JP2008250111A - Base multiplying agent, resin composition using the same and article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a base multiplying agent that is more inexpensive and has preferable heat resistance, and to provide a resin composition and a photosensitive resin composition containing the base multiplying agent. <P>SOLUTION: The base multiplying agent has at least one structure expressed by formula (1) and is decomposed by heating at 150°C or higher in the presence of an amino compound to produce an amino compound. In formula (1), each of R<SP>1</SP>to R<SP>5</SP>independently represents a hydrogen atom, halogen atom, hydroxyl group, amino group, mercapto group, nitro group, silyl group, silanol group or monovalent organic group and may be identical to or different from one another or may be bonded to one another to form a cyclic structure; and R<SP>6</SP>represents a substituted or unsubstituted aliphatic hydrocarbon group or a substituted or unsubstituted aromatic hydrocarbon group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a base proliferating agent and a resin composition containing the same. More specifically, the present invention relates to a base proliferating agent that has high heat resistance, is easy to synthesize and can be produced at low cost, a resin composition and a photosensitive resin composition containing the base proliferating agent, and the photosensitive resin. The present invention relates to an article having high heat resistance and high stability, at least a part of which is formed by a cured product of the conductive resin composition.

Photosensitive resins that cure or change solubility upon irradiation with radiation such as ultraviolet rays are generally those having good solubility in the exposed area (positive type) and those having good solubility in the unexposed area (negative). Type). In the case of the negative type, since the photosensitive resin itself is cured and becomes insoluble by exposure, the photosensitive resin often remains on the substrate and becomes a part of the product as a functional film.
Negative-type photosensitive resins have been used initially in, for example, paints, printing inks, overcoat layers, adhesives, printing masters, etc., but in recent years, solder resists for wiring protection of printed wiring boards, interlayer insulating films, Applications have been extended to color filter pixels, antireflection films, resists for forming holograms, and the like.

In general, the negative photosensitive resin is a type that cures a compound having an ethylenically unsaturated bond using radical polymerization, an epoxy compound or oxetane compound using an acid or base, or an aromatic compound. There are proposed a type in which, for example, a cross-linking reaction or a condensation reaction is performed to insolubilize, and a type in which a polymer is cross-linked and insolubilized using an azo compound.
A type using an azo compound and a type using radical polymerization have been put into practical use for a long time and used for various applications.
Negative photosensitive resins using radical polymerization are highly sensitive and have a long history, so many types of ethylenically unsaturated group-containing compounds and photoradical generators are on the market. There is an advantage that can be designed. On the other hand, there is a problem that heat resistance is limited due to the inhibition of polymerization by oxygen and the necessity of an ethylenically unsaturated bond.

Negative photosensitive resin compositions that use acids and bases can be used for applications that require relatively high heat resistance, such as electronic parts, because cured products can use epoxy compounds that have excellent heat resistance. It is being considered.
Therefore, a problem arises when additives such as a photopolymerization initiator remaining in the coating film adversely affect product performance when used as a part of a product as a functional film such as an insulating film. . It is known that when a photosensitive resin cured with a photoacid generator is used as an insulating film for an electronic component or the like, the wiring may be corroded in a high-temperature and high-humidity environment.

For this reason, negative photosensitive resins using photobase generators that generate bases that act not only as photoacid generators but also as curing catalysts such as epoxy resins are the focus of attention for applications in direct contact with metals. Has been.
The photobase generator is a compound that generates a base by decomposition or rearrangement reaction by absorbing light. By using a base as the curing agent, a cured film can be formed without corroding the metal.
Although there is great expectation for a photosensitive resin composition using a photobase generator in the above circumstances, a photobase generator having high sensitivity to light from a general high-pressure mercury lamp is known. Absent.

Therefore, Patent Document 1 proposes a photosensitive material using a base growth reaction. A photosensitive material that utilizes a base growth reaction is a compound that generates a base by the action of a small amount of base generated from a photobase generator to generate a base by decomposition or rearrangement. It is a material based on the idea of making up for the lack of sensitivity.
Using this concept, even if a low-sensitivity photobase generator is used, the number of bases can be increased by a growth reaction as long as a small amount of base is generated. I can do it. However, the base proliferating agent as disclosed in Patent Document 1 has a problem that the synthesis is complicated and the cost is high.
Furthermore, since the base proliferating agent as disclosed in Patent Document 1 generates an amine by intramolecular cleavage reaction, introduction of a structure in which the decomposition product takes a stable structure after decomposition (electron withdrawing group) For this reason, there are problems that the heat resistance is lowered and the synthesis route is complicated.

JP 2000-330270 A

  The present invention has been accomplished in view of the above circumstances, and its main purpose is a cheaper and better heat-resistant base proliferating agent, a resin composition containing the base proliferating agent, and photosensitivity. A resin composition is provided.

  In order to solve the above object, the base proliferating agent provided by the present invention has at least one structure represented by the following formula (1), and decomposes by heating at 150 ° C. or higher in the presence of an amino compound. A base proliferating agent characterized by producing an amino compound.

（式（１）において、Ｒ^１〜Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、アミノ基、メルカプト基、ニトロ基、シリル基、シラノール基、又は１価の有機基であり、それらは互いに同一であっても異なっていても良く、それらが互いに結合を介して環状構造を形成していても良い。Ｒ^６は置換又は無置換の脂肪族炭化水素基、或いは置換又は無置換の芳香族炭化水素基である。）

(In Formula (1), R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a silyl group, a silanol group, or a monovalent organic group, They may be the same as or different from each other, and they may form a cyclic structure through a bond to each other, R ⁶ represents a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted Aromatic hydrocarbon group.)

  In the base proliferating agent according to the present invention, an aromatic ring is directly bonded to an oxygen atom of a urethane bond, and the heat resistance is excellent. Therefore, it can be applied to applications requiring heat resistance such as a photosensitive polyimide precursor such as polyamic acid or a photosensitive polybenzoxazole precursor, which requires heat resistance of 150 ° C. or higher.

  Since the base proliferating agent according to the present invention can be synthesized in one step by an addition reaction between a phenol derivative and an isocyanate ester, there is no elimination component at the time of synthesis, and it is inexpensive and easy to purify. Furthermore, since both the phenol derivatives and isocyanates used as raw materials have many types of commercially available compounds and many structural options, it is possible to synthesize a base proliferating agent having characteristics corresponding to the application at a lower cost. Is possible.

  The base proliferating agent of the present invention is preferably added in combination with a compound that generates an amino compound by the action of light or heat, but when there is no compound that generates an amino compound by the action of light or heat, It is hydrolyzed by the catalytic action of an amino compound produced by the thermal decomposition of to produce an amino compound.

In the base proliferating agent of the present invention, it is preferable that at least one of R ^{1 to} R ⁵ in the formula (1) is an electron donating group. When an electron donating group is introduced into the aromatic ring, the electron density of the urethane bond is increased and the stability is improved. As a result, the heat resistance is improved. Examples of the electron donating group include a hydroxyl group, a primary amino group, a secondary amino group, a tertiary amino group, an alkoxy group, an alkylthio group, an oxyacyl group, an amide group, an alkyl group, and an aryl group.

  The base proliferating agent of the present invention is hydrolyzed by heating at 150 ° C. or higher in the presence of an amino compound to produce an amino compound. Therefore, it is preferable that the reaction system contains water or a functional group (such as amic acid or dicarboxylic acid) that can supply water.

  In the base proliferating agent of the present invention, the 5% weight loss temperature is preferably 150 ° C. or more from the viewpoint of heat resistance.

  The base proliferating agent of the present invention preferably has no absorption in a wavelength region of 400 nm or more, and more preferably has no absorption in a wavelength region of 360 nm or more. When absorption is at 400 nm or more, when added to the photosensitive resin composition, light from the light source is absorbed, resulting in a decrease in sensitivity. In general, the main emission wavelengths of high-pressure mercury lamps used for exposure are 436 nm (g-line), 405 nm (h-line), and 365 nm (i-line). More preferably, it has no absorption in the wavelength region.

Next, the resin composition according to the present invention contains the base proliferating agent according to the present invention and a compound that promotes curing or condensation reaction by the action of a base.
Since the resin composition according to the present invention contains the base proliferating agent according to the present invention and a compound that accelerates curing or condensation reaction by the action of a base, the resin composition is usually cured by heating the resin composition. . Since the base proliferating agent according to the present invention contained in the resin composition of the present invention is a neutral compound before decomposition, the storage stability of the resin composition of the present invention is good.

  In the resin composition according to the present invention, the compound that accelerates the curing or condensation reaction by the action of the base has a molecular weight of 1000 or more, there is no stickiness of the surface after drying, and handling of the sample after coating is possible. It is preferable because it becomes easy.

  In the resin composition according to the present invention, it is preferable to combine a polyamic acid as a compound that accelerates the curing or condensation reaction by the action of the base. Polyamic acid is a polyimide precursor having alkali solubility, and when polyamic acid is used, a resin composition excellent in heat resistance and mechanical properties can be obtained.

  The resin composition according to the present invention preferably further contains a compound that generates an amino compound by the action of light or heat. Especially, it can be set as the highly sensitive photosensitive resin composition by combining with the compound which generate | occur | produces an amino compound by light.

The resin composition according to the present invention is suitably used as a pattern forming material.
For example, by applying the resin composition according to the present invention in a predetermined pattern or forming it into a predetermined shape and then heating to an appropriate temperature, the base proliferating agent of the present invention is hydrolyzed and the amino compound is propagated. The Later or at the same time, by applying sufficient heat to the reaction of the compound that accelerates the curing or condensation reaction by the action of the base contained in the resin composition, it can be cured to form a predetermined pattern.
When the resin composition according to the present invention further contains a compound that generates an amino compound by the action of heat, the amino compound is generated from the compound that generates the amino compound by heating appropriately. The base proliferating agent is hydrolyzed to grow the amino compound. By selecting a compound that decomposes at a lower temperature than the base proliferating agent to be combined to produce an amino compound, the amino compound can be propagated by heating at a lower temperature than when the base proliferating agent is used alone.

On the other hand, when the resin composition according to the present invention is used as a photosensitive resin composition, it is applied to a predetermined pattern or formed into a predetermined shape, and then irradiated to the desired pattern as necessary. In, a base is generated from a compound (photobase generator) that generates an amino compound by light. Thereafter, by heating to an appropriate temperature, the base proliferating agent is hydrolyzed and the base is propagated.
Later or simultaneously, by applying sufficient heat to the curing reaction, it is possible to form a cured part and an uncured part in the irradiated part and the unirradiated part, respectively, and to form a desired pattern irradiated with light. it can.

According to the present invention, a polyamic acid, which has conventionally been difficult to obtain a solubility contrast between an exposed portion and an unexposed portion, can also be obtained by combining a photobase generator and a base proliferating agent of the present invention. Thus, a good pattern shape can be obtained without application of a dissolution inhibitor or dissolution inhibitor.
That is, the polyamic acid needs to have a high imidation temperature, but the conventional base proliferating agent has low heat resistance, and the base proliferating agent decomposes even in the unexposed area at the imidization temperature to generate a base. There was a problem that the solubility contrast could not be satisfactorily taken between the exposed part and the unexposed part. On the other hand, since the base proliferating agent of the present invention has high heat resistance, it can be suitably combined with polyamic acid.
Further, as described above, the base proliferating agent of the present invention has water base or a functional group capable of supplying water (such as amic acid and dicarboxylic acid) because the base proliferative reaction mechanism is based on hydrolysis. In particular, the progress of the reaction of proliferating the base is accelerated.

  The resin composition according to the present invention is used as a pattern forming material, paint or printing ink, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, reflection. When used as a material for forming a protective film, hologram, or building material, the material cost is low, and the photosensitive resin composition to be used has high sensitivity, so that it can be manufactured at a lower cost.

  In addition, the article according to the present invention is at least partly formed of a cured product of the resin composition according to the present invention, a printed matter, a color filter, an electronic component, an interlayer insulating film, a wiring coating film, an optical member, light It is an article of a circuit, an optical circuit component, an antireflection film, a hologram, or a building material.

In the base proliferating agent of the present invention, an aromatic ring is directly bonded to an oxygen atom of a urethane bond, and the heat resistance is excellent. Therefore, it can be applied to applications requiring heat resistance such as a photosensitive polyimide precursor such as polyamic acid or a photosensitive polybenzoxazole precursor, which requires heat resistance of 150 ° C. or higher.
Since the base proliferating agent of the present invention can be easily synthesized using an existing compound, it can be obtained at low cost. The base proliferating agent according to the present invention has a wide range of structure selection because many types of raw materials are available.
Further, since the base proliferating agent of the present invention is hydrolyzed by the catalytic action of an amino compound, the decomposition reaction is accelerated when used in a system containing water.

  In addition, since the resin composition containing the base proliferating agent of the present invention as an essential component has a latent amino group, the storage stability is good even if it contains a curing component. Furthermore, the resin composition of this invention can be hardened | cured with the amino compound produced | generated by heating.

  According to the present invention, a combination with a base proliferating agent that generates an amino compound by a hydrolysis reaction of the present invention, even for polyamic acid, which has conventionally had difficulty in obtaining a solubility contrast between an exposed area and an unexposed area. Thus, a photosensitive resin composition having high sensitivity and capable of obtaining a good pattern shape can be obtained.

  The resin composition according to the present invention is cured by irradiation of light, such as a pattern forming material (resist), a coating material, a printing ink, an adhesive, a filler, an electronic material, a molding material, three-dimensional modeling, or the like. It can be used in all known fields and products where changing materials are used, but in particular, paints, printing inks, color filters, electronic components, and interlayer insulation films that require heat resistance and require high reliability. Suitable for forming wiring coating films, optical members, optical circuits, optical circuit components, antireflection films, holograms or building materials.

  The printed material, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram, or building material according to the present invention is a highly heat-resistant resin. Since at least a part is formed by the cured product of the composition, the product or film has high heat resistance and high stability, and thus has a merit of high production yield.

  The present invention is described in detail below. In the present invention, the irradiation light includes not only electromagnetic waves having wavelengths in the visible and invisible regions, but also particle beams such as electron beams, and radiation or ionizing radiation that collectively refers to electromagnetic waves and particle beams. For curing the resin composition, an electromagnetic wave, an electron beam, ionizing radiation or the like having a wavelength of 2 μm or less is mainly used.

First, the base proliferating agent according to the present invention will be described.
The base proliferating agent provided by the present invention has at least one structure represented by the following formula (1) and decomposes by heating at 150 ° C. or more in the presence of an amino compound to produce an amino compound. It is a characteristic base proliferating agent.

（式（１）において、Ｒ^１〜Ｒ^５は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、アミノ基、メルカプト基、ニトロ基、シリル基、シラノール基、又は１価の有機基であり、それらは互いに同一であっても異なっていても良く、それらが互いに結合を介して環状構造を形成していても良い。Ｒ^６は置換又は無置換の脂肪族炭化水素基、或いは置換又は無置換の芳香族炭化水素基である。）

(In Formula (1), R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a silyl group, a silanol group, or a monovalent organic group, They may be the same as or different from each other, and they may form a cyclic structure through a bond to each other, R ⁶ represents a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted Aromatic hydrocarbon group.)

  The base proliferating agent of the present invention is decomposed by heating to generate an amino compound. In the presence of an amino compound, it is hydrolyzed by heating at a lower temperature due to its catalytic action to generate an amino compound. Therefore, the hydrolysis reaction rate increases in the presence of water.

  In addition, it can confirm that the said hydrolysis has occurred by measuring a NMR spectrum and observing the hydrogen of a phenolic hydroxyl group.

  Furthermore, when the base proliferating agent according to the present invention has two or more structures represented by the following formula (1), the base proliferating agent may generate a compound having two or more amino groups. The compound having two or more amino groups can also function as a cross-linkable site with respect to, for example, an epoxy compound or an oxetane compound. Here, the term “crosslinking” refers to generation of a crosslinking bond, and the term “crosslinking” refers to a bond formed by bridging any two atoms among molecules composed of atoms bonded in a chain. In this case, the bond may be within the same molecule or between other molecules (Chemical Dictionary Tokyo Chemical Doujin p.1082).

In Formula (1), R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a silyl group, a silanol group, or a monovalent organic group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. The amino group may be a primary amino group (—NH ₂ ), a secondary amino group, or a tertiary amino group. The secondary amino group is a mono-substituted amino group, for example, methylamino group, ethylamino group, propylamino group, isopropylamino group, tert-butylamino group, anilino group, anisidino group, phenetidino group, toluidino group, xylidino group. , Pyridylamino group, thiazolylamino group, benzylamino group, benzylideneamino group and the like. The tertiary amino group is a disubstituted amino group, which may be cyclic, and is a dimethylamino group, diethylamino group, dibutylamino group, ethylmethylamino group, butylmethylamino group, diamylamino group, dibenzylamino group. , Diphenethylamino group, diphenylamino group, ditolylamino group, dixylamino group, methylphenylamino group, benzylmethylamino group, pyrrolidino group, piperidino group, piperazino group, morpholino group, 1-pyrrolyl group, 1- A pyrazolyl group, 1-imidazolyl group, 1-triazolyl group and the like can be mentioned.

Examples of the monovalent organic group include groups having a hydrocarbon skeleton such as a substituted or unsubstituted saturated or unsaturated aliphatic hydrocarbon group and a substituted or unsubstituted aromatic hydrocarbon group. The aliphatic hydrocarbon group may be linear, branched or cyclic. The monovalent organic group preferably has about 1 to 20 carbon atoms. These monovalent organic groups may contain bonds and substituents other than hydrocarbon groups such as heteroatoms such as oxygen and nitrogen.
As a bond other than a hydrocarbon group such as a hetero atom contained in a group having a hydrocarbon skeleton, an ether bond, a thioether bond, a carbonyl bond, an ester bond, an amide bond, a urethane bond, a carbonate bond, etc. A halogen atom, a hydroxyl group, a mercapto group, a cyano group, a silyl group, a silanol group, a nitro group, an unsaturated alkyl ether group, an aryl ether group, an unsaturated alkyl thioether group, an aryl thioether group, and the like are exemplified, but not particularly limited.

Preferred examples of the monovalent organic group include an alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 4 to 13 carbon atoms, a cyclic alkenyl group having 4 to 13 carbon atoms, a phenoxyalkyl group having 7 to 16 carbon atoms, C7-20 arylalkyl group, C2-11 cyanoalkyl group, C1-10 hydroxyalkyl group, C1-10 alkoxy group, C2-11 amide group, carbon number 1 to 10 alkylthio groups, C1 to C10 acyl groups, C2 to C11 oxyacyl groups, C6 to C20 aryl groups, electron donating groups and / or electron withdrawing groups Examples thereof include 6-20 aryl groups, electron-donating groups, and / or benzyl groups substituted with electron-withdrawing groups.
The alkyl moiety may be linear, branched or cyclic.

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

  Examples of the alkoxy group having 1 to 10 carbon atoms include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, sec-butoxy group, pentyloxy group, iso-pentyloxy group, and neo-pentyl. Examples thereof include an oxy group, a hexyloxy group, a heptyloxy group, and an octyloxy group. Examples of the amide group having 2 to 11 carbon atoms include an acetamide group. Examples of the alkylthio group having 1 to 10 carbon atoms include methylthio group, ethylthio group, n-propylthio group, iso-propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, and iso-pentylthio group. Group, neo-pentylthio group, hexylthio group, heptylthio group, octylthio group. Examples of the acyl group having 1 to 10 carbon atoms include formyl group, acetyl group, propionyl group, isobutyryl group, valeryl group, and cyclohexylcarbonyl group. Examples of the oxyacyl group having 2 to 11 carbon atoms include an acetoxy group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group. Examples of the electron donating group that may be substituted with the aryl group include a hydroxyl group, a halogen atom, an alkyl group, and a methoxy group. Examples of the electron withdrawing group include a nitro group, a carbonyl group, A nitrile group etc. are mentioned.

In the formula (1), R ^{1 to} R ⁵ may be the same as or different from each other, and they may form a cyclic structure through a bond. The cyclic structure formed by the substituents through a bond includes not only an aliphatic ring structure such as a cyclohexyl group, but also, for example, an aromatic ring bonded to R ² and R ³ to form a naphthalene structure included. Further, the ring structure may be an aromatic condensed ring or an aliphatic ring structure, and may further contain a hetero atom other than a carbon atom as a ring constituent atom.

In Formula (1), R ^{1 to} R ⁵ may be —O (C═O) NH—R ⁶ in Formula (1). R ^{1 to} R ⁵ may be a substituent containing an aromatic hydrocarbon substituted with —O (C═O) NH—R ⁶ .

Since the base proliferating agent of the present invention is based on the mechanism as described above, R ^{1 to} R ⁵ represented by the formula (1) can exhibit the function intended by the present invention regardless of the structure. To do. From the hydrolysis mechanism, the higher the electron density of carbon of the carbonyl group in the carbamate bond, the more difficult it is to be decomposed. Therefore, particularly for applications that require a high decomposition temperature, the formula (1) shows. R ^{1 to} R ⁵ are preferably electron donating groups. The electron donating group in this case refers to a substituent that can easily give an electron to the bonding electron side compared to a hydrogen atom (Chemical Dictionary, 1st edition, Tokyo Chemical Dojin, p.929). Examples include a primary amino group, a secondary amino group, a tertiary amino group, an alkoxy group, an alkylthio group, an oxyacyl group, an amide group, an alkyl group, and an aryl group. The alkyl group here includes a linear or branched alkyl group, a cyclic alkyl group, a phenoxyalkyl group, and an arylalkyl group. The aryl group includes an aryl group which may be substituted with an electron donating group such as a hydroxyl group, a halogen atom, an alkyl group, or a methoxy group.

Similarly, when R ^{6 is} also electron-donating, it has an action of increasing the electron density of carbon of the carbonyl group in the carbamate bond, so that heat resistance is improved, and therefore a substituted or unsubstituted aliphatic hydrocarbon group. Alternatively, a substituted or unsubstituted aromatic hydrocarbon group is used. Also, the higher the basicity of the amine after decomposition, the greater the action as a curing catalyst in the resin composition. From this point of view, R ⁶ is a substituted or unsubstituted aliphatic hydrocarbon group. It is preferable that

In the formula (1), the aliphatic hydrocarbon group represented by R ⁶ is linear, branched, cyclic, or a combination thereof, and preferably has 1 to 20 carbon atoms. The aliphatic hydrocarbon group for R ⁶ includes an ester bond, an ether bond, a thioether bond, an amide bond, a urethane bond, a urea bond, a thiocarbamate bond, a carbodiimide bond, or a carbonate bond in the middle of the carbon skeleton. Also good.
Specific examples of the substituted or unsubstituted aliphatic hydrocarbon group for R ⁶ include, for example, adamantyl, dodecyl, hexadecyl, octyl, cyclohexyl, isobornyl, norbornyl, heptyl, pentyl, benzyl, methylbenzyl, methoxybenzyl, and chloroethyl. , Chloropropyl, chlorobenzyl, fluorobenzyl group and the like.

  When the base proliferating agent of the present invention is mixed and used in a resin composition, the curability of the resin composition, the physical properties after curing, and the target solvent or process to be given affinity / solubility It is preferable to appropriately adjust the structure and physical properties depending on the temperature applied in step (b).

As a suitable example of the base proliferating agent of the present invention, in the formula (1), R ³ is an electron donating group, R ¹ , R ² , R ⁴ , R ⁵ are hydrogen, and R ⁶ is Examples thereof include compounds having a cyclic aliphatic hydrocarbon group. In such a case, a highly versatile base proliferating agent that exhibits sufficient transparency, good heat resistance, and solubility and can be applied to a wide range of resin compositions can be obtained. When the base proliferating agent having the above structure is used, the curability is improved, the sensitivity, hardness, strength, adhesion, etc. of the cured film are improved, the pattern edge shape is improved, and the substrate is developed. It is possible to obtain a photosensitive resin composition in which the residue on the exposed surface due to the reduction is reduced and the development time is shortened.

The base proliferating agent in the present invention can be synthesized using various known methods. For example, in the case of a compound in which R ³ is a methoxy group, R ¹ , R ² , R ⁴ , and R ⁵ are hydrogen and R ⁶ is a cyclohexyl group, 4-methoxyphenol and cyclohexyl isocyanate are mixed with dibutyl It can be obtained quantitatively by stirring at 60 ° C. under a nitrogen stream in tetrahydrofuran dried using tin dilaurate as a catalyst.
Other methods include a method of synthesizing by a condensation reaction of 4-methoxyphenyl chloroformate and cyclohexylamine.
From the viewpoints of cost of raw materials, availability, and commercially available types, it is preferable to synthesize by a reaction between a hydroxyl group-containing compound and an isocyanate because it can be produced at a lower cost.

The method for synthesizing the base proliferating agent of the present invention will be illustrated more specifically, but the present invention is not limited by the following method.
A 100 ml three-necked flask was heated in a nitrogen stream and sufficiently dried. Then, with careful attention to moisture in the air, 1.24 g [10 mmol] of p-methoxyphenol and dried tetrahydrofuran (THF) 15 ml was added and stirred. Thereto, 1.30 ml [1.25 g 10 mmol] of cyclohexyl isocyanate and 2 drops of dibutyltin dilaurate were added, and the mixture was stirred for 17 hours while heating to 60 ° C. in a dried nitrogen stream.
At this time, the reaction solvent to be used is not limited to tetrahydrofuran (hereinafter referred to as THF), and may be any solvent in which the final product is dissolved, and various organic polar solvents are suitably used. In order to increase the yield of the reaction, it is preferable to carry out the equipment and reagents used for the reaction with care so that moisture is not mixed into the reaction system as much as possible.

  As described above, the isocyanate used here is not only cyclohexyl isocyanate (cyclohexyl isocyanate), but can be appropriately selected according to the purpose. Specifically, 1-adamantyl isocyanate, octyl isocyanate, 2-chloroethyl isocyanate, 3-chloropropyl isocyanate, 2-chlorobenzyl isocyanate, n-dodecyl isocyanate, trichloromethyl isocyanate, 4-isocyanate 4- Fluorobenzyl, hexadecyl isocyanate, n-hexyl isocyanate, hexyl isocyanate, heptyl isocyanate, benzyl isocyanate, pentyl isocyanate, 2-methylbenzyl isocyanate, 3-methylbenzyl isocyanate, 4-methylbenzyl isocyanate , 4-methoxybenzyl isocyanate, phenyl isocyanate and the like.

  Further, the hydroxyl group-containing compound used here is not limited to 4-methoxyphenol, and various phenolic hydroxyl group-containing compounds can be used according to the purpose. For example, phenol, hydroquinone, phloroglicinol, 4-methoxyphenol, 2-methoxyphenol, 3-methoxyphenol, 2,6-dimethoxyphenol, 3,5-dimethoxyphenol, 4-ethoxyphenol, m-cresol, o- Examples include cresol, p-cresol, 2,6-dimethylphenol, 3,5-dimethylphenol, 2,4,6-trimethylphenol, 2,6-dimethoxycresol, 4-acetoxyphenol, and the like. As long as it is included in the prescribed range, it is not limited to these.

  In this manner, the solvent of the reaction liquid stirred for several hours is removed by distilling or throwing it into water or the like, and the target product is taken out. By performing a treatment such as recrystallization, the base proliferating agent of the present invention can be obtained. The purification method is not limited to recrystallization, and any known method such as sublimation purification or column chromatography can be used, but recrystallization is preferable from the viewpoint of cost.

The base proliferating agent according to the present invention is excellent in heat resistance because the aromatic ring is directly bonded to the urethane bond, the conjugated structure is extended, and the urethane bond is stable. In addition, when the base proliferating agent of the present invention has two or more —O (C═O) NH—R ⁶ having the structure represented by the above formula (1), a plurality of bases are generated from one molecule. Therefore, the molecular weight per generated base is reduced, and the amount of addition when added to the resin composition can be reduced.

  The molecular weight of the base proliferating agent of the present invention is preferably 100 to 3000 from the viewpoints of ease of handling, curability, solubility and compatibility. If it is less than 100, the aromatic ring and urethane bond cannot be contained in the molecule, and the object of the present invention to improve heat resistance cannot be achieved. When it is larger than 3000, the solubility is lowered or the site where the base is generated is likely to be localized, and when used as a pattern forming material, it becomes difficult to reproduce a fine pattern as the mask pattern. The molecular weight is a weight average molecular weight when the base proliferating agent of the present invention has a repeating unit, and refers to a value in terms of polystyrene by gel permeation chromatography (GPC).

  When the base proliferating agent of the present invention is used as a component of a photosensitive resin composition, in order to increase the sensitivity of the photosensitive resin composition, the emission wavelength of a high-pressure mercury lamp generally used for exposure of the photosensitive resin Thus, it is preferable that the three wavelengths of 365 nm (i-line), 405 nm (h-line), and 436 nm (g-line) having relatively high intensity have as little absorption as possible. Specifically, the base proliferating agent of the present invention preferably has no absorption in a wavelength region of 400 nm or more, and more preferably has no absorption in a wavelength region of 360 nm or more. When absorption is at 400 nm or more, when added to the photosensitive resin composition, light from the light source is absorbed, resulting in a decrease in sensitivity. In general, the main emission wavelengths of a high-pressure mercury lamp used for exposure are 436 nm (g-line), 405 nm (h-line), and 365 nm (i-line), and among these, the largest emission intensity is 365 nm. More preferably, the region does not have absorption.

From the viewpoint of heat resistance, the 5% weight loss temperature of the base proliferating agent according to the present invention is preferably 150 ° C. or higher, more preferably 190 ° C. or higher, and even more preferably 200 ° C. or higher. .
Here, the 5% weight reduction temperature is the time when the weight of the sample is reduced by 5% from the initial weight when the weight reduction is measured using a thermogravimetric analyzer in the same manner as in the examples of the present invention described later. (In other words, the temperature is 95% of the initial sample weight).

The base proliferating agent preferably has high solubility when blended in the resin composition from the viewpoint of improving coating suitability, transparency after curing, sensitivity during exposure, and the like.
From the viewpoint of coating suitability at the time of coating, the base proliferating agent is particularly preferably highly soluble in a solvent. Specifically, it is preferable that the solubility of the base proliferating agent in the solvent used in the resin composition, particularly any of the general-purpose solvents described later, is 0.1% by weight or more.

Next, the resin composition according to the present invention will be described.
The resin composition according to the present invention contains the base proliferating agent according to the present invention and a compound that accelerates curing or condensation reaction by the action of a base as essential components, and further, if necessary, light, or You may contain other components, such as a compound (light or a heat base generator) which produces | generates an amino compound by the effect | action of a heat | fever, and a high molecular weight binder component.

  The resin composition according to the present invention is applied to a predetermined pattern or formed into a predetermined shape, and then a stimulus such as heat is applied to cause the decomposition reaction of the base proliferating agent according to the present invention to proceed. The action causes a change in the curing and / or solubility of the compound that accelerates the curing or condensation reaction. Since the resin composition according to the present invention contains the base proliferating agent according to the present invention as an essential component, there is an advantage that it is excellent in heat resistance before the curing reaction and is low in cost.

  In particular, when the base proliferating agent according to the present invention is contained in a resin composition together with a photobase generator, the resin composition according to the present invention can be used as a photosensitive resin composition. When the photosensitive resin composition according to the present invention is irradiated with light after being applied or formed into a predetermined shape, a base is generated by the photobase generator in the light irradiation portion. Thereafter, by heating at an appropriate temperature, the base proliferating agent is decomposed by the catalytic action of the base generated from the photobase generator to generate a base. Thereafter, by further heating, various reactions such as a polymerization reaction and a dehydration ring closure reaction proceed depending on the type of the compound that accelerates the curing or condensation reaction by the action of the base, thereby causing a change in curing and / or solubility. . Therefore, when light is irradiated in a pattern using an appropriate mask or the like, only the light-irradiated portion is cured by appropriate heating because the curing or condensation reaction is promoted by the action of the base, and thus it is appropriately selected. A desired pattern can be formed by eluting unexposed portions with a solvent or an aqueous solution. Furthermore, when the base proliferating agent according to the present invention used is used together with a compound that causes a dehydration condensation reaction by heating such as polyamic acid, the photosensitive resin composition according to the present invention is subjected to light irradiation in a pattern shape. After heating, a desired pattern can be formed by developing only the unexposed area with an alkaline solution.

  In order for the resin composition according to the present invention to exhibit a sufficient effect, the base proliferating agent according to the present invention is 0.1% by weight or more of the total solid content of the resin composition. It is preferable from the point which prevents that the cure rate becomes slow. The base proliferating agent according to the present invention is more preferably 1% by weight or more based on the total solid content of the resin composition from the viewpoint of high sensitivity. In addition, solid content of a resin composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

On the other hand, the compound used in the resin composition of the present invention that accelerates the curing or condensation reaction by the action of a base is a compound having a substituent that promotes the curing or condensation reaction by the catalytic action of a base. A compound that accelerates the curing or condensation reaction by the action of a base can be used together with the base proliferating agent of the present invention to achieve the purpose of shortening the reaction time or reducing the reaction temperature.
As a compound which accelerates | stimulates hardening or a condensation reaction by the effect | action of the base which concerns on the said invention, the compound which has 1 or 2 or more of epoxy groups and oxetanyl groups can be used, for example.

  Among the compounds having an epoxy group, examples of monofunctional epoxy compounds include, for example, phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1, 2-butylene oxide, 1,3-butadiene monooxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxy Examples include methylcyclohexene oxide and 3-vinylcyclohexene oxide.

Examples of polyfunctional epoxy compounds having two or more epoxy groups include, for example, bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, brominated bisphenol A diglycidyl ether, and brominated bisphenol F. Diglycidyl ether, brominated bisphenol S diglycidyl ether, epoxy novolac resin, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, 3,4-epoxycyclohexylmethyl-3 ′ , 4′-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bi (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexylene oxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3 ′ , 4′-epoxy-6′-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide, ethylene glycol di (3,4-epoxycyclohexylmethyl) ether, ethylene bis (3,4 4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, di-2-ethylhexyl epoxyhexahydrophthalate, 1,4-butanediol diglycidyl ether, 1,6-hexanedi All diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ethers, 1,1,3-tetradecadiene dioxide, limonene dioxide, 1,2, Examples include 7,8-diepoxyoctane and 1,2,5,6-diepoxycyclooctane.
By using a polyfunctional compound, it is possible to obtain a hard, high heat-resistant compound having a higher crosslinking density.

  Among the compounds having an oxetanyl group, examples of monofunctional oxetane include, for example, 3-ethyl-3-hydroxymethyloxetane, 3- (meth) allyloxymethyl-3-ethyloxetane, (3-ethyl-3 -Oxetanylmethoxy) methylbenzene, 4-fluoro- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, 4-methoxy- [1- (3-ethyl-3-oxetanylmethoxy) methyl] benzene, [ 1- (3-ethyl-3-oxetanylmethoxy) ethyl] phenyl ether, isobutoxymethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl (3-ethyl-3-oxetanylmethyl) ether, isobornyl (3-Ethyl-3-oxetanylmethyl) ether, 2-ethyl Ruhexyl (3-ethyl-3-oxetanylmethyl) ether, ethyldiethylene glycol (3-ethyl-3-oxetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyloxyethyl (3- Ethyl-3-oxetanylmethyl) ether, dicyclopentenyl (3-ethyl-3-oxetanylmethyl) ether, tetrahydrofurfuryl (3-ethyl-3-oxetanylmethyl) ether, tetrabromophenyl (3-ethyl-3-oxetanyl) Methyl) ether, 2-tetrabromophenoxyethyl (3-ethyl-3-oxetanylmethyl) ether, tribromophenyl (3-ethyl-3-oxetanylmethyl) ether, 2-tribromophenoxyethyl (3- Til-3-oxetanylmethyl) ether, 2-hydroxyethyl (3-ethyl-3-oxetanylmethyl) ether, 2-hydroxypropyl (3-ethyl-3-oxetanylmethyl) ether, butoxyethyl (3-ethyl-3- Oxetanylmethyl) ether, pentachlorophenyl (3-ethyl-3-oxetanylmethyl) ether, pentabromophenyl (3-ethyl-3-oxetanylmethyl) ether, bornyl (3-ethyl-3-oxetanylmethyl) ether, and the like. .

  Examples of polyfunctional oxetanes having two or more oxetanyl groups include 3,7-bis (3-oxetanyl) -5-oxa-nonane, 3,3 ′-(1,3- (2-methylenyl) pro Pandiylbis (oxymethylene)) bis- (3-ethyloxetane), 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,2-bis [(3-ethyl-3-oxetanyl) Methoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyl Lenglycol bis (3-ethyl-3-oxetanylmethyl) ether, tricyclodecanediyldimethylene (3-ethyl-3-oxetanylmethyl) ether, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, 1 , 4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol Tetrakis (3-ethyl-3-oxetanylmethyl) ether, polyethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol Olpentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified Dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated Scan phenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) include polyfunctional oxetanes such as ether.

Other examples of the compound that accelerates the curing or condensation reaction by the action of a base include polyamic acid that is a polyimide precursor, polyhydroxyamide that is a polybenzoxazole precursor, and the like.
In the resin composition according to the present invention, it is preferable to combine a polyamic acid as a compound that accelerates the curing or condensation reaction by the action of the base. A polyamic acid is a polyimide precursor having alkali solubility, and when a polyamic acid is used, a photosensitive resin composition excellent in heat resistance and mechanical properties can be obtained.
The polyamic acid needs to have a high imidation temperature, and the conventional base proliferating agent has a problem in terms of heat resistance for use with the polyamic acid, but the base proliferating agent of the present invention has high heat resistance. Therefore, it can combine suitably.
Further, as described above, the base proliferating agent of the present invention has water base or a functional group capable of supplying water (such as amic acid and dicarboxylic acid) because the base proliferative reaction mechanism is based on hydrolysis. In particular, the progress of the reaction of proliferating the base is accelerated.
Therefore, according to the present invention, a polyamic acid, which has conventionally been difficult to obtain a solubility contrast between the exposed portion and the unexposed portion, is also dissolved by the combination with the base proliferating agent by the hydrolysis reaction of the present invention. A good pattern shape can be obtained without application of a dissolution inhibitor.

When using a polymer precursor whose thermosetting temperature is lowered by the catalytic action of a base, such as a polyimide precursor or a polybenzoxazole precursor, first, such a polymer precursor, a photobase generator, An electromagnetic wave is irradiated to the part which wants to leave the pattern on the coating film or molded object of the photosensitive resin composition which combined the base proliferation agent based on this invention. Then, a basic substance is generated and propagated in the irradiated portion, and the thermosetting temperature of that portion is selectively lowered. Next, while the irradiated portion is thermally cured, the non-irradiated portion is heated at a processing temperature that is not thermally cured, and only the irradiated portion is cured. Next, a non-irradiated portion is dissolved with a predetermined developer (such as an organic solvent or a basic aqueous solution) to form a pattern made of a thermoset. This pattern is further heated as necessary to complete thermosetting. Through the above steps, a desired two-dimensional resin pattern (general plane pattern) or three-dimensional resin pattern (three-dimensionally shaped shape) is obtained.
The base proliferating agent used in the photosensitive resin composition that forms a pattern in this way must have heat resistance so that it does not decompose and generate a base at the heating temperature at which only the irradiated portion of the polymer precursor is cured. It is. Since the base proliferating agent according to the present invention has high heat resistance and high thermal decomposition temperature, the base proliferating agent in the unexposed part is stable even at a heating temperature at which only the irradiated part of the polymer precursor is cured, such as 160 ° C. Therefore, it is possible to form a pattern suitably without generating a base. The base proliferating agent according to the present invention used in the photosensitive resin composition is selected as appropriate in consideration of the 5% weight reduction temperature in consideration of the thermosetting temperature of the polymer precursor used in combination. .

  As a method for producing a polyamic acid, conventionally known methods can be applied. For example, (1) A technique 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 polyamic acid include ethylene tetracarboxylic dianhydride, butane tetracarboxylic dianhydride, cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, pyro Merit acid dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 3,3′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Biphenyltetracarboxylic dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride, 2,2 ', 6,6'-biphenyltetracarboxylic dianhydride, 2,2- Bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, bis (3,4-dicarboxyphenyl) Nyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,1-bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (2,3-dicarboxyphenyl) ) Methane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoro Propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) -1,1,1,3,3,3-hexafluoropropane dianhydride, 1,3-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 Thing,

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-hexafulpropane dianhydride 2,2-bis {4- [3- (1,2-dicarboxy) phenoxy] phenyl} -1,1,1,3,3,3-propane dianhydride, 2,3,6,7 -Naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 1,2,5,6-naphthalene tetracarboxylic dianhydride, 1,2,3,4-benzene Tetracarboxylic dianhydride, 3,4,9, 0 Bae Li Ren dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride, 1,2,7,8-phenanthrene tetracarboxylic acid dianhydride, and the like. 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 an acid dianhydride into which fluorine is introduced or an acid dianhydride having an alicyclic skeleton is used as the acid dianhydride to be used in combination, the transparency of the polyimide precursor is improved. Also, rigid acid dianhydrides such as pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, etc. When used, the linear thermal expansion coefficient of the finally obtained polyimide becomes small.

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

Bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, bis [4- (3-aminophenoxy) phenyl] ether, bis [4- (4-amino) Phenoxy) phenyl] ether, 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [3- (3-Aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3 3,3-hexafluoropropane, 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] ben 1,4-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (3-amino Phenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -Α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4'-bis [4- (4-aminophenoxy) benzoyl ] Diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzen) ) Phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4 , 4′-Dibiphenoxybenzophenone, 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) -3,3 3 ′, 3′-tetramethyl-1,1′-spirobiindane, 6,6′-bis (4-aminophenoxy) -3,3,3 ′, 3′-tetramethyl-1,1′-spirobiindane, , 3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane, α, ω-bis ( -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-diaminododecane, 1,2-diaminocyclohex 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] A diamine obtained by substituting some or all of the hydrogen atoms on the aromatic ring of the above diamine with a substituent selected from a fluoro group, a methyl group, a methoxy group, a trifluoromethyl group, or a trifluoromethoxy group. Can 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.

  Moreover, it is preferable from the point of workability | operativity after application | coating that the molecular weight of the compound which accelerates | stimulates hardening or a condensation reaction by the effect | action of the said base is 1000 or more. More preferably, the compound has a molecular weight of 2000 or more. The molecular weight is a weight average molecular weight in the case where the compound that accelerates the curing or condensation reaction by the action of the base used in the present invention has a repeating unit, and is a polystyrene equivalent value by gel permeation chromatography (GPC). Say.

  The base proliferating agent and the compound that accelerates the curing or condensation reaction by the action of the base can be used alone or in combination. A preferable blending ratio of the compound that accelerates the curing or condensation reaction by the action of the base is 1% by weight or more and 99% by weight or less, more preferably 5% by weight or more and 95% by weight with respect to the entire solid content of the resin composition. % Or less.

When partially curing the resin composition of the present invention with or without light irradiation (when used as a photosensitive resin composition), in order to form a distribution of the presence of bases with or without exposure It is preferable to add a photobase generator.
A known photobase generator can be used as the photobase generator. Examples of the photobase generator include the following oxime ester compounds and oxime ester polymers.

  Moreover, as a photobase generator, the following quaternary ammonium salt type compounds are mentioned, for example.

  Moreover, as a photobase generator, the following acyl compounds are mentioned, for example.

  Moreover, as a photobase generator, the following carbamate compounds etc. are mentioned, for example.

  These photobase generators can be used alone or in combination. A preferable blending ratio of these photobase generators is 0.1% by weight or more and 35% by weight or less, more preferably 1% by weight or more and 10% by weight or less based on the entire solid content of the resin composition.

The photosensitive resin composition of the present invention containing a photobase generator is desirably heated at a temperature between 100 ° C. and 250 ° C., preferably between 150 ° C. and 220 ° C. after exposure. In this heating step, a reaction in which the base generated by the photobase generator decomposes the base proliferating agent and a curing reaction or condensation reaction using the base as a catalyst occur almost simultaneously, and the resin composition becomes insoluble, Solubility changes.

  In addition, the compound other than the base proliferating agent according to the present invention does not inhibit the sensitivity of the resin composition with respect to the irradiation light, and therefore does not have absorption in the wavelength region where the irradiation wavelength and the absorption wavelength of the photobase generator overlap. preferable.

In the photosensitive resin composition of the present invention, a polymer compound may be blended as a binder resin in order to adjust the film-forming property in an uncured state of the composition and the physical properties of the coated film after curing.
As the binder resin, any known polymer compound can be used according to the use of the resin composition. Further, as the polymer compound, any of a non-reactive polymer and a reactive polymer may be used. The polymer compound used as the binder component preferably has a weight average molecular weight of 3000 or more, and if the molecular weight is too large, the solubility and processing characteristics are deteriorated. It is preferable that it is below 000,000. Here, the weight average molecular weight in the present invention refers to a value in terms of polystyrene by gel permeation chromatography (GPC).

Examples of the non-reactive polymer and the reactive polymer include organic polymers such as tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. Isocyanates; Polymers and copolymers of acrylic or vinyl compounds such as vinyl acetate, vinyl chloride, acrylic esters and methacrylic esters; Styrenic resins such as polystyrene; Acetal resins such as formal resins and butyral resins; Silicone resins; Phenoxy Resin; Epoxy resin represented by bisphenol A type epoxy resin, etc .; Urethane resin such as polyurethane; Phenol resin; Ketone resin; Xylene resin; Polyamide resin; Polyimide resin; Polyphenylene ether resin; Polybenzoxazole resin; Cyclic polyolefin resin; Polycarbonate resin; Polyester resin; Polyarylate resin; Polystyrene resin; Novolak resin; Cycloaliphatic polymer such as polycarbodiimide, polybenzimidazole, polynorbornene; Any known polymer compound such as a polymer may be used.
Each of the polymer compounds as described above may be used alone or in combination of two or more.

  Further, when the resin composition according to the present invention contains a non-reactive polymer compound, the non-reactive polymer compound is 1% by weight or more and 97% by weight of the solid content of the entire resin composition depending on the application. It is preferable to contain so that it may become the following. When the amount of the non-reactive polymer compound is more than 97% by weight, the reactivity of the curing reaction and condensation reaction due to the catalytic action of the base tends to decrease.

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, compounds having a polymerizable unsaturated bond such as an ethylenic double bond, other curing reactive compounds, dyes, surfactants, leveling agents, plasticizers, fine particles, sensitizers, 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 the functions or forms include pigments, fillers, fibers, and the like.
The blending ratio of these optional components is preferably in the range of 0.1 wt% to 95 wt% with respect to the entire solid content of the resin composition. When the amount is less than 0.1% by weight, the effect of adding the additive is hardly exhibited, and when the amount exceeds 95% by weight, the characteristics of the resin composition according to the present invention are hardly reflected in the final product.

  When a large amount of a component that absorbs irradiation light is blended in the resin composition, light does not reach the photobase generator sufficiently, and sensitivity is lowered. Therefore, from the point of emphasizing the sensitivity of the resin composition, the transmission of the resin composition according to the present invention in the wavelength region where the emission wavelength of the irradiation light source and the absorption wavelength of the photobase generator mixed in the resin composition overlap. It is preferable to appropriately select components used in the resin composition by adjusting the rate to be 20% or more.

  Moreover, you may dilute the resin composition which concerns on this invention to a suitable density | concentration using a solvent. As the solvent, various general-purpose solvents such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and the like; 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, n acetate 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, lactic acid Esters such as methyl and ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, and 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; N, N-dimethylform Amides such as amide, N, N-dimethylacetamide; pyrrolidones such as N-methylpyrrolidone; lactones such as γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, and other organic polar solvents, and the like. , Aromatic hydrocarbons such as benzene, toluene and xylene, and other organic nonpolar solvents. As the reactive diluent, a compound having a reactive functional group in the structure, such as an ethylenically unsaturated compound that is liquid at room temperature, may be used as a solvent. These solvents are used alone or in combination. These solvents may be used after filtering impurities by various known methods such as a filter having a pore diameter of about 0.05 μm to 0.2 μm.

  Moreover, even if the resin composition is transparently dissolved using a solvent, if the compatibility of the solids contained in the resin composition is low, if the solvent evaporates during coating, A precipitate is formed, and sufficient transparency cannot be obtained. Therefore, when a highly transparent coating film or molded body such as an optical member is required, a base proliferating agent having high compatibility with other solid components in the resin composition may be appropriately selected and used. preferable. When high transparency is required, the total light transmittance (JIS K7105) is preferably 90% or more and 95% or more when the thickness of the coating film formed by curing the resin composition is 10 μm. More preferably.

  The resin composition according to the present invention includes the photobase proliferating agent according to the present invention, which is an essential component, a compound that accelerates the curing or condensation reaction by the action of a base, and a photobase generator and a high molecular weight as necessary. It can be prepared by mixing other optional components such as a binder component depending on the case and application.

  The resin composition according to the present invention obtained in this way is a pattern forming material (resist), a coating material, a printing ink, an adhesive, a filler, an electronic material, a molding material, three-dimensional modeling, etc. by light irradiation or heating. It can be used in all known fields and products in which a material that is cured or changes in solubility is used. In particular, paints, printing inks, color filters, electronic components, interlayer insulation films, wiring coating films, optical members, optical circuits, optical circuit components, antireflection films, which require heat resistance and require high reliability, Suitable for forming holograms or building materials.

For example, in the case of a color filter, a pixel portion, a light shielding portion (black matrix) provided at the boundary of the pixel portion, a protective film, and a spacer for maintaining a cell gap are formed from a cured product of the photosensitive resin composition. can do.
In the case of an electronic component, for example, an underfill agent and a sealant for a semiconductor device can be exemplified.
Interlayer insulation films for buildup substrates that require heat resistance and insulation reliability, interlayer insulation films for fuel cells, insulation coatings for automobile parts and home appliances, etc. are made of cured products of the above resin compositions. Can be formed.

Examples of the wiring protective film include a solder resist that is a wiring protective layer on the surface of the printed wiring board, and a surface coating of the electric wire.
In the case of an optical member, examples thereof include overcoats of various optical lenses, optical circuit components such as antireflection films, optical waveguides, and branching devices, relief-type and volume-type holograms, and the like.
In the case of building materials, wallpaper materials, wall materials, floor materials, and other skin materials with low volatile components, adhesive / adhesive materials, inks, and the like can be exemplified.

  The printed matter, color filter, electronic component, interlayer insulating film, wiring coating film, optical member, optical circuit, optical circuit component, antireflection film, hologram, or building material according to the present invention has high heat resistance and high stability. Since at least a part of the cured resin composition is formed, there are advantages of low cost and high sensitivity.

Example 1
A 100 ml three-necked flask was heated in a nitrogen stream and sufficiently dried. Then, with careful attention to moisture in the air, 1.24 g [10 mmol] of p-methoxyphenol and dried tetrahydrofuran (THF) 15 ml was added and stirred. Thereto, 1.30 ml [1.25 g 10 mmol] of cyclohexyl isocyanate and 2 drops of dibutyltin dilaurate were added, and the mixture was stirred for 17 hours while heating to 60 ° C. in a dried nitrogen stream.
After completion of the reaction, the precipitate was reprecipitated with 2 L of distilled water, and the resulting white precipitate was recrystallized with ethyl acetate-hexane to obtain 2.35 g of the desired product (base proliferating agent 1) having the following structural formula.
¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 7.57 (1H, d, NH), 6.99 (2H, d, Ar), 6.89 (2H, d, Ar), 4. 47 (1H, m, -CH ( cyclohexyl)), 3.73 (3H, s, -OCH 3), 1.82 (2H, d, -CH 2 (cyclohexyl)), 1.69 (2H, m, _{-CH 2 (cyclohexyl)), 1.54} (2H, m, -CH 2 (cyclohexyl)), 1.23 (2H, m, -CH 2 (cyclohexyl)), 1.06 (4H, m, -CH ₂ (cyclohexyl))

(Example 2)
A 100 ml three-necked flask was heated in a nitrogen stream and sufficiently dried, then 1.10 g [10 mmol] of hydroquinone and 15 ml of dried tetrahydrofuran (THF) were added while paying sufficient attention to moisture in the air. And stirred. Thereto, 2.59 ml of cyclohexyl isocyanate [2.534 g 20 mmol] and 2 drops of dibutyltin dilaurate were added, and the mixture was stirred at 60 ° C. for 17 hours in a dried nitrogen stream.
After completion of the reaction, reprecipitation was performed with 2 L of distilled water, and the resulting white precipitate was recrystallized with ethyl acetate-hexane to obtain 3.41 g of the desired product (white powder, base proliferating agent 2) having the following structural formula. .
¹ H NMR (400 MHz, DMSO-d6) δ (ppm): 7.6 (2H, br, NH) 7.05 (4H, d, Ar), 3.30 (2H, m, —CH (cyclohexyl)) , 1.82 (4H, d, -CH 2 (cyclohexyl)), 1.68 (4H, m, -CH 2 (cyclohexyl)), 1.54 (4H, m, -CH 2 (cyclohexyl)), 1 _{.23 (4H, m, -CH 2} (cyclohexyl)), 1.11 (8H, m, -CH 2 (cyclohexyl))

(Example 3)
A 100 ml three-necked flask was heated in a nitrogen stream and sufficiently dried. Then, with careful attention to moisture in the air, 1.24 g [10 mmol] of p-methoxyphenol and dried tetrahydrofuran (THF) 15 ml was added and stirred. Thereto were added 1.77 g [10 mmol] of adamantyl isocyanate and 2 drops of dibutyltin dilaurate, and the mixture was heated to 70 ° C. in a dried nitrogen stream and stirred for 48 hours.
After completion of the reaction, the solvent was distilled off and the residue was purified by column chromatography with chloroform to obtain 2.71 g of the desired product (base proliferating agent 3) having the following structural formula.
¹ H NMR (400 MHz, CDCL ₃ ) δ (ppm): 7.02 (2H, d, Ar), 6.86 (2H, d, Ar), 4.85 (1H, d, NH), 3.79 _{(3H, s, -OCH 3)} , 2.10 (3H, d, -CH (adamantyl)), 2.00 (6H, m, -CH 2 (adamantyl)), 1.68 (6H, m, - CH ₂ (adamantyl))

（実施例４）
１００ｍｌの３つ口フラスコを窒素気流下加熱し、十分乾燥させた後、空気中の水分に対して十分注意しながら、p−ニトロフェノール １．３９ｇ ［１０ｍｍｏｌ］、および乾燥させたテトラヒドロフラン（ＴＨＦ） １５ｍｌを投入し撹拌した。そこへシクロヘキシルイソシアネート １．３０ｍｌ ［１．２５ｇ １０ｍｍｏｌ］と ジブチル錫ジラウレート ２滴を添加し、乾燥させた窒素気流下７０℃に加熱しつつ、４８時間撹拌をした。
反応終了後、溶媒を留去し、クロロホルムによるカラムクロマトグラフィーによって生成し、下記構造式を有する目的物（塩基増殖剤４）２．４２ｇを得た。
^１Ｈ ＮＭＲ（４００ＭＨｚ，ＣＤＣＬ_３） δ（ｐｐｍ）: ８．２４（２Ｈ，ｄ，Ａｒ）， ７．３１（２Ｈ，ｄ，Ａｒ），５．０１（１Ｈ，ｄ，ＮＨ)，３．５７（１Ｈ，ｍ，−CH（cyclohexyl））， ２．０２（２Ｈ，ｄ，−CH₂（cyclohexyl）），１．７7（２Ｈ，ｍ，−CH₂（cyclohexyl））， １．６４（２Ｈ，ｍ，−CH₂（cyclohexyl）），１．３8（２Ｈ，ｍ，−CH₂（cyclohexyl））， １．２３（４Ｈ，ｍ，−CH₂（cyclohexyl））

Example 4
A 100 ml three-necked flask was heated in a nitrogen stream and sufficiently dried. Then, with careful attention to moisture in the air, 1.39 g [10 mmol] of p-nitrophenol and dried tetrahydrofuran (THF) 15 ml was added and stirred. Thereto, cyclohexyl isocyanate 1.30 ml [1.25 g 10 mmol] and 2 drops of dibutyltin dilaurate were added and stirred for 48 hours while heating to 70 ° C. in a dried nitrogen stream.
After completion of the reaction, the solvent was distilled off and the residue was produced by column chromatography with chloroform to obtain 2.42 g of the desired product (base proliferating agent 4) having the following structural formula.
¹ H NMR (400 MHz, CDCL ₃ ) δ (ppm): 8.24 (2H, d, Ar), 7.31 (2H, d, Ar), 5.01 (1H, d, NH), 3.57 (1H, m, -CH (cyclohexyl )), 2.02 (2H, d, -CH 2 (cyclohexyl)), 1.77 (2H, m, -CH 2 (cyclohexyl)), 1.64 (2H, _{m, -CH 2 (cyclohexyl))} , 1.38 (2H, m, -CH 2 (cyclohexyl)), 1.23 (4H, m, -CH 2 (cyclohexyl))

(Comparative Example 1)
A 100 ml three-necked flask was heated under a nitrogen stream and sufficiently dried, and then 20 ml of dried 2-propanol (IPA) was added and stirred while paying sufficient attention to moisture in the air. Thereto, 3.00 g [24 mmol] of cyclohexyl isocyanate and 2 drops of dibutyltin dilaurate were added, followed by stirring for 17 hours while heating to 60 ° C. in a dried nitrogen stream.
After completion of the reaction, reprecipitation was performed with 2 L of distilled water, and the resulting white precipitate was recrystallized with ethyl acetate-hexane to obtain 4.02 g of the desired product (Comparative Base Proliferating Agent 1) having the following structural formula.
¹ H NMR (400 MHz, CDCL ₃ ) δ (ppm): 4.89 (1H, m, —CH (cyclohexyl)), 4.47 (1H, br, NH), 3.46 (1H, m, CH ( i-Pr)), 1.93 ( 2H, d, -CH 2 (cyclohexyl)), 1.69 (2H, m, -CH 2 (cyclohexyl)), 1.59 (2H, m, -CH 2 ( cyclohexyl)), 1.34 (2H, m, -CH 2 (cyclohexyl)), 1.22 (6H, d, -CH 3 (i-Pr)), 1.27 (4H, m, -CH 2 ( cyclohexyl))

(Test)
(1) Pyrolysis temperature measurement Using a differential type differential thermal balance (product name: TG8120, manufactured by Rigaku Corporation), the base proliferating agents 1 to 4 can be obtained at a temperature increase rate of 10 ° C./min in a nitrogen atmosphere. The 5% weight loss temperature of Comparative Base Growth Agent 1 was measured. The results are shown in Table 1 below.

  From the above results, it has been clarified that the base proliferating agent according to the present invention is excellent in heat resistance because the aromatic ring is directly bonded to the oxygen atom of the urethane bond. In particular, it was found that a base proliferating agent using phenol in which a methoxy group as an electron donating group was substituted at the 4-position had a higher thermal decomposition temperature and excellent heat resistance.

(2) Thermal decomposition behavior The following samples were prepared, and the decomposition behavior of the base proliferating agent was measured using a nuclear magnetic resonance apparatus (NMR) (JNM-LA-400WB manufactured by JEOL Ltd.).
Sample A: 5 mg of base proliferating agent 3 dissolved in 500 μl of DMSO-d6.
Sample B: 5 mg of base proliferating agent 3 dissolved in 500 μl of DMSO-d6 and heated in an oil bath at 150 ° C. for 10 minutes.
Sample C: 5 mg of base proliferating agent 3 and 1 mg of dimethylpiperidine dissolved in 500 μl of DMSO-d6 and heated in an oil bath at 150 ° C. for 10 minutes.
Sample D: 5 mg of base proliferating agent 3 dissolved in 500 μl of DMSO-d6 and heated in an oil bath at 200 ° C. for 10 minutes.

As a result, Sample A and Sample B gave exactly the same spectrum, but for Sample C, the peak derived from the base proliferating agent disappeared, and in addition to the dimethylpiperidine peak, 4-methoxyphenol and 1 -The peak of adamantylamine appeared. For sample D 1, the peak intensity derived from the base proliferating agent decreased, and new peaks for 4-methoxyphenol and 1-adamantylamine appeared.
From this result, it was confirmed that the base proliferating agent 3 was decomposed by heating at 150 ° C. in the presence of dimethylpiperidine to become 4-methoxyphenol and 1-adamantylamine. Furthermore, it was confirmed that by heating at 200 ° C., it decomposes itself to generate an amine.

(3) Curability evaluation Polyglycidyl methacrylate-methyl methacrylate copolymer (weight average molecular weight 15000 copolymerization ratio 1: 3) 0.85 g, photobase generator 0.05 g having the following structure, base proliferating agent of Example 3 3 0.10 g was dissolved in 5 ml of tetrahydrofuran to prepare a photosensitive resin composition. (Photosensitive resin composition 1)

The photosensitive resin composition 1 was spin-coated on glass, dried at 80 ° C. for 3 minutes on a hot plate, and then subjected to 5J ultraviolet rays in terms of h-line using a manual exposure device (MA-1200 manufactured by Dainippon Screen Co., Ltd.). Irradiation was performed, and thereafter, heating was performed on a hot plate at 160 ° C. for 5 minutes to form a cured film of the photosensitive resin composition 1 on glass.
When the cured film was immersed in tetrahydrofuran for 1 hour at room temperature, it was confirmed that it was insoluble without elution.

Claims (15)

A base proliferating agent having at least one structure represented by the following formula (1) and decomposing by heating at 150 ° C. or more in the presence of an amino compound to produce an amino compound.

(In Formula (1), R ^{1 to} R ⁵ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an amino group, a mercapto group, a nitro group, a silyl group, a silanol group, or a monovalent organic group, They may be the same as or different from each other, and they may form a cyclic structure through a bond to each other, R ⁶ represents a substituted or unsubstituted aliphatic hydrocarbon group, or a substituted or unsubstituted Aromatic hydrocarbon group.) 2. The base proliferating agent according to claim 1, wherein at least one of R ^{1 to} R ⁵ in the formula (1) is an electron donating group.   The electron donating group is a hydroxyl group, primary amino group, secondary amino group, tertiary amino group, alkoxy group, alkylthio group, oxyacyl group, amide group, alkyl group, or aryl group. 2. The base proliferating agent according to 2.   The base proliferating agent according to any one of claims 1 to 3, wherein a 5% weight loss temperature is 150 ° C or higher.   The base proliferating agent according to any one of claims 1 to 4, which has no absorption in a wavelength region of 400 nm or more.   6. The base proliferating agent according to claim 1, wherein the base proliferating agent is obtained from a reaction between an isocyanate and a phenol derivative.   The base proliferating agent according to any one of claims 1 to 6, wherein the base compound is hydrolyzed by heating at 150 ° C or higher in the presence of an amino compound to produce an amino compound.   8. A resin composition comprising the base proliferating agent according to claim 1 and a compound that accelerates curing or condensation reaction by the action of a base.   The compound which accelerates | stimulates hardening or a condensation reaction by the effect | action of the said base has a molecular weight of 1000 or more, The resin composition characterized by the above-mentioned.   The resin composition according to claim 8 or 9, wherein the compound that accelerates the curing or condensation reaction by the action of the base is a polyamic acid.   The resin composition according to any one of claims 8 to 10, further comprising a compound that generates an amino compound by the action of light or heat.   The resin composition according to claim 11, which contains a compound that generates an amino compound by the action of light and is a photosensitive resin composition.   The resin composition according to claim 8, wherein the resin composition is used as a pattern forming material.   14. A coating material or printing ink, or a color filter, an electronic component, an interlayer insulating film, a wiring coating film, an optical member, an optical circuit, an optical circuit component, an antireflection film, a hologram, or a building material. The resin composition in any one.   A printed material, a color filter, an electronic component, an interlayer insulating film, a wiring coating film, an optical member, light, at least partly formed of the resin composition according to any one of claims 8 to 14 or a cured product thereof. Articles that are either circuits, optical circuit components, antireflection films, holograms, or building materials.