyl thioxanthone, 1- (4-phenylthiophenyl) -1,2-octanedione-2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] -1- (O-acetyloxime), 4-benzoyl-methyldiphenylsulfide, 1-hydroxy-cyclohexyl-phenylketone, 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1- Butanone, α-dimethoxy-α-phenylacetophenone, phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2-methyl- 1- [4- (methylthio) phenyl] -2- (4-morpholinyl) -1-propanone etc. are mentioned.

The photo-radical generator can be easily obtained as a commercially available product, and specific examples thereof include, for example, IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE 250 (above, manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, KAYACURE BMSEA Nippon Gunpowder 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.

It is also possible to use these optical radical generators independently, or to use two or more types together.

It is preferable that content in the case of containing (D-2) component in the photosensitive resin composition of this invention is 0.1 mass part-30 mass parts with respect to 100 mass parts of (A) component, More preferably, it is 0.5 mass part- It is 20 mass parts, Especially preferably, it is 1 mass part-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 coating film may fall, or the image development defect of an unexposed part may occur.

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) 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 0.01 mass part-20 mass parts preferably with respect to a total of 100 mass parts of (A) component and (B) component. 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 and is introduce | transduced in a composition when the photosensitive resin composition of this invention satisfy | fills requirement (Z1). More specifically, it is a compound which has a structure which can form bridge | crosslinking structure by thermal reaction with the thermally reactive site | part (for example, a carboxyl group and / or phenolic hydroxyl group) of (B) component. Hereinafter, although a specific example is given, it is not limited to these. The thermal crosslinking agent is preferably selected from, for example, a crosslinkable compound having two or more substituents selected from an (E1) alkoxymethyl group and a hydroxymethyl group or a crosslinkable compound represented by the following formula (2). . These crosslinking agents can be used individually or in combination of 2 or more types.

When the crosslinking | crosslinked compound which has two or more substituents chosen from the alkoxy methyl group and the hydroxymethyl group of (E1) component is exposed to the high temperature at the time of thermosetting, a crosslinking reaction advances by dehydration condensation reaction. 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 the Mitsui Cytec Co., Ltd. glycoluril compound (brand name: Cymel (trademark) 1170, PowderLink (trademark) 1174), methylated urea resin (brand name: UFR (trademark) 65), butyl Urea resin (brand name: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), DIC Corporation urea / formaldehyde-based resin (high condensation type, brand name: becamine (registered trademark)) J-300S, same P-955, same N), etc. are mentioned.

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

As a specific example of the alkoxy methylation melamine, hexamethoxy methyl melamine etc. are mentioned, for example. As a commercial item, the methoxymethyl type melamine compound (brand name: Cymel (trademark) 300, copper 301, copper 303, copper 350) made by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compound (brand name: Mycote (trademark) ) 506, copper 508), methoxymethyl type melamine compound made by Sanwa Chemical (brand name: Nikarak (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, copper MX-302), etc. Can be 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 (trademark) 303 (made by Mitsui Cytec Co., Ltd.) etc. are mentioned, As a commercial item of the said benzoguanamine compound, a brand name: Cymel (registered trademark) 1123 (Mitsui Cytec Co., Ltd.) 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. Also available as a commercial item, Specific examples thereof include 26 DMPC, 46 DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, BI25X-TPA (above, Asahi Organic Materials Co., Ltd. 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.

Moreover, the photosensitive resin composition of this invention can contain the crosslinkable compound represented by following formula (2) as (E2) component.

[Formula 10]

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

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

[Formula 11]

[Formula 12]

As a commercial item, it is epoxide GT-401, copper GT-403, copper GT-301, copper GT-302, Celoxide 2021, Celoxide 3000 (trade name of Daicel Chemical Industries, Ltd.), and an alicyclic epoxy resin Denacol EX-252 (brand name made by Nagase ChemteX Co., Ltd.), CY175, CY177, CY179 (more than product name made by CIBA-GEIGY AG), Araldite CY-182, copper CY-192, copper CY-184 (more than , Brand name made by CIBA-GEIGY AG), Epiclone 200, copper 400 (more than, brand name made by DIC Corporation), Epicoat 871, copper 872 (more, brand name made by emulsified shell epoxy company), ED-5661, ED -5662 (above, Cellan coating Co., Ltd. brand name) etc. are mentioned. In addition, these crosslinkable compounds can be used individually or in combination of 2 or more types.

Among them, the compounds represented by the formulas E2-1 and E2-2 having a cyclohexene oxide structure from the viewpoints of process resistance, such as heat resistance, solvent resistance, internal resistance, plastic resistance, and transparency, and epoxide GT-401 , GT-403, GT-301, GT-302, Celoxide 2021, Celoxide 3000 are preferred.

Moreover, as an E component, the crosslinked structure is formed by thermal reaction with the heat reactive site | part (for example, a carboxyl group and / or phenolic hydroxyl group) of (B) component other than what was shown as (E1) component and (E2) component. A compound which can be used 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-diglycidyl Aminomethyl) cyclohexane, and epoxy compounds such as N, N, N ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane, VESTANAT B1358 / 100, VESTAGON BF 1540 (or more, iso Cyanurate-type modified polyisocyanate, Degussa Japan Co., Ltd., Takeate (registered trademark) B-882N, Copper takeate B-7075 (above, isocyanurate type modified polyiso) Isocyanate compounds, such as cyanate and Mitsui Chemical Co., Ltd., etc. are mentioned.

As the E component, a polymer having two or more structures capable of forming a crosslinked structure by thermal reaction with a thermally reactive portion (for example, a carboxyl group and / or a phenolic hydroxyl group) of the component (B) can be used. . Specifically, for example, a polymer produced by using a compound having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate , 2-isocyanatoethyl methacrylate (2-isocyanatoethyl methacrylate) (Carenz MOI [manufactured using a compound having an alkoxysilyl group such as 3-methacryloxypropyltrimethoxysilane, etc.) Registered trademark], Showa Denko Co., Ltd., 2-isocyanatoethyl acrylate (2-isocyanato ethyl acrylate- () (Karenzu AIO [registered trademark], Showa Denko Corporation)), etc. Compound having an isocyanate group or 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM [registered trademark], Showa Denko Co., Ltd.) )), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate And polymers prepared using compounds having a block isocyanate group such as Karens MOI-BP (registered trademark) and Showa Denko Co., Ltd. etc. These polymers may be used alone or in combination of a plurality of polymers. May be prepared or a polymer may be prepared in combination with other compounds.

When the component (B) has a group which reacts with at least one group selected from the group consisting of a group represented by a hydroxyl group, a carboxyl group, an amide group and an amino group, a group represented by a hydroxyl group, a carboxyl group, an amide group or an amino group is 2 The compound which has two or more can be used as (E) component.

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

Content when selecting (E) component as a crosslinking agent in the photosensitive resin composition of this invention is 1 mass part-50 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, Preferably it is 1 It is mass parts-40 mass parts, More preferably, they are 1 mass part-30 mass parts. When the content of the crosslinkable compound is small, the density of crosslinking formed by the crosslinkable compound is not sufficient, so that the effect of improving heat resistance, solvent resistance, resistance to long-term firing, etc. after pattern formation may not be obtained. have. 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) A component is a compound which has 2 or more of ethylenic polymerizable groups. The compound which has two or more ethylenic polymerizable groups here means the compound which has two or more polymerizable groups in one molecule, and these polymerizable groups are in the molecule terminal, These polymerizable groups are an acrylate group and methacryl It means at least 1 sort (s) of polymeric group selected from the group which consists of a late group, a vinyl group, and an allyl group.

In the solution of the negative photosensitive resin composition in the 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 (when the compound is a polymer, a weight average molecular weight) of 1,000 or less is preferable.

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.

Said polyfunctional acrylate compound can be easily obtained as a commercial item, As a specific example, KYARAD 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, HX620, R-551, R-712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, Copper PET-30, copper RP-1040 (above, Nippon Kayaku Co., Ltd.), aronix M-210, copper M-240, copper M-6200, copper M-309, copper M-400, copper M-402 , M-405, M-450, M-7100, M-8030, M-8060, M-1310, M-1600, M-1960, M-8100, M-8530 , M-8560, M-9050 (above, product made by Toa Synthetic Co., Ltd.), biscot 295, copper 300, copper 360, copper GPT, copper 3PA, copper 400, copper 260, copper 312, copper 335HP (more , 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-TM MT, 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, Shin-Nakamura Chemical Co., Ltd. product) 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 mass parts-200 mass parts with respect to 100 mass parts which is a sum total of (A) component and (B) component, More preferably, Is 10 parts by mass to 150 parts by mass, and particularly preferably 50 parts by mass to 150 parts by mass. 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, a tack may arise in the coating film after prebaking, or the unexposed part may become a melt | dissolution defect 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 two or more functional groups which form a covalent bond with an acid. Examples of the functional group that forms a covalent bond with such an acid include an epoxy group, an alkoxymethyl group, and a hydroxymethyl group.

Examples of the compound having two or more epoxy groups include tris (2,3-epoxypropyl) isocyanurate, 1,4-butanediol diglycidyl ether, and 1,2-epoxy-4- (epoxyethyl ) Cyclohexane, glycerol triglycidyl ether, diethylene glycol diglycidyl ether, 2,6-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, the compound which is a commercial item can also be used from the point which is easy to obtain. 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 (made by Toto Kasei Co., Ltd.); Epoxy resins having a cyclohexene oxide structure such as epoxide GT-401, copper GT-403, copper GT-301, copper GT-302, Celoxide 2021, and Celoxide 3000 (manufactured by Daicel Chemical Industries, Ltd.); Bisphenol A type epoxy, such as epicoat 1001, copper 1002, copper 1003, copper 1004, copper 1007, copper 1009, copper 1010, copper 828 (above, emulsified shell epoxy (manufactured by Japan Epoxy Resin Co., Ltd.)) Suzy; Bisphenol F-type epoxy resins such as Epicoat 807 (emulsified Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin Co., Ltd.)); Phenol novolac-type epoxy resins such as epicoat 152, copper 154 (above, emulsified shell epoxy (manufactured by Japan Epoxy Resin Co., Ltd.), EPPN201, and copper 202 (manufactured by Nippon Kayaku Co., Ltd.); EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, EOCN-1027 (above, Nippon Kayaku Co., Ltd.), Epicoat 180S75 (Emulsion Shell Epoxy Co., Ltd. (currently Japan Epoxy Resin ( Cresol novolak-type epoxy resins, such as the note)); Denacol EX-252 (manufactured by Nagase Chemtex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, Copper CY-192, Copper CY-184 (above, made by CIBA-GEIGY AG), Epiclone 200 , Copper 400 (above, Dai Nippon Inky Chemical Co., Ltd. (current DIC Corporation), Epicoat 871, copper 872 (above, Emulsion shell epoxy Co., Ltd. (current Japan Epoxy Resin Co., Ltd.)) Alicyclic epoxy resins such as ED-5661 and ED-5662 (above, manufactured by Celanese Coating Co., Ltd.); Denacol EX-611, East EX-612, East EX-614, East EX-622, East EX-411, East EX-512, East EX-522, East EX-421, East EX-313, East EX-314 And aliphatic polyglycidyl ethers such as EX-321 (manufactured by Nagase Chemtex Co., Ltd.).

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.

Examples of the compound having two or more substituents selected from an alkoxymethyl group and a hydroxymethyl group include compounds such as alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine, and phenoplast-based compounds. have.

Specific examples of the alkoxy methylated glycoluril are as described in the above paragraph [0151].

Specific examples of the alkoxy methylated benzoguanamine are as described in the above paragraph.

Specific examples of the alkoxy methylated melamine are as described in the above paragraph.

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 (trademark) 303 (made by Mitsui Cytec Co., Ltd.) etc. are mentioned, As a commercial item of the said benzoguanamine compound, a brand name: Cymel (registered trademark) 1123 (Mitsui Cytec Co., Ltd.) etc. are mentioned.

Specific examples of the phenoplast-based compound are as described in the above paragraph.

Furthermore, as (G) 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.

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 they are 5 mass parts-200 mass parts on the basis of, More preferably, they are 50 mass parts-150 mass parts. When this ratio is too small, the photocurability of a negative photosensitive resin composition may fall, On the other hand, when excessive, developability of an unexposed part may fall and it may become a cause of a residual film or a residue.

<Other additives>

Furthermore, the photosensitive resin composition of this invention is 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. Dissolution accelerator and the like.

<Photosensitive resin composition>

The photosensitive resin composition of this invention is a photosensitive resin composition containing following (A) component, (B) component, (C) solvent, and (D) component, Furthermore, as needed, the crosslinking agent of (E) component, ( It may further contain one or more of a compound having two or more ethylenically polymerizable groups of the F) component, a compound having two or more functional groups which form a covalent bond with an acid of the component (G), and other additives. Composition.

(A) component: The polymer which has following (A1) and (A2) as needed, (A3)

(A1) liquid-repellent group

(A2) trialkoxy silyl group

(A3) at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group and an amino group,

(B) component: alkali-soluble resin,

(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 containing 0.1 mass part-20 mass parts (A) component with respect to 100 mass parts of (B) components, and these components melt | dissolved in (C) solvent.

[2]: 0.1 part by mass to 20 parts by mass of the component (A) and 5 parts by mass to 100 parts by mass of the component (D) are contained in 100 parts by mass of the component (B), and these components are dissolved in the solvent (C). The photosensitive resin composition whose further (D) component is the (D-1) component as a photosensitive resin composition which became.

[3]: 0.1 part by mass to 20 parts by mass of the component (A) and 5 parts by mass to 100 parts by mass of (D) component with respect to 100 parts by mass of the component (B), and these components are dissolved in the solvent (C). As a photosensitive resin composition, Furthermore, as a photosensitive resin composition containing 1 mass part-50 mass parts with respect to 100 mass parts which are the sum total of (A) component and (B) component, the said (E) component further said ( Photosensitive resin composition whose D) component is (D-1) 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 mass%-80 mass%, For example, 5 mass It is%-60 mass%, or 10 mass%-50 mass%. Here, solid content means what remove | excluding the (C) solvent from all the components of the photosensitive resin composition.

Although the preparation method of the photosensitive resin composition of this invention is not specifically limited, As the preparation method, (A) component (specific polymer) is melt | dissolved in the (C) solvent, for example, Covalent bond is formed by alkali-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 functional groups by 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 copolymer obtained by the polymerization reaction in (C) solvent can also be used as it is, and in this case, it is the solution of this (A) component similarly to the above (B) When the component, (D) component, and (E) component, (F) component, and (G) component are added to make a uniform solution, additional (C) solvent may be added for the purpose of concentration adjustment. It may be. At this time, the (C) solvent used in the formation process of a specific copolymer and the (C) solvent used for density | concentration adjustment at the time of preparation of the photosensitive resin composition may be the same, and may differ.

And it is preferable to use, after filtering the solution of the prepared photosensitive resin composition 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, and then preliminarily drying it with a hot plate or an oven. Then, the photosensitive resin film is formed by heat-processing this coating film.

As conditions of this heat processing, the heating temperature and heating time suitably selected from the range of the temperature of 70-160 degreeC and time 0.3-60 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 micrometer-30 micrometers, for example, 0.2 micrometer-10 micrometers, and further are 0.3 micrometer-8 micrometers, for example.

On the coating film obtained as described above, a mask having a predetermined pattern is mounted to irradiate light such as ultraviolet light and develop with an alkali developer, so that either the exposed portion or the unexposed portion is washed away by the material composition, and the remaining pattern shape If necessary, a relief pattern having a sharp cross section can be obtained by performing heating at 80 ° C to 140 ° C for 0.5 to 10 minutes.

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

Among the above, tetraethylammonium hydroxide 0.1-2.58 mass% aqueous solution is generally used as a developing solution of a photoresist, and also in this photosensitive resin composition of this invention, this alkaline developing solution is used, without causing problems, such as a swelling of a film | membrane. It can develop well.

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 heat curing, and specifically, by heating using a hot plate, an oven, or the like, it is excellent in heat resistance, transparency, planarization property, low water absorption, chemical resistance, and the like. 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.

And the postbaking can obtain the cured film which has a favorable pattern shape made into the objective.

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.

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 number average molecular weight and the weight average molecular weight of a polymer is as follows.

[Measurement of number average molecular weight and weight average molecular weight of a polymer]

The measurement of the number average molecular weight and the weight average molecular weight of the polymer was carried out under the following conditions using Shodex (registered trademark) KF-804L and 803L as a column using a GPC system manufactured by Japan Spectroscopy as an apparatus.

Column oven: 40 ℃

Flow rate: 1ml / min

In addition, the following number average molecular weight (henceforth Mn) and a weight average molecular weight (henceforth Mw) are represented by polystyrene conversion value.

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

MMA: Methyl methacrylate

HEMA: 2-hydroxyethyl methacrylate

HPMA: 4-hydroxyphenyl methacrylate

HPMA-QD: Compound synthesized by condensation of 1 mol of 4-hydroxyphenylmethacrylate with 1.1 mol of 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride

CHMI: N-cyclohexylmaleimide

PFHMA: 2- (perfluorohexyl) ethyl methacrylate

TMSSMA: methacryloxypropyl tris (trimethylsiloxy) silane

MAA: methacrylic acid

MAAm: methacrylamide

KBM-503: 3-methacryloxypropyltriethoxysilane

P7: A styrene polymer obtained by mixing a polymer of 85% of hydroxystyrene and 15% of styrene and a polymer of 70% of hydroxystyrene and 30% of styrene in a 3: 7 ratio.

AIBN: α, α'-azobisisobutyronitrile

QD: 1 mol of α, α, α'-tris (4-hydroxyphenyl) -1-ethyl-4-isopropylbenzene with 2 mol of 1,2-naphthoquinone-2-diazide-5-sulfonylchloride Compounds synthesized by condensation

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

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

CHN: cyclohexanone

MIBK: methyl isobutyl ketone

TMAH: tetramethylammonium hydroxide

Synthesis Example 1

5.00 g of PFHMA, 2.87 g of KBM-503, 1.00 g of HEMA, 1.38 g of CHMI, and 0.51 g of AIBN were dissolved in 25.14 g of PGME, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P1). ). Mn of the obtained acrylic polymer was 4900 and Mw was 6600.

Synthesis Example 2

5.00 g of PFHMA, 3.83 g of KBM-503, 1.51 g of HEMA, and 0.52 g of AIBN were dissolved in 25.32 g of PGME, and reacted at 80 ° C. for 20 hours to obtain an acrylic polymer solution (solid content concentration of 30% by mass) (P2). Mn of the obtained acrylic polymer was 4800 and Mw was 6700.

Synthesis Example 3

An acrylic polymer solution (solid content concentration of 30% by mass) was obtained by dissolving PFHMA 5.00g, MMA 1.16g, HEMA 1.00g, CHMI 1.38g, and AIBN 0.43g in PGME 20.93g and reacting at 80 ° C for 20 hours (P3). Mn of the obtained acrylic polymer was 4800 and Mw was 6600.

Synthesis Example 4

5.00 g of PFHMA, 0.98 g of MAAm, 1.00 g of HEMA, 1.38 g of CHMI, and 0.42 g of AIBN were dissolved in 20.51 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 4900 and Mw was 6700.

Synthesis Example 5

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. (P5). Mn of the obtained acrylic polymer was 3100 and Mw was 6100.

Synthesis Example 6

The acrylic polymer solution (solid content concentration 40 mass%) was obtained by melt | dissolving MAA 100.00g, HEMA 188.89g, MMA 190.37g, CHMI 262.96g, and AIBN 47.50g in PGME 1184.59g, and making it react at 80 degreeC for 20 hours (P6). Mn of the obtained acrylic polymer was 3800 and Mw was 7300.

Synthesis Example 7

2.50 g of HPMA-QD, 2.58 g of TMSSMA, 5.26 g of PFHMA, 0.70 g of MAA, 1.46 g of CHMI, and 0.33 g of AIBN were dissolved in 51.3 g of CHN and stirred at 110 ° C. for 20 hours to give an acrylic polymer solution (solid content concentration of 20% by mass). Was obtained (P8). Mn of the obtained acrylic polymer was 7,200 and Mw was 11,000.

Synthesis Example 8

5.00 g of PFHMA, 6.70 g of KBM-503 and 0.59 g of AIBN were dissolved in 28.68 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 6700 and Mw was 9800.

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). (P10). Mn of the obtained acrylic polymer was 3000 and Mw was 4400.

<Examples 1 to 11> and <Comparative Examples 1 to 4>

Each component of (A)-(E) and a solvent are mixed with the composition shown in Table 1, and the addition amount of a solvent is adjusted so that solid content concentration of a final composition may be 21.0 mass%, Examples 1-7, Comparative Examples 1-2. Photosensitive resin composition was prepared. Moreover, the photosensitive resin composition of Examples 8-11 and Comparative Examples 3-4 was prepared by adjusting the addition amount of a solvent so that solid content concentration of a final composition may be 17.0 mass%. In addition, the composition ratio in Table 1 shall show the ratio in solid content. On the other hand, Examples 1-10 and Comparative Examples 1-3 are positive photosensitive resin compositions, and Example 11 and Comparative Example 4 are negative photosensitive resin compositions.

TABLE 1

[Evaluation of wettability: Examples 1 to 10 and Comparative Examples 1 to 3]

After apply | coating the photosensitive resin composition on ITO-glass using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 100 degreeC, and formed the coating film of 1.7 micrometers in film thicknesses. A rectangular pattern having a length of 50 µm and a width of 100 µm was formed on the coating film by a Canon UV irradiation device PLA-600FA through a mask formed in the shape of a base tree so that the bank width was 30 µm. Ultraviolet rays with an intensity of 5.5 mW / cm ² were irradiated for a certain time. Thereafter, the development was carried out by immersing in a 2.58% TMAH aqueous solution for 20 seconds, and then flowing water was washed with ultrapure water for 20 seconds. Subsequently, post-baking was performed by hardening the coating film in which this rectangular pattern was formed by heating at the temperature of 230 degreeC for 30 minutes. On the rectangular opening of the obtained cured film, about 20 pl of the solution was discharged using Inkjet Designer by Cluster Technology Co., Ltd. at a drive waveform of B, a repetition frequency of 1 kHz, and a drive voltage of 8V. As the discharge solution, the solution described in Japanese Patent Application No. 2016-141326, Example 1-1 was used. The obtained results are shown in Table 2.

[Evaluation of wettability: Example 11 and Comparative Example 4]

After apply | coating the photosensitive resin composition on ITO-glass using a spin coater, it prebaked on the hotplate for 120 second at the temperature of 100 degreeC, and the coating film of 1.2 micrometers in thickness was formed. Light intensity at 365 nm by Canon Inc. ultraviolet irradiation apparatus PLA-600FA through the mask formed in the base material so that the rectangular pattern (light shielding part) of 80 micrometers in length and 160 micrometers in width may be 50 micrometers in this coating film. Was irradiated with ultraviolet rays having a 5.5 mW / cm ² for a predetermined time. After developing by immersing in 0.4% TMAH aqueous solution for 60 second after that, flowing water was wash | cleaned for 30 second with ultrapure water. Subsequently, the coating film in which this rectangular pattern was formed was heated at 230 degreeC for 30 minutes, and post-baking was hardened. On the rectangular opening of the obtained cured film, about 20 pl of the solution was discharged using Inkjet Designer by Cluster Technology Co., Ltd. at a drive waveform of B, a repetition frequency of 1 kHz, and a drive voltage of 8V. As the discharge solution, the solution described in Japanese Patent Application No. 2016-141326, Example 1-1 was used. The obtained results are shown in Table 2.

<Evaluation criteria of wettability>

○: The solution is completely wet with the rectangular opening.

X: The part where a solution is not wetted in a rectangular opening part is observed.

TABLE 2

As shown in Table 2, Examples 1 to 11 had good wettability of the rectangular opening. On the other hand, in Comparative Examples 1-4, sufficient wettability could not be confirmed.

Claims (14)

The thermosetting photosensitive resin composition containing following (A) component, (B) component, (C) solvent, and (D) component.
(A) component: The polymer which has the following groups (A1) and (A2)
(A1) liquid-repellent group
(A2) a trialkoxy silyl group,
(B) component: alkali-soluble resin,
(C) a solvent,
(D) component: Photosensitive agent. The method of claim 1,
The photosensitive resin composition whose (A) component is a polymer which has the following (A3) further.
(A3): At least 1 group chosen from the group which consists of a hydroxyl group, a carboxyl group, an amide group, and an amino group. The method according to claim 1 or 2,
The photosensitive resin composition which satisfy | fills at least any one of following (Z1)-(Z4).
(Z1): It further contains the crosslinking agent which is (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): The component (D) is an optical radical generating agent, and further contains a compound having two or more ethylenic double bonds as the component (F);
(Z4): The component (D) is a photoacid generator, and further contains, as the component (G), a compound having two or more functional groups which form a covalent bond with an acid generated from the component (D). The method according to any one of claims 1 to 3,
The photosensitive resin composition whose (D) component is a quinonediazide compound. The method of claim 3,
The photosensitive resin composition whose (D) component is a quinonediazide compound and satisfy | fills any one of said (Z1) or (Z2). The method according to any one of claims 1 to 5,
The photosensitive resin composition of the at least 1 group which the said liquid repellent group of (A) component is chosen from a fluoroalkyl group, a polyfluoroether group, a silyl ether group, and a polysiloxane group of 3-10 carbon atoms. The method according to any one of claims 1 to 6,
The photosensitive resin composition whose polymer of (A) component is an acrylic polymer. The method of claim 7, wherein
The photosensitive resin composition whose number average molecular weight of the acrylic polymer of (A) component is 2,000-100,000 in polystyrene conversion. The method according to any one of claims 1 to 8,
The photosensitive resin composition whose number average molecular weight of alkali-soluble resin of (B) component is 2,000-50,000 in polystyrene conversion. The method according to any one of claims 1 to 9,
(B) 0.1 mass part-20 mass parts (A) component are 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 3 to 10,
(E) A component is 1 mass part-50 mass parts 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 which consists of a thermosetting material of the photosensitive resin composition of any one of Claims 1-11. The display element which has a cured film of Claim 12. The display element which has the cured film of Claim 12 as an image forming partition.