JP4997806B2 - Photosensitive resin composition, article, and negative pattern forming method - Google Patents

Description

The present invention relates to a photosensitive resin composition having excellent resolution, low cost, and a wide range of options applicable to the structure of a polymer precursor, and in particular, a product or member formed through a patterning step using electromagnetic waves. A polymer precursor resin composition that can be suitably used as a material (for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material, or an adhesive), and the resin composition It relates to the manufactured article.
Furthermore, the present invention relates to a photosensitive resin composition having excellent resolution, low cost, and a wide range of options applicable to the structure of a polyimide precursor or polybenzoxazole precursor, and is particularly formed through a patterning process using electromagnetic waves. A precursor resin composition of polyimide or polybenzoxazole which can be suitably used as a material of a product or member (for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material or an adhesive), and The present invention relates to an article produced using the resin composition.

Conventionally, a polyimide resin having excellent heat resistance, electrical characteristics, and mechanical characteristics has been used as a surface protective film for semiconductor elements, an interlayer insulating film, and an insulating material for electronic components (Non-patent Document 1).
Furthermore, in recent years, polybenzoxazole, which has a similar processing process applied to solve the problems of polyimide and has low water absorption and low dielectric constant, and polybenzimidazole with excellent adhesion to the substrate, etc. are also energetic. Has been studied.

  In addition, circuit pattern formation on semiconductor integrated circuits and printed circuit boards is complicated and diverse, such as the formation of a resist agent on the surface of the material, exposure to predetermined locations, removal of unnecessary portions by etching, etc., and cleaning of the substrate surface. In order to simplify the circuit pattern manufacturing process, a heat-resistant photosensitive material that can be used by leaving a necessary portion of the resist as an insulating material after pattern formation by exposure and development is used to simplify the circuit pattern manufacturing process. It is desired. As these materials, heat-resistant photosensitive materials using polyimide as a base polymer have been proposed.

  As such photosensitive polyimide, for example, in Patent Document 1, a system composed of a polyimide precursor and dichromate was first proposed. However, this material has practical advantages such as high photosensitivity and high film forming ability, but lacks storage stability and has the disadvantage that chromium ions remain in polyimide. Did not come. Furthermore, in Patent Document 2, a compound in which a photosensitive group is introduced into a polyamic acid which is a polyimide precursor by an ester bond, and in Patent Document 3, an amine compound having a methacryloyl group is added to a polyamic acid in a polyimide precursor. A compound in which an amino group and a carboxyl group are ion-bonded has been introduced. However, the covalent bond type photosensitive polyimide represented by the ester bond has a problem in that the synthesis process is complicated and the cost is increased. In addition, the ion-bonded photosensitive polyimide has a problem that the bonding force between the polyimide skeleton and the photosensitive group is small and the exposed part is dissolved, so that the remaining film ratio is lowered and it is difficult to increase the film thickness. (Non-Patent Document 2). Many of these compounds are organic solvent developable, and in view of cost and environmental burden, compounds that can be developed with an alkaline aqueous solution are more desirable.

  Such polymer precursors such as polyimide precursors and polybenzoxazole precursors use an aromatic monomer as a basic skeleton so as to be excellent in heat resistance and mechanical properties. In general, a polymer precursor such as a polyimide precursor having an aromatic ring as a basic skeleton has a wide absorption band in the ultraviolet-visible region of wavelength 450 nm or less, particularly in the i-line (wavelength: 365 nm) region. Therefore, when UV-visible light is irradiated, there is a problem that the photochemical reaction does not proceed sufficiently in the exposed area due to low translucency, resulting in low sensitivity and deterioration of the pattern shape. As the application range of heat-resistant photosensitive materials widens, material requirements are becoming increasingly diverse, and a thick film forming ability is required for photosensitive polyimide. When the formation pattern is a thick film, the problem of low light transmission becomes more serious. Therefore, a photosensitive system having photoreactive activity in the g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) region in order to realize a heat-resistant photosensitive resin excellent in both film properties and sensitivity. Construction of is indispensable.

  In recent years, photobase generators have attracted attention as one of new pattern forming materials. However, in order to apply an existing photobase generator to a system such as a polyimide precursor or a polybenzoxazole precursor, there is a problem in the absorption wavelength. That is, many existing photobase generators have an absorption wavelength of 400 nm or less, and when added to a polyimide precursor or polybenzoxazole precursor as an imidization accelerator by photoreaction, a polyimide precursor or polybenzoxazole precursor Since the absorption wavelength of the photobase generator overlaps, a problem arises in terms of sensitivity. Therefore, in order to realize a heat-resistant photosensitive resin that is excellent in terms of heat resistance, mechanical properties, and sensitivity, a wavelength region of 400 nm or more, such as g-line (wavelength: 436 nm), h-line (wavelength: 405 nm) There is a need for a base generator having photoreactive activity in the region.

Japanese Patent Publication No.49-17374 Japanese Patent Publication No.55-30207 JP 54-145794 A “Latest Polyimide: Fundamentals and Applications”, ENTS, 2002, p. 327-338 “Latest Trends in Polymer Materials for Electronic Components III”, Sumibe Techno Research, 2004, p. 36-39

  The present invention has been achieved in view of the above circumstances, and its main purpose is to provide a high sensitivity and a large solubility contrast regardless of the type of the polymer precursor, resulting in a sufficient process margin. It is in providing the photosensitive resin composition which can obtain a pattern with a favorable shape, keeping it.

The photosensitive resin composition according to the present invention contains a photobase generator composed of a salt of a carboxylic acid and an amine represented by the following formula (1), and a polymer precursor, and the polymer precursor itself Is characterized in that the reaction to the final product is promoted by the action of a basic substance .

（式中、Ｘ^１、Ｘ^２は独立に酸素原子もしくは硫黄原子を示す。Ｒ^１〜Ｒ^９は独立に水素原子、ハロゲン原子、ヒドロキシル基、メルカプト基、ニトロ基、シリル基、シラノール基、もしくは１価の有機基を示す。Ｒ^１０、Ｒ^１１、Ｒ^１２は水素原子、もしくは１価の有機基を示す。但し、Ｒ^１０、Ｒ^１１、Ｒ^１２の少なくとも１つは、１価の有機基である。）

(In the formula, X ¹ and X ² independently represent an oxygen atom or a sulfur atom. R ^{1 to} R ⁹ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or R ¹⁰ , R ¹¹ and R ^{12 each} represent a hydrogen atom or a monovalent organic group, provided that at least one of R ¹⁰ , R ¹¹ and R ¹² is a monovalent organic group. .)

The salt of carboxylic acid and amine represented by the above formula (1) cannot maintain the salt state by photodecarboxylation reaction of carboxylic acid when irradiated with electromagnetic waves, and generates an amine that is a basic substance. It acts as a very effective photosensitive component for a polymer precursor whose reaction to the final product is promoted by the action of a base, such as a polyimide precursor.
In particular, a salt of a carboxylic acid and an amine represented by the above formula (1) functions as a photobase generator having a photoreactive activity in a wavelength region of 400 nm or more, and thus has a wide i-line (wavelength: 365 nm) region. Also for a polymer precursor such as a polyimide precursor having an aromatic ring having an absorption band as a basic skeleton, when irradiated with ultraviolet-visible light, g-line (wavelength: 436 nm) or h-line (wavelength) : 405 nm) by using light in at least one of the wavelength regions, the photochemical reaction can be sufficiently advanced in the exposed portion, and a highly sensitive photosensitive resin composition can be achieved.
According to the present invention, since a salt of a carboxylic acid and an amine represented by the above formula (1) functions as a highly sensitive photobase generator, the electromagnetic wave on the coating film or molded body of the photosensitive resin composition The solubility difference between the irradiated part and the non-irradiated part can be increased, and as a result, a pattern having a good shape can be obtained while maintaining a sufficient process margin.

  The polymer precursor used in the photosensitive resin composition of the present invention is a compound that itself promotes the reaction to the final product by the action of a basic substance. A compound whose reaction to the final product is accelerated and whose solubility is changed by heating is preferably used.

  In the photosensitive resin composition of the present invention, the amine used for the salt of the carboxylic acid and the amine is preferably an aliphatic amine from the viewpoint of using a highly basic amine.

  Moreover, in the photosensitive resin composition of this invention, it is preferable that the said salt of carboxylic acid and amine has absorption of the electromagnetic waves with a wavelength of 400 nm or more. Typical emission wavelengths of a high-pressure mercury lamp, which is a general exposure light source, are 436 nm, 405 nm, and 365 nm, and the polymer precursor used in the present invention often has absorption in a wavelength region of less than 400 nm. Therefore, in the case of absorption of electromagnetic waves having a wavelength of 400 nm or more, it is possible to improve the sensitivity of the photosensitive resin composition without overlapping the absorption wavelengths of the polymer precursor and the photobase generator. is there.

  In one embodiment of the present invention, irradiation sensitivity can be improved by adding a sensitizer to the photosensitive resin composition.

In one embodiment of the present invention, a polyimide precursor such as polyamic acid or a polybenzoxazole precursor can be used as the polymer precursor of the photosensitive resin composition. When such a polymer precursor is used, a photosensitive resin composition excellent in heat resistance and mechanical properties can be obtained.
According to the present invention, a polyimide precursor or a polybenzoxazole precursor, which has conventionally had difficulty in obtaining a solubility contrast between an exposed area and an unexposed area, can be obtained without application of a dissolution inhibitor or a dissolution inhibitor. A pattern shape can be obtained.

Furthermore, this invention also provides the negative pattern formation method using the said photosensitive resin composition. The negative pattern forming method according to the present invention irradiates the surface of a coating film or molded body made of the photosensitive resin composition with an electromagnetic wave in a predetermined pattern, and performs post-treatment (usually heat treatment) as necessary. ) To selectively reduce the solubility of the coating film or the electromagnetic wave irradiation site of the molded article, and then develop using a solvent that reduces the solubility as a developer.
In the negative pattern forming method, a photosensitive resin composition is used by combining a polymer precursor and a salt of a carboxylic acid and an amine represented by the above formula (1) as a photobase generator. The negative pattern formation which develops is possible, without using the resist film for protecting the coating film which consists of, or the surface of a molded object from a developing solution.

As described above, according to the present invention, a photosensitive resin composition can be prepared and used by a simple method of mixing an additive with a polymer precursor. The salt of carboxylic acid and amine represented by the above formula (1) contained in the photosensitive resin composition according to the present invention is a photobase generator that liberates a basic compound by decarboxylation accompanying absorption of electromagnetic waves. It can be applied to various polymer precursors that function and have a reaction in which a base acts as a catalyst. Therefore, the photosensitive resin composition according to the present invention can select a final polymer structure from a wide range without being limited by the pattern formation process.
Furthermore, the photosensitive resin composition according to the present invention can be applied to a wider range of applications by applying a polyimide precursor or a polybenzoxazole precursor that has been applied to various applications as a polymer precursor. Therefore, it can be used as a photosensitive polyimide resin composition or a photosensitive polybenzoxazole resin composition having excellent heat resistance and mechanical properties.
In particular, the salt of carboxylic acid and amine represented by the above formula (1) has a photoreactive activity in a wavelength region of 400 nm or more. Therefore, even in general polyamic acid having strong absorption in the i-line (wavelength: 365 nm) region, light in at least one of the g-line (wavelength: 436 nm) and h-line (wavelength: 405 nm) should be used. Therefore, it is possible to perform the exposure efficiently, and it exerts a great effect in improving the sensitivity and increasing the thickness.
According to the present invention, a polyimide precursor or a polybenzoxazole precursor, which has conventionally had difficulty in obtaining a solubility contrast between an exposed area and an unexposed area, can be obtained without application of a dissolution inhibitor or a dissolution inhibitor. A pattern shape can be obtained.

Moreover, since the photosensitive polymer precursor resin composition according to the present invention can select a polymer precursor having a wide range of structures, the polymer obtained thereby has heat resistance, dimensional stability, insulating properties, etc. Since the function can be imparted, it is suitable as a film or coating film for all known members to which these polymers are applied.
In particular, the photosensitive resin composition according to the present invention is mainly used as a pattern forming material (resist), and the pattern formed thereby functions as a component imparting heat resistance and insulation as a permanent film, for example, Suitable for forming color filters, flexible display films, semiconductor devices, electronic components, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, other optical components, or building materials Yes.
In addition, a photosensitive polyimide precursor resin composition, which is one form of the polymer precursor resin composition, and a photosensitive polybenzoxazole precursor resin composition are polyimide or polybenzoxazole precursors having a wide range of structures. Therefore, the cured product obtained can be imparted with functions characteristic of polyimide and polybenzoxazole, such as heat resistance, dimensional stability, and insulation properties. It is suitable as a film, coating film or three-dimensional structure for all known members to which oxazole is applied.

The present invention will be described in detail below.
In the present invention, (meth) acryloyl means acryloyl and / or methacryloyl, (meth) acryl means acryl and / or methacryl, and (meth) acrylate means It means that either acrylate or methacrylate may be used.
Further, in the present invention, the electromagnetic wave causing the decarboxylation reaction of the salt of carboxylic acid and amine is not limited as long as it can cause the decarboxylation reaction, and not only the electromagnetic waves having wavelengths in the visible and invisible regions. , A particle beam such as an electron beam, and radiation or ionizing radiation collectively referring to electromagnetic waves and particle beams.

  The photosensitive resin composition according to the present invention is characterized by containing a salt of a carboxylic acid and an amine represented by the following formula (1) and a polymer precursor.

（式中、Ｘ^１、Ｘ^２は独立に酸素原子もしくは硫黄原子を示す。Ｒ^１〜Ｒ^９は独立に水素原子、ハロゲン原子、ヒドロキシル基、メルカプト基、ニトロ基、シリル基、シラノール基、もしくは１価の有機基を示す。Ｒ^１０、Ｒ^１１、Ｒ^１２は水素原子、もしくは１価の有機基を示す。但し、Ｒ^１０、Ｒ^１１、Ｒ^１２の少なくとも１つは、１価の有機基である。）

(In the formula, X ¹ and X ² independently represent an oxygen atom or a sulfur atom. R ^{1 to} R ⁹ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or R ¹⁰ , R ¹¹ and R ^{12 each} represent a hydrogen atom or a monovalent organic group, provided that at least one of R ¹⁰ , R ¹¹ and R ¹² is a monovalent organic group. .)

The salt of carboxylic acid and amine represented by the above formula (1) cannot maintain the salt state by photodecarboxylation reaction of carboxylic acid when irradiated with electromagnetic waves, and generates an amine that is a basic substance. It acts as a very effective photosensitive component for a polymer precursor whose reaction to the final product is promoted by the action of a base, such as a polyimide precursor.
In particular, a salt of a carboxylic acid and an amine represented by the above formula (1) functions as a photobase generator having a photoreactive activity in a wavelength region of 400 nm or more, and thus has a wide i-line (wavelength: 365 nm) region. Also for a polymer precursor such as a polyimide precursor having an aromatic ring having an absorption band as a basic skeleton, when irradiated with ultraviolet-visible light, g-line (wavelength: 436 nm) or h-line (wavelength) : 405 nm) by using light in at least one of the wavelength regions, the photochemical reaction can be sufficiently advanced in the exposed portion, and a highly sensitive photosensitive resin composition can be achieved.
According to the present invention, since a salt of a carboxylic acid and an amine represented by the above formula (1) functions as a highly sensitive photobase generator, the electromagnetic wave on the coating film or molded body of the photosensitive resin composition The solubility difference between the irradiated part and the non-irradiated part can be increased, and as a result, a pattern having a good shape can be obtained while maintaining a sufficient process margin.

First, the salt of carboxylic acid and amine represented by the above formula (1) will be described.
This compound comprises a carboxylic acid having a xanthone ring or a thioxanthone ring and an amine compound.
The carboxylic acid having a xanthone ring or thioxanthone ring is represented by the general formula (2).

X ¹ and X ² independently represent an oxygen atom or a sulfur atom. R ^{1 to} R ⁹ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or a monovalent organic group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. Examples of the monovalent organic group include groups having a hydrocarbon skeleton such as a substituted or unsubstituted saturated or unsaturated alkyl group and a substituted or unsubstituted aromatic group. These monovalent organic groups may contain bonds or substituents other than hydrocarbon groups such as heteroatoms in the organic group. These may be linear, branched or cyclic. The monovalent organic group preferably has about 1 to 20 carbon atoms.
As a bond other than a hydrocarbon group such as a hetero atom contained in a group having a hydrocarbon skeleton, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, etc. Halogen atom, hydroxyl group, mercapto group, cyano group, silyl group, silanol group, alkoxy group, nitro group, acetyl group, acetoxy group, unsaturated alkyl ether group, aryl ether group, unsaturated alkyl thioether group, aryl thioether group, etc. There is no particular limitation.

Preferred examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 4 to 13 carbon atoms, a cycloalkenyl group having 4 to 13 carbon atoms, a phenoxyalkyl group having 7 to 16 carbon atoms, An arylalkyl group having 7 to 20 carbon atoms, a cyanoalkyl group having 2 to 11 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, and a carbon number An acyl group having 1 to 10 carbon atoms, an ester group having 2 to 11 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms substituted by an electron-donating group and / or an electron-withdrawing group, and electron donation And a benzyl group, a cyano group, a thiomethyl group and the like substituted with a functional group and / or an electron-withdrawing group.
The alkyl moiety may be linear, branched or cyclic.

  Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, tert-butyl, pentyl, and iso-pentyl. Group, neo-pentyl group, hexyl group, heptyl group and octyl group. Examples of the cycloalkyl group having 4 to 13 carbon atoms include a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the C 4-13 cycloalkenyl group include a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptynyl group, and a cyclooctenyl group. Examples of the phenoxyalkyl group having 7 to 16 carbon atoms include phenoxymethyl group, phenoxyethyl group, phenoxy-n-propyl group, phenoxy-iso-propyl group, phenoxy-n-butyl group, phenoxy-sec-butyl group, Examples include phenoxy-tert-butyl group, phenoxypentyl group, phenoxy-iso-pentyl group, phenoxy-neo-pentyl group and phenoxyhexyl group. Examples of the arylalkyl group having 7 to 20 carbon atoms include phenylmethyl group, phenylethyl group, phenyl-n-propyl group, phenyl-iso-propyl group, phenyl-n-butyl group, phenyl-sec-butyl group, Phenyl-tert-butyl group, phenylpentyl group, phenyl-iso-pentyl group, phenyl-neo-pentyl group, phenylhexyl group, naphthylmethyl group, naphthylethyl group, naphthyl-n-propyl group, naphthyl-iso-propyl group Naphthyl-n-butyl group, naphthyl-sec-butyl group, naphthyl-tert-butyl group, naphthylpentyl group, naphthyl-iso-pentyl group, naphthyl-neo-pentyl group, naphthylhexyl group. Examples of the cyanoalkyl group having 2 to 11 carbon atoms include cyanomethyl group, cyanoethyl group, cyano-n-propyl group, cyano-iso-propyl group, cyano-n-butyl group, cyano-sec-butyl group, cyano- Examples include tert-butyl group, cyanopentyl group, cyano-iso-pentyl group, cyano-neo-pentyl group, and cyanohexyl group. Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl group, hydroxyethyl group, hydroxy-n-propyl group, hydroxy-iso-propyl group, hydroxy-n-butyl group, hydroxy-sec-butyl group, Examples thereof include a hydroxy-tert-butyl group, a hydroxypentyl group, a hydroxy-iso-pentyl group, a hydroxy-neo-pentyl group, and a hydroxyhexyl group.

  Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, pentyloxy group, iso-pentyloxy group, and neo-pentyl. Examples thereof include an oxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. Examples of the alkylthio group having 1 to 10 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and iso-pentylthio group. Group, neo-pentylthio group, hexylthio group, heptylthio group and octylthio group. Examples of the acyl group having 1 to 10 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group. Examples of the ester group having 2 to 11 carbon atoms include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, and an isopropoxycarbonyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group. Examples of the electron donating group include a hydroxyl group, a halogen atom (such as chlorine, bromine and iodine), an alkyl group, and a methoxy group. Examples of the electron withdrawing group include a nitro group, a carbonyl group, and a nitrile group.

Moreover, the ease of decarboxylation can be adjusted by introducing a hydrogen atom or a substituent other than a hydrogen atom at the positions of R ⁸ and R ⁹ . From this viewpoint, examples of the monovalent organic group that can be introduced at the positions of R ⁸ and R ⁹ include, in addition to a hydrogen atom, for example, a saturated or unsaturated alkyl group, a saturated or unsaturated halogenated alkyl group, or phenyl And aromatic groups such as naphthyl. These monovalent organic groups may contain bonds and substituents other than the above-described hydrocarbon groups such as heteroatoms in the organic group, and in particular, have about 1 to 20 carbon atoms, preferably have a carbon number. It is preferable that it is about 1-8. These may be linear, branched or cyclic.
Furthermore, the substituent that can be introduced at the positions of R ⁸ and R ⁹ includes a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, a nitro group, and an acetyl group as long as the characteristics are not impaired. An acetoxy group, an unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group, or the like may be used.

  The method for synthesizing the compound represented by the general formula (2) is not particularly limited. For example, specifically, salicylic acid or thiosalicylic acid or a derivative of these compounds in concentrated sulfuric acid, and thiophenoxyacetic acid, phenoxyacetic acid, or these It is obtained by dehydration cyclization reaction with a derivative of the compound (for example, Macromol. Rapid Commun. 2003, 24, 718-723).

  On the other hand, an amine compound constituting a salt of a carboxylic acid and an amine represented by the above formula (1) is represented by the following general formula (3).

式（３）において、Ｒ^１０、Ｒ^１１、Ｒ^１２は独立に水素原子もしくは、１価の有機基である。但し、Ｒ^１０、Ｒ^１１、Ｒ^１２の少なくとも１つは、１価の有機基である。
Ｒ^１０〜Ｒ^１２の位置に導入し得る1価の有機基としては、例えば、置換又は無置換の飽和又は不飽和アルキル基、置換又は無置換の芳香族基が挙げられる。これらの1価の有機基は、有機基中にヘテロ原子等の炭化水素基以外の結合や置換基を含んでよく、特に、炭素数が１〜２０程度、好ましくは炭素数が１〜１２程度であることが好ましい。これらは、直鎖でも分岐でも環状でも良い。また、Ｒ^１０〜Ｒ^１２のうちの２つ以上が連結し環状になっていても良い。
炭化水素骨格を有する基に含まれるヘテロ原子等の炭化水素基以外の結合としては、エーテル結合、チオエーテル結合、カルボニル結合、エステル結合、アミド結合、ウレタン結合、カーボネート結合など、また置換基としては、ハロゲン原子、ヒドロキシル基、メルカプト基、１級アミノ基、２級アミノ基、３級アミノ基、シアノ基、シリル基、シラノール基、アルコキシ基、ニトロ基、アセチル基、アセトキシ基、不飽和アルキルエーテル基、アリールエーテル基、不飽和アルキルチオエーテル基、アリールチオエーテル基等が挙げられるが特に限定されない。

In the formula (3), R ¹⁰ , R ¹¹ and R ¹² are each independently a hydrogen atom or a monovalent organic group. However, at least one of R ¹⁰ , R ¹¹ , and R ¹² is a monovalent organic group.
Examples of the monovalent organic group may be introduced to the position of R ¹⁰ to R ^12, for example, substituted or unsubstituted, saturated or unsaturated alkyl group include substituted or unsubstituted aromatic group. These monovalent organic groups may contain a bond or substituent other than a hydrocarbon group such as a heteroatom in the organic group, and particularly have about 1 to 20 carbon atoms, preferably about 1 to 12 carbon atoms. It is preferable that These may be linear, branched or cyclic. Also, two or more of R ^{10 to} R ¹² may be connected to form a ring.
As a bond other than a hydrocarbon group such as a hetero atom contained in a group having a hydrocarbon skeleton, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, etc. Halogen atom, hydroxyl group, mercapto group, primary amino group, secondary amino group, tertiary amino group, cyano group, silyl group, silanol group, alkoxy group, nitro group, acetyl group, acetoxy group, unsaturated alkyl ether group , Aryl ether groups, unsaturated alkyl thioether groups, aryl thioether groups, and the like, but are not particularly limited.

By changing the number of hydrogen atoms introduced at the positions of R ^{10 to} R ¹² and the kind of the substituent, it is possible to change the physical properties such as basicity, thermal properties, and solubility of the amine. The amine having higher basicity has a stronger catalytic effect on the dehydration condensation reaction and the like in imidization, and the catalytic effect in the dehydration condensation reaction and the like at a lower temperature can be expressed with a smaller amount of addition. That is, even if the salt of the carboxylic acid and amine represented by the above formula (1) has a low sensitivity to electromagnetic waves, the generated basic substance has a large catalytic effect, so that it appears as a photosensitive resin composition. Sensitivity is improved.
In view of the large catalytic effect as described above, the basic substance generated by the cleavage reaction accompanying the absorption of electromagnetic waves of the salt of the carboxylic acid and amine represented by the formula (1) is preferably an aliphatic amine. Among these, secondary or tertiary aliphatic amines are preferable from the viewpoint of basicity. However, even when an aliphatic primary amine is used, a sufficient catalytic effect can be obtained as compared with the case where an aromatic amine is used. Therefore, among aliphatic amines, from the viewpoints of thermal properties such as 5% weight loss temperature, 50% weight loss temperature, thermal decomposition temperature, other physical properties such as solubility, ease of synthesis and cost, etc. It is desirable to select as appropriate.

From the viewpoint of generating such an aliphatic amine, achieving high sensitivity, and increasing the solubility contrast of the unexposed portion of the exposed portion, all of the bonds directly bonded to the nitrogen atoms of R ^{10 to} R ¹² It is preferable that the atom is a hydrogen atom or a carbon atom having SP3 orbital (except when all of R ^{10 to} R ¹² are hydrogen atoms).
Examples of the substituent in which the atom directly bonded to the nitrogen atom is a carbon atom having an SP3 orbital include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon. And one or more aliphatic hydrocarbon groups selected from the group consisting of groups. In addition, the said aliphatic hydrocarbon group may have substituents, such as an aromatic group, or may contain bonds other than hydrocarbons, such as a hetero atom, in a hydrocarbon chain. Preferred are saturated or unsaturated alkyl group having 1 to 20 carbon atoms, cycloalkyl group having 4 to 13 carbon atoms, phenoxyalkyl group having 7 to 26 carbon atoms, arylalkyl group having 7 to 26 carbon atoms, carbon number 1-20 hydroxyalkyl groups are mentioned. Specific examples include, but are not limited to, a methyl group, an ethyl group, an ethynyl group, a propyl group, an isopropyl group, an n-butyl group, a cyclohexyl group, an isobornyl group, a norbornyl group, an adamantyl group, and a benzyl group. It is not a thing.
That is, all of R ^{10 to} R ¹² are one or more selected from the group consisting of a hydrogen atom, or a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group. It is preferable that it is an aliphatic hydrocarbon group of (except the case where all of R < ¹⁰ > -R < ¹² > are hydrogen atoms). Among these, an aliphatic tertiary amine is preferable from the viewpoint of basicity.

  Examples of amines include primary amines such as n-butylamine, amylamine, hexylamine and octylamine, secondary amines such as diethylamine, dipropylamine, diisopropylamine and dibutylamine, trimethylamine, triethylamine and tripropylamine. , Tributylamine, triethylenediamine, 1,4-diazabicyclo [2.2.2] octane, quinuclidine and aliphatic tertiary amines such as 3-quinuclidinol, aromatic tertiary amines such as dimethylaniline, and isoquinoline Heterocyclic tertiary amines such as pyridine, collidine, and betapicoline, ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, etc. Diamines, triamines, such as diethylenetriamine, other tetramine compounds include benzyl amine.

In the present invention, a compound having two or more amino groups in the molecule may be used. For example, in 1,4-diazabicyclo [2.2.2] octane having two amino groups, an aromatic component-containing carboxylic acid that undergoes two photodecarboxylation reactions per molecule of amine is used. Use neutral salt.
Conversely, in the case of a compound having two carboxylic acids by linking two aromatic component-containing carboxylic acids that undergo photodecarboxylation, one molecule of aromatic component carboxylic acid is applied to two monoamine molecules. Use neutral salt.

The present invention is intended to be applied to a resin composition as a combination salt so that the carboxyl group and amino group of an aromatic component-containing carboxylic acid that undergoes a decarboxylation reaction by absorption of electromagnetic waves are equimolar. In such a range, a compound having any number of carboxyl groups and a compound having any number of amino groups can be used in combination.
Furthermore, they may not be single, and from the viewpoint of solubility in the matrix, a plurality of salts, and further a plurality of aromatic component-containing carboxylic acids and amines can be used in combination.

Moreover, sensitivity is improved by introducing one or more substituents into any position among the substituents R ^{1 to} R ¹² in the molecule of the salt of the carboxylic acid and amine represented by the above formula (1). It is possible to improve or adjust the wavelength of light to be absorbed.
In particular, the substituents R ^{1 to} R ⁷ on the aromatic ring can be introduced by relatively freely selecting the type of substituent from the viewpoint of improving sensitivity or adjusting the absorption wavelength. Thereby, it is possible to improve the sensitivity of the photosensitive resin composition in consideration of the absorption wavelength of the polymer precursor to be combined.

  The amine produced by the photodecomposition reaction of the carboxylic acid and amine salt represented by the above formula (1) and the carboxylic acid salt of the carboxylic acid and amine represented by the above formula (1) is the present invention. It is preferable not to decompose at the heating temperature (if the polymer is a polyimide precursor, the imidization temperature) performed after the exposure to the coating film of the photosensitive resin composition. Specifically, the temperature when the salt of carboxylic acid and amine represented by the above formula (1) or the amine used is reduced by 5% from the initial weight by heating (5% weight reduction) Temperature) is preferably 100 ° C. or higher. Furthermore, when the photosensitive resin composition of the present invention is used as a product, it is preferable that no amine remains in the photosensitive resin composition, so that a heating process performed after development (when the polymer is a polyimide precursor) , An amine that decomposes or volatilizes in the imidization process). Specifically, the temperature (50% weight reduction temperature) when the amine is heated and 50% weight is reduced from the initial weight is preferably 400 ° C. or less.

  Since typical emission wavelengths of a high-pressure mercury lamp, which is a general exposure light source, are 436 nm, 405 nm, and 365 nm, in the photosensitive resin composition of the present invention, the salt of the carboxylic acid and the amine is 436 nm or 405 nm. And it is preferable to have absorption in at least one wavelength among electromagnetic waves having a wavelength of 365 nm. Furthermore, in the photosensitive resin composition of this invention, it is preferable that the said salt of carboxylic acid and amine has absorption of the electromagnetic waves with a wavelength of 400 nm or more. Since the polymer precursor used in the present invention often has absorption in a wavelength region of less than 400 nm, when it has absorption of electromagnetic waves having a wavelength of 400 nm or more, absorption of the polymer precursor and the photobase generator. This is because the sensitivity can be improved without overlapping the wavelengths. From the viewpoint of using a typical emission wavelength of a high-pressure mercury lamp which is a general exposure light source, among others, the salt of carboxylic acid and amine has absorption at at least one of electromagnetic waves having wavelengths of 436 nm and 405 nm. It is preferable.

  On the other hand, the polymer precursor used in the photosensitive resin composition of the present invention is a substance that itself is a polymer and finally becomes a polymer that exhibits desired physical properties by an intramolecular reaction such as an intramolecular ring closure reaction. Preferably, it means a unit that forms a repeating unit having a cyclic structure with elimination of a water molecule and / or an alcohol molecule in the intramolecular ring-closing reaction.

The polymer precursor used in the present invention is preferably soluble in any solvent (organic solvent or aqueous solution). If it is soluble in a solvent (an organic solvent or an aqueous solution), by changing the solubility of the polymer precursor in the solvent, using the soluble solvent as a developer, an organic solvent, It is possible to develop with a basic aqueous solution, an acidic aqueous solution, or a neutral aqueous solution.
Here, the term “soluble in a solvent” specifically means that the dissolution rate of the coating film formed on the substrate at 25 ° C. in the solvent is 100 Å / sec or more. The dissolution rate is more preferably 1000 kg / sec or more.
For example, what is soluble in a basic aqueous solution is specifically that the dissolution rate of a coating film formed on a substrate in a 0.1 wt% tetramethylammonium hydroxide (TMAH) aqueous solution at 25 ° C. It is more than sec. The dissolution rate is more preferably 1000 kg / sec or more. Furthermore, the dissolution rate with respect to a 2.38 wt% tetramethylammonium hydroxide aqueous solution, which is a more commonly used developer, is preferably 100 kg / sec or more, and more preferably 1000 kg / sec or more. . When the dissolution rate according to the above definition is less than 100 Å / sec, the development time is delayed, workability and productivity are deteriorated, and it is difficult to obtain a solubility contrast between the exposed and unexposed areas.
Accordingly, the dissolution rate of the photosensitive resin composition of the present invention in a solvent is preferably 100 Å / sec or more, more preferably 1000 Å / sec or more, at 25 ° C. preferable.

  As a specific procedure for measuring the dissolution rate, a polymer precursor coating film formed on a substrate such as alkali-free glass was heated to 25 ° C. and stirred with a developer (0.1 wt% The film thickness measured after being immersed in a TMAH aqueous solution or a basic aqueous solution such as a 2.38 wt% TMAH aqueous solution, an organic solvent, etc., rinsed with distilled water and dried, and the initial film thickness The difference is defined as the amount of film reduction, and the amount of film reduction divided by the time of immersion in the developer is the dissolution rate per unit time at 25 ° C.

In addition, when a photosensitive resin composition is actually used in a predetermined photosensitive pattern formation process in order to obtain sufficient solubility contrast between the exposed area and the unexposed area, pattern exposure and, if necessary, The ratio of the solubility of the unexposed part and the exposed part in the developing solution before the developing process, obtained by performing a post-process (usually a heating process) (dissolution rate per unit time in the developing solution of the unexposed part / exposed part) The dissolution rate per unit time in the developer is preferably 10 or more.
The dissolution rate per unit time is determined in the same manner as in the above method. After the pattern exposure is performed on the coating film of the photosensitive resin composition and the heating after the exposure is performed, the dissolution rate of the exposed area and the unexposed area is determined. For each.

In the present invention, a polymer precursor whose reaction to the final product is promoted by the action of a basic substance is typically used. Here, the mode in which the reaction of the polymer precursor to the final product is promoted by the action of the basic substance is only the mode in which the polymer precursor is changed to the final product only by the action of the basic substance. In addition, an embodiment is included in which the reaction temperature of the polymer precursor to the final product is lowered by the action of the basic substance as compared with the case where there is no action of the basic substance.
If there is a reaction temperature difference due to the presence or absence of such a basic substance, an appropriate temperature at which only the polymer precursor coexisting with the basic substance reacts to the final product using the reaction temperature difference. By heating at, only the polymer precursor coexisting with the basic substance reacts with the final product and the solubility in the solvent changes. Therefore, the solubility of the polymer precursor in a certain solvent can be changed depending on the presence or absence of the basic substance, and thus patterning by development using the solvent as a developing solution becomes possible. Therefore, the polymer precursor used in the present invention is a polymer precursor whose reaction to the final product is promoted by the action of a basic substance, and whose solubility is lowered by heating compared to before heating. Are preferably used.

As the polyimide precursor and polybenzoxazole precursor, any polyimide precursor or polybenzoxazole precursor can be used because of its mechanism, and a mixture of two or more separately synthesized polymer precursors. But it ’s okay.
Here, a polyamic acid represented by the formula (5) is suitably used as the polyimide precursor, and a polyamide alcohol as described later is suitably used as the polybenzoxazole precursor.

（式（５）中、Ｒ^１３は４価の有機基である。Ｒ^１４は２価の有機基である。）
なお、Ｒ^１３の４価は酸と結合するための価数のみを示しているが、他に更なる置換基を有していても良い。同様に、Ｒ^１４の２価はアミンと結合するための価数のみを示しているが、他に更なる置換基を有していても良い。
ポリアミック酸は、酸２無水物とジアミンを溶液中で混合するのみで得られるので、１段階の反応で合成することができ、合成が容易で低コストで入手できるので好ましい。

(In Formula (5), R ¹³ is a tetravalent organic group. R ¹⁴ is a divalent organic group.)
Incidentally, tetravalent R ¹³ represents only valence for bonding with the acid, but may have further substituents other. Similarly, although the divalent value of R ¹⁴ indicates only the valence for bonding with the amine, it may have other substituents.
Since polyamic acid can be obtained only by mixing acid dianhydride and diamine in a solution, it can be synthesized by a one-step reaction, is easy to synthesize and can be obtained at low cost, and is preferable.

  In the case of using a polymer precursor whose thermal curing temperature is lowered by the catalytic action of a base, such as a polyimide precursor or a polybenzoxazole precursor, first, such a polymer precursor and the above formula (1) An electromagnetic wave is irradiated to the part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the salt of carboxylic acid and amine represented by these. Then, a basic substance is generated in the irradiated portion, and the thermosetting temperature of that portion is selectively lowered. Next, while the irradiated portion is thermally cured, the non-irradiated portion is heated at a processing temperature that is not thermally cured, and only the irradiated portion is cured. Next, a non-irradiated portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired two-dimensional resin pattern (general plane pattern) or three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

In the present invention, the salt of carboxylic acid and amine represented by the above formula (1) functions as a highly sensitive photobase generator, and the electromagnetic wave irradiation site on the coating film or molded body of the photosensitive resin composition. Therefore, even if a basic aqueous solution is used instead of an organic solvent, excellent developability can be obtained.
As a secondary effect, when the polymer precursor to be used is a polyamic acid, it is sufficient even if the temperature required for imidization is low due to the catalytic effect of the basic substance. It can be lowered to 250 ° C. or lower. In order to imidize the conventional polyamic acid, the final cure temperature had to be 300 ° C. or higher, so the use was limited. However, it became possible to lower the final cure temperature, so a wider range Applicable to usage.

In addition, regarding the polyimide precursor, for applications where the heat resistance and dimensional stability of the finally obtained polyimide are severe, the part derived from acid dianhydride has an aromatic structure, and the part derived from diamine Is preferably a wholly aromatic polyimide precursor containing an aromatic structure. Therefore, the structure derived from the diamine component is also preferably a structure derived from an aromatic diamine.
Here, the wholly aromatic polyimide precursor is a polyimide precursor obtained by copolymerization of an aromatic acid component and an aromatic amine component, or polymerization of an aromatic acid / amino component, and a derivative thereof. The aromatic acid component is a compound in which all four acid groups forming the polyimide skeleton are substituted on the aromatic ring, and the aromatic amine component is the two amino groups forming the polyimide skeleton. Both are compounds substituted on the aromatic ring, and the aromatic acid / amino component is a compound in which both the acid group and amino group forming the polyimide skeleton are substituted on the aromatic ring. However, as is clear from the specific examples of raw materials described later, it is not necessary for all acid groups or amino groups to be present on the same aromatic ring.

  As a method for producing the polyimide precursor of the present invention, a conventionally known method can be applied. For example, (1) A method of synthesizing a polyamic acid as a precursor from an acid dianhydride and a diamine. (2) A polyimide precursor is synthesized by reacting a carboxylic acid such as an ester acid or an amic acid monomer with a monohydric alcohol, an amino compound, or an epoxy compound synthesized with an acid dianhydride. However, the method is not limited to this.

  Examples of the acid dianhydride applicable to the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane tetracarboxylic dianhydride. , Aliphatic tetracarboxylic dianhydrides such as cyclopentanetetracarboxylic dianhydride; pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′ , 3,3′-benzophenone tetracarboxylic dianhydride, 2,3 ′, 3,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,3 ′, 3,4′-biphenyltetracarboxylic dianhydride, 2,2 , 6,6'-biphenyltetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride , Bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride Bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1, 1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, , 3-bis [( , 4-Dicarboxy) benzoyl] benzene dianhydride, 1,4-bis [(3,4-dicarboxy) benzoyl] benzene dianhydride, 2,2-bis {4- [4- (1,2- Dicarboxy) phenoxy] phenyl} propane dianhydride,

2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} propane dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride Bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, 4,4′-bis [4- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, 4,4′-bis [3- (1,2-dicarboxy) phenoxy] biphenyl dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis { 4- [3- (1,2-dicarboxy) phenoxy] phenyl} ketone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfone dianhydride, bis {4- [3- (1,2-dicarbo Cis) phenoxy] phenyl} sulfone dianhydride, bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} sulfide dianhydride, bis {4- [3- (1,2-dicarboxy) Phenoxy] phenyl} sulfide dianhydride, 2,2-bis {4- [4- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,3,6 , 7-naphthalenetetracarboxylic dianhydride, 1,1,1,3,3,3-hexafluoro-2,2-bis (2,3- or 3,4-dicarboxyphenyl) propane dianhydride, 1,4,5,8-naphthalenetetraca Boronic acid dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic Acid dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,7,8-phenanthrenetetracarboxylic dianhydride, pyridinetetracarboxylic dianhydride, sulfonyldiphthalic anhydride , Aromatic tetra such as m-terphenyl-3,3 ', 4,4'-tetracarboxylic dianhydride, p-terphenyl-3,3', 4,4'-tetracarboxylic dianhydride Examples thereof include carboxylic dianhydrides. These may be used alone or in combination of two or more. And as a particularly preferred tetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetra Carboxylic dianhydride, 2,2 ′, 6,6′-biphenyltetracarboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 2,2-bis (3,4-di Carboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride.

  When acid dianhydride into which fluorine is introduced or acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the physical properties such as solubility and thermal expansion coefficient are adjusted without significantly impairing transparency. It is possible. Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. If used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small, but it tends to inhibit the improvement of transparency, so it may be used in combination while paying attention to the copolymerization ratio.

  On the other hand, the amine component can also be used alone or in combination of two or more diamines. The diamine component used is not limited, but p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diamino. Diphenyl ether, 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl sulfide, 3,3′-diaminodiphenyl sulfone, 3,4′-diaminodiphenyl sulfone, 4,4 '-Diaminodiphenylsulfone, 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4' -Diaminodiph Nylmethane, 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2,2 -Di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1,1,3,3,3-hexa Fluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 1,1-di (3-aminophenyl) -1 -Phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane, 1,3-bis ( 3-Aminophenoxy) benzene, 1,3 Bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (3-aminobenzoyl) benzene, 1, 3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene, 1,3-bis (3-amino-α, α -Dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,4-bis ( 4-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dito Trifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 2 , 6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) pyridine, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-amino) Phenoxy) biphenyl, bis [4- (3-aminophenoxy) phenyl] ketone, bis [4- (4-aminophenoxy) phenyl] ketone, bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide,

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzen) ) Phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4 , 4′-Dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) -3,3 Like 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane Aromatic amines;

  1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω -Bis (3-aminobutyl) polydimethylsiloxane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl] ether, bis [ 2- (2-aminoethoxy) ethyl] ether, bis [2- (3-aminoprotoxy) ethyl] ether, 1,2-bis (aminomethoxy) ethane, 1,2-bis (2-aminoethoxy) ethane 1,2-bis [2- (aminomethoxy) ethoxy] ethane, 1,2-bis [2- (2-aminoethoxy) ethoxy] ethane Ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12 An aliphatic amine such as diaminododecane;

1,2-diaminocyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 1,2-di (2-aminoethyl) cyclohexane, 1,3-di (2-aminoethyl) cyclohexane, 1,4 -Di (2-aminoethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,6-bis (aminomethyl) bicyclo [2.2.1] heptane, 2,5-bis (aminomethyl) bicyclo [2.2.1] Alicyclic diamines such as heptane. Examples of guanamines include acetoguanamine, benzoguanamine, and the like, and some or all of the hydrogen atoms on the aromatic ring of the diamine are fluoro group, methyl group, methoxy group, trifluoromethyl group, or trifluoromethoxy group. Diamines substituted with substituents selected from the group can also be used.
Furthermore, depending on the purpose, any one or two or more of the ethynyl group, benzocyclobuten-4′-yl group, vinyl group, allyl group, cyano group, isocyanate group, and isopropenyl group serving as a crosslinking point, Even if it introduce | transduces into some or all of the hydrogen atoms on the aromatic ring of diamine as a substituent, it can be used.

The diamine can be selected depending on the desired physical properties. If a rigid diamine such as p-phenylenediamine is used, the finally obtained polyimide has a low expansion coefficient. Rigid diamines include p-phenylenediamine, m-phenylenediamine, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2, 6 as diamines in which two amino groups are bonded to the same aromatic ring. -Diaminonaphthalene, 2,7-diaminonaphthalene, 1,4-diaminoanthracene and the like can be mentioned.
In addition, diamines in which two or more aromatic rings are bonded by a single bond, and two or more amino groups are each bonded directly or as part of a substituent on a separate aromatic ring, for example, There exists what is represented by following formula (6). Specific examples include benzidine and the like.

(A is a natural number of 1 or more, and the amino group is bonded to the meta position or the para position with respect to the bond between the benzene rings.)

Furthermore, in the above formula (6), a diamine having a substituent at a position where the amino group on the benzene ring is not substituted and which does not participate in the bond with another benzene ring can also be used. These substituents are monovalent organic groups, but they may be bonded to each other.
Specific examples include 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-ditrifluoromethyl-4,4′-diaminobiphenyl, 3,3′-dichloro-4,4′-diamino. Biphenyl, 3,3′-dimethoxy-4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl and the like can be mentioned.
When the finally obtained polyimide is used as an optical waveguide or an optical circuit component, the transmittance for electromagnetic waves having a wavelength of 1 μm or more can be improved by introducing fluorine as a substituent of the aromatic ring.

On the other hand, when a diamine having a siloxane skeleton such as 1,3-bis (3-aminopropyl) tetramethyldisiloxane is used as the diamine, the elastic modulus of the finally obtained polyimide is lowered and the glass transition temperature is lowered. be able to.
Here, the selected diamine is preferably an aromatic diamine from the viewpoint of heat resistance. However, depending on the desired physical properties, the diamine may be an aliphatic diamine or siloxane within a range not exceeding 60 mol%, preferably not exceeding 40 mol%. Non-aromatic diamines such as diamines may be used.

On the other hand, in order to synthesize a polyimide precursor, for example, while cooling a solution in which 4,4′-diaminodiphenyl ether as an amine component is dissolved in an organic polar solvent such as N-methylpyrrolidone, 3 ′, 4,4′-biphenyltetracarboxylic dianhydride is gradually added and stirred to obtain a polyimide precursor solution.
The polyimide precursor synthesized in this way has a copolymerization ratio of the aromatic acid component and / or aromatic amine component as large as possible when the final polyimide obtained is required to have heat resistance and dimensional stability. Is preferred. Specifically, the proportion of the aromatic acid component in the acid component constituting the repeating unit of the imide structure is preferably 50 mol% or more, particularly preferably 70 mol% or more, and the amine component constituting the repeating unit of the imide structure The proportion of the aromatic amine component in the total is preferably 40 mol% or more, particularly preferably 60 mol% or more, and particularly preferably a wholly aromatic polyimide.

  As the polyamide alcohol which is a polybenzoxazole precursor used in the present invention, a compound represented by the general formula (7) is preferably used, and the compound is obtained by combining a dicarboxylic acid derivative such as a dicarboxylic acid halide and dihydroxydiamine with an organic solvent. It can be obtained by addition reaction.

（式（７）中、Ｒ^１５は２価の有機基である。Ｒ^１６は４価の有機基である。）
なお、Ｒ^１５の２価は酸と結合するための価数のみを示しているが、他に更なる置換基を有していても良い。同様に、Ｒ^１６の４価はアミン及びヒドロキシル基と結合するための価数のみを示しているが、他に更なる置換基を有していても良い。

(In formula (7), R ¹⁵ is a divalent organic group. R ¹⁶ is a tetravalent organic group.)
In addition, although the divalent value of R ¹⁵ indicates only the valence for bonding with an acid, it may have another substituent. Similarly, the tetravalent value of R ¹⁶ indicates only the valency for bonding with an amine and a hydroxyl group, but may have other substituents.

Examples of the dicarboxylic acid and derivatives thereof used as necessary include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-benzophenone dicarboxylic acid, 3,4′-benzophenone dicarboxylic acid, 3,3′- Benzophenone dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 3,4′-biphenyl dicarboxylic acid, 3,3′-biphenyl dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 3,4′-diphenyl ether dicarboxylic acid, 3 , 3′-diphenyl ether dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, 3,4′-diphenylsulfone dicarboxylic acid, 3,3′-diphenylsulfone dicarboxylic acid, 4,4′-hexafluoroisopropylidene dibenzoic acid ,
4,4′-dicarboxydiphenylamide, 1,4-phenylenediethanic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,2-trifluoroethane, bis (4-carboxy Phenyl) tetraphenyldisiloxane, bis (4-carboxyphenyl) tetramethyldisiloxane, bis (4-carboxyphenyl) sulfone, bis (4-carboxyphenyl) methane, 5-t-butylisophthalic acid, 5-bromoisophthalic acid 5-fluoroisophthalic acid, 5-chloroisophthalic acid, 2,2-bis- (p-carboxyphenyl) propane, 4,4 ′-(p-phenylenedioxy) dibenzoic acid, 2,6-naphthalenedicarboxylic acid Or an active ester thereof with these acid halides and hydroxybenzotriazole It can be exemplified, but the invention is not limited thereto. These may be used alone or in combination of two or more.

  Specific examples of hydroxydiamine include, for example, 3,3′-dihydroxybenzidine, 3,3′-diamino-4,4′-dihydroxybiphenyl, 4,4′-diamino-3,3′-dihydroxybiphenyl, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone, bis- (3-amino-4-hydroxyphenyl) methane, 2,2- Bis- (3-amino-4-hydroxyphenyl) propane, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2,2-bis- (4-amino-3-hydroxyphenyl) Hexafluoropropane, bis- (4-amino-3-hydroxyphenyl) methane, 2,2-bis- (4-amino-3) Hydroxyphenyl) propane, 4,4′-diamino-3,3′-dihydroxybenzophenone, 3,3′-diamino-4,4′-dihydroxybenzophenone, 4,4′-diamino-3,3′-dihydroxydiphenyl ether, 3,3′-diamino-4,4′-dihydroxydiphenyl ether, 1,4-diamino-2,5-dihydroxybenzene, 1,3-diamino-2,4-dihydroxybenzene, 3-diamino-4,6-dihydroxy Examples include, but are not limited to, benzene. These may be used alone or in combination of two or more.

Polymer precursors such as polyimide precursors and polybenzoxazole precursors have a film thickness of 1 μm in order to increase the sensitivity of the photosensitive resin composition and obtain a pattern shape that accurately reproduces the mask pattern. Furthermore, it is preferable that the transmittance is at least 5% or more with respect to the exposure wavelength, and it is more preferable that the transmittance is 15% or more.
The high transmittance of polymer precursors such as polyimide precursors and polybenzoxazole precursors with respect to the exposure wavelength means that there is less light loss, and a highly sensitive photosensitive resin composition can be used. Obtainable.
In addition, when exposure is performed using a high-pressure mercury lamp, which is a general exposure light source, a transmittance with respect to an electromagnetic wave having a wavelength of at least 436 nm, 405 nm, and 365 nm is formed on a film having a thickness of 1 μm. Is preferably 5% or more, more preferably 15%, and still more preferably 50% or more.
In the case of exposure with a KrF laser having a wavelength of 248 nm, the transmittance at 248 nm is preferably 5% or more, more preferably 15%, more preferably 50% or more when formed on a film having a thickness of 1 μm. .

The weight average molecular weight of a polymer precursor such as a polyimide precursor is preferably in the range of 3,000 to 1,000,000, and in the range of 5,000 to 500,000, depending on the application. More preferably, it is more preferably in the range of 10,000 to 500,000. When the weight average molecular weight is less than 3,000, it is difficult to obtain sufficient strength when a coating film or film is used. In addition, the strength of the film is reduced when heat treatment or the like is performed to obtain a polymer such as polyimide. On the other hand, when the weight average molecular weight exceeds 1,000,000, the viscosity increases and the solubility decreases, so that it is difficult to obtain a coating film or film having a smooth surface and a uniform film thickness.
The molecular weight used here is a value in terms of polystyrene measured by gel permeation chromatography (GPC), which may be the molecular weight of a polymer precursor itself such as a polyimide precursor, or chemical imidization with acetic anhydride or the like. It may be after processing.

  In addition, the solvent at the time of the polyimide precursor or polybenzoxazole precursor synthesis is preferably a polar solvent, and representative examples include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylformamide. , N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethylsulfoxide, hexamethylphosphoamide, pyridine, dimethylsulfone, tetramethylenesulfone, dimethyltetra Examples include methylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone, and these solvents are used alone or in combination of two or more. In addition to these, non-polar solvents such as benzene, benzonitrile, 1,4-dioxane, tetrahydrofuran, butyrolactone, xylene, toluene, cyclohexanone, and the like can be used as a solvent. It is used as a reaction regulator, a volatilization regulator of a solvent from the product, a film smoothing agent, and the like.

The photosensitive resin composition according to the present invention may be a simple mixture of a carboxylic acid and amine salt represented by the above formula (1), a polymer precursor, and a solvent. A photosensitive resin composition may be prepared by blending a sensitizer, a light or thermosetting component, a non-polymerizable binder resin other than the polymer precursor, and other components.
Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the photosensitive resin composition. Moreover, when using polyamic acid as a precursor, you may use the solution obtained by the synthesis reaction of polyamic acid as it is, and may mix other components there as needed.

In the case where sufficient sensitivity cannot be obtained because the absorption wavelength of the salt of the carboxylic acid and amine represented by the above formula (1) overlaps with the absorption wavelength of the polymer precursor, addition of a sensitizer as a means for improving sensitivity May be effective. Further, even when the salt of carboxylic acid and amine represented by the above formula (1) has an absorption wavelength in the wavelength band of electromagnetic waves that pass through the polymer precursor, a sensitizer is added as a means for improving sensitivity. be able to. However, it is necessary to take into consideration the film physical properties of the resulting pattern, particularly the decrease in film strength and heat resistance, accompanying the decrease in the content of the polymer precursor due to the addition of the sensitizer.
Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, cyanine and derivatives thereof, merocyanine and derivatives thereof, coumarins and derivatives thereof, ketocoumarins and derivatives thereof, and ketobiscoumarins. And derivatives thereof, cyclopentanone and derivatives thereof, cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, quinoline derivatives and derivatives thereof, styrylquinoline derivatives and derivatives thereof, thioxanthene derivatives, xanthene derivatives and Derivatives, oxonol-based and derivatives thereof, rhodamine-based and derivatives thereof, pyrylium salts and derivatives thereof.

Specific examples of cyanine, merocyanine and derivatives thereof include 3,3′-dicarboxyethyl-2,2′thiocyanine bromide, 1-carboxymethyl-1′-carboxyethyl-2,2′-quinocyanine bromide, 1,3′-diethyl-2,2′-quinothiocyanine iodide, 3-ethyl-5-[(3-ethyl-2 (3H) -benzothiazolidene) ethylidene] -2-thioxo-4- And oxazolidine.
Specific examples of coumarin, ketocoumarin and derivatives thereof include 3- (2′-benzimidazole) -7-diethylaminocoumarin, 3,3′-carbonylbis (7-diethylaminocoumarin), and 3,3′-carbonylbiscoumarin. 3,3′-carbonylbis (5,7-dimethoxycoumarin), 3,3′-carbonylbis (7-acetoxycoumarin) and the like.
Specific examples of thioxanthone and derivatives thereof include diethyl thioxanthone and isopropyl thioxanthone.

Other examples include benzophenone, acetophenone, anthrone, p, p'-tetramethyldiaminobenzophenone (Michler ketone), phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, N-acetyl-p-nitroaniline, p-nitro. Aniline, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, N-acetyl-4-nitro-1-naphthylamine, picramide, 1,2-benzanthraquinone, 3-methyl-1,3-diaza-1,9- Benzanthrone, p, p'-tetraethyldiaminobenzophenone, 2-chloro-4-nitroaniline, dibenzalacetone, 1,2-naphthoquinone, 2,5-bis- (4'-diethylaminobenzal) -cyclopentane, 2,6-bis- (4′-diethyla Minobenzal) -cyclohexanone, 2,6-bis- (4′-dimethylaminobenzal) -4-methyl-cyclohexanone, 2,6-bis- (4′-diethylaminobenzal) -4-methyl-cyclohexanone, 4, 4'-bis- (dimethylamino) -chalcone, 4,4'-bis- (diethylamino) -chalcone, p-dimethylaminobenzylideneindanone, 1,3-bis- (4'-dimethylaminobenzal) -acetone 1,3-bis- (4′-diethylaminobenzal) -acetone, N-phenyl-diethanolamine, Np-tolyl-diethylamine, and the like.
In the present invention, one or more of these sensitizers can be used.

Examples of the solvent used in the composition include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether, ethylene glycol Glycol monoethers (so-called cellosolves) such as monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; ethyl acetate, acetic acid Chill, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, Esters such as dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, Halogenated hydrocarbons such as 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; N, N- Amides such as methylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide; Pyrrolidones such as N-methylpyrrolidone; Lactones such as γ-butyrolactone; Sulfoxides such as dimethylsulfoxide And other organic polar solvents, and aromatic hydrocarbons such as benzene, toluene, and xylene, and other organic nonpolar solvents. These solvents are used alone or in combination.
Among them, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide, dimethyl sulfoxide, hexa Polar solvents such as methylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl-γ-butyrolactone It is mentioned as a suitable thing.

  As the photocurable component, a compound having one or more ethylenically unsaturated bonds can be used. For example, an amide monomer, a (meth) acrylate monomer, a urethane (meth) acrylate oligomer, a polyester (meth) Aromatic vinyl compounds such as acrylate oligomers, epoxy (meth) acrylates, hydroxyl group-containing (meth) acrylates, and styrene can be exemplified. In addition, when the polyimide precursor has a carboxylic acid component such as polyamic acid in the structure, the use of an ethylenically unsaturated bond-containing compound having a tertiary amino group causes the carboxylic acid of the polyimide precursor to have an ionic bond. When the photosensitive resin composition is formed, the contrast of the dissolution rate of the exposed area and the unexposed area is increased.

  When using a photocurable compound having such an ethylenically unsaturated bond, a photoradical generator may be further added. Examples of the photo radical generator include benzoin such as benzoin, benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether and alkyl ethers thereof; acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2 Acetophenones such as phenylacetophenone, 1,1-dichloroacetophenone, 1-hydroxyacetophenone, 1-hydroxycyclohexyl phenyl ketone and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-1-one Anthraquinones such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-tertiary-butylanthraquinone, 1-chloroanthraquinone and 2-amylanthraquinone; 2,4-dimethyl Thioxanthone such as luthioxanthone, 2,4-diethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylthioxanthone; ketals such as acetophenone dimethyl ketal and benzyldimethyl ketal; 2,4,6-trimethylbenzoyldiphenylphosphine oxide Monoacylphosphine oxides or bisacylphosphine oxides; benzophenones such as benzophenone; and xanthones.

  In order to impart processing characteristics and various functionalities to the resin composition according to the present invention, various organic or inorganic low-molecular or high-molecular compounds may be blended. For example, dyes, surfactants, leveling agents, plasticizers, fine particles and the like can be used. The fine particles include organic fine particles such as polystyrene and polytetrafluoroethylene, inorganic fine particles such as colloidal silica, carbon, and layered silicate, and these may have a porous or hollow structure. The function or form includes pigments, fillers, fibers, and the like.

In the photosensitive resin composition according to the present invention, the polymer precursor (solid content) is based on the entire solid content of the photosensitive resin composition from the viewpoint of film physical properties of the pattern to be obtained, particularly film strength and heat resistance. 30% by weight or more, preferably 50% by weight or more. The salt of the carboxylic acid and amine represented by the formula (1) is usually 0.01 to 50 parts by weight with respect to 100 parts by weight of the solid content of the polymer precursor contained in the photosensitive resin composition. The content is preferably within the range of 0.1 to 30 parts by weight. If it is less than 0.01 part by weight, the effect of promoting cyclization reaction tends to be insufficient, and if it exceeds 50 parts by weight, it becomes difficult to satisfy various physical properties required for the finally obtained resin cured product.
Moreover, it is preferable that the compounding quantity of the said sensitizer shall be less than 50 weight part with respect to 100 weight part of solid content of a polymer precursor, and it is more preferable to set it as less than 30 weight part. In addition, in order to prevent deterioration of various physical properties required for the finally obtained resin cured product, the total of the salt of the carboxylic acid and amine represented by the formula (1) and the sensitizer is 100 parts by weight of the polyimide precursor. 50 parts by weight or less is desirable.
Moreover, the mixture ratio of other arbitrary components has the preferable range of 0.1 to 95 weight% with respect to the whole solid content of the photosensitive resin composition. When the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when it exceeds 95% by weight, the properties of the finally obtained resin cured product are not easily reflected in the final product. In addition, solid content of the photosensitive resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

  The photosensitive resin composition according to the present invention can be used in various coating processes and molding processes to produce films and molded articles having a three-dimensional shape.

The polyimides and polybenzoxazoles obtained from the photosensitive resin composition of the present invention are good because the original properties such as heat resistance, dimensional stability and insulation are not impaired.
For example, the 5% weight loss temperature measured in nitrogen of polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably 250 ° C. or higher, more preferably 300 ° C. or higher. In particular, when used in applications such as electronic parts that pass through the solder reflow process, if the 5% weight loss temperature is 300 ° C. or less, defects such as bubbles occur due to the decomposition gas generated in the solder reflow process. There is a fear.
Here, the 5% weight reduction temperature is the time when the weight of the sample is reduced by 5% from the initial weight when the weight loss is measured using a thermogravimetric analyzer (in other words, the sample weight becomes 95% of the initial weight). Temperature). Similarly, the 10% weight reduction temperature is a temperature at which the sample weight is reduced by 10% from the initial weight.

The glass transition temperature of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention is preferably as high as possible from the viewpoint of heat resistance, but in applications where a thermoforming process is considered like an optical waveguide, It is preferable to show a glass transition temperature of about 120 ° C. to 450 ° C., and it is more preferable to show a glass transition temperature of about 200 ° C. to 400 ° C. Here, the glass transition temperature in the present invention is tan δ (tan δ = loss elastic modulus (tan δ) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the photosensitive resin composition can be formed into a film shape. It is obtained from the peak temperature of E ″) / storage elastic modulus (E ′)). The dynamic viscoelasticity measurement can be performed, for example, with a viscoelasticity measuring apparatus Solid Analyzer RSA II (manufactured by Rheometric Scientific) at a frequency of 3 Hz and a temperature rising rate of 5 ° C./min. When the polyimide and polybenzoxazole obtained from the photosensitive resin composition cannot be formed into a film shape, the temperature is determined based on the inflection point of the baseline of the differential thermal analyzer (DSC).
From the viewpoint of the dimensional stability of the polyimide and polybenzoxazole obtained from the photosensitive resin composition of the present invention, the linear thermal expansion coefficient is preferably 60 ppm or less, and more preferably 40 ppm or less. In the case of forming a film on a silicon wafer in a manufacturing process of a semiconductor element or the like, 20 ppm or less is more preferable from the viewpoint of adhesion and warpage of the substrate. Here, the linear thermal expansion coefficient in this invention can be calculated | required with the thermomechanical analyzer (TMA) of the film of the polyimide and polybenzoxazole obtained from the photosensitive resin composition obtained by this invention. Using a thermomechanical analyzer (for example, Thermo Plus TMA8310 (manufactured by Rigaku Corporation), the heating rate is 10 ° C./min, and the tensile load is 1 g / 25,000 μm ² so that the weight per cross-sectional area of the evaluation sample is the same. .

As described above, the photosensitive resin composition according to the present invention can be used in various ways by the salt of carboxylic acid and amine represented by the above formula (1) functioning as a highly sensitive photobase generator. Various polymer precursors can be applied, and the structure of the finally obtained polymer can be selected from a wide range.
In addition, according to the present invention, a photosensitive resin composition can be obtained by a simple method of simply mixing a salt of a carboxylic acid represented by the above formula (1) and an amine with a polymer precursor. Excellent cost performance.
Furthermore, due to the catalytic effect of the amine generated by the irradiation of electromagnetic waves, the processing temperature required for the reaction to the final product such as imidization can be reduced. Is possible.

  The photosensitive resin composition according to the present invention is a known resin material such as printing ink, adhesive, filler, electronic material, optical circuit component, molding material, resist material, building material, three-dimensional modeling, and optical member. Can be used in all fields and products.

  The photosensitive resin composition according to the present invention is used in a wide range of fields and products in which properties such as heat resistance, dimensional stability, and insulation are effective, such as paints or printing inks, color filters, and films for flexible displays. It is preferably used as a material for forming semiconductor devices, electronic parts, interlayer insulating films, wiring coating films, optical circuits, optical circuit parts, antireflection films, holograms, optical members, or building materials. Specific examples include buffer coating films for semiconductor devices, interlayer insulating films of multilayer wiring boards, and the like. Printed matter, color filter, flexible display film, semiconductor device, electronic component, interlayer insulating film, wiring coating film, optical circuit, at least part of which is formed of the photosensitive resin composition according to the present invention or its thermoset Articles of any of optical circuit components, antireflection films, holograms, optical members or building materials are provided.

  In particular, a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is mainly used as a pattern forming material (resist), and the pattern formed thereby is a permanent film made of polyimide or polybenzoxazole. Functions as a component that imparts heat resistance and insulation as, for example, color filters, flexible display films, electronic components, semiconductor devices, interlayer insulating films, wiring coating films, optical circuits, optical circuit components, antireflection films, It is suitable for forming other optical members or electronic members.

Next, the negative pattern forming method according to the present invention irradiates the surface of the coating film or molded body made of the photosensitive resin composition according to the present invention with electromagnetic waves in a predetermined pattern, and heat treatment as necessary. Or the like, and after selectively reducing the solubility of the electromagnetic wave irradiation site of the coating film or molded article, development is performed using a solvent that reduces the solubility as a developer. .
When the photosensitive resin composition according to the present invention is applied on some support and irradiated with electromagnetic waves in a predetermined pattern, a salt of the carboxylic acid and amine represented by the above formula (1) is formed only in the exposed portion. Cleavage produces a basic substance. The basic substance acts as a catalyst that promotes the reaction of the polymer precursor in the exposed area to the final product.

  If the basic substance reacts directly with the polymer precursor in the exposed area to the final product, and only the polymer precursor in the exposed area is selectively reduced in solubility in a certain solvent, exposure will occur. It becomes possible to develop by dissolving only the unexposed part where the solubility is not lowered without using any post-treatment, using a solvent having a lowered solubility as a developer.

  The photosensitive resin composition of the present invention includes N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N, N-diethylacetamide, N, N- Dimethyl methoxyacetamide, dimethyl sulfoxide, hexamethylphosphoamide, N-acetyl-2-pyrrolidone, pyridine, dimethyl sulfone, tetramethylene sulfone, dimethyltetramethylene sulfone, diethylene glycol dimethyl ether, cyclopentanone, γ-butyrolactone, α-acetyl- After being dissolved in a polar solvent such as γ-butyrolactone, it is applied to the surface of a substrate such as a silicon wafer, a metal substrate, or a ceramic substrate by dipping, spraying, screen printing, spin coating, etc. By removing the part, the coating surface has no adhesiveness on the substrate surface Can be given. Although there is no restriction | limiting in particular in the thickness of a coating film, it is preferable that it is 0.5-50 micrometers, and it is more desirable that it is 1.0-20 micrometers from a sensitivity and a development speed surface. As drying conditions of the apply | coated coating film, 80-100 degreeC and 1 minute-20 minutes are mentioned, for example.

  This coating film is irradiated with electromagnetic waves through a mask having a predetermined pattern, and is exposed to a pattern. After heating, the unexposed portion of the film is developed and removed with an appropriate developer to obtain a desired pattern. A patterned film can be obtained.

  The exposure method and exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure, and may be a g-line stepper, an i-line stepper, a contact / proximity exposure machine using an ultra-high pressure mercury lamp, a mirror projection exposure machine, Alternatively, a projector or a radiation source that can irradiate other ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

In the negative pattern forming method according to the present invention, post-treatment such as heat treatment may be performed between the exposure step and the development step as necessary. The post-treatment here is a treatment for selectively reducing the solubility of an electromagnetic wave irradiation site of the coating film or molded body in a certain solvent.
The post-treatment such as heat treatment is, for example, a treatment in which only the polymer precursor in the exposed portion coexisting with the basic substance is reacted with the final product. Therefore, when performing the heat treatment, for example, it is performed at a temperature at which the cyclization rate of the polymer precursor is different between the exposed portion where the basic substance is present and the unexposed portion where the basic substance is not present. Is preferred.

For example, when imidizing a polyimide precursor, the preferable temperature range of the heat processing at this stage is usually about 60 ° C to 200 ° C. When the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to create a difference in the imidization ratio between the exposed and unexposed areas under realistic process conditions. On the other hand, if the heat treatment temperature is 200 ° C. or higher, a neutral compound that generates a basic substance is thermally decomposed by an intramolecular cleavage reaction accompanying absorption of electromagnetic waves, or even in an unexposed area where no amine exists. Due to the progress of imidization, a difference in solubility between the exposed portion and the unexposed portion is difficult to occur.
Specifically, for example, heating is performed at 120 to 200 ° C. for 1 minute to 20 minutes.
This heat treatment may be any method as long as it is a publicly known method, and specific examples thereof include air, a circulation oven in a nitrogen atmosphere, heating with a hot plate, and the like, but are not particularly limited.

The developer used in the development step is not particularly limited and can be appropriately selected according to the polymer precursor to be used, such as a basic aqueous solution or an organic solvent.
The basic aqueous solution is not particularly limited. For example, in addition to an aqueous solution of tetramethylammonium hydroxide (TMAH) having a concentration of 0.01% by weight to 10% by weight, preferably 0.05% by weight to 5% by weight, diethanolamine, diethylamino Ethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl methacrylate, cyclohexylamine , Aqueous solutions of ethylenediamine, hexamethylenediamine, tetramethylammonium and the like.
The solute may be one type or two or more types, and may contain 50% or more of the total weight, more preferably 70% or more, and an organic solvent or the like as long as water is contained.
The organic solvent is not particularly limited, but polar solvents such as N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, γ-butyrolaclone, dimethylacrylamide, methanol, Add alcohols such as ethanol and isopropanol, esters such as ethyl acetate and propylene glycol monomethyl ether acetate, ketones such as cyclopentanone, cyclohexanone, isobutyl ketone, and methyl isobutyl ketone alone or in combination of two or more. May be. After development, wash with water. Also in this case, alcohols such as ethanol and isopropyl alcohol, esters such as ethyl lactate and propylene glycol monomethyl ether acetate may be added to water.
After development, if necessary, rinse with water or a poor solvent and dry at 80 to 100 ° C. to stabilize the pattern. In order to make this relief pattern heat resistant, a patterned high heat resistant resin layer is formed by heating at a temperature of 180 to 500 ° C., preferably 200 to 350 ° C. for several tens of minutes to several hours. The

(Production Example 1)
20 mL of concentrated sulfuric acid and 1.9 g (13 mmol) of thiosalicylic acid were placed in a nitrogen-substituted 100 mL eggplant flask and stirred at room temperature for 5 minutes. To this solution, 8.4 g (50 mmol) of thiophenylacetic acid was added over 30 minutes, and the mixture was stirred at room temperature for 1 hour and at 80 ° C. for 2 hours, and then allowed to stand at room temperature for 15 hours. The reaction solution was poured into 200 mL of hot water and heated under reflux for 5 minutes. The solution was cooled, and the resulting precipitate was collected by filtration and recrystallized from dioxane / water to give 2.8 g (9.4 mmol, yield 75%) of 2- (carboxymethylthio) thioxanthone as a brown solid. Obtained.

  2- (Carboxymethylthio) thioxanthone (1.0 g, 3.3 mmol) and 3-quinuclidinol (0.42 g, 3.3 mmol) are dissolved in dioxane with heating, and after cooling, the precipitate obtained by adding a poor solvent is collected by filtration. As a result, 1.2 g (2.8 mmol, yield: 85%) of 3-quinuclidinol salt of 2- (carboxymethylthio) thioxanthone was obtained.

(Production Example 2)
20 mL of concentrated sulfuric acid and 1.9 g (13 mmol) of thiosalicylic acid were placed in a nitrogen-substituted 100 mL eggplant flask and stirred at room temperature for 5 minutes. To this solution, 7.6 g (50 mmol) of phenoxyacetic acid was added over 30 minutes, and the mixture was stirred at room temperature for 1 hour and at 80 ° C. for 2 hours, and then allowed to stand at room temperature for 15 hours. The reaction solution was poured into 200 mL of hot water and heated under reflux for 5 minutes. The solution was cooled, and the resulting precipitate was collected by filtration and recrystallized from dioxane / water to give 2.6 g (9.0 mmol, yield 72%) of 2- (carboxymethoxy) thioxanthone as a brown solid. Obtained.

  0.95 g (3.3 mmol) of 2- (carboxymethoxy) thioxanthone and 0.42 g (3.3 mmol) of 3-quinuclidinol are dissolved by heating in dioxane, and after cooling, a precipitate obtained by adding a poor solvent is collected by filtration. As a result, 1.2 g (2.9 mmol, yield: 87%) of 3-quinuclidinol salt of 2- (carboxymethoxy) thioxanthone was obtained.

(Production Example 3)
In a 500 mL four-neck separable flask purged with nitrogen, 44.5 g (222 mmol) of oxydianiline and 250 mL of dehydrated N-methyl-2-pyrrolidone were placed and dissolved by stirring in an ice bath. To this solution, 48.5 g (222 mmol) of pyromellitic dianhydride was added and stirred for 2 hours in an ice bath. The reaction solution was reprecipitated with acetone, and the precipitate obtained by filtration was dried under reduced pressure at room temperature for 8 hours, whereby polyamic acid (polyimide precursor 1) was quantitatively obtained as a white solid.

Example 1
0.85 g of the polyimide precursor 1 and 0.15 g of 3-quinuclidinol salt of 2- (carboxymethylthio) thioxanthone represented by the following structural formula are dissolved in 9 g of N-methyl-2-pyrrolidone, and the photosensitivity of the present invention. A photosensitive resin composition (photosensitive resin composition 1) was obtained.

(Example 2)
0.85 g of the polyimide precursor 1 and 0.15 g of 3-quinuclidinol salt of 2- (carboxymethoxy) thioxanthone represented by the following structural formula are dissolved in 9 g of N-methyl-2-pyrrolidone, and the photosensitivity of the present invention. A resin composition (photosensitive resin composition 2) was obtained.

(Comparative Example 1)
Only 1.0 g of the polyimide precursor 1 was dissolved in 9 g of N-methyl-2-pyrrolidone to obtain a photosensitive resin composition (photosensitive resin composition 3) of a comparative example.

(Comparative Example 2)
0.95 g of the polyimide precursor 1 and 0.05 g of 3-quinuclidinol were dissolved in 9 g of N-methyl-2-pyrrolidone to obtain a photosensitive resin composition (photosensitive resin composition 4) of a comparative example.

<Test>
(1) Thermosetting temperature Using the photosensitive resin composition 3 containing no amine and the photosensitive resin composition 4 containing the amine used in the salt of the carboxylic acid and amine of the examples, the presence of amine The difference of the imidation ratio of the polyimide precursor by presence or absence was observed.
Photosensitive resin composition 3 and photosensitive resin composition 4 were each spin-coated on a chromium-plated glass plate to a final film thickness of 2 μm and dried on an 80 ° C. hot plate for 30 minutes. Then, 10J ultraviolet-visible light irradiation was performed in h line conversion with a manual exposure device (manufactured by Dainippon Screen Co., Ltd., MA-1200). The infrared spectroscopic spectrum of this coating film was measured using IR-610 manufactured by JASCO Corporation and HOTPLATE EC-1200 manufactured by ASONE Co., Ltd. while heating from room temperature at 5 ° C./min to 350 ° C.
The spectrum derived from the precursor disappeared with heating, and a peak derived from polyimide generated by heating appeared. In order to confirm the progress of imidization, when the peak area of 1663 cm ⁻¹ derived from the precursor before the measurement was taken as 1, the amount of decrease in the peak area during the heating process was plotted.
The result is as shown in FIG. In the photosensitive resin composition 4, the decrease in the precursor occurs at a lower temperature than in the photosensitive resin composition 3, and the difference in the imidization rate depending on the presence or absence of amine may be maximized at around 175 ° C. all right.

(2) Pattern formation The photosensitive resin composition 1 (Example 1) was spin-coated on a glass plate so as to have a final film thickness of 2 μm, and dried on a hot plate at 80 ° C. for 30 minutes. There, 5J ultraviolet-visible light irradiation was performed in h line conversion with a manual exposure device (Dainippon Screen Co., Ltd., MA-1200),
Then, after heating for 5 minutes on a 170 degreeC hotplate, it immersed in the solution which added 10 wt% of isopropanol to the tetramethylammonium hydroxide 2.38% solution. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, those samples were heated at 300 ° C. for 1 hour to perform imidization.
From this result, it became clear that the photosensitive resin composition of the present invention can form a good pattern.

FIG. 1 is a graph showing a relationship between a thermosetting temperature after irradiation of ultraviolet-visible light to a photosensitive resin composition and a polyimide precursor peak.

Claims (12)

A photobase generator comprising a salt of a carboxylic acid and an amine represented by the following formula (1), and a polymer precursor, the polymer precursor itself becoming a final product by the action of a basic substance A photosensitive resin composition in which the reaction is promoted.

(In the formula, X ¹ and X ² independently represent an oxygen atom or a sulfur atom. R ^{1 to} R ⁹ independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a mercapto group, a nitro group, a silyl group, a silanol group, or R ¹⁰ , R ¹¹ and R ^{12 each} represent a hydrogen atom or a monovalent organic group, provided that at least one of R ¹⁰ , R ¹¹ and R ¹² is a monovalent organic group. .)   2. The photosensitive resin composition according to claim 1, wherein the polymer precursor itself is one in which the reaction to the final product is promoted by the action of a basic substance and the solubility is changed by heating. .   The photosensitive resin composition according to claim 1 or 2, wherein the amine used in the salt of the carboxylic acid and the amine is an aliphatic amine.   The photosensitive resin composition according to any one of claims 1 to 3, wherein the salt of the carboxylic acid and the amine has absorption of an electromagnetic wave having a wavelength of 400 nm or more.   Furthermore, the photosensitive resin composition in any one of Claims 1 thru | or 4 containing a sensitizer.   The photosensitive resin composition according to claim 1, wherein the polymer precursor is a polyimide precursor.   The photosensitive resin composition according to claim 6, wherein the polyimide precursor is a polyamic acid. The photosensitive resin composition according to any one of claims 1 to 5 wherein the polymeric precursor is a polybenzoxazole precursor.   Paint or printing ink, or color filter, flexible display film, semiconductor device, electronic component, interlayer insulation film, wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material The photosensitive resin composition according to any one of claims 1 to 8, which is used as a material.   A printed material, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, at least partly formed of the photosensitive resin composition according to any one of claims 1 to 9 or a cured product thereof. Article of any of wiring coating film, optical circuit, optical circuit component, antireflection film, hologram, optical member or building material.   The surface of the coating film or molded body comprising the photosensitive resin composition according to any one of claims 1 to 9 is irradiated with electromagnetic waves in a predetermined pattern, and the electromagnetic wave irradiation site of the coating film or molded body is dissolved. A negative pattern forming method in which, after selectively reducing the property, development is performed using a solvent having a reduced solubility as a developer.   The negative pattern forming method according to claim 11, wherein after the irradiation with the electromagnetic wave, a heat treatment is performed to selectively reduce the solubility of the electromagnetic wave irradiation site of the coating film or the molded body.

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