JP5747431B2 - Photosensitive resin composition, pattern forming material comprising the photosensitive resin composition, pattern forming method, article using the photosensitive resin composition, and base generator - Google Patents

Description

  The present invention relates to a photosensitive resin composition using a base generator that generates a base by irradiation and heating of electromagnetic waves, and a base generator that can be used in such a photosensitive resin composition, and in particular, patterning by electromagnetic waves. A photosensitive resin that can be suitably used as a material of a product or member formed through a process or a curing acceleration process (for example, an electronic component, an optical product, a molding material of an optical component, a layer forming material, or an adhesive). The present invention relates to a composition, a pattern forming material comprising the photosensitive resin composition, a pattern forming method, and an article produced using the resin composition.

The photosensitive resin composition is used, for example, for electronic parts, optical products, molding materials for optical parts, layer forming materials, adhesives, and the like, and is particularly suitably used for products or members formed through a patterning process using electromagnetic waves. It is coming.
For example, polyimide, which is a polymer material, exhibits top-class performance among organic materials such as heat resistance, dimensional stability, and insulation characteristics, so it is widely applied to insulating materials for electronic components. It has been actively used as a coating film, a base material for flexible printed wiring boards, and the like.
In recent years, in order to solve the problems that polyimide has, polybenzoxazole, which has low water absorption and low dielectric constant, and polybenzimidazole with excellent adhesion to the substrate, to which processing processes similar to polyimide are applied, etc. It has been studied energetically.

  In general, polyimide is poorly soluble in a solvent and difficult to process. As a method for patterning polyimide into a desired shape, patterning is performed by exposure and development in the state of a polyimide precursor having excellent solvent solubility, and then heat treatment. For example, there is a method of obtaining a polyimide pattern by imidization by the method described above.

Various methods have been proposed as means for forming a pattern using a polyimide precursor. Two typical ones are as follows.
(1) A method of forming a pattern by providing a photosensitive resin on the polyimide precursor as a resist layer, and the polyimide precursor does not have a pattern forming capability. A method of forming a pattern by its action. Alternatively, a method in which a photosensitive component is mixed with a polyimide precursor to form a resin composition, and a pattern is formed by the action of the photosensitive component.

  As a typical patterning technique using the above (2), (i) a polyimide precursor polyamic acid acts as a dissolution inhibitor before exposure to electromagnetic waves, and after exposure, a carboxylic acid is formed to form a dissolution accelerator; The naphthoquinonediazide derivative is mixed, and pattern formation is performed by increasing the contrast of the dissolution rate of the exposed area and unexposed area to the developer, followed by imidization to obtain a polyimide pattern (Patent Document 1) (Ii) A methacryloyl group is introduced into the polyimide precursor via an ester bond or an ionic bond, a photo radical generator is added thereto, and the exposed area is crosslinked to dissolve the exposed and unexposed areas in the developer. A method to obtain a polyimide pattern by forming a pattern by increasing the speed contrast and then imidizing it Etc. have been put into practical use (Patent Document 2).

  Compared with the method (1), the method (2) does not require a resist layer and can greatly simplify the process. However, in the method (i), a naphthoquinonediazide derivative is used to increase the solubility contrast. When the amount of addition is increased, there is a problem that the original physical properties of the polyimide cannot be obtained. Further, the method (ii) has a problem that the structure of the polyimide precursor is restricted.

  As another patterning technique, (iii) a polyamic acid as a polyimide precursor is mixed with a photobase generator and heated after exposure to cause cyclization to proceed by the action of a base generated by exposure. A technique for obtaining a polyimide pattern by reducing the solubility, forming a pattern by increasing the contrast of the dissolution rate in the developing solution of the exposed part and the unexposed part, and then imidizing is reported ( Patent Document 3).

  As another example of the photosensitive resin composition using the photobase generator, there is an example using an epoxy compound (for example, Patent Document 4). By irradiating the photobase generator with light, amines are generated in the layer containing the epoxy compound, so that the amines act as an initiator or a catalyst, and the epoxy compound can be cured only in the exposed area. Pattern formation can be performed.

JP 52-13315 A JP 54-145794 A JP-A-8-227154 Japanese Patent Laid-Open No. 2003-212856

  A photosensitive resin composition using a photobase generator is a resin composition because a photosensitive polymer precursor can be obtained simply by mixing a photobase generator at a certain ratio with an existing polymer precursor. The process for manufacturing is simple. In particular, a polyimide precursor in which the structure of a precursor compound used in the past is restricted has an advantage of high versatility because it can be applied to polyimide precursors having various structures. However, since conventional photobase generators have low sensitivity, there has been a problem that the amount of electromagnetic wave irradiation increases. When the amount of electromagnetic wave irradiation increases, there is also a problem that the processing amount (throughput) per unit time decreases.

Also, for example, when combined with a polyimide precursor, a polyimide precursor that is originally highly soluble in the developer due to the mechanism that only the exposed part is imidized by the catalytic action of the base generated by exposure and that part becomes insoluble in the developer. As for the exposed area, the dissolution rate of the exposed area is also fast, and there is a limit to increasing the solubility contrast of the exposed area and the unexposed area.
The higher the solubility contrast between the exposed and unexposed areas, the higher the residual film ratio after development and the better the pattern can be obtained. It was necessary to adjust the concentration and the amount of the photobase generator, and to add a dissolution accelerator, resulting in a small process margin.

  The present invention has been made in view of the above circumstances, and its main purpose is excellent in sensitivity and a base generator that can be used regardless of the type of the polymer precursor, and excellent in sensitivity and polymer precursor. Provided is a photosensitive resin composition capable of obtaining a pattern having a good shape while maintaining a sufficient process margin, with a large solubility contrast between the exposed and unexposed areas, regardless of the type. There is to do.

  The photosensitive resin composition according to the present invention is represented by a polymer precursor whose reaction to the final product is accelerated by a basic substance or by heating in the presence of the basic substance, and represented by the following chemical formula (1): And a base generator that generates a base upon irradiation with electromagnetic waves and heating.

In chemical formula (1), R ¹ and R ² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹ and R ² may combine to form a cyclic structure. However, at least one of R ¹ and R ² is a monovalent organic group. R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, halogen or a monovalent organic group (provided that the monovalent organic group in R ³ , R ⁴ , R ⁵ and R ⁶ is saturated or A saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, or an aryl thioether group), which may be the same or different. However, at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is a hydrocarbon group, or two or more of R ³ , R ⁴ , R ⁵ and R ⁶ are bonded. To form a ring structure.

The base generator represented by the chemical formula (1) has the specific structure described above, and generates an amine that is a basic substance by irradiation with electromagnetic waves and heating.
The polymer precursor is promoted to react with the final product by the basic substance generated from the base generator or by heating in the presence of the basic substance.

  In the photosensitive resin composition according to the present invention, the base generator may be a kind of a polymer precursor applicable to have absorption at at least one of wavelengths of electromagnetic waves of 365 nm, 405 nm, or 436 nm. It is preferable from the point of increase.

  In the photosensitive resin composition according to the present invention, the polymer precursor includes a compound and polymer having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzo. One or more selected from the group consisting of oxazole precursors is preferably used.

  In the photosensitive resin composition according to the present invention, it is preferable that the polymer precursor is soluble in a basic solution because the solubility contrast between the exposed portion and the unexposed portion can be increased.

  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 having excellent physical properties such as heat resistance, dimensional stability, and insulating properties can be obtained. The polyimide precursor is preferably a polyamic acid from the viewpoint of easy availability of raw materials.

Furthermore, the second object of the present invention is to provide a pattern forming method using the photosensitive resin composition.
In the pattern forming method according to the present invention, a coating film or a molded body is formed using the photosensitive resin composition, the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern, and after irradiation or simultaneously with irradiation. It develops, after heating, reducing the solubility of the said irradiation site | part, and developing.

  In the pattern formation method, a coating film or a molded body made of a photosensitive resin composition is used by combining a polymer precursor and a compound represented by the chemical formula (1) as a base generator. A pattern for performing development can be formed without using a resist film for protecting the surface from the developer.

  The third object of the present invention is characterized in that the base is generated by irradiation with electromagnetic waves and heating, which is represented by the following chemical formula (2), which is excellent in sensitivity and has a wide range of applicable polymer precursors. Another object is to provide a base generator.

In the chemical formula (2), R ¹¹ and R ¹² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹¹ and R ¹² may combine to form a cyclic structure. However, at least one of R ¹¹ and R ¹² is a monovalent organic group. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each hydrogen, halogen or a monovalent organic group (provided that the monovalent organic group in the R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is saturated or A saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, or an aryl thioether group), which may be the same or different. However, at least one of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a hydrocarbon group, or R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a combination of two or more of them. To form a ring structure.

  The base generator represented by the chemical formula (2) has the above specific structure, and generates an amine that is a basic substance by irradiation with electromagnetic waves and heating.

  Since the base generator represented by the chemical formula (2) has more types of polymer precursors that can be applied to absorb at least one of the wavelengths of electromagnetic waves of 365 nm, 405 nm, or 436 nm. preferable.

  The base generator represented by the chemical formula (2) has an increased number of types of polymer precursors whose molar extinction coefficient can be applied to be 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at 405 nm. To preferred.

In the photosensitive resin composition of the present invention, the base generator represented by the chemical formula (1) included is conventionally used by generating a base by irradiation with electromagnetic waves and further promoting the generation of the base by heating. The photosensitive resin composition has high sensitivity compared to the photobase generator that has been used. The photosensitive resin composition of the present invention has a phenolic hydroxyl group when the base is generated in addition to the change in solubility of the polymer precursor by the base derived from the base generator by irradiation with electromagnetic waves and heating. Since the solubility in a basic aqueous solution changes due to the loss of the water, it is possible to further increase the difference in solubility between the exposed and unexposed portions of the photosensitive resin composition of the present invention. As a result of obtaining a large solubility contrast between the exposed portion and the unexposed portion, a pattern having a good shape can be obtained while maintaining a sufficient process margin.
Furthermore, in the photosensitive resin composition of the present invention, unlike an acid, a base does not cause metal corrosion, so that a more reliable cured film can be obtained.
In addition, when the pattern forming step includes a heating step, the photosensitive resin composition of the present invention can use the heating step in heating that promotes the generation of a base. , It has the advantage that the irradiation amount of electromagnetic waves can be reduced. Therefore, when used in a process including such a heating process, the photosensitive resin composition of the present invention can be streamlined compared to a conventional resin composition that generates a base only by electromagnetic wave irradiation.
In addition, the base generator represented by the chemical formula (2) is superior in sensitivity to a conventionally used photobase generator and can efficiently generate a base. Moreover, the base generator represented by the chemical formula (2) can be applied to various polymer precursors.

FIG. 1 is a graph showing the relationship between the thermosetting temperature after ultraviolet irradiation of a fully exposed coating film and an unexposed coating film prepared using the photosensitive resin composition (1), and the remaining amount of the polyimide precursor. is there. FIG. 2 is a graph showing the relationship between the exposure amount and the remaining film ratio, which was prepared using the photosensitive resin compositions (2) and (3) and the comparative photosensitive resin composition (1).

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 acrylate and / or methacrylate. means.
In the present invention, the electromagnetic wave is not only an electromagnetic wave having a wavelength in the visible and invisible regions, but also a particle beam such as an electron beam, and radiation or a general term for the electromagnetic wave and the particle beam, unless the wavelength is specified. Contains ionizing radiation. In this specification, irradiation with electromagnetic waves is also referred to as exposure. Note that electromagnetic waves with wavelengths of 365 nm, 405 nm, and 436 nm may be referred to as i-line, h-line, and g-line, respectively.

<Photosensitive resin composition>
The photosensitive resin composition according to the present invention includes a polymer precursor whose reaction to the final product is accelerated by a basic substance or by heating in the presence of the basic substance, and a chemical formula (1) below. And a base generator that generates a base upon irradiation with electromagnetic waves and heating.

In chemical formula (1), R ¹ and R ² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹ and R ² may combine to form a cyclic structure. However, at least one of R ¹ and R ² is a monovalent organic group. R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, halogen, or a monovalent organic group, and may be the same or different. Two or more of R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to form a cyclic structure.

The base generator represented by the chemical formula (1) has the above specific structure, and (—CH═CH—C (═O) —) moiety is isomerized into a cis isomer by irradiation with electromagnetic waves, The base (amine) NHR ¹ R ² is generated by heating. Further, when the amine is generated, the structure represented by the chemical formula (1) is cyclized. As a result, the phenolic hydroxyl group is lost and the solubility in the developer is lowered.

  In the polymer precursor, the reaction to the final product is promoted by the action of the basic substance generated from the base generator, and the solubility usually changes.

  Due to such a change in solubility of the base generator and the polymer precursor, the photosensitive resin composition according to the present invention has a large difference in solubility between the exposed part and the unexposed part. The characteristic contrast increases, and pattern formation becomes possible.

  The photosensitive resin composition of the present invention has a wide range of applicable polymer precursors, and is widely applied in fields where it is possible to take advantage of characteristics such as changes in solubility between the polymer precursor and the base generator. For example, it is suitably applied in a field where the characteristics of the photosensitive polyimide precursor resin composition and its imidized product can be utilized. According to the present invention, a polyimide precursor that is originally highly soluble in a developer can also be suitably used.

  Hereinafter, the base generator of the photosensitive resin composition according to the present invention, the polymer precursor, and other components that can be appropriately included as necessary will be described in order.

<Base generator contained in photosensitive resin composition>
The base generator contained in the photosensitive resin composition according to the present invention is represented by the following chemical formula (1) and generates a base upon irradiation with electromagnetic waves and heating.

In chemical formula (1), R ¹ and R ² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹ and R ² may combine to form a cyclic structure. However, at least one of R ¹ and R ² is a monovalent organic group. R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, halogen, or a monovalent organic group, and may be the same or different. Two or more of R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to form a cyclic structure.

  The base generator of the present invention is a kind of photobase generator and generates a base only by being irradiated with electromagnetic waves. However, generation of a base is promoted by appropriate heating. The base generator of the present invention can efficiently generate a base with a small amount of electromagnetic wave irradiation by combining electromagnetic wave irradiation and heating. The photobase generator refers to an agent that does not exhibit activity under normal conditions of normal temperature and pressure, but generates a base when electromagnetic waves are applied as an external stimulus.

Since the base generator contained in the photosensitive resin composition according to the present invention has the specific structure described above, (—CH═CH—C (═O) — in chemical formula (1) is irradiated with electromagnetic waves. ) Moiety isomerizes to the cis isomer and further cyclized by heating to produce the base amine, NHR ¹ R ² . The temperature at which the imidization reaction of the polyimide precursor is initiated can be lowered by the catalytic action of the amine.

  When the base generator represented by the chemical formula (1) is cyclized, the phenolic hydroxyl group disappears, the solubility changes, and in the case of a basic aqueous solution, the solubility decreases. Thereby, when the polymer precursor contained in the photosensitive resin composition according to the present invention is a polyimide precursor or a polybenzoxazole precursor, the solubility is further reduced due to the reaction of the precursor to the final product. It has a function of assisting, and it becomes possible to increase the solubility contrast between the exposed portion and the unexposed portion.

R ¹ and R ² are each independently a hydrogen atom or a monovalent organic group, and at least one of R ¹ and R ² is a monovalent organic group. NHR ¹ R ² is a base (in the present invention, “basic substance” is simply referred to as a base), but R ¹ and R ² are each an organic group that does not contain an amino group. Is preferred. If an amino group is contained in R ¹ and R ² , the base generator itself becomes a basic substance, which accelerates the reaction of the polymer precursor, resulting in a solubility contrast between the exposed and unexposed areas. There is a risk of the difference becoming smaller. However, when there is a difference in basicity between the electromagnetic wave irradiation and the base generated after heating, such as when an amino group is bonded to the aromatic ring present in the organic group of R ¹ and R ^2. May be used even if the organic group of R ¹ and R ² contains an amino group.
Examples of the monovalent organic group include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.

R ¹ and R ² may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient.

The bond other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited, and is an ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond ( -N = C (-R)-, -C (= NR)-, wherein R is a hydrogen atom or a monovalent organic group), carbonate bond, sulfonyl bond and the like.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited, and is a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a nitro group, a carboxyl group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and thioether group, an amino group (-NH _2, -NHR, -NRR ': Here, R and R' are each independently a hydrocarbon group. These groups may be linear, branched or cyclic.
Examples of the substituent other than the hydrocarbon group in the organic group of R ¹ and R ² include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a nitro group, and an acyl group. An acyloxy group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group are preferred.

Since the produced amine is NHR ¹ R ^2, it is a primary amine or a secondary amine. The amine includes an aliphatic amine and an aromatic amine, respectively.

Further, the NHR ¹ R ^{2 to be} produced is not only a basic substance such as a monoamine having only one NH group capable of forming an amide bond, but also 2 NH groups capable of forming an amide bond such as diamine, triamine and tetraamine. It may be a basic substance having two or more. When the generated NHR ¹ R ² is a basic substance having two or more NH groups, an NH group capable of forming an amide bond is formed at one or more terminals of R ¹ and / or R ^{2 in} the formula (1). The structure which the photolatent part which generate | occur | produces the base which has by irradiation of electromagnetic waves and a heating has couple | bonded further is mentioned. As the photolatent site, a residue other than R ¹ and / or R ² in the formula (1) is further bonded to one or more terminals of R ¹ and / or R ² in the formula (1). Structure.

  Aliphatic primary amines include methylamine, ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, pentylamine, isoamylamine, tert-pentylamine, cyclopentylamine, hexylamine, cyclohexylamine , Heptylamine, cycloheptaneamine, octylamine, 2-octaneamine, 2,4,4-trimethylpentan-2-amine, cyclooctylamine and the like.

  Examples of the aromatic primary amine include aniline, 2-aminophenol, 3-aminophenol, and 4-aminophenol.

  Aliphatic secondary amines include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, aziridine, azetidine, pyrrolidine, piperidine, azepan, azocan, methylaziridine, dimethylaziridine, methylazetidine, dimethyl Examples thereof include azetidine, trimethylazetidine, methylpyrrolidine, dimethylpyrrolidine, trimethylpyrrolidine, tetramethylpyrrolidine, methylpiperidine, dimethylpiperidine, trimethylpiperidine, tetramethylpiperidine, pentamethylpiperidine and the like, among which alicyclic amine is preferable.

  Aromatic secondary amines include methylaniline, diphenylamine, and N-phenyl-1-naphthylamine.

  As amines higher than diamine, ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, Linear aliphatic alkylenediamines such as 1,9-nonanediamine and 1,10-decanediamine; 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl- 1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3- Branched aliphatic alkylenediamine such as dimethyl-1,4-butanediamine; cyclohexanediamine, methylcyclohexanediamine, isophoronedia , Alicyclic diamines such as norbornane dimethylamine, tricyclodecane dimethylamine, mensendiamine; p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diamino Examples thereof include aromatic diamines such as diphenylmethane; triamines such as benzenetriamine, melamine and 2,4,6-triaminopyrimidine; and tetraamines such as 2,4,5,6-tetraaminopyrimidine.

Depending on the substituents introduced at the positions of R ¹ and R ² , the thermophysical properties and basicity of the basic substance to be generated are different.
Catalytic action, such as lowering the reaction start temperature for the reaction from the polymer precursor to the final product, is more effective as a catalyst with a basic substance having a higher basicity, and a lower temperature with a smaller amount of addition. Reaction to the final product is possible. In general, secondary amines have higher basicity than primary amines, and their catalytic effect is greater.
In addition, aliphatic amines are preferred over aromatic amines because they are more basic.

From this, the amine generated from the base generator represented by the chemical formula (1) of the present invention is preferably a secondary amine, more preferably a secondary aliphatic amine, and R ¹ and R ^2. Secondary aliphatic amines in which are bonded to each other are particularly preferred.
The secondary aliphatic amine to which R ¹ and R ² are bonded is preferably generated, but the amine other than the secondary aliphatic amine may be generated as long as it does not depart from the gist of the present invention.

  The base generated from the base generator represented by the chemical formula (1) preferably has one NH group capable of forming an amide bond. When the generated base has two or more NH groups capable of forming an amide bond, the base generator has two or more amide bonds that are cleaved by irradiation with electromagnetic waves and heating, for example, cinnamic acid derivatives There will be two or more photophores, such as residues, per molecule. In such a case, since the molecular weight is usually increased, there is a problem that the solvent solubility is deteriorated. In addition, when there are two or more photophores in one molecule, it becomes a base if one amide bond where the photophore and the base are bonded is cleaved, but a base that still contains the photophore has a large molecular weight. Therefore, the diffusibility is deteriorated, and the sensitivity when used as a base generator is deteriorated. Furthermore, when synthesizing a base generator, if there is one light-absorbing group, it is synthesized by adding an excessive amount of a relatively inexpensive base, but if there are two or more light-absorbing groups, it is relatively expensive. It is necessary to add an excessive amount of the raw material of the photophore portion. In addition, in the case of a base having two or more NH groups capable of forming an amide bond, there is a problem that purification after synthesis is difficult. In particular, when combined with a polyimide precursor or a polybenzoxazole precursor, it is preferable to have one NH group capable of forming an amide bond.

  On the other hand, when combined with an epoxy compound or an imidazole compound, the base generated from the base generator represented by the chemical formula (1) is one having two or more NH groups capable of forming an amide bond. It can be suitably used because it can function not only as a curing accelerator but also as a curing agent.

Further, from the viewpoint of the thermophysical properties of the leaving base and the basicity, the organic groups of R ¹ and R ² each independently preferably have 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly carbon. It is preferable that it is number 1-8.

As a suitable combination, R ¹ and R ² are each independently a monovalent organic group, and may have a C 1-10 alkyl group which may have a substituent, or may have a substituent. A cycloalkyl group having 4 to 12 carbon atoms, R ¹ and R ² may be the same or different, and R ¹ and R ² may be bonded to form a cyclic structure; There may be a case where a hetero atom bond may be included. The alkyl group preferably further has 1 to 8 carbon atoms, and the cycloalkyl group preferably further has 4 to 10 carbon atoms. Also, cycloaliphatic amine which is the R ¹ and R ² are bonded which may have a substituent cyclic structure having 4 to 12 carbon atoms are also preferred.

R ^{3 to} R ⁶ are each independently a hydrogen atom, a halogen, or a monovalent organic group. Two or more of R ³ , R ⁴ , R ^5, and R ⁶ may be bonded to form a cyclic structure, and may include a hetero atom bond.
Examples of the halogen include fluorine, chlorine, bromine and the like.
The monovalent organic group is not particularly limited, and examples thereof include a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, and a saturated or unsaturated halogenated alkyl group. These organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms in the organic group, and these may be linear or branched.

The bond other than the hydrocarbon group in the organic group of R ^{3 to} R ⁶ is not particularly limited, and is an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, A sulfonyl bond etc. are mentioned.

The substituent other than the hydrocarbon group in the organic group of R ^{3 to} R ⁶ is not particularly limited, and is a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a nitro group, a carboxyl group, an acyl group, an acyloxy group, a sulfino group, a sulfo group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and thioether group, an amino group (-NH _2, -NHR, -NRR ': Here, R and R' are each independently a hydrocarbon group. These groups may be linear, branched or cyclic.
Among them, examples of the substituent other than the hydrocarbon group in the organic group of R ^{3 to} R ⁶ include a halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, an alkoxy group, an alkoxycarbonyl group, a nitro group, and an acyl group. Groups, acyloxy groups, saturated or unsaturated alkyl ether groups, saturated or unsaturated alkyl thioether groups, aryl ether groups, and aryl thioether groups are preferred.

Two or more of R ^{3 to} R ⁶ may be bonded to form a cyclic structure.
The cyclic structure is a combination of two or more selected from the group consisting of saturated or unsaturated alicyclic hydrocarbons, heterocycles, and condensed rings, and the alicyclic hydrocarbons, heterocycles, and condensed rings. The structure which becomes may be sufficient. For example, R ³ to R ⁶ are formed by combining two or more of them, naphthalene share atoms of the benzene ring of R ³ to R ⁶ are attached, anthracene, phenanthrene, and fused ring indene You may do it.

Moreover, it is possible to adjust the wavelength of light to be absorbed by introducing one or more substituents into the substituents R ^{3 to} R ⁶ of the present invention. It can also be absorbed. The absorption wavelength can be shifted to a longer wavelength by introducing a substituent that extends the conjugated chain of the aromatic ring. 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.

  As a guideline of what substituents should be introduced to shift the absorption wavelength with respect to a desired wavelength, the Interspection of the Ultraviolet Products (AI Scott 1964) and the spectrum of organic compounds The table described in the identification method 5th edition (RM Silverstein 1993) can be referred to.

R ^{3 to} R ⁶ 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, and an aryloxyalkyl group having 7 to 16 carbon atoms (—ROAr ), An aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, an alkoxy group having 1 to 10 carbon atoms, and 2 to 11 carbon atoms An amide group, an alkylthio group having 1 to 10 carbon atoms (-SR), 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 electron donating group, and / or Alternatively, an aryl group having 6 to 20 carbon atoms substituted with an electron-withdrawing group, a benzyl group substituted with an electron-donating group and / or an electron-withdrawing group, a cyano group, and a methylthio group (—SCH ₃ ) are preferable. The alkyl moiety may be linear, branched or cyclic.
In addition, as R ^{3 to} R ⁶ , two or more of them are bonded, and a condensed ring such as naphthalene, anthracene, phenanthrene, indene, etc. is shared by sharing the atoms of the benzene ring to which R ^{3 to} R ⁶ are bonded. Even if it forms, it is preferable from the point which absorption wavelength becomes long.

  The structure represented by the chemical formula (1) is a trans isomer and / or a cis isomer, and only the trans isomer may be used or a mixture of the trans isomer and the cis isomer may be used, but the solubility contrast is increased. Therefore, the trans isomer ratio is preferably 90 to 100%, and it is more preferable to use only the trans isomer.

  When the base generator represented by the chemical formula (1) is used in combination with a polyimide precursor or a polybenzoxazole precursor, the temperature (5% when the weight is reduced by 5% from the initial weight by heating. % Weight reduction temperature) is preferably 100 ° C. or higher. In the case of a polyimide precursor or a polybenzoxazole precursor, it is necessary to use a high boiling point solvent such as N-methyl-2-pyrrolidone when forming a coating film. Can form a coating film under dry conditions that reduce the influence of the residual solvent. Thereby, the reduction | decrease of the solubility contrast by the influence of a residual solvent in an exposed part and an unexposed part can be suppressed.

  Moreover, since it is preferable that impurities derived from the base generator of the present invention do not remain in the product using the photosensitive resin composition of the present invention, the base generator of the present invention is a heating process (for example, after development) (for example, When the polymer to be combined is a polyimide precursor, it is preferably decomposed or volatilized by an imidization process). Specifically, the temperature when the 50% weight is reduced from the initial weight (50% weight reduction temperature) is preferably 400 ° C. or less, and more preferably 350 ° C. or less. Moreover, it is preferable that the boiling point of the generated base is 25 ° C. or more because the handleability at room temperature is improved. In the case where the boiling point of the generated base is not 25 ° C. or higher, the amine produced during drying tends to evaporate when it is formed into a coating film, which may make the operation difficult.

In the photosensitive resin composition according to the present invention, the heating temperature for generating a base from the base generator represented by the chemical formula (1) is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. . Heating by the temperature (for example, room temperature) of the environment where the base generator is placed may be used, and in this case, the base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. From the viewpoint of increasing the reaction rate and generating the base efficiently, the heating temperature for generating the base is preferably 30 ° C. or higher, more preferably 60 ° C. or higher, still more preferably 100 ° C. or higher, Especially preferably, it is 120 degreeC or more. However, depending on the polymer precursors used in combination, for example, the unexposed part may be cured by heating at 60 ° C. or higher, so that the suitable heating temperature is not limited to the above.
Moreover, in order to prevent decomposition | disassembly other than base generation | occurrence | production of the base generator represented by said Formula (1), it is preferable to heat at 300 degrees C or less.

  The base generator represented by the formula (1) generates a base only by irradiation with electromagnetic waves, but generation of the base is promoted by heating appropriately. Therefore, in order to generate a base efficiently, when using the base generator represented by the formula (1), the base is generated by heating after exposure or simultaneously with exposure. Exposure and heating may be performed alternately. The most efficient method is a method of heating simultaneously with exposure.

  The method for synthesizing the base generator represented by the chemical formula (1) of the present invention will be described by taking 2-hydroxycinnamic acid amide as an example, but the present invention is not limited thereto. The base generator of the present invention can be synthesized by a plurality of conventionally known synthesis routes.

2-hydroxycinnamic amide can be synthesized, for example, by reacting 2-hydroxy cinnamic acid with cyclohexylamine. The desired product can be obtained by dissolving 2-hydroxycinnamic acid and cyclohexylamine in tetrahydrofuran in the presence of a condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and stirring.
Cinnamic acid into which each substituent is introduced can be synthesized by performing wittig reaction, Knoevenagel reaction, or Perkin reaction on hydroxybenzaldehyde having a corresponding substituent.

  The base generator represented by the chemical formula (1) of the present invention absorbs at least a part of the exposure wavelength in order to sufficiently exhibit the function of base generation for the polymer precursor to be the final product. It is necessary to have. The wavelength of a high-pressure mercury lamp that is a general exposure light source includes 365 nm, 405 nm, and 436 nm. For this reason, it is preferable that the base generator represented by the chemical formula (1) of the present invention absorbs at least one electromagnetic wave having a wavelength of 365 nm, 405 nm, or 436 nm. In such a case, it is preferable because the number of applicable polymer precursors is further increased.

  The base generator represented by the chemical formula (1) has a molar extinction coefficient of 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at 405 nm, and the number of applicable polymer precursors further increases. It is preferable from the point.

The fact that the base generator represented by the chemical formula (1) of the present invention has absorption in the wavelength region is expressed by the chemical formula (1) in a solvent (for example, acetonitrile) that does not absorb in the wavelength region. bases generating agent 1 × ¹⁰ -4 mol / L or less of the concentration ^{(usually, 1 × 10 -4 mol / L~1} × 10 -5 mol / L or so. so as to give suitable absorption intensity, as appropriate, And may be clarified by measuring the absorbance with an ultraviolet-visible spectrophotometer (for example, UV-2550 (manufactured by Shimadzu Corporation)).

<Polymer precursor>
The polymer precursor used in the photosensitive resin composition of the present invention means a substance that finally becomes a polymer exhibiting the desired physical properties by reaction, and the reaction includes intermolecular reaction and intramolecular reaction. The polymer precursor itself may be a relatively low molecular compound or a high molecular compound.
The polymer precursor of the present invention is a compound whose reaction to the final product is promoted by a basic substance or by heating in the presence of the basic substance. Here, in the aspect in which the polymer precursor is accelerated by the basic substance or by heating in the presence of the basic substance, the reaction to the final product is accelerated only by the action of the basic substance. In addition to the mode of changing to the final product, the mode includes the mode in which the reaction temperature of the polymer precursor to the final product is lowered by the action of the basic substance as compared to 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 a solvent such as a developer changes. Therefore, the solubility of the polymer precursor in the solvent can be changed depending on the presence or absence of the basic substance, and thus patterning by development can be performed using the solvent as a developer.

  The polymer precursor of the present invention can be used without particular limitation as long as the reaction to the final product is promoted by the basic substance as described above or by heating in the presence of the basic substance. is there. The following are typical examples, but the invention is not limited to these. In addition, as a polymer precursor, it may be used individually by 1 type, and may be used in mixture of 2 or more types.

[Polymer precursor that becomes polymer by intermolecular reaction]
Examples of the polymer precursor that becomes a target polymer by intermolecular reaction include a compound having a reactive substituent and a polymerization reaction and a polymer, or a compound that forms a bond (crosslinking reaction) between molecules. And polymers. Examples of the reactive substituent include an epoxy group, an oxetane group, a thiirane group, an isocyanate group, a hydroxyl group, and a silanol group. In addition, the polymer precursor includes a compound that undergoes hydrolysis and polycondensation between molecules, and the reactive substituent includes -SiX of the polysiloxane precursor (where X is an alkoxy group, an acetoxy group, an oxime). And a hydrolyzable group selected from the group consisting of a group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen).

Examples of the compound having a reactive substituent and undergoing a polymerization reaction include a compound having one or more epoxy groups, a compound having one or more oxetane groups, and a compound having one or more thiirane groups. .
Examples of the polymer that has a reactive substituent and undergoes a polymerization reaction include a polymer having two or more epoxy groups (epoxy resin), a polymer having two or more oxetane groups, and two or more thiiranes. And a polymer having a group. The compounds and polymers having an epoxy group are specifically described below, but compounds and polymers having an oxetane group and a thiirane group can also be used in the same manner.

(Compound having epoxy group and polymer)
The compound and polymer having one or more epoxy groups are not particularly limited as long as they have one or more epoxy groups in the molecule, and conventionally known compounds can be used.
The base generator generally also has a function as a curing catalyst for a compound having one or more epoxy groups in the molecule.

When using a compound having one or more epoxy groups in the molecule or a polymer (epoxy resin) having two or more epoxy groups in the molecule, two functional groups having reactivity with the epoxy group are contained in the molecule. Two or more compounds may be used in combination. Here, examples of the functional group having reactivity with an epoxy group include a carboxyl group, a phenolic hydroxyl group, a mercapto group, a primary or secondary aromatic amino group, and the like. It is particularly preferable to have two or more of these functional groups in one molecule in consideration of three-dimensional curability.
Moreover, it is preferable to use what introduce | transduced the said functional group into the polymer side chain of weight average molecular weight 3,000-100,000. If it is less than 3,000, film strength is lowered and tackiness is caused on the surface of the cured film, which may cause impurities and the like to easily adhere. On the other hand, if it exceeds 100,000, the viscosity may increase, which is not preferable.

  Examples of the polymer having one or more epoxy groups in the molecule include epoxy resins, bisphenol A type epoxy resins derived from bisphenol A and epichlorohydrin, bisphenol F type epoxy derived from bisphenol F and epichlorohydrin. Resin, bisphenol S type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, bisphenol F novolak type epoxy resin, alicyclic epoxy resin, diphenyl ether type epoxy resin, hydroquinone type epoxy resin, Polyfunctional epoxy resins such as naphthalene type epoxy resin, biphenyl type epoxy resin, fluorene type epoxy resin, trifunctional type epoxy resin and tetrafunctional type epoxy resin, There are lysidyl ester type epoxy resins, glycidyl amine type epoxy resins, hydantoin type epoxy resins, isocyanurate type epoxy resins, aliphatic chain epoxy resins, etc. These epoxy resins may be halogenated and hydrogenated. It may be. As commercially available epoxy resin products, for example, JER Coat 828, 1001, 801N, 806, 807, 152, 604, 630, 871, YX8000, YX8034, YX4000 manufactured by Japan Epoxy Resin Co., Ltd., Epicron manufactured by DIC Corporation 830, EXA835LV, HP4032D, HP820, EP4100 series, EP4000 series, EPU series, manufactured by ADEKA Co., Ltd., Celoxide series (2021, 2021P, 2083, 2085, 3000, etc.) manufactured by Daicel Chemical Industries, Ltd., Eporide series, EHPE Series, YD series, YDF series, YDFN series, YDB series by Toto Kasei Co., Ltd., Denacol series by Nagase ChemteX, Epolite series by Kyoeisha Chemical Co., Ltd. Although's etc. but the invention is not limited thereto. Two or more of these epoxy resins may be used in combination. Among these, bisphenol-type epoxy resins are preferable because grades having different molecular weights are widely available as compared with other various epoxy compounds, and adhesiveness and reactivity can be arbitrarily set.

On the other hand, examples of the compound that crosslinks between molecules include a combination of a compound having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule. By the reaction with the hydroxyl group, a urethane bond is formed between the molecules, and the polymer can be formed.
As a polymer that undergoes a cross-linking reaction between molecules, for example, a combination of a polymer having two or more isocyanate groups in the molecule (isocyanate resin) and a polymer having two or more hydroxyl groups in the molecule (polyol) Is mentioned.
A combination of a compound that undergoes a cross-linking reaction between molecules and a polymer may be used. For example, a combination of a polymer (isocyanate resin) having two or more isocyanate groups in the molecule and a compound having two or more hydroxyl groups in the molecule, and a compound having two or more isocyanate groups in the molecule Examples include a combination of polymers (polyols) having two or more hydroxyl groups in the molecule.

(Compounds and polymers having isocyanate groups)
As the compound and polymer having an isocyanate group, any known compound can be used without particular limitation as long as it has two or more isocyanate groups in the molecule. As such a compound, in addition to low molecular weight compounds represented by p-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate, oligomers, A polymer having an isocyanate group in the side chain or terminal of a polymer having a weight average molecular weight of 3,000 or more may be used.

(Compounds having a hydroxyl group and polymers)
The compound and polymer having an isocyanate group are usually used in combination with a compound having a hydroxyl group in the molecule. The compound having such a hydroxyl group is not particularly limited as long as it has two or more hydroxyl groups in the molecule, and known compounds can be used. As such a compound, in addition to low molecular weight compounds such as ethylene glycol, propylene glycol, glycerin, diglycerin and pentaerythritol, a polymer having a weight average molecular weight of 3,000 or more has a hydroxyl group in the side chain or terminal. A molecule may be used.

(Polysiloxane precursor)
Examples of the compound that undergoes hydrolysis and polycondensation between molecules include polysiloxane precursors.
As the polysiloxane precursor, Y _n SiX _(4-n) (wherein Y represents an alkyl group, fluoroalkyl group, vinyl group, phenyl group, or hydrogen which may have a substituent, A hydrolyzable group selected from the group consisting of an alkoxy group, an acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a halogen, where n is an integer from 0 to 3. And the hydrolyzed polycondensate of the organosilicon compound. Among these, those in which n is 0 to 2 in the above formula are preferable. Further, from the viewpoint that the silica-dispersed oligomer solution is easily prepared and easily available, the hydrolyzable group is preferably an alkoxy group.
There is no restriction | limiting in particular as said organosilicon compound, A well-known thing can be used. For example, trimethoxysilane, triethoxysilane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltrit-butoxysilane, ethyltribromosilane, ethyltrimethoxysilane, ethyltriethoxysilane , N-propyltriethoxysilane, n-hexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, dimethoxydiethoxysilane, dimethyldichlorosilane, dimethyldimethoxysilane , Diphenyldimethoxysilane, vinyltrimethoxysilane, trifluoropropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane γ-glycidoxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, γ-mercaptopropyltrimethoxysilane, β- (3 4-epoxycyclohexyl) ethyltrimethoxysilane, fluoroalkylsilanes known as fluorine-based silane coupling agents, and their hydrolysis condensates or cohydrolysis condensates; and mixtures thereof.

[Polymer precursor that becomes polymer by intramolecular ring-closing reaction]
Examples of the polymer precursor that finally becomes a polymer that exhibits the desired physical properties by the intramolecular ring-closing reaction include a polyimide precursor and a polybenzoxazole precursor. These precursors may be a mixture of two or more separately synthesized polymer precursors.
Hereinafter, although the polyimide precursor and polybenzoxazole precursor which are the preferable polymer precursors of this invention are demonstrated, this invention is not limited to these.

(Polyimide precursor)
As the polyimide precursor, a polyamic acid having a repeating unit represented by the following chemical formula (3) is preferably used.

In formula (3), R ⁷ is a tetravalent organic group. R ⁸ is a divalent organic group.

In addition, although the tetravalence of R ⁷ shows only the valence for bonding with an acid, it may have another substituent. Similarly, the divalent value of R ⁸ indicates only the valence for bonding to the amine, but may have other substituents.

  Polyamic acid is preferable because it can be obtained by simply mixing acid dianhydride and diamine in a solution, so that it can be synthesized by a one-step reaction, and can be synthesized easily and at low cost.

  As a secondary effect, when the polymer precursor to be used is a polyamic acid, the final curing temperature is less than 300 ° C., more preferably because 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.

Polyamic acid is obtained by the reaction of acid dianhydride and diamine. From the viewpoint of imparting excellent heat resistance and dimensional stability to the finally obtained polyimide, R ⁷ or R ^{8 in the} above chemical formula (3). Is preferably an aromatic compound, and R ⁷ and R ⁸ are more preferably aromatic compounds. At this time, in R ⁷ of the chemical formula (3), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ⁷ may be bonded to the same aromatic ring. May be bonded to different aromatic rings. Similarly, in R ⁸ of the chemical formula (3), two groups ((—NH—) ₂ ) bonded to R ⁸ may be bonded to the same aromatic ring or bonded to different aromatic rings. You may do it.

  The polyamic acid represented by the chemical formula (3) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.

  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 reaction for obtaining the polyimide precursor of the present invention include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, and methylcyclobutane. Aliphatic tetracarboxylic dianhydrides such as tetracarboxylic dianhydride and 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 Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3', 3,4'-biphenyltetracarboxylic acid Anhydride, 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-di Carboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxy) Phenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexa Fluoropropane dianhydride, , 3-bis [(3,4-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, and p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, 3,3′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 3, 3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl Sulfone, 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, , 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-hexafluoropropane, 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-amino) Phenoxy) benzene, 1,3-bis (4-a Nophenoxy) 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-ditrifluoromethyl) Rubenzyl) 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-aminophenoxy) 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 Such as 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, etc. 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 -Aliphatic amines 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 (4). Specific examples include benzidine and the like.

In the chemical formula (4), 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 benzene rings.

Furthermore, in the above formula (4), it is also possible to use a diamine having a substituent at a position where the amino group on the benzene ring is not substituted without being involved in the bond with another benzene ring. 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 less 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.

<Polybenzoxazole precursor>
As the polybenzoxazole precursor used in the present invention, a polyamide alcohol having a repeating unit represented by the following chemical formula (5) is preferably used.

  Polyamide alcohol can be synthesized by a conventionally known method. For example, it can be obtained by addition reaction of a dicarboxylic acid derivative such as a dicarboxylic acid halide and dihydroxydiamine in an organic solvent.

In the chemical formula (5), R ⁹ is a divalent organic group. R ¹⁰ is a tetravalent organic group.

In addition, although the divalent value of R ⁹ indicates only the valence for bonding with an acid, it may have another substituent. Similarly, the tetravalent value of R ¹⁰ indicates only the valency for bonding with an amine and a hydroxyl group, but may have other substituents.

Polyamide alcohol having a repeating unit represented by the chemical formula (5) gives excellent heat resistance and dimensional stability to the finally obtained polybenzoxazole. In the chemical formula (5), R ⁹ or R ¹⁰ is preferably an aromatic compound, and R ⁹ and R ¹⁰ are more preferably aromatic compounds. At this time, in R ⁹ of the chemical formula (5), two groups (—CO—) ₂ bonded to R ⁹ may be bonded to the same aromatic ring or bonded to different aromatic rings. May be. Similarly, in R ¹⁰ of the chemical formula (5), four groups ((—NH—) ₂ (—OH) ₂ ) bonded to R ¹⁰ may be bonded to the same aromatic ring, It may be bonded to different aromatic rings.

  The polyamide alcohol represented by the chemical formula (5) may be composed of a single repeating unit or may be composed of two or more kinds of repeating units.

  Examples of the dicarboxylic acid and its derivatives applicable to the reaction for obtaining the polybenzoxazole precursor include phthalic acid, isophthalic acid, terephthalic acid, 4,4′-benzophenone dicarboxylic acid, and 3,4′-benzophenone dicarboxylic acid. 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'-diphenyl sulfone dicarboxylic acid, 3,4'-diphenyl sulfone dicarboxylic acid, 3,3'-diphenyl sulfone dicarboxylic acid, 4,4'- Hexafluoroisopropylidene dibenzoic acid, 4 4′-dicarboxydiphenylamide, 1,4-phenylenediethanoic acid, 1,1-bis (4-carboxyphenyl) -1-phenyl-2,2,2-trifluoroethane, bis (4-carboxyphenyl) 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 These acid halides and active esters with hydroxybenzotriazole, etc. 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- Droxyphenyl) 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- Examples thereof include, but are not limited to, dihydroxybenzene. 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 little loss of electromagnetic waves, and a highly sensitive photosensitive resin composition is used. Can be obtained.

  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%, particularly preferably 50% or more.

  The weight average molecular weight of a polymer precursor such as a polyimide precursor or a polybenzoxazole precursor is preferably in the range of 3,000 to 1,000,000, although it depends on the application, 5,000 to 500. 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, the solubility tends to decrease, and 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 thereof include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, and 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.

  Since the solubility of polyamic acid and polybenzoxazole precursor decreases due to the reaction to the final product by the action of the basic substance, the base generation of the base generator represented by the chemical formula (1) By combining with a decrease in solubility, the photosensitive resin composition of the present invention has an advantage that the solubility contrast between the exposed portion and the unexposed portion can be further increased.

<Other ingredients>
The photosensitive resin composition according to the present invention may be a simple mixture of the base generator represented by the chemical formula (1), one or more kinds of polymer precursors, and a solvent. Alternatively, a photosensitive resin composition may be prepared by blending a 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.

  Usable general-purpose solvents include, for example, diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and other ethers; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, Glycol monoethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether (so-called cellosolves); ketones such as methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone; acetic acid Ethyl, butyl acetate, vinegar n-propyl, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), methoxypropyl acetate, ethoxypropyl acetate, dimethyl oxalate, Esters such as methyl lactate and ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane Halogenated hydrocarbons such as 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o-dichlorobenzene, m-dichlorobenzene; Amides such as muamide, 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 further include 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.

As long as the effect of the present invention is not hindered, the photosensitive resin composition of the present invention may contain other photosensitive components that generate an acid or a base by light as an auxiliary role of the base generator of the present invention. good. Further, a base proliferating agent or a sensitizer may be added.
Examples of the compound that generates an acid by light include a photosensitive diazoquinone compound having a 1,2-benzoquinonediazide or 1,2-naphthoquinonediazide structure. US Pat. Nos. 2,772,972, 2,797, No. 213, No. 3,669,658. In addition, known photoacid generators such as triazine and derivatives thereof, sulfonic acid oxime ester compounds, sulfonic acid iodonium salts, and sulfonic acid sulfonium salts can be used. Examples of the compound that generates a base by light include 2,6-dimethyl-3,5-dicyano-4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl. Examples include -4- (2′-nitrophenyl) -1,4-dihydropyridine, 2,6-dimethyl-3,5-diacetyl-4- (2 ′, 4′-dinitrophenyl) -1,4-dihydropyridine, and the like. it can.

A base proliferating agent that generates a base by a decomposition or rearrangement reaction by the action of a small amount of base generated from the base generator may be used in combination. Examples of the base proliferating agent include a compound having 9-fluorenylmethyl carbamate bond, 1,1-dimethyl-2-cyanomethyl carbamate bond ((CN) CH ₂ C (CH ₃ ) ₂ OC (O) NR ₂ ), Compounds having a paranitrobenzyl carbamate bond, compounds having a 2,4-dichlorobenzyl carbamate bond, and other urethane compounds described in paragraphs 0010 to 0032 of JP 2000-330270 A And urethane compounds described in paragraphs 0033 to 0060 of JP-A-2008-250111.

Addition of a sensitizer may be effective when it is desired to make the base generator sufficiently use the energy of electromagnetic waves having a wavelength that passes through the polymer to improve sensitivity.
In particular, when the absorption of the polyimide precursor is also at a wavelength of 360 nm or more, the effect of adding a sensitizer is great. Specific examples of compounds called sensitizers include thioxanthone and derivatives thereof such as diethylthioxanthone, coumarins and derivatives thereof, ketocoumarin and derivatives thereof, ketobiscoumarin and derivatives thereof, cyclopentanone and derivatives thereof , Cyclohexanone and derivatives thereof, thiopyrylium salts and derivatives thereof, thioxanthene series, xanthene series and derivatives thereof.

Specific examples of coumarin, ketocoumarin and derivatives thereof include 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. Furthermore, benzophenone, acetophenone, phenanthrene, 2-nitrofluorene, 5-nitroacenaphthene, benzoquinone, 2-ethylanthraquinone, 2-tertiarybutylanthraquinone, 1,2-benzanthraquinone, 1,2-naphthoquinone, etc. Is mentioned.
Since these exhibit a particularly excellent effect in combination with a base generator, a sensitizer exhibiting an optimal sensitizing action is appropriately selected depending on the structure of the base generator.

  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 base generator represented by the chemical formula (1) is usually 0.1 to 95% by weight, preferably 0.5 to 60% by weight based on the solid content of the polymer precursor contained in the photosensitive resin composition. %. If it is less than 0.1% by weight, the solubility contrast between the exposed part and the unexposed part may not be sufficiently increased. It is hard to be done. In addition, a base generator may be used individually by 1 type, and may be used in mixture of 2 or more types.
When used as a curing agent, such as when combined with an epoxy compound, it is usually contained in the range of 0.1 to 95% by weight, preferably 0.5 to 60% by weight, depending on the degree of curing.
On the other hand, when used as a curing accelerator, it can be cured with a small amount of addition, and the base generator represented by the chemical formula (1) is a solid content of the polymer precursor contained in the photosensitive resin composition. On the other hand, it is usually 0.1 to 30% by weight, preferably 0.5 to 20% by weight.
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.
Moreover, the mixture ratio of arbitrary components other than a solvent has the preferable range of 0.1 weight%-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.

  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.

When a polyimide precursor or a polybenzoxazole precursor is used as a polymer precursor as an embodiment of the photosensitive resin composition of the present invention, the resulting polyimide and polybenzoxazole have heat resistance, dimensional stability, and insulating properties. From the viewpoint of securing the above properties, the 5% weight loss temperature measured in nitrogen of the polyimide and polybenzoxazole 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 loss temperature means that when the weight loss is measured using a thermogravimetric analyzer, the weight of the sample is reduced by 5% from the initial weight (that is, 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 preferably exhibits a glass transition temperature of about 120 ° C. to 450 ° C., more preferably about 200 ° C. to 380 ° 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. E ″) / determined from the peak temperature of the storage elastic modulus (E ′). As the dynamic viscoelasticity measurement, for example, the frequency is increased by 3 Hz using a viscoelasticity measuring device Solid Analyzer RSA II (manufactured by Rheometric Scientific). If the polyimide and polybenzoxazole obtained from the photosensitive resin composition cannot be formed into a film shape, the temperature is determined by the inflection point of the baseline of differential thermal analysis (DTA). To do.

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.
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 so that the weight per cross-sectional area of the evaluation sample is the same. ² is obtained.

As described above, according to the present invention, the photosensitive resin composition can be obtained by a simple method of simply mixing the base generator represented by the chemical formula (1) with the polymer precursor. Excellent cost performance.
The aromatic component-containing carboxylic acid constituting the base generator represented by the chemical formula (1) and the amine can be obtained at low cost, and the price as a photosensitive resin composition can be suppressed.
The photosensitive resin composition according to the present invention can be applied to promote the reaction of a wide variety of polymer precursors to the final product by the base generator represented by the chemical formula (1). The structure of the resulting polymer can be selected from a wide range.
Furthermore, since the base generator represented by the chemical formula (1) is cyclized when the base is generated and the phenolic hydroxyl group disappears, the solubility in a developer such as a basic solution is changed, and the polymer precursor is changed. In the case of a polyimide precursor, a polybenzoxazole precursor or the like, it helps to lower the solubility of the photosensitive resin composition and contributes to the improvement of the solubility contrast in the exposed and unexposed areas.
Also, due to the catalytic effect of amines and other basic substances generated by electromagnetic wave irradiation, the processing temperature required for reactions such as cyclization such as imidation from polyimide precursors or polybenzoxazole precursors to final products is reduced. Therefore, it is possible to reduce the load on the process and damage to the product due to heat.
Furthermore, since the base generator of the present invention that generates a base by irradiation and heating of electromagnetic waves includes a heating step in the step of obtaining a final product from the polymer precursor, the heating step can be used. The amount can be reduced, and the process can be effectively used.

  The photosensitive resin composition according to the present invention is the same as the photosensitive resin composition according to the present invention in printing ink, paint, sealing agent, adhesive, electronic material, optical circuit component, molding material, resist material, building material, light. It can be used for all known fields and products in which resin materials are used, such as modeling and optical members. It can be suitably used both for applications that are used by exposing the entire surface, such as paints, sealants, and adhesives, and for applications that form patterns such as permanent films and release films.

  The photosensitive resin composition according to the present invention can be used in a wide range of fields, products such as heat resistance, dimensional stability, and insulation, such as paints, printing inks, sealants, or adhesives, or It is suitably used as a forming material for display devices, semiconductor devices, electronic components, micro electro mechanical systems (MEMS), optical members or building materials. For example, specifically, as a forming material for an electronic component, a sealing material and a layer forming material can be used for a printed wiring board, an interlayer insulating film, a wiring covering film, and the like. Moreover, as a forming material of a display device, a layer forming material or an image forming material can be used for a color filter, a film for flexible display, a resist material, an alignment film, and the like. Further, as a material for forming a semiconductor device, a resist material, a layer forming material such as a buffer coat film, or the like can be used. Further, as a material for forming an optical component, it can be used as an optical material or a layer forming material for a hologram, an optical waveguide, an optical circuit, an optical circuit component, an antireflection film, or the like. Moreover, as a building material, it can use for a coating material, a coating agent, etc. It can also be used as a material for an optically shaped object. A printed matter, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, an optically shaped article, an optical member, or a building material is provided.

  Since it has the above characteristics, the photosensitive resin composition according to the present invention can also be used as a pattern forming material. In particular, when a photosensitive resin composition containing a polyimide precursor or a polybenzoxazole precursor is used as a pattern forming material (resist), the pattern formed thereby is a permanent film made of polyimide or polybenzoxazole. Functions as a component that imparts heat resistance and insulation, such as color filters, flexible display films, electronic components, semiconductor devices, interlayer insulation films, wiring coating films, optical circuits, optical circuit components, antireflection films, etc. It is suitable for forming an optical member or an electronic member.

<Pattern formation method>
The pattern forming method according to the present invention includes forming a coating film or a molded body made of the photosensitive resin composition according to the present invention, irradiating the coating film or the molded body with electromagnetic waves in a predetermined pattern, and after irradiation or It develops, after heating simultaneously with irradiation, changing the solubility of the said irradiation site | part, and developing.

  The photosensitive resin composition according to the present invention is coated on some support to form a coating film, or a molded body is formed by a suitable molding method, and the coating film or molded body is formed into a predetermined pattern shape. Is irradiated with electromagnetic waves and heated at the same time as irradiation or irradiation, the base generator represented by the above chemical formula (1) is isomerized and cyclized only in the exposed portion to produce 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.

  When 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 chemical formula (1) The part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base generator represented by these is exposed. When heated after exposure or simultaneously with exposure, a basic substance is generated in the exposed portion, and the thermosetting temperature of that portion is selectively lowered. After the exposure or simultaneously with the exposure, the exposed portion is heat-cured but the unexposed portion is heated at a processing temperature that is not heat-cured to cure only the exposed portion. The heating step for generating the basic substance and the heating step for performing the reaction for curing only the exposed portion (post-exposure baking described later) may be the same step or different steps. Next, the unexposed 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 negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  Further, even when using a polymer precursor that initiates the reaction by the catalytic action of a base, such as a compound having an epoxy group or a cyanate group and a polymer, first, such a polymer precursor, and The part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base generator represented by said Formula (1) is exposed. When it is heated after exposure or simultaneously with exposure, a basic substance is generated in the exposed area, the reaction of the compound having an epoxy group or cyanate group and a polymer in that area is initiated, and only the exposed area is cured. The heating step for generating the basic substance and the heating step for performing the reaction for curing only the exposed portion (post-exposure baking described later) may be the same step or different steps. Next, the unexposed 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 negative two-dimensional resin pattern (general plane pattern) or a three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.

  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. Removing part More, it is possible to provide a tack-free coating on the substrate surface. 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 the exposure apparatus used in the exposure process are not particularly limited, and may be contact exposure or indirect exposure. A contact / proximity exposure machine using a g-line stepper, i-line stepper, ultrahigh pressure mercury lamp, or mirror projection exposure machine. Alternatively, a projector or a radiation source that can irradiate ultraviolet rays, visible rays, X-rays, electron beams, or the like can be used.

The heating temperature for generating a heated base after exposure or simultaneously with exposure is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. Heating by the temperature (for example, room temperature) of the environment where the photosensitive resin composition is placed may be used, and in that case, a base is gradually generated. Further, since the base is also generated by heat generated as a by-product during irradiation with electromagnetic waves, heating may be performed substantially simultaneously with the heat generated as a by-product during irradiation with electromagnetic waves. From the viewpoint of increasing the reaction rate and efficiently generating amine, the heating temperature for generating the base is preferably 30 ° C or higher, more preferably 60 ° C or higher, still more preferably 100 ° C or higher, Especially preferably, it is 120 degreeC or more. However, depending on the polymer precursors used in combination, for example, the unexposed part may be cured by heating at 60 ° C. or higher, so that the suitable heating temperature is not limited to the above.
For example, in the case of an epoxy resin, a preferable heat treatment temperature range is appropriately selected depending on the type of the epoxy resin, but is usually about 100 ° C to 150 ° C.

The coating film of the photosensitive resin composition according to the present invention is a post-exposure bake (Post) between the exposure process and the development process in order to physically accelerate the cross-linking reaction or to perform a reaction to cure only the exposed area. It is preferable to perform Exposure Bake (PEB). The PEB should be performed at a temperature at which the reaction rate such as the imidization rate differs between the site where the base is present and the site where the base is not present without irradiation due to the action of the base generated by electromagnetic wave irradiation and heating. Is preferred. For example, in the case of imidization, the preferable heat treatment temperature range is usually about 60 ° C to 200 ° C, more preferably 120 ° C to 200 ° C. When the heat treatment temperature is lower than 60 ° C., the imidization efficiency is poor, and it becomes difficult to cause a difference in the imidization ratio between the exposed portion and the unexposed portion under realistic process conditions. On the other hand, when the heat treatment temperature exceeds 200 ° C., imidization may proceed even in an unexposed portion where no amine is present, and it is difficult to cause a difference in solubility between the exposed portion and the unexposed portion.
Any method may be used for the heat treatment as long as it is a known method, and specific examples thereof include heating with a circulating oven in a nitrogen atmosphere or a hot plate, or a hot plate, but is not particularly limited.
In the present invention, a base is generated from the base generator by irradiation with electromagnetic waves and heating. The heating and PEB process for generating the base may be the same process or separate processes.

(Developer)
The developer used in the development step is not particularly limited as long as the solvent that changes the solubility of the irradiation site is used as the developer, and is appropriately selected according to the polymer precursor to be used, such as a basic aqueous solution or an organic solvent. It is possible to select.

Although it does not specifically limit as basic aqueous solution, For example, other than tetramethylammonium hydroxide (TMAH) aqueous solution whose density | concentration is 0.01 weight%-10 weight%, Preferably, 0.05 weight%-5 weight%. , Diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, triethylamine, diethylamine, methylamine, dimethylamine, dimethylaminoethyl acetate, dimethylaminoethanol, dimethylaminoethyl Examples of the aqueous solution include methacrylate, cyclohexylamine, ethylenediamine, hexamethylenediamine, and tetramethylammonium.
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, 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, other tetrahydrofuran, chloroform, acetonitrile and the like alone or Two or more types may be added in combination. After development, washing is performed with water or a poor solvent. 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

<A base generator that is represented by the chemical formula (2) and generates a base by irradiation and heating of electromagnetic waves>
The base generator according to the present invention is represented by the following chemical formula (2) and is characterized in that it generates a base upon irradiation with electromagnetic waves and heating.

In the chemical formula (2), R ¹¹ and R ¹² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹¹ and R ¹² may combine to form a cyclic structure. However, at least one of R ¹¹ and R ¹² is a monovalent organic group. R ¹³ , R ¹⁴ , R ^15, and R ¹⁶ are each hydrogen, halogen, or a monovalent organic group, and may be the same or different. Two or more of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to form a cyclic structure. However, at least one of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a monovalent organic group.

  The base generator represented by the chemical formula (2) has the above specific structure, and generates an amine that is a basic substance by irradiation with electromagnetic waves and heating.

Since the base generator according to the present invention has the above specific structure, the (—CH═CH—C (═O) —) moiety in the chemical formula (2) is isomerized into a cis isomer when irradiated with electromagnetic waves. And cyclized by heating to produce the base amine, NHR ¹¹ R ¹² . The temperature at which the imidization reaction of the polyimide precursor is initiated can be lowered by the catalytic action of the amine.

  When the base generator represented by the chemical formula (2) is cyclized, the phenolic hydroxyl group disappears, the solubility changes, and in the case of a basic aqueous solution, the solubility decreases. Thereby, the photosensitive resin composition containing the base generator represented by the chemical formula (2) has the precursor in the case where the polymer precursor contained in the composition is a polyimide precursor or a polybenzoxazole precursor. It has a function of further assisting in lowering the solubility due to the reaction with the final product, and it is possible to increase the solubility contrast between the exposed portion and the unexposed portion.

R ¹¹ and R ¹² in the chemical formula (2) may be the same as R ¹ and R ² mentioned in the base generator represented by the chemical formula (1).
R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ in the chemical formula (2) are the same as R ³ , R ⁴ , R ⁵ and R ⁶ mentioned in the base generator represented by the chemical formula (1). can do. However, at least one of R ^{13 to} R ¹⁶ is a halogen or a monovalent organic group.

  The structure represented by the chemical formula (2) is a trans isomer and / or a cis isomer, and only the trans isomer may be used or a mixture of the trans isomer and the cis isomer may be used, but the solubility contrast is increased. Therefore, the trans isomer ratio is preferably 90 to 100%, and it is more preferable to use only the trans isomer.

  Since the base generator represented by the chemical formula (2) has more types of polymer precursors that can be applied to absorb at least one of the wavelengths of electromagnetic waves of 365 nm, 405 nm, or 436 nm. preferable.

  The base generator represented by the chemical formula (2) has a molar extinction coefficient of 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at 405 nm, and the number of applicable polymer precursors further increases. It is preferable from the point.

  The base generator represented by the chemical formula (2) has at least one organic group, and by appropriately selecting the organic group, it is possible to absorb at wavelengths of 405 nm, 436 nm, etc. in addition to 365 nm. And having a feature that is excellent in the kind and sensitivity of the polymer precursor that can be applied to the photosensitive resin composition.

R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ 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, and an aryl having 7 to 16 carbon atoms. An oxyalkyl group (-ROAr group), an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 2 to 11 carbon atoms having a cyano group, an alkyl group having 1 to 10 carbon atoms having a hydroxyl group, and an alkoxy having 1 to 10 carbon atoms Group, amide group having 2 to 11 carbon atoms, alkylthio group having 1 to 10 carbon atoms (-SR group), acyl group having 1 to 10 carbon atoms, ester group having 2 to 11 carbon atoms, aryl having 6 to 20 carbon atoms Group, electron donating group and / or electron withdrawing group substituted aryl group having 6 to 20 carbon atoms, electron donating group and / or electron withdrawing group substituted benzyl group, cyano group and methylthio group (- SCH ₃₎ It is preferred. The alkyl moiety may be linear, branched or cyclic.

Since the base generator represented by the chemical formula (1) according to the present invention has excellent sensitivity as compared with conventionally used photobase generators, various applications are possible. Bases such as acid-base indicators such as acid-base indicators, as described in detail above, not limited to combining with a polymeric precursor whose reaction to the final product is facilitated by heating in the presence of a basic substance or in the presence of a basic substance Thus, various photosensitive compositions can be formed in combination with a compound whose structure and physical properties change. Such a photosensitive composition is a paint, printing ink, sealing material, or adhesive as described above, or an image forming medium, a color filter, a film for flexible display, a semiconductor device, an electronic component, an interlayer insulating film, It can be used as a material for forming a wiring coating film, an optical circuit, an optical circuit component, an antireflection film, a hologram, an optical member, or a building material.
For example, when an image forming layer is exposed in an image forming medium obtained by coating or impregnating a base material with an image forming layer containing at least a photobase generator and an acid-base indicator, the photobase generator However, the present invention can also be applied to an image forming medium characterized in that a base that reacts with an acid-base indicator is generated and an image is formed.

Hereinafter, the present invention will be specifically described with reference to examples. These descriptions do not limit the present invention. In the examples, parts represent parts by weight unless otherwise specified.
Moreover, each measurement and experiment were performed using the apparatus shown below.
¹ H NMR measurement: JEOL JNM-LA400WB, manufactured by JEOL Ltd.
Manual exposure: manufactured by Dainippon Kaken, MA-1100
Absorbance measurement: UV-2550 manufactured by Shimadzu Corporation, UV-visible spectrophotometer
5% weight loss temperature measurement: manufactured by Shimadzu Corporation, simultaneous differential heat / thermogravimetric measurement device DTG-60
Infrared absorption spectrum measurement: FTS 7000, manufactured by Varian Technologies Japan Limited
Heating of the coating film: As One Co., Ltd., HOT PLATE EC-1200 (may be described as a hot plate in this example)

(Synthesis Example 1: Synthesis of polyimide precursor)
Di (4-aminophenyl) ether (10.0 g, 50 mmol) was put into a 300 mL three-necked flask, dissolved in 105.4 mL of dehydrated N, N-dimethylacetamide (DMAc), and an ice bath under a nitrogen stream. The mixture was stirred while cooling. Thereto, 14.7 g (50 mmol) of 3,3 ′, 4,4′-biphenyltetracarboxylic acid 3,4: 3 ′, 4′-dianhydride was added little by little. The solution was stirred for 5 hours, and the solution was reprecipitated with dehydrated diethyl ether, and the precipitate was dried at room temperature under reduced pressure for 17 hours to obtain a polyamic acid (polyimide precursor (1)) having a weight average molecular weight of 10,000. Was quantitatively obtained as a white solid.

(Synthesis Example 2: Synthesis of polysiloxane precursor)
To a 100 ml flask equipped with a condenser, 5 g of phenyltriethoxysilane, 10 g of triethoxysilane, 0.05 g of ammonia water, 5 ml of water and 50 ml of propylene glycol monomethyl ether acetate were added. The solution was stirred using a semicircular type mechanical stirrer and reacted at 70 ° C. for 6 hours with a mantle heater. Subsequently, ethanol and residual water produced by the condensation reaction with water were removed using an evaporator. After completion of the reaction, the flask was left to reach room temperature to prepare an alkoxysilane condensate (alkoxysilane condensate (1)).

( Reference Production Example 1: Synthesis of Reference Base Generator (1))
Under a nitrogen atmosphere, 1.00 g (6.1 mmol) of o-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 100 mL of dehydrated tetrahydroxyfuran in a 300 mL three-necked flask, and 1-ethyl-3- (3-dimethyl) is dissolved. Aminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.17 g (6.1 mmol, 1.0 eq) was added. Under an ice bath, 0.7 ml (6.1 mmol, 1.0 eq) of cyclohexylamine (manufactured by Kanto Chemical Co., Inc.) was added, followed by stirring at room temperature for 3 days. The reaction solution was washed with brine and dried over sodium sulfate. By purification by silica gel column chromatography (developing solvent: chloroform / methanol 1/0 to 20/1), 350 mg of a reference base generator (1) represented by the following chemical formula (6) was obtained.

( Reference Production Example 2: Synthesis of Reference Base Generator ( A ))
In a 100 mL flask, 2.00 g of potassium carbonate was added to 15 mL of methanol. In a 50 mL flask, 4.29 g (10 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.52 g of 2-hydroxy-4-methoxybenzaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 10 mmol) was dissolved in 10 mL of methanol and slowly added dropwise to a well-stirred potassium carbonate solution. After stirring for 3 hours, after confirming the completion of the reaction by thin layer chromatography, the mixture was filtered to remove potassium carbonate and concentrated under reduced pressure. After concentration, 50 mL of 1N aqueous sodium hydroxide solution was added and stirred for 1 hour. After completion of the reaction, the precipitate was removed by filtration, and concentrated hydrochloric acid was added dropwise to make the reaction solution acidic. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 1.46 g (7.52 mmol) of 2-hydroxy-4-methoxycinnamic acid.
Under a nitrogen atmosphere, 1.01 g (5.2 mmol) of 2-hydroxy-4-methoxycinnamic acid was dissolved in 40 mL of dehydrated tetrahydroxyfuran in a 300 mL three-necked flask, and 1-ethyl-3- (3- 0.99 g (5.2 mmol) of dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, 0.79 g (5.2 mmol) of 1-hydroxybenzotriazole (manufactured by Tokyo Chemical Industry Co., Ltd.) was slowly added dropwise. After returning to room temperature and stirring for about 30 minutes, 0.5 ml (4.2 mmol) of cyclohexylamine (manufactured by Kanto Chemical Co., Inc.) was added. After 10 minutes, 0.10 g (0.86 mmol) of 4- (dimethylamino) pyridine was added and stirred overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with ethyl acetate, the mixture was washed with an aqueous hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, and dried over sodium sulfate. 350 mg of a reference base generator ( A ) represented by the following chemical formula (7) was obtained by purification by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1).

( Reference Production Example 3: Synthesis of Reference Base Generator (3))
In a 100 mL three-necked flask under nitrogen atmosphere, 0.50 g (3.1 mmol) of o-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was dissolved in 40 mL of dehydrated tetrahydroxyfuran, and 1-ethyl-3- (3-dimethyl) was dissolved. 0.59 g (3.1 mmol, 1.0 eq) of aminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. Piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.3 ml, 3.1 mmol, 1.0 eq) was added in an ice bath, and the mixture was stirred overnight at room temperature. The reaction mixture was concentrated, extracted with chloroform, washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and brine, and filtered to obtain 450 mg of a reference base generator (3) represented by the following chemical formula (8).

( Reference Production Example 4: Synthesis of Reference Base Generator (4))
Under a nitrogen atmosphere, 1.00 g (6.1 mmol) of o-coumaric acid (manufactured by Tokyo Chemical Industry Co., Ltd.) is dissolved in 40 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask, and 1-ethyl-3- (3-dimethyl) is dissolved. 1.4 g (7.3 mmol, 1.2 eq) of aminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. In an ice bath, 1.0 ml (7.3 mmol, 1.2 eq) of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight at room temperature. The reaction solution was concentrated, extracted with chloroform, washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and brine, and filtered to obtain 171 mg of a reference base generator (4) represented by the following chemical formula (9).

( Reference Production Example 5: Synthesis of Reference Base Generator (5))
In Production Example 4, instead of using 1.0 ml (7.3 mmol, 1.2 eq) of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.6 ml (7.3 mmol, pyrrolidine (manufactured by Tokyo Chemical Industry Co., Ltd.)) In the same manner as in Production Example 4 except that 1.2 eq) was used, 360 mg of the reference base generator (5) represented by the following chemical formula (10) was obtained.

( Reference Production Example 6: Synthesis of Reference Base Generator (6))
In Production Example 4, instead of using 1.0 ml (7.3 mmol, 1.2 eq) of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.82 ml (7. 379 mg of a reference base generator (6) represented by the following chemical formula (11) was obtained in the same manner as in Production Example 4 except that 3 mmol, 1.2 eq) was used.

( Reference Production Example 7: Synthesis of Reference Base Generator (7))
In Production Example 4, instead of using 1.0 ml (7.3 mmol, 1.2 eq) of dipropylamine (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 ml (7.3 mmol, 7.3 mmol, diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was used. In the same manner as in Production Example 4 except that 1.2 eq) was used, 498 mg of a reference base generator (7) represented by the following chemical formula (12) was obtained.

( Reference Production Example 8: Synthesis of Reference Base Generator (8))
In a 100 mL flask, 500 mg (3.0 mmol) of 2-hydroxy-cinnamic acid was dissolved in 20 ml of dioxane, and 200 μl (2.8 mmol, 0.9 eq) of thionyl chloride was slowly added dropwise. After stirring for 10 minutes, 0.9 ml (6.6 mmol, 2.2 eq) of 2,6-dimethylpiperidine was added. After completion of the reaction, the reaction solution was concentrated and dissolved in water. Extraction with chloroform, followed by washing with a saturated aqueous sodium hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, followed by filtration gave 64 mg of a reference base generator (8) represented by the following chemical formula (13).

( Reference Production Example 9: Synthesis of Reference Base Generator ( B ))
In a 100 mL flask, 2.00 g of potassium carbonate was added to 15 mL of methanol. In a 50 mL flask, 2.67 g (6.2 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide and 945 mg (6.2 mmol) of 2-hydroxy-4-methoxybenzaldehyde were dissolved in 10 mL of methanol and a well-stirred potassium carbonate solution. The solution was slowly dripped into. After stirring for 3 hours, the completion of the reaction was confirmed by TLC, followed by filtration to remove potassium carbonate and concentration under reduced pressure. After concentration, 50 mL of 1N aqueous sodium hydroxide solution was added and stirred for 1 hour. After completion of the reaction, triphenylphosphine oxide was removed by filtration, and then concentrated hydrochloric acid was added dropwise to acidify the reaction solution. The precipitate was collected by filtration and washed with a small amount of chloroform to obtain 1.00 g of 2-hydroxy-4-methoxycinnamic acid. Subsequently, in a 100 mL three-necked flask, 500 mg (3.0 mmol) of 2-hydroxy-4-methoxycinnamic acid was dissolved in 40 mL of dehydrated tetrahydroxyfuran, and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was dissolved. 0.586 g (3.0 mmol) of salt (EDC) was added. After 30 minutes, 0.3 ml (3.0 mmol) of piperidine was added. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with diethyl ether, the mixture was washed with saturated aqueous sodium hydrogen carbonate solution, 1N hydrochloric acid and saturated brine. Thereafter, purification by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 10/1) yielded 64 mg of a reference base generator ( B ) represented by the following chemical formula (14).

(Production Example 10: Synthesis of base generator (10))
In Production Example 9, instead of using 945 mg (6.2 mmol) of 2-hydroxy-4-methoxybenzaldehyde, 1.45 g (6.2 mmol) of 3,5-di-tert-butylsalicylaldehyde was used. In the same manner as in Production Example 9, 1.20 g of 3,5-di-tert-butyl-2-hydroxycinnamic acid was obtained instead of 2-hydroxy-4-methoxycinnamic acid. Subsequently, 500 mg (1.8 mmol) of 3,5-di-tert-butyl-2-hydroxycinnamic acid was dissolved in 20 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask, and 0.416 g (2.2 mmol) of EDC was dissolved. Was added. After 30 minutes, 0.21 mL (2.2 mmol) of piperidine was added and stirred overnight at room temperature. The reaction solution was concentrated, extracted with chloroform, washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and brine, and filtered to obtain 320 mg of a base generator (10) represented by the following chemical formula (15).

(Production Example 11: Synthesis of base generator (11))
Production Example 9 Production Example 9 except that instead of 945 mg (6.2 mmol) of 2-hydroxy-4-methoxybenzaldehyde, 1.07 g (6.2 mmol) of 2-hydroxy-1-naphthaldehyde was used. In the same manner as in Example 9, 1.20 g of 3- (2-hydroxy-1-naphthalenyl) -acrylic acid was obtained instead of 2-hydroxy-4-methoxycinnamic acid. Subsequently, in a 100 mL three-necked flask, 1.00 g (4.67 mmol) of 3- (2-hydroxy-1-naphthalenyl) -acrylic acid was dissolved in 20 mL of dehydrated tetrahydroxyfuran, and 1.07 g (5.60 mmol) of EDC was dissolved. Was added. After 30 minutes, 0.64 mL (5.60 mmol) of cyclohexylamine was added and stirred overnight at room temperature. The reaction solution was concentrated, extracted with chloroform, washed with dilute hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and brine, and filtered to obtain 520 mg of a base generator (11) represented by the following chemical formula (16).

(Production Example 12: Synthesis of base generator (12))
In the same manner as in Production Example 11, 1.20 g of 3- (2-hydroxy-1-naphthalenyl) -acrylic acid was obtained. Subsequently, in Production Example 11, instead of using cyclohexylamine 0.64 mL (5.60 mmol), piperidine 0.65 ml (5.60 mmol) was used in the same manner as in Production Example 11 and represented by the following chemical formula (17). 480 mg of the base generator (12) obtained was obtained.

(Production Example 13: Synthesis of base generator (13))
In the same manner as in Production Example 11, 1.20 g of 3- (2-hydroxy-1-naphthalenyl) -acrylic acid was obtained. Subsequently, in Preparation Example 11, instead of using cyclohexylamine 0.64 mL (5.60 mmol), except that dipropylamine 0.92 ml (5.60 mmol) is used, in the same manner as Preparation Example 11, the following chemical formula (18) 620 mg of the base generator (13) represented by

(Comparative Production Example 1: Synthesis of Comparative Base Generator (1))
Further, as a comparative base generator (1), Macromolecules A.I. Mochizuki, Vol. 28, no. 1, 1995, [(4,5-dimethoxy-2-nitrobenzyl) oxy] carbonyl-2,6-dimethylpiperidine (hereinafter abbreviated as “DNCDP”) represented by the following chemical formula (19). Synthesized).

<Evaluation of base generator>
For the synthesized base generators ( 10 ) to (13), the comparative base generator (1 ), and the reference base generators (1) to (8), (A) and (B) , the following measurements were performed, evaluated. The results of molar extinction coefficient and 5% weight loss temperature are shown in Table 1. Table 2 shows the results of the base generating ability. In Table 2, the base generation rate is a percentage of the number of moles of base generated relative to the number of moles of the base generator used, and the base generation rate of each base generator is the ratio of light irradiation and heating combined. It is.

(1) Molar extinction coefficient The base generators ( 10 ) to (13), the comparative base generator (1 ), and the reference base generators (1) to (8), (A) and (B) were each acetonitrile. Was dissolved at a concentration of 1 × 10 ⁻⁴ mol / L, a quartz cell (optical path length: 10 mm) was filled with the solution, and the absorbance was measured.

(2) 5% weight loss temperature Heat resistance of base generators ( 10 ) to (13), comparative base generator (1 ), and reference base generators (1) to (8), (A) and (B) In order to evaluate the properties, a 5% weight loss temperature was measured for each sample under the conditions of a sample weight of 3.4 mg and a heating rate of 10 ° C./min.

(3) Base generating ability 1 mg each for the base generators ( 10 ) to (13), the comparative base generator (1 ), and the reference base generators (1) to (8), (A) and (B) Were prepared and each was dissolved in deuterated dimethyl sulfoxide in a quartz NMR tube. Using a filter that transmits 20% of i-line and a high-pressure mercury lamp, one was irradiated with light at ² J / cm ² , and the other was irradiated with light at 20 J / cm ² . The remaining one was not irradiated with light. ¹ H NMR of each sample was measured to determine the isomerization ratio.
Reference base generator (1) is 5.1% isomerization when 2J / cm ² irradiation was 34.0% isomerization when 20 J / cm ² irradiation. When the isomerized sample was heated to 160 ° C., 98% of the isomerized compound was cyclized, and a base was generated along with it, resulting in the base generation rate shown in Table 2. The base generation rate was similarly determined for the base generators ( 10 ) to (13), the comparative base generator (1 ), and the reference base generators (1) to (8), (A) and (B). Asked. The results are shown in Table 2, respectively. Base generator (12) and (13) high base developmental potential for, 20 J / cm ² instead of irradiation to 6J / cm ² irradiation.
In the comparative base generator (1), generation of base was not confirmed by irradiation at ² J / cm ² . When irradiated with 20 J / cm ² , 4.8% of base was generated.
From these results, it was found that the base generators ( 10 ) to (13) of the present invention have a low molar extinction coefficient compared to the comparative base generator (1), but can generate a base efficiently.

( Reference Example 1: Preparation of Reference Photosensitive Resin Composition (1))
A reference photosensitive resin composition (1) having the composition shown below was prepared.
Polyimide precursor (1): 8 parts by weight Reference base generator (1): 2 parts by weight Solvent (DMAc (dimethylacetamide)): 90 parts by weight

(Creation of coating film)
Three reference photosensitive resin compositions (1) were prepared, and each was spin-coated on a chrome-plated glass so that the final film thickness was 1 μm, and dried on a hot plate at 100 ° C. for 5 minutes. Three coating films were obtained. One film was exposed at ² J / cm ² in terms of i-line. Another sheet was exposed in a pattern at 10 J / cm ² in i-line conversion. The remaining one coating film was not exposed.

( Reference Example 2: Preparation of Reference Photosensitive Resin Composition (2))
A reference photosensitive resin composition (2) having the composition shown below was prepared using the reference base generator (3).
Polyimide precursor (1): 85 parts by weight Reference base generator (3): 15 parts by weight Solvent (N-methyl-2-pyrrolidone): 733 parts by weight

( Reference Example 3: Preparation of Reference Photosensitive Resin Composition ( B ))
Instead of reference base generator in Reference Example 2 (3), except for using the reference base generator (B), in the same manner as in Reference Example 2, Reference photosensitive resin composition (B) was prepared.

(Comparative Example 1: Preparation of comparative photosensitive resin composition (1))
A comparative photosensitive resin composition (1) was prepared in the same manner as in Reference Example 2, except that the comparative base generator (1) was used instead of the reference base generator (3) in Reference Example 2.

(Creation of coating film)
Each of the reference photosensitive resin compositions (2) and ( B ) and the comparative photosensitive resin composition (1) was spin-coated on a chrome-plated glass so as to have a final film thickness of 4 μm. It was dried on a hot plate for 15 minutes to obtain 5, 8 and 6 coating films, respectively. Except for one sheet, the entire surface was exposed with a high-pressure mercury lamp using a manual exposure machine. The four coating films of the reference photosensitive resin composition (2) were exposed at 0, 500, 700, and 4000 mJ / cm ² , respectively. The seven coating films of the reference photosensitive resin composition ( B ) were each exposed at 0, 10, 30, 50, 100, 300, and 1000 mJ / cm ² . The five coating films of the comparative photosensitive resin composition (1) were exposed at 0, 500, 1000, 2000, and 4000 mJ / cm ² , respectively. The remaining one sheet was exposed in a pattern. Thereafter, each coating film was heated at 155 ° C. for 10 minutes.

<Evaluation of photosensitive resin composition>
(1) Thermosetting temperature
The infrared absorption spectrum was measured for the whole surface exposed coating film and the unexposed coating film prepared using the reference photosensitive resin composition (1) while heating from room temperature to 350 ° C. at 5 ° C./min. In order to confirm the progress of imidization, FIG. 1 shows the results of plotting the amount of decrease in peak intensity due to heating, based on the peak intensity of 1605 cm ⁻¹ derived from the precursor before measurement.
From FIG. 1, it can be seen that in Reference Example 1, the difference in the imidization ratio between the two samples is maximized around 160 ° C. Moreover, the spectrum derived from the polyimide precursor disappeared with the heating, and the peak derived from the polyimide appeared, so that it was confirmed that the reaction from the polyimide precursor to the polyimide proceeded.

(2) Residual film rate
The reference photosensitive resin compositions (2), ( B ), and the comparative photosensitive resin composition (1) were used to prepare a coating film that was exposed on the entire surface, and a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, respectively. The film was dipped in a 9: 1 mixed solution of isopropanol at room temperature for 10 minutes, and the remaining film thickness on the glass was measured. The results are shown in FIG. In the figure, the normalized residual film ratio was defined as film thickness after development × 100 / maximum film thickness after development.

Since the residual film rate increased with the increase in the amount of UV irradiation, it was shown that the base generator generated amine by UV irradiation and heating, and imidization proceeded. The reference photosensitive resin composition ( B ) had a normalized film thickness of about 1 at 50 mJ / cm ² , and the reference photosensitive resin composition (2) had a normalized film thickness of about 1 at 500 mJ / cm ² . In contrast, Comparative photosensitive resin composition (1) is 500 mJ / in cm ² residual film ratio is 0, the normalized thickness at 1000 mJ / cm ² was about 1. Since the residual film rate increased with the increase in the amount of UV irradiation, it was shown that the base generator generated a base by UV irradiation and heating, and imidization proceeded. From these results, it was revealed that the reference photosensitive resin composition proceeded with imidization with a small exposure amount as compared with the comparative photosensitive resin composition, and the sensitivity was high. It was revealed that the reference photosensitive resin composition ( B ) proceeds with imidization with a particularly small exposure amount.

Since the residual film rate increased with the increase in the amount of UV irradiation, it was shown that the base generator generated a base by UV irradiation and heating, and imidization proceeded. It was revealed that the reference photosensitive resin composition proceeds with imidization with a small exposure amount as compared with the comparative photosensitive resin composition, and the sensitivity was high. It was revealed that the reference photosensitive resin composition ( B ) proceeds with imidization with a particularly small exposure amount.

(3) Pattern forming ability
About the coating film exposed to the pattern shape created using the reference photosensitive resin composition (1), after heating for 5 minutes on a 170 degreeC hotplate, the tetramethylammonium hydroxide 2.38 weight% aqueous solution and isopropanol were added. It was immersed in the mixed solution at 9: 1. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, it was heated at 350 ° C. for 1 hour to perform imidization. From this result, it was revealed that the reference photosensitive resin composition can form a good pattern.
Moreover, about the coating film exposed to the pattern shape created using reference photosensitive resin composition (2) or ( B ), the solution which mixed tetramethylammonium hydroxide 2.38weight% aqueous solution and isopropanol by 9: 1. Soaked in. As a result, a pattern was obtained in which the exposed portion remained undissolved in the developer. Furthermore, it was heated at 350 ° C. for 1 hour to perform imidization. From this result, it was revealed that the reference photosensitive resin composition can form a good pattern. The reference photosensitive resin composition (2) formed a pattern at 500 mJ / cm ² , and the reference photosensitive resin composition ( B ) formed a pattern at 100 mJ / cm ² . On the other hand, when the comparative photosensitive resin composition (1) was tested in the same manner, a pattern was finally formed at 2000 mJ / cm ² .

( Reference Examples 4 to 5: Preparation of Reference Photosensitive Resin Compositions (4) to (5))
Using the reference base generator (5) or (7), reference photosensitive resin compositions (4) and (5) having the compositions shown below were prepared.
Epoxy resin (manufactured by jER828 Japan Epoxy Resin): 15 parts by weight Reference base generator (5) or (7): 15 parts by weight Solvent (N-methyl-2-pyrrolidone): 370 parts by weight

Two pieces each of the reference photosensitive resin compositions (4) and (5) weighing 500 mg on the examiner were prepared. Using a manual exposure machine, one side was exposed to 100 J / cm ^{2 in} terms of i-line. All four examiners were heated at 160 ° C. for 30 minutes. As a result of NMR measurement of the sample after heating, formation of a new peak was confirmed in the sample irradiated with both samples of the reference photosensitive resin composition (4) and (5), but a new peak was observed in the unirradiated sample. The formation of was not confirmed.

Each of the reference photosensitive resin compositions (4) and (5) was spin-coated on a chrome-plated glass so as to have a final film thickness of 0.5 μm, and dried on a hot plate at 80 ° C. for 15 minutes. Two coating films of each reference photosensitive resin composition were obtained. About 1 sheet of the coating film of each reference photosensitive resin composition, 10 J / cm < ² > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Thereafter, each coating film was heated at 160 ° C. for 30 minutes. The heated coating film was immersed in a mixed solution of isopropanol and chloroform (isopropanol: chloroform = 4: 1 (volume ratio)) at room temperature for 10 minutes. It became clear that the resin was cured. On the other hand, about 2 sheets heated without exposure, it melt | dissolved in the said mixed solution.

( Reference Example 6: Preparation of reference photosensitive resin composition (6))
It consists of 100 parts by weight of hexamethylene diisocyanate (manufactured by Kanto Chemical) as the isocyanate resin, 150 parts by weight of polytetrahydrofuran (manufactured by Aldrich) as the resin having a hydroxyl group, 10 parts by weight of the reference base generator (3), and 500 parts by weight of tetrahydrofuran. A reference photosensitive resin composition (6) was prepared.

Was spin-coated to a final thickness of 0.5μm on a glass reference photosensitive resin composition (6) is chrome-plated, and dried 5 minutes at 60 ° C. on a hot plate, reference photosensitive resin composition One coating film was obtained. The obtained coating film was subjected to 1 J / cm ² overall exposure with a high-pressure mercury lamp using a manual exposure machine. Then, when it heated at 120 degreeC for 10 minute (s) and cooled to room temperature, the low-elasticity solid substance was obtained and it confirmed that hardening with an isocyanate group and a hydroxyl group advanced.

( Reference Example 7: Preparation of reference photosensitive resin composition (7))
100 parts by weight of the alkoxysilane condensate (1) and 10 parts by weight of the reference base generator (3) are mixed and then dissolved in 500 parts by weight of tetrahydrofuran as a solvent to prepare a reference photosensitive resin composition (7). did.

Reference photosensitive resin composition (7) was spin-coated to a final thickness of 0.5μm on glass which has been chromium plated, and dried 5 minutes at 80 ° C. on a hot plate, reference photosensitive resin composition Two coating films were obtained. About 1 sheet of the coating film of each reference photosensitive resin composition, 10 J / cm < ² > whole surface exposure was performed with the high pressure mercury lamp using the manual exposure machine. Thereafter, each of the exposed coating film and the unexposed coating film was heated at 120 ° C. for 30 minutes. Infrared absorption spectrum measurement was performed on each sample before and after heating. As a result, for the sample after heating of the exposed coating film, a peak of 1020 cm ^-1 attributed to the Si-O-Si bond indicating polymerization appeared, and it was attributed to Si-OCH ₃ indicating the raw material. The peaks at 2850 cm ^-1 and 850 cm ^-1 were reduced compared to the sample before heating. In the sample after heating the unexposed film, a peak of 1020 cm ^-1 attributed to the Si-O-Si bond, indicating that it was polymerized, appeared. It was small. As a result, it has been clarified that, when exposure is performed using a reference base generator, a base is generated and the polymerization of the alkoxysilane condensate is promoted.

Claims (10)

A polymer precursor whose reaction to the final product is accelerated by heating in the presence of a basic substance or in the presence of a basic substance, and a base expressed by the following chemical formula (1) and irradiated and heated by electromagnetic waves A photosensitive resin composition comprising a base generator that generates water.
In chemical formula (1), R ¹ and R ² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹ and R ² may combine to form a cyclic structure. However, at least one of R ¹ and R ² is a monovalent organic group. R ³ , R ⁴ , R ⁵ and R ⁶ are each hydrogen, halogen or a monovalent organic group (provided that the monovalent organic group in R ³ , R ⁴ , R ⁵ and R ⁶ is saturated or A saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, or an aryl thioether group), which may be the same or different. Two or more of R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to form a cyclic structure. However, at least one of R ³ , R ⁴ , R ⁵ and R ⁶ is a hydrocarbon group, or two or more of R ³ , R ⁴ , R ⁵ and R ⁶ are bonded. To form a ring structure.   2. The photosensitive resin composition according to claim 1, wherein the base generator has absorption at at least one of wavelengths of electromagnetic waves of 365 nm, 405 nm, or 436 nm.   The polymer precursor is selected from the group consisting of a compound and polymer having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and a polybenzoxazole precursor. The photosensitive resin composition of Claim 1 or 2 characterized by including the above.   The photosensitive resin composition according to claim 1, wherein the polymer precursor is soluble in a basic solution.   The photosensitive resin composition according to any one of claims 1 to 4, wherein the polymer precursor is a polyimide precursor or a polybenzoxazole precursor.   The pattern formation material which consists of the photosensitive resin composition as described in any one of the said Claims 1 thru | or 5.   A coating film or a molded body is formed using the photosensitive resin composition according to any one of claims 1 to 5, and the coating film or the molded body is irradiated with electromagnetic waves in a predetermined pattern, and after irradiation. Alternatively, the pattern forming method is characterized in that development is performed after heating at the same time as irradiation to change the solubility of the irradiated portion. A base generator represented by the following chemical formula (2) and generating a base by irradiation and heating of electromagnetic waves.
In the chemical formula (2), R ¹¹ and R ¹² are each independently hydrogen or a monovalent organic group, and may be the same or different. R ¹¹ and R ¹² may combine to form a cyclic structure. However, at least one of R ¹¹ and R ¹² is a monovalent organic group. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each hydrogen, halogen or a monovalent organic group (provided that the monovalent organic group in the R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is saturated or A saturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, or an aryl thioether group), which may be the same or different. Two or more of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ may be bonded to form a cyclic structure. However, at least one of R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a hydrocarbon group, or R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are a combination of two or more of them. To form a ring structure.   The base generator according to claim 8, wherein the base generator has absorption at at least one of wavelengths of electromagnetic waves of 365 nm, 405 nm, and 436 nm.   The base generator according to claim 8 or 9, wherein the molar extinction coefficient is 100 or more at an electromagnetic wave wavelength of 365 nm, or 1 or more at a wavelength of 405 nm.