JP5768348B2 - Thermal base generator, polymer precursor composition, and article using the composition - Google Patents

Description

  The present invention relates to a thermal base generator that generates a base by heating, a polymer precursor composition using the thermal base generator, and an article produced using the composition.

The polymer precursor composition has been used in, for example, electronic parts, optical products, molding materials for optical parts, layer forming materials, adhesives, and the like.
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, polybenzoxazole and polybenzimidazole have poor solubility in solvents and are difficult to process. Therefore, polymer precursors with excellent solvent solubility can be used as a method for making such polymers into a desired shape. In many cases, it is made into a desired shape in the state, and then heated at a high temperature of about 350 ° C. to 400 ° C. to form a thermally stable polyimide, polybenzoxazole, or polybenzimidazole as a layer or a molded product.

  However, in recent years, materials used for electronic components, semiconductor devices, and the like have diversified, and there are electronic components that cannot withstand high-temperature processes (for example, 350 ° C.) for achieving sufficient polymerization. For example, build-up substrates that are widely used to meet the demands of high-density packaging, and packaging substrates that use glass epoxy resin or bismaleimide-triazine resin as the core substrate material are more heat resistant than silicon substrates. It cannot be heated above 250 ° C. Therefore, a technology capable of converting a polymer precursor into a polymer such as polyimide at a lower temperature than before has been desired so that a polymer material such as polyimide can be used in these low heat resistant substrates.

  As a technique for lowering the temperature of imidization, in Patent Document 1, neutralization of secondary amine is generated by causing thermal decomposition to polyamic acid, which is a polyimide precursor, at a temperature of 200 ° C. or less. A technique for mixing a thermal base generator as a compound is disclosed. However, in the thermal base generator specifically disclosed in Patent Document 1, when heated, carbon dioxide (carbon dioxide gas) is always generated simultaneously with the amine, which causes generation of outgas. When outgas is generated from the polymer coating film, “blowing” occurs in the polymer coating film, resulting in a problem that the strength of the cured film is reduced.

  In addition, by mixing a photobase generator with the polyamic acid of the polyimide precursor and heating after exposure, the cyclization proceeds by the action of the base generated by the exposure, and the solubility in the developer is reduced, thereby exposing. There has been reported a method of obtaining a polyimide pattern by forming a pattern by increasing the contrast of the dissolution rate in the developing solution of the part and the unexposed part, followed by imidization (Patent Document 2).

  As the photosensitive resin composition as described above, a photosensitive resin composition containing a photocyclization type photobase generator that generates an amine compound without decarboxylation by irradiation of light and a base reactive resin is provided. Yes (Patent Document 3). However, the photobase generator described in Patent Document 3 does not generate a base only by heating.

JP 2007-056196 A JP-A-8-227154 JP 2009-80452 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a thermal base generator that generates a base by heating and hardly generates outgas, and the thermal base generator. The present invention provides a polymer precursor composition that can be converted from a polymer precursor to a polymer at a lower temperature and that does not easily generate outgas, while having good storage stability, and It is to provide used articles.

  The thermal base generator according to the present invention is represented by the following chemical formula (1) and is characterized by generating a base by heating.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は有機基であり、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^１及びＲ^２の少なくとも１つは有機基である。Ｒ^１及びＲ^２における前記有機基は、炭化水素基、及び、炭化水素基に炭化水素基以外の結合や置換基を含んでいる基、よりなる群から選択される少なくとも１種であり、当該炭化水素基以外の結合は、エーテル結合、チオエーテル結合、カルボニル結合、チオカルボニル結合、エステル結合、アミド結合、ウレタン結合、イミノ結合、カーボネート結合、スルホニル結合、スルフィニル結合、及びアゾ結合よりなる群から選択される少なくとも１種であり、当該炭化水素基以外の置換基は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シアノ基、イソシアノ基、シアナト基、イソシアナト基、チオシアナト基、イソチオシアナト基、シリル基、シラノール基、アルコキシ基、アルコキシカルボニル基、カルバモイル基、チオカルバモイル基、ニトロ基、ニトロソ基、カルボキシル基、カルボキシラート基、アシル基、アシルオキシ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、ヒドロキシイミノ基、飽和又は不飽和アルキルエーテル基、飽和又は不飽和アルキルチオエーテル基、アリールエーテル基、アリールチオエーテル基、アミノ基、及びアンモニオ基よりなる群から選択される少なくとも１種である（但し、Ｒ^１及びＲ^２の少なくともいずれか１つの末端が−（Ｃ＝Ｏ）−Ｃ（Ｒ）＝ＣＨ_２又は−（Ｃ＝ＮＨ）−Ｃ（Ｒ）＝ＣＨ_２（ここでＲは水素又は置換基）である場合を除く）。
Ｒ^３は、水素、又は炭化水素基である。
Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基であり、同一であっても異なっていても良い。Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それらの２つ以上が結合して環状構造を形成していても良く、当該環状構造はヘテロ原子の結合を含んでいても良い。但し、Ｒ^３が水素である場合には、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それらの２つ以上が結合して環状構造を形成しており、当該環状構造はヘテロ原子の結合を含んでいても良い。
Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７における前記有機基は、飽和又は不飽和アルキル基、飽和又は不飽和シクロアルキル基、アリール基、アラルキル基、シアノ基、シアナト基、イソシアナト基、チオシアナト基、イソチオシアナト基、アルコキシ基、アルコキシカルボニル基、カルバモイル基、チオカルバモイル基、カルボキシル基、カルボキシラート基、アシル基、アシルオキシ基、ヒドロキシイミノ基、及び、炭化水素基以外の結合や置換基を含んでいる前記いずれかの基、よりなる群から選択される少なくとも１種であり、当該炭化水素基以外の結合は、エーテル結合、チオエーテル結合、カルボニル結合、チオカルボニル結合、エステル結合、アミド結合、ウレタン結合、イミノ結合、カーボネート結合、スルホニル結合、スルフィニル結合、及びアゾ結合よりなる群から選択される少なくとも１種であり、当該炭化水素基以外の置換基は、ハロゲン原子、水酸基、メルカプト基、スルフィド基、シアノ基、イソシアノ基、シアナト基、イソシアナト基、チオシアナト基、イソチオシアナト基、シリル基、シラノール基、アルコキシ基、アルコキシカルボニル基、カルバモイル基、チオカルバモイル基、ニトロ基、ニトロソ基、カルボキシル基、カルボキシラート基、アシル基、アシルオキシ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、ヒドロキシイミノ基、飽和又は不飽和アルキルエーテル基、飽和又は不飽和アルキルチオエーテル基、アリールエーテル基、アリールチオエーテル基、アミノ基、及びアンモニオ基よりなる群から選択される少なくとも１種である。）

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. may form a, may contain a binding heteroatom. However, the organic group in .R ¹ and R ² at least one of R ¹ and R ² is an organic group, a hydrocarbon group And at least one selected from the group consisting of a bond other than a hydrocarbon group or a substituent on the hydrocarbon group, and the bond other than the hydrocarbon group is an ether bond, a thioether bond, It is at least one selected from the group consisting of a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond. Substituents other than the hydrocarbon group are halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl Group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxy It is at least one selected from the group consisting of an imino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, an aryl thioether group, an amino group, and an ammonio group (provided that R ¹ And At least one of the ends of R ² is - at (C = NH) -C (R ) = CH 2 ( wherein R is hydrogen or a substituent) - (C = O) -C (R) = CH 2 or Except in some cases).
R ³ is hydrogen or a hydrocarbon group.
R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group. Group, phosphono group, phosphonate group, amino group, ammonio group or organic group, which may be the same or different. Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be bonded to form a cyclic structure, and the cyclic structure may include a hetero atom bond. However, when R ³ is hydrogen, two or more of R ⁴ , R ⁵ , R ⁶ and R ⁷ are bonded to form a cyclic structure, and the cyclic structure is a hetero atom bond. May be included.
The organic group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, a cyano group, a cyanato group, an isocyanato group, a thiocyanato group, Containing a bond or substituent other than an isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, and hydrocarbon group Any group is at least one selected from the group consisting of, and the bond other than the hydrocarbon group is an ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond Bond, carbonate bond, sulfonyl bond, sulfini A substituent selected from the group consisting of a bond and an azo bond, and the substituent other than the hydrocarbon group is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group , Thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo Groups, sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups, hydroxyimino groups, saturated or unsaturated alkyl ether groups, saturated or unsaturated alkyl thioether groups, aryl ether groups, aryl thioether groups, amino groups, and ammo groups. It is at least one selected from the group consisting of O group. )

  Since the thermal base generator represented by the chemical formula (1) has the above specific structure and generates a basic substance only by heating, it is heated by a basic substance or in the presence of a basic substance. When used in combination with various polymer precursors that promote the reaction to the final product, polymerization can be used at a lower temperature, and it is a versatile thermal base generator. Since the thermal base generator according to the present invention does not generate a base unless it is heated, a polymer precursor composition having high storage stability can be obtained when used in combination with various polymer precursors. Furthermore, since the thermal base generator according to the present invention does not generate a gas such as carbon dioxide when generating a base as described later, it solves the problems associated with outgassing, Appearance is improved.

  Further, the polymer precursor composition according to the present invention includes a polymer precursor whose reaction to the final product is promoted by heating with a basic substance or in the presence of the basic substance, and the above-described present invention. It contains such a thermal base generator.

  The polymer precursor composition according to the present invention is a final product of a thermal base generator represented by the chemical formula (1) and generating a base by heating, by heating with a basic substance or in the presence of a basic substance. Combined with a polymer precursor that promotes the reaction to the product, it can be converted from a polymer precursor to a polymer at a lower temperature and has less outgassing while having good storage stability. is there.

  The thermal base generator of the present invention preferably has a thermal decomposition starting temperature of 40 ° C. or higher and 350 ° C. or lower. When the thermal decomposition start temperature is high, there is a concern that the yield of circuit wiring or the like is reduced due to the high temperature process. On the other hand, if the thermal decomposition starting temperature is too low, the storage stability may be impaired.

  In the present invention, the thermal base generator is preferably represented by the following formula (2) from the viewpoint of strong basicity and large catalytic effect.

（式（２）中、Ｒ^１及びＲ^２は、それぞれ独立に、置換基を有してもよい炭素数１〜２０のアルキル基、又は置換基を有してもよい炭素数４〜２２のシクロアルキル基である。Ｒ^１及びＲ^２は、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。）

(In the formula (2), ^{R 1} and ^{R 2} are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent of carbon atoms which may 4-22 of having A cycloalkyl group, 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; May be included.)

  In the polymer precursor composition according to the present invention, examples of the polymer precursor include compounds and polymers having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, a polysiloxane precursor, a polyimide precursor, and poly One or more selected from the group consisting of benzoxazole precursors are preferably used.

  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 polymer precursor composition. When such a polymer precursor is used, a polymer precursor 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.

  The present invention also provides a printed material, a paint, a sealant, an adhesive, a display device, a semiconductor device, an electronic component, a microelectromechanical system, at least a part of which is formed from the polymer precursor composition or a cured product thereof. Articles of either stereolithic objects, optical members or building materials are also provided.

The thermal base generator of the present invention has a structure represented by the formula (1), so that a base is generated by heating and is combined with various polymer precursors to obtain a composition having high storage stability. This produces an effect that it is difficult to generate outgas.
By using the thermal base generator of the present invention, the polymer precursor composition of the present invention can be converted from a polymer precursor to a polymer at a lower temperature while being excellent in storage stability, and is outgassed. The effect that it is hard to generate is produced.
Furthermore, in the polymer precursor composition of the present invention, unlike the acid, since the base does not cause metal corrosion, a more reliable cured film can be obtained.

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.
<Heat base generator>
The thermal base generator according to the present invention is represented by the following chemical formula (1) and is characterized by generating a base by heating.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は有機基であり、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^１及びＲ^２の少なくとも１つは有機基である。Ｒ^３は、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基である。Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基であり、同一であっても異なっていても良い。Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それらの２つ以上が結合して環状構造を形成していても良く、当該環状構造はヘテロ原子の結合を含んでいても良い。但し、Ｒ^３が水素である場合には、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それらの２つ以上が結合して環状構造を形成しており、当該環状構造はヘテロ原子の結合を含んでいても良い。）

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And at least one of R ¹ and R ² is an organic group, and R ³ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide. A group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group, R ⁴ , R ⁵ , R ⁶ and R ⁷ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl A group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, which may be the same or different, and R ⁴ , R ⁵ , R ^6, and R ⁷ are bonded together. A cyclic structure, which may contain a heteroatom bond, provided that R ³ is hydrogen, R ⁴ , R ⁵ , R ⁶ and R ^7. Are bonded to each other to form a cyclic structure, and the cyclic structure may include a heteroatom bond.)

  The thermal base generator of the present invention refers to an agent that does not exhibit activity under normal conditions of normal temperature and pressure, but generates a base when heated as an external stimulus. The thermal base generator of the present invention generates a base only by being heated, but generation of the base may be promoted by appropriately irradiating electromagnetic waves.

Since the thermal base generator according to the present invention has the above-mentioned specific structure, the (—CR ³ ═CH—C (═O) —) moiety in the formula (1) is represented by the following formula by heating, as shown by the following formula. Isomerized to the cis form and further cyclized to produce the base (NHR ¹ R ² ). By the catalytic action of the base, the temperature at which the reaction when the polymer precursor becomes the final product can be lowered, or the curing reaction where the polymer precursor becomes the final product can be started.

  Since the thermal base generator represented by the chemical formula (1) has the above specific structure and generates a basic substance only by heating, it is heated by a basic substance or in the presence of a basic substance. When used in combination with various polymer precursors that promote the reaction to the final product, polymerization can be used at a lower temperature, and it is a versatile thermal base generator. Since the thermal base generator according to the present invention does not generate a base unless it is heated, a polymer precursor composition having high storage stability can be obtained when used in combination with various polymer precursors. Furthermore, since the thermal base generator according to the present invention does not generate a gas such as carbon dioxide when generating a base as described above, it solves the problems associated with outgassing, Appearance is improved.

R ¹ and R ² are each independently a hydrogen atom or an organic group, but at least one of R ¹ and R ² is an 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 R ¹ and R ² contain an amino group, the thermal base generator itself becomes a basic substance, which accelerates the reaction of the polymer precursor, and the stability of the polymer precursor composition is poor. There is a fear. However, when the basicity and difference with the base generated after heating occur, for example, when an amino group is bonded to the aromatic ring present in the organic group of R ¹ and R ² , R ¹ And an organic group in R ² may be used even if it contains an amino group.
Examples of the 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.
The organic group in R ¹ and R ² is usually a monovalent organic group, but in the case of forming a cyclic structure described later, the generated NHR ¹ R ² is an NH group capable of forming an amide bond such as diamine. In the case of a basic substance having two or more, it can be a divalent or higher organic group.

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 as long as the effect of the present invention is not impaired. An ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, and an ester bond Amide bond, urethane bond, imino bond (-N = C (-R)-, -C (= NR)-, where R is a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, azo bond Etc. From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (— R)-, -C (= NR)-: where R is a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ¹ and R ² is not particularly limited as long as the effect of the present invention is not impaired. A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, Isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group Acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and Arylthioether group, a Amino group (-NH2, -NHR, -NRR ': wherein, R and R' are each independently a hydrocarbon group). The hydrogen contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and 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 sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, Silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group , A phosphinyl group, a phosphono group, a phosphonato group, a hydroxyimino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, and an aryl thioether group.

Since the base to be generated is NHR ¹ R ² , primary amines, secondary amines, or heterocyclic compounds can be mentioned. The amine includes an aliphatic amine and an aromatic amine, respectively. In addition, the heterocyclic compound here means that NHR ¹ R ² has a cyclic structure and has aromaticity. Non-aromatic heterocyclic compounds that are not aromatic heterocyclic compounds are included here in aliphatic amines as alicyclic amines.

Further, the NHR ¹ R ^{2 to be} generated is not only a base such as monoamine having only one NH group capable of forming an amide bond, but also two or more NH groups capable of forming an amide bond such as diamine, triamine, and tetraamine. It may be a base. In the case where the generated NHR ¹ R ² is a base 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). Examples include a structure in which a heat latent site that generates a base having heat is further bonded. As the thermal latent 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.

Among the generated NHR ¹ R ² , 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. In addition, as an aromatic heterocyclic compound having an NH group capable of forming an amide bond, an imino bond (—N═C (—R) —, —C (═NR) — Here, R preferably has a hydrogen atom or a monovalent organic group), and examples thereof include imidazole, purine, triazole, and derivatives thereof.

Bases having two or more NH groups capable of forming an amide bond include ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7- Linear aliphatic alkylenediamines such as heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 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 Branched aliphatic alkylenediamines such as 1,4-butanediamine and 2,3-dimethyl-1,4-butanediamine; diethylenetriamine, triethylenetetra Emissions, polyethylene amines represented by tetraethylenepentamine general formula _{NH 2 (CH 2 CH 2 NH} ) , such as _n H; cyclohexane diamine, methylcyclohexane diamine, isophorone diamine, norbornane dimethylamine, tricyclodecane dimethylamine, Men Cycloaliphatic diamines such as sendiamine; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, p-xylylenediamine, m-xylylenediamine, 4,4′-diaminodiphenylmethane, diaminodiphenylsulfone; benzenetriamine And triamines such as 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 thermal properties and basicity of the generated base 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.

In addition, the base generated in the present invention is preferably a secondary amine and / or a heterocyclic compound, and particularly preferably a secondary amine, from the viewpoint of increasing the sensitivity as a thermal base generator. It is presumed that this is because the use of a secondary amine or a heterocyclic compound eliminates active hydrogen at the amide bond site, thereby changing the electron density and improving the sensitivity of isomerization.

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.

  The structure of the secondary amine and / or heterocyclic compound generated is preferably represented by the following formula (2).

（式（２）中、Ｒ^１及びＲ^２は、それぞれ独立に、有機基であり、置換基を有してもよい炭素数１〜２０のアルキル基、又は置換基を有してもよい炭素数４〜２２のシクロアルキル基である。Ｒ^１及びＲ^２は、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。）

(In Formula (2), R ¹ and R ² are each independently an organic group, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon. A cycloalkyl group having a number of 4 to 22. R ¹ and R ² may be the same or different, and R ¹ and R ² may combine to form a cyclic structure; And may contain a bond of a heteroatom.)

In R ¹ and R ² of formula (2), the alkyl group may be linear or branched. The alkyl group preferably further has 1 to 12 carbon atoms, and the cycloalkyl group preferably further has 4 to 10 carbon atoms. Further, the alicyclic amine has a cyclic structure of R ¹ and R ² are bonded carbon atoms which may have a substituent 4-14 also preferred. Moreover, heterocyclic compounds become R ¹ and R ² are bonded which may have a substituent ring structure having 2 to 12 carbon atoms are also preferred.

In Formula (1), each R ³ is independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, A phosphinyl group, a phosphono group, a phosphonato group, or an organic group.
In the present invention, in particular, when R ³ in formula (1) is not hydrogen but the specific functional group described above, even if all of R ^{4 to} R ⁷ are hydrogen, the base is formed only by heating. Occur. This is because when R ³ in formula (1) is not hydrogen but the specific functional group described above, (—CR ³ ═CH— in formula (1) is due to the effect of steric hindrance of R ^3. It is presumed that the C (= O)-) moiety is easily isomerized into a cis isomer and a base is generated only by heating. When R ³ in the formula (1) is not hydrogen but the specific functional group described above, the solubility in an organic solvent is improved as compared with the case where R ³ is hydrogen, or a polymer precursor and The effect of improving the affinity of can also be expected. For example, when R ³ is an organic group such as an alkyl group or an aryl group, the solubility in an organic solvent is improved. For example, when R ³ is a halogen such as fluorine, the affinity with a polymer precursor containing a halogen such as fluorine is improved. For example, when R ³ has a silyl group or a silanol group, the affinity with the polysiloxane precursor is improved.

Examples of the halogen include fluorine, chlorine, bromine and the like.
The organic group is not particularly limited as long as the effect of the present invention is not impaired, and is 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. , Cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, etc. Is mentioned. 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 organic group in R ³ is usually a monovalent organic group.
The bond other than the hydrocarbon group in the organic group of R ³ is not particularly limited, and is not particularly limited as long as the effect of the present invention is not impaired. An ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, Ester bond, amide bond, urethane bond, imino bond (—N═C (—R) —, —C (═NR) —, where R is a hydrogen atom or an organic group), carbonate bond, sulfonyl bond, sulfinyl bond, An azo bond etc. are mentioned. From the viewpoint of heat resistance, the bond other than the hydrocarbon group in the organic group includes an ether bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, and an imino bond (—N═C (— R)-, -C (= NR)-: where R is a hydrogen atom or an organic group), a carbonate bond, a sulfonyl bond, and a sulfinyl bond.

The substituent other than the hydrocarbon group in the organic group of R ³ is not particularly limited as long as the effects of the present invention are not impaired. A halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, Cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group , Sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and aryl thioether group , Amino group (-NH 2, —NHR, —NRR ′: R and R ′ are each independently a hydrocarbon group. The hydrogen contained in the substituent may be substituted with a hydrocarbon group. Further, the hydrocarbon group contained in the substituent may be any of linear, branched, and cyclic.
Among them, the substituent other than the hydrocarbon group in the organic group of R ³ includes a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group, a thiocyanato group, an isothiocyanato group, and a silyl group. , Silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group Group, phosphono group, phosphonato group, hydroxyimino group, saturated or unsaturated alkyl ether group, saturated or unsaturated alkyl thioether group, aryl ether group, and aryl thioether group are preferred.

R ³ includes, for example, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a cycloalkyl group having 4 to 13 carbon atoms such as a cyclopentyl group and a cyclohexyl group; a cyclopentenyl group and a cyclohexenyl group. C4-C13 cycloalkenyl group; C7-C16 aryloxyalkyl group (-ROAr group) such as phenoxymethyl group, 2-phenoxyethyl group, 4-phenoxybutyl group; benzyl group, 3-phenylpropyl An aralkyl group having 7 to 20 carbon atoms such as a group; an alkyl group having 2 to 11 carbon atoms having a cyano group such as a cyanomethyl group and a β-cyanoethyl group; an alkyl group having 1 to 10 carbon atoms having a hydroxyl group such as a hydroxymethyl group , a methoxy group, an alkoxy group having 1 to 10 carbon atoms such as an ethoxy group, acetamido group, benzenesulfonyl cyanamide group (C ₆ H SO ₂ NH ₂ -) amide group having 2 to 11 carbon atoms such as a methylthio group, an alkylthio group having 1 to 10 carbon atoms such as an ethylthio group (-SR group), 1 to 10 carbon atoms such as an acetyl group, a benzoyl group Aryl groups having 2 to 11 carbon atoms such as acyl groups, methoxycarbonyl groups, and acetoxy groups (-COOR groups and -OCOR groups), phenyl groups, naphthyl groups, biphenyl groups, tolyl groups and the like. 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 ) is preferred. The alkyl moiety may be linear, branched or cyclic.

Next, R ⁴ , R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, A sulfonato group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, which may be the same or different. Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be bonded to form a cyclic structure, and the cyclic structure may include a hetero atom bond. The organic group in R ^{4 to} R ⁷ is usually a monovalent organic group, but may form a divalent or higher organic group when forming a cyclic structure described later.
However, when R ³ is hydrogen, R ⁴ , R ⁵ , R ⁶ and R ⁷ are combined with each other to form a cyclic structure, and the cyclic structure is a heteroatom. It may contain bonds.

When R ³ is hydrogen, two or more of R ⁴ , R ⁵ , R ⁶ and R ⁷ are bonded to form a cyclic structure, thereby allowing R ⁴ , R ⁵ , R ⁶ and Since the electronic state of the benzene ring to which R ⁷ is bonded changes, the (—CR ³ ═CH—C (═O) —) moiety in the formula (1) is easily isomerized into a cis isomer, and only heating is performed. It is presumed that a base is generated.

As the substituents other than the halogen, the organic group, the hydrocarbon group in the organic group, and the substituent other than the hydrocarbon group in the organic group in R ^{4 to} R ⁷ , the same as those described in the above R ³ can be used. Can be used.

When R ³ is hydrogen, two or more of R ^{4 to} R ⁷ are bonded to form a cyclic structure, and the cyclic structure is saturated or unsaturated. The structure may be a combination of two or more selected from the group consisting of alicyclic hydrocarbons, heterocyclic rings, and condensed rings, and alicyclic hydrocarbons, heterocyclic rings, and condensed rings. For example, R ^{4 to} R ⁷ may be a condensed ring such as naphthalene, anthracene, phenanthrene, fluorene, indene and the like, in which two or more of them are bonded and share the atoms of the benzene ring to which R ^{4 to} R ⁷ are bonded A condensed heterocyclic compound such as hydrocarbon, xanthene, and thioxanthone may be formed.

Examples of the structure in which two or more of R ^{4 to} R ⁷ are bonded to form a cyclic structure include the following structures, but are not limited thereto.

（式中、Ｒ^１及びＲ^２、並びに、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ式（１）と同様である。Ｒ^８は、環状構造に更に有していてもよい置換基を表し、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基である。ｍは０又は１以上の整数である。ｍ個のＲ^８は、同一であっても異なっていても良い。Ｘは、２つの酸素原子と結合可能な連結基である。）

(In the formula, R ¹ and R ² , and R ⁴ , R ⁵ , R ⁶ and R ⁷ are the same as those in formula (1), respectively. R ⁸ may be further substituted in the cyclic structure. Represents a group, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, amino group, An ammonio group or an organic group, m is 0 or an integer of 1 or more, m R ^{8 s} may be the same or different, and X is a linking group capable of binding to two oxygen atoms. .)

X in the above chemical formula may contain a hetero atom, and may have a substituent, a linear, branched or cyclic, saturated or unsaturated aliphatic or aromatic hydrocarbon group having 1 to 20 carbon atoms. A hydrogen silicide group which may contain a hetero atom, may have a substituent, and may contain a linear, branched or cyclic silicon-silicon double bond having 1 to 20 silicon atoms, ether A linking group selected from the group consisting of a bond, a thioether bond, a carbonyl bond, a thiocarbonyl bond, a sulfonyl bond, and a sulfinyl bond is preferable. For example, as X, alkylene which may have a substituent such as —CH ₂ —, —CHR—, —CR (OR) — (where R is an alkyl group), — (CH ₂ ) _n —, etc. Group, —CH═CH—, orthophenylene group, —SiH ₂ — and the like.

When R ³ is hydrogen, R ^{4 to} R ⁷ are bonded to each other, and two or more of them are bonded to each other and share a benzene ring atom to which R ^{4 to} R ⁷ are bonded to share naphthalene, anthracene, It is preferable that condensed ring hydrocarbons such as phenanthrene, fluorene and indene, and condensed heterocyclic compounds such as xanthene and thioxanthone are formed from the viewpoint that the change in the electronic state becomes large and the base generation temperature is lowered.
When R ³ is hydrogen, R ^{4 to} R ⁷ form a heterocyclic compound containing a heteroatom such as oxygen or sulfur. This is preferable from the viewpoint that the generation temperature is lowered.

On the other hand, when R ³ is a substituent other than hydrogen, all of R ^{4 to} R ⁷ may be hydrogen atoms and are not particularly limited. When any of R ^{4 to} R ⁷ has a substituent, the substituent includes 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 carbon. An aryloxyalkyl group having 7 to 16 carbon atoms (-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, carbon C1-C10 alkoxy group, C2-C11 amide group, C1-C10 alkylthio group (-SR group), C1-C10 acyl group, C2-C11 ester group, Carbon An aryl group having 6 to 20 atoms, an electron donating group and / or an electron withdrawing group substituted with an aryl group having 6 to 20 carbon atoms, an electron donating group and / or a benzyl group with an electron withdrawing group substituted, or a cyano group And methylthio group ( SCH _3), etc. are preferable. The alkyl moiety may be linear, branched or cyclic.

  Further, the structure represented by the chemical formula (1) has a geometric isomer, but it is preferable to use only the trans isomer. However, cis isomers that are geometric isomers may be mixed during synthesis and purification steps and storage, and in this case, a mixture of trans isomer and cis isomer may be used. It is preferable that the ratio of cis-isomer is less than 10%.

  In the thermal base generator represented by the chemical formula (1), the bond that is most easily decomposed by heat is an amide bond. Therefore, the thermal base generator represented by the chemical formula (1) preferably has a thermal decomposition starting temperature of 40 ° C. or higher and 350 ° C. or lower. When the thermal decomposition start temperature is high, there is a concern that the yield of circuit wiring or the like is reduced due to the high temperature process. On the other hand, if the thermal decomposition starting temperature is too low, the storage stability may be impaired.

In the present invention, the thermal decomposition starting temperature of the thermal base generator represented by the chemical formula (1) refers to the lowest temperature among the thermal decomposition temperatures measured in the following solid state or solution.
As a solid state, 5% weight reduction temperature of the thermal base generator represented by the chemical formula (1) is used as an index. Here, the 5% weight loss temperature is the time when the weight of the sample is reduced by 5% from the initial weight when the weight loss is measured using a thermogravimetric analyzer (that is, when the weight of the sample becomes 95% of the initial weight). ) Temperature.
In the solution, the temperature at which 10 mol% of base is generated is used as an index in NMR measurement of a 2 mg / mL solution of the thermal base generator represented by the chemical formula (1). Regarding the temperature at which 10 mol% of base is generated, for example, a thermal base generator is dissolved in a deuterated solvent such as deuterated DMSO at 2 mg / mL to prepare a solution for NMR measurement, and a sample that is sequentially heated is prepared. The sequentially heated sample is subjected to ¹ H-NMR measurement using an NMR apparatus (eg, 400 MHz NMR apparatus, specific example: JEOL JNM-LA400WB, manufactured by JEOL Ltd.) and generated from a thermal base generator. It is obtained by measuring the amount of base (mol%) obtained.

The 5% weight loss temperature in the solid state tends to be higher than the thermal decomposition temperature in the solution. Further, the 5% weight loss temperature in the solid state tends to be higher than the temperature at which the reaction of the polymer precursor is initiated by the base generated in the coating film composed of the polymer precursor and the thermal base generator. . This is because a certain amount of space is required for the rotation of the molecule for isomerization of the (—CR ³ ═CH—C (═O) —) moiety in the formula (1) into a cis isomer, It is presumed that the thermal base generator in is because it is difficult to secure the space. When used as a polymer precursor composition in a coating film, the thermal base generator is dispersed in the polymer precursor, so that the thermal base generator is thermally decomposed in the polymer precursor composition. It is estimated that the temperature is closer to the thermal decomposition temperature in the solution than the thermal decomposition temperature in the solid state of the single substance.

In the thermal base generator represented by the chemical formula (1), the thermal decomposition starting temperature is preferably adjusted as appropriate depending on the polymer precursor to be combined. The thermal decomposition starting temperature represented by the chemical formula (1) can be adjusted by appropriately selecting the substituent R ^{3 and} R ^{4 to} R ⁷ .
For example, when the polymer precursor is used in combination with a polyimide precursor or a polybenzoxazole precursor, in the thermal base generator represented by the chemical formula (1), the thermal decomposition start temperature is 100 ° C. or higher and 350 ° C. It is preferable that it is below, Furthermore, it is preferable that it is 150 to 250 degreeC. 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.
On the other hand, when the polymer precursor is used in combination with a compound having a epoxy group, an isocyanate group, an oxetane group, or a thiirane group, and a polymer or a polysiloxane precursor, the thermal base represented by the above chemical formula (1). In the generator, the thermal decomposition starting temperature is preferably 40 ° C. or higher and 200 ° C. or lower, and more preferably 50 ° C. or higher and 150 ° C. or lower. In the case of compounds and polymers having an epoxy group, an isocyanate group, an oxetane group, or a thiirane group, and a polysiloxane precursor, the temperature required for curing is lower than the above polyimide precursor, etc. This is because a relatively low temperature is preferable.

  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. When the boiling point of the generated base is not 25 ° C. or higher, when it is used as a coating film, the amine generated during drying tends to evaporate, which may make the operation difficult. When the generated base is used as a curing accelerator that does not remain in the film, if the weight loss of the generated base at 350 ° C. is 80% or more, the base remains in the cured polymer. It is preferable because it is easy to suppress the above. However, when the generated base is used as a crosslinking agent or a curing agent remaining in the film, the weight reduction of the generated base is not a problem.

The heating temperature for generating a base when using the thermal base generator represented by the formula (1) is appropriately selected depending on the polymer precursor to be combined and the purpose, and is not particularly limited. 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.
Moreover, in order to prevent decomposition | disassembly other than base generation | occurrence | production of the thermal base generator represented by said Formula (1), it is preferable to heat at 300 degrees C or less.

Examples of the method for synthesizing the thermal base generator represented by the formula (1) of the present invention include the following methods.
When introducing a substituent into R ³ of the formula (1), first, hydroxyphenyl- (C═O) —R ³ into which each substituent is introduced (for example, when R ³ is a methyl group, 2'-hydroxyphenylmethylketone) is synthesized. For example, by carrying out Friedel-Crafts acylation reaction to a phenol having a corresponding substituent, it is possible to synthesize hydroxyphenyl- (C═O) —R ₃ into which each substituent is introduced. Next, a cinnamic acid derivative into which each substituent is introduced is synthesized by performing a wittig reaction, a Knoevenagel reaction, or a Perkin reaction on hydroxyphenyl- (C═O) —R ³ into which each substituent is introduced. Then, an appropriately selected amine or basic substance can be condensed with the cinnamic acid derivative into which each of the above substituents is introduced to obtain the target product.

When R ^{3 in the} formula (1) is a hydrogen atom, first, hydroxybenzaldehyde into which each substituent is introduced is synthesized. The synthesis of hydroxybenzaldehyde into which each substituent is introduced can be synthesized by performing Duff reaction or Vilsmeier-Haack reaction on the phenol having the corresponding substituent. Next, a cinnamic acid derivative in which each substituent is introduced into hydroxybenzaldehyde into which each substituent is introduced is synthesized in the same manner as described above. Then, an appropriately selected amine or basic substance can be condensed with the cinnamic acid derivative into which each of the above substituents is introduced to obtain the target product.
The method for synthesizing the thermal base generator of the present invention is not limited to this. The thermal base generator of the present invention can be synthesized by combining a plurality of conventionally known synthesis routes.

<Polymer precursor composition>
The polymer precursor composition according to the present invention includes a polymer precursor whose reaction to the final product is promoted by heating with a basic substance or in the presence of a basic substance, and the following according to the present invention: It is represented by the chemical formula (1) and contains a thermal base generator that generates a base by heating.

（式（１）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素又は有機基であり、同一であっても異なっていても良い。Ｒ^１及びＲ^２は、それらが結合して環状構造を形成していても良く、ヘテロ原子の結合を含んでいても良い。但し、Ｒ^１及びＲ^２の少なくとも１つは有機基である。Ｒ^３は、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、又は有機基である。Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、水素、ハロゲン、水酸基、メルカプト基、スルフィド基、シリル基、シラノール基、ニトロ基、ニトロソ基、スルフィノ基、スルホ基、スルホナト基、ホスフィノ基、ホスフィニル基、ホスホノ基、ホスホナト基、アミノ基、アンモニオ基又は有機基であり、同一であっても異なっていても良い。Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それらの２つ以上が結合して環状構造を形成していても良く、当該環状構造はヘテロ原子の結合を含んでいても良い。但し、Ｒ^３が水素である場合には、Ｒ^４、Ｒ^５、Ｒ^６及びＲ^７は、それらの２つ以上が結合して環状構造を形成しており、当該環状構造はヘテロ原子の結合を含んでいても良い。）

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. And at least one of R ¹ and R ² is an organic group, and R ³ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide. A group, a silyl group, a silanol group, a nitro group, a nitroso group, a sulfino group, a sulfo group, a sulfonate group, a phosphino group, a phosphinyl group, a phosphono group, a phosphonato group, or an organic group, R ⁴ , R ⁵ , R ⁶ and R ⁷ is hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl A group, a phosphono group, a phosphonato group, an amino group, an ammonio group, or an organic group, which may be the same or different, and R ⁴ , R ⁵ , R ^6, and R ⁷ are bonded together. A cyclic structure, which may contain a heteroatom bond, provided that R ³ is hydrogen, R ⁴ , R ⁵ , R ⁶ and R ^7. Are bonded to each other to form a cyclic structure, and the cyclic structure may include a heteroatom bond.)

As described above, the thermal base generator represented by the formula (1) has the above specific structure, so that the (—CR ³ ═CH—C (═O) —) moiety is converted into a cis isomer by heating. And the base (NHR ¹ R ² ) is generated by further heating. In addition, the polymer precursor is promoted to react with the final product by the action of the base generated from the thermal base generator. As a result, the polymer precursor composition of the present invention has an effect that it can be converted from a polymer precursor to a polymer at a lower temperature and does not easily generate outgas, while having good storage stability. Since the polymer precursor composition of the present invention can reduce the processing temperature required for the reaction, it is possible to reduce the load on the process and the damage to the product due to heat. Moreover, since the base used does not cause metal corrosion unlike an acid, a more reliable cured film can be obtained. In addition, the aspect which converts into a polymer only by the effect | action of a base is also contained in the aspect converted into a polymer from a polymer precursor at lower temperature.

  The polymer precursor composition of the present invention is typically used as a non-photosensitive resin composition or a thermosetting resin composition. However, when the polymer precursor itself has a photosensitive portion or a photosensitive component is further added, it may function as a photosensitive resin composition.

Hereinafter, components of the polymer precursor composition according to the present invention will be described. The thermal base generator used in the polymer precursor composition according to the present invention is the same as the thermal base generator according to the present invention. Since the same thing can be used, description here is abbreviate | omitted. Therefore, the polymer precursor and other components that can be appropriately included as necessary will be described in order.
As the thermal base generator and the polymer precursor, one kind may be used alone, or two or more kinds may be mixed and used.

<Polymer precursor>
The polymer precursor used in the polymer precursor composition of the present invention means a substance that finally becomes a polymer showing 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. .

  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.

[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 thermal base generator generally 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, YDCN series, YDB series, phenoxy resin (polyethylene synthesized from bisphenols and epichlorohydrin) B carboxymethyl having an epoxy group at both ends with polyether; YP series, etc.), Nagase ChemteX Corporation of Denacol series manufactured by Kyoeisha but Chemical Co. Epo light series, and the like are 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, YnSiX (4-n) (wherein Y represents an alkyl group, fluoroalkyl group, vinyl group, phenyl group, or hydrogen which may have a substituent, and X represents an alkoxy group. , An acetoxy group, an oxime group, an enoxy group, an amino group, an aminoxy group, an amide group, and a hydrolyzable group selected from the group consisting of halogens, where n is an integer from 0 to 3. Examples include organosilicon compounds and hydrolyzed polycondensates of the organosilicon compounds. 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.

（式（３）中、Ｒ^９は４価の有機基である。Ｒ^１０は２価の有機基である。Ｒ^１１及びＲ^１２は、水素原子、又は１価の有機基である。ｎは１以上の自然数である。）

(In Formula (3), R ⁹ is a tetravalent organic group. R ¹⁰ is a divalent organic group. R ¹¹ and R ¹² are a hydrogen atom or a monovalent organic group. (It is a natural number of 1 or more.)

Examples of the case where R ¹¹ and R ¹² are monovalent organic groups include alkyl groups, alkenyl groups, alkynyl groups, aryl groups, and C _n H _2n OC _m H _{2m + 1} containing an ether bond in these groups. The structure represented can be mentioned.
As the polyimide precursor, a polyamic acid in which R ¹¹ and R ¹² are hydrogen atoms is preferably used from the viewpoint of alkali developability.

In addition, although the tetravalence of R ⁹ shows only the valence for bonding with an acid, it may have another substituent. Similarly, the divalent value of R ¹⁰ indicates only the valence for bonding with 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.
Further, when the polymer precursor to be used is a polyamic acid, it is sufficient even if the temperature required for imidization is low due to the catalytic effect of the basic substance, so the final curing temperature is lowered to less than 300 ° C, more preferably to 250 ° C or less. It is possible. 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 ⁹ or R ¹⁰ in the chemical formula (3). 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 (3), four groups ((—CO—) ₂ (—COOH) ₂ ) bonded to R ⁹ may be bonded to the same aromatic ring. May be bonded to different aromatic rings. Similarly, in R ¹⁰ of the chemical formula (3), two groups ((—NH—) ₂ ) bonded to R ¹⁰ 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.

  Using acid dianhydride with fluorine introduced or acid dianhydride having an alicyclic skeleton as the acid dianhydride to be used in combination adjusts physical properties such as solubility and thermal expansion without losing transparency. 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, 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′-diaminodiphenylsulfide, 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 3,3′-diaminobenzophenone, 4,4 ′ -Diaminobenzophenone, 3,4'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2-di (3-aminophenyl) propane, 2 , 2-Di (4-aminophenyl) propa 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-amino Phenyl) -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- (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-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, α-ditrifluoromethylben) L) 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.

（化学式（４）中、ａは１以上の自然数、アミノ基はベンゼン環同士の結合に対して、メタ位または、パラ位に結合する。）

(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 the 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 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.

（化学式（５）中、Ｒ^１３は２価の有機基である。Ｒ^１４は４価の有機基である。ｎは１以上の自然数である。）

(In the chemical formula (5), R ¹³ is a divalent organic group. R ¹⁴ is a tetravalent organic group. N is a natural number of 1 or more.)

In addition, although the divalent value of R ¹³ indicates only the valence for bonding with an acid, it may have another substituent. Similarly, the tetravalent value of R ¹⁴ indicates only the valency for bonding with an amine and a hydroxyl group, but may have other substituents.

The 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 ¹³ and R ¹⁴ is preferably an aromatic compound, and R ¹³ and R ¹⁴ are more preferably aromatic compounds. At this time, in R ¹³ of the chemical formula (5), two groups (—CO—) ₂ bonded to the R ¹³ may be bonded to the same aromatic ring or bonded to different aromatic rings. May be. Similarly, in R ¹⁴ of the chemical formula (5), four groups ((—NH—) ₂ (—OH) ₂ ) bonded to R ¹⁴ 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.

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.

<Other ingredients>
The polymer precursor composition according to the present invention may be a simple mixture of the thermal base generator represented by the chemical formula (1), one or more polymer precursors, and a solvent. The polymer precursor composition may be prepared by blending a light or thermosetting component, a non-polymerizable binder resin other than the polymer precursor, and other components.

  Various general-purpose solvents can be used as a solvent for dissolving, dispersing or diluting the polymer precursor 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.

  Examples of general-purpose solvents that can be used include ethers such as diethyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, and diethylene glycol dimethyl ether; ethylene glycol monomethyl ether, ethylene glycol mono Glycol monoethers (so-called cellosolves) such as ethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether; methyl ethyl ketone, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc. Ketones; ethyl acetate, butyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, acetate esters of the above glycol monoethers (for example, methyl cellosolve acetate, ethyl cellosolve acetate), propylene Esters such as glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dimethyl oxalate, methyl lactate, ethyl lactate; alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, glycerin; methylene chloride, 1,1-dichloroethane, 1,2-dichloroethylene, 1-chloropropane, 1-chlorobutane, 1-chloropentane, chlorobenzene, bromobenzene, o- Halogenated hydrocarbons such as chlorobenzene and m-dichlorobenzene; N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylmethoxyacetamide and the like Amides of N; pyrrolidones such as N-methyl-2-pyrrolidone and N-acetyl-2-pyrrolidone; lactones such as γ-butyrolactone and α-acetyl-γ-butyrolactone; sulfoxides such as dimethyl sulfoxide, dimethyl sulfone, Examples include sulfones such as tetramethylene sulfone and dimethyltetramethylene sulfone, phosphoric acid amides such as hexamethylphosphoamide, and other organic polar solvents, and aromatics such as benzene, toluene, xylene, and pyridine. Hydrocarbons and their Other organic nonpolar solvents are also included. These solvents are used alone or in combination.

  Among them, polar solvents such as propylene glycol monomethyl ether, methyl ethyl ketone, cyclopentanone, cyclohexanone, ethyl acetate, propylene glycol monomethyl ether acetate, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, γ-butyrolactone, toluene, etc. Aromatic hydrocarbons and mixed solvents composed of these solvents are preferred.

  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 polymer precursor 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, a photosensitive component that generates an acid or a base by light can be added to the polymer precursor composition of the present invention as an auxiliary role of the thermal base generator of the present invention. good. Further, a base proliferating agent or a sensitizer may be added.

  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 polymer precursor composition according to the present invention, the polymer precursor (solid content) is the entire solid content of the polymer precursor composition from the viewpoint of film physical properties of the obtained pattern, particularly film strength and heat resistance. The content is preferably 30% by weight or more and 50% by weight or more.
The thermal base generator represented by the chemical formula (1) is usually 0.1 to 95% by weight, preferably 0.5 to 0.5% based on the solid content of the polymer precursor contained in the polymer precursor composition. It is contained within the range of 60% by weight. If it is less than 0.1% by weight, curing may not be sufficient, and if it exceeds 95% by weight, the properties of the finally obtained resin cured product are hardly reflected in the final product.
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, curing is possible with a small amount of addition, and the thermal base generator represented by the chemical formula (1) is a polymer precursor contained in the polymer precursor composition. It is preferable to make it contain 0.1 to 30 weight% normally with respect to solid content, Preferably it is 0.5 to 20 weight%.
In addition, solid content of a polymer precursor composition is all components other than a solvent, and a liquid monomer component is also contained in solid content.

  Moreover, the blending ratio of optional components other than the other solvent is preferably in the range of 0.1% by weight to 95% by weight with respect to the entire solid content of the polymer precursor 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 polymer precursor 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 polymer precursor composition of the present invention, the resulting polyimide and polybenzoxazole have heat resistance, dimensional stability, insulation. From the viewpoint of securing properties such as property, 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.

The glass transition temperature of the polyimide and polybenzoxazole obtained from the polymer precursor 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, such as an optical waveguide. The glass transition temperature is preferably 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) by dynamic viscoelasticity measurement when polyimide and polybenzoxazole obtained from the polymer precursor composition can be formed into a film shape. (E ″) / storage elastic modulus (E ′)). The dynamic viscoelasticity measurement is performed by using, for example, a viscoelasticity measuring apparatus Solid Analyzer RSA II (manufactured by Rheometric Scientific) at a frequency of 3 Hz. When the polyimide and polybenzoxazole obtained from the polymer precursor composition cannot be formed into a film shape, the temperature at the inflection point of the baseline of differential thermal analysis (DTA) can be performed. Judge with.

From the viewpoint of dimensional stability of the polyimide and polybenzoxazole obtained from the polymer precursor 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 polymer precursor 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, it is possible to remove the polymer precursor from the polymer precursor at a lower temperature by a simple method of simply mixing the polymer precursor with the thermal base generator represented by the chemical formula (1). It is possible to obtain a polymer precursor composition that can be converted into molecules and hardly generate outgas and can be applied to various uses.
Since the aromatic component-containing carboxylic acid constituting the thermal base generator represented by the chemical formula (1) and the basic substance can be obtained at a relatively low price, the price as a polymer precursor composition is also suppressed. It is done.
The polymer precursor 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 thermal base generator represented by the chemical formula (1). The polymer structure obtained can be selected from a wide range.
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 it is difficult to generate outgas, the problems associated with outgas generation are solved, and the strength and appearance of the cured film are improved.

  The polymer precursor composition according to the present invention can be used in a wide range of fields, products such as paints, printing inks, sealants, or adhesives, in which properties such as heat resistance, dimensional stability, and insulation are effective. 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.

  Further, according to the present invention, a printed material, a paint, a sealant, an adhesive, a display device, a semiconductor device, and an electronic component, at least partly formed of the polymer precursor composition according to the present invention or a cured product thereof. Articles of either microelectromechanical systems, optical components or building materials are provided.

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. The manufactured thermal base generator confirmed the chemical structure by ¹ H NMR measurement (JEOL JNM-LA400WB, manufactured by JEOL Ltd.).
Moreover, each measurement and experiment were performed using the apparatus shown below.
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 dianhydride was added little by little. After completion of the addition, the mixture was stirred in an ice bath for 5 hours, and the solution was dehydrated. The precipitate was re-precipitated with diethyl ether, and the precipitate was dried at room temperature under reduced pressure for 17 hours to quantitatively obtain a polyamic acid (polyimide precursor (1)) having a weight average molecular weight of 10,000 as a white solid.

(Production Example 1: Synthesis of thermal base generator (1))
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 (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.07 g (6.2 mmol) of 2-hydroxy-1-naphthaldehyde (Tokyo) Kasei Kogyo Co., Ltd.) was dissolved in 10 mL of methanol and slowly dropped into a well-stirred potassium carbonate solution. 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 1.20 g of 3- (2-hydroxy-1-naphthalenyl) -acrylic 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-ethyl-3- (3- 1.07 g (5.60 mmol) of dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, piperidine 0.65 ml (5.60 mmol) (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 480 mg of a thermal base generator (1) represented by the following chemical formula (6).

(Production Example 2: Synthesis of thermal base generator (2))
In a 500 mL eggplant flask, 10.0 g (72.4 mmol) of sesamol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 15.2 g (109 mmol, 1.5 eq) of hexamethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with trifluoroacetic acid. It was dissolved in 100 ml (manufactured by Kanto Chemical Co., Ltd.) and reacted at 95 ° C. for 10 hours. After completion of the reaction, 200 ml of 1N hydrochloric acid was added in an ice bath and stirred for 15 minutes. After completion of the stirring, the mixture was extracted with chloroform and washed with hydrochloric acid / saturated saline to obtain 2.38 g (14.3 mmol) of 6-hydroxy-3,4-methylenedioxybenzaldehyde.
Subsequently, 2.00 g of potassium carbonate was added to 20 mL of methanol in a 200 mL flask. In a 100 mL flask, 6.15 g (14.3 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.38 g (14.14) of 6-hydroxy-3,4-methylenedioxybenzaldehyde. 3 mmol) was dissolved in 25 mL of methanol and slowly added dropwise to a well-stirred potassium carbonate solution. After stirring for 3 hours, the completion of the reaction was confirmed by thin layer chromatography, followed by filtration to remove potassium carbonate and concentration under reduced pressure. After concentration, 30 mL of 1N aqueous sodium hydroxide solution was added and stirred overnight. 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 2.90 g (13.9 mmol) of 2-hydroxy-4,5-methylenedioxycinnamic acid.
Subsequently, 2.90 g (13.9 mmol) of 2-hydroxy-4,5-methylenedioxycinnamic acid was dissolved in 40 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask under a nitrogen atmosphere, and 1- 3.20 g (16.7 mmol, 1.2 eq) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, 1.65 ml (16.7 mmol, 1.2 eq) of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with chloroform, the mixture was washed with an aqueous hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, and dried over sodium sulfate. By purifying by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 50/1), 485 mg (1.76 mmol) of a thermal base generator (2) represented by the following chemical formula (7) was obtained.

(Production Example 3: Synthesis of thermal base generator (3))
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 (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.07 g (6.2 mmol) of 1-hydroxy-2-naphthaldehyde (Tokyo) Kasei Kogyo Co., Ltd.) was dissolved in 10 mL of methanol and slowly dropped into a well-stirred potassium carbonate solution. 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 1.31 g of 3- (1-hydroxy-2-naphthalenyl) -acrylic acid. Subsequently, in a 100 mL three-necked flask, 1.00 g (4.67 mmol) of 3- (1-hydroxy-2-naphthalenyl) -acrylic acid was dissolved in 20 mL of dehydrated tetrahydroxyfuran, and 1-ethyl-3- (3- 1.07 g (5.60 mmol) of dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, piperidine 0.65 ml (5.60 mmol) (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 520 mg of a thermal base generator (3) represented by the following chemical formula (8).

(Production Example 4: Synthesis of thermal base generator (4))
2-hydroxy-1-Anthracenecarboxaldehyde was synthesized according to the method described in Journal of Heterocyclic Chemistry (1987), 24 (3), 565-9.
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 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.38 g (6.2 mmol) of 2-hydroxy-1-anthracenecarboxaldehyde were added. Dissolved in 10 mL of methanol and slowly added dropwise to a well-stirred potassium carbonate solution. 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 1.19 g of 3- (2-hydroxy-1-anthracenyl) -acrylic acid. Subsequently, 1.00 g (3.78 mmol) of 3- (2-hydroxy-1-anthracenyl) -acrylic acid was dissolved in 20 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask, and 1-ethyl-3- (3- 0.87 g (4.54 mmol) of dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, 0.53 ml (4.54 mmol) of piperidine (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 380 mg of a thermal base generator (4) represented by the following chemical formula (9).

(Production Example 5: Synthesis of thermal base generator (5))
2-hexyl-1,3-benzodioxole was synthesized with reference to Catalysis Communications (2008), 9 (5), 645-649.
In a 200 ml four-necked flask under an argon stream, 2-hexyl-1,3-benzodioxole (10.31 g, 50 mmol), lead tetraacetate (Tokyo Chemical Industry Co., Ltd.) (30.5 g, 55.0 mmol) 1.1 eq) and DMF (100 ml) were added, and the mixture was stirred and reacted at 80 ° C. for 5 hours. After completion of the reaction, the reaction mixture was allowed to cool and extracted by adding ethyl acetate and water. All of the obtained organic phases were combined, washed with water and saturated brine, and dried over sodium sulfate. The desiccant was filtered off and concentrated. Subsequently, 50 ml of 1N aqueous sodium hydroxide solution was added and stirred overnight. After completion of the reaction, ethyl acetate was extracted. All of the obtained organic phases were combined, washed with water and saturated brine, and dried over sodium sulfate. The desiccant was filtered off and concentrated, and the resulting crude product was purified by silica gel column chromatography to give 2-hexylbenzo [d] [1,3] dioxol-5-ol (2-hexylbenzo [d] [ 1,3] dioxol-5-ol) was obtained.
In a 100 mL eggplant flask, 1.0 g (4.50 mmol) of 2-hexylbenzo [d] [1,3] dioxol-5-ol, 0.94 g (6.75 mmol) of hexamethylenetetramine (manufactured by Tokyo Chemical Industry Co., Ltd.) , 1.5 eq) was dissolved in 10 ml of trifluoroacetic acid (manufactured by Kanto Chemical Co., Ltd.) and reacted at 95 ° C. for 10 hours. After completion of the reaction, 20 ml of 1N hydrochloric acid was added in an ice bath and stirred for 15 minutes. After the completion of stirring, the mixture is extracted with chloroform and washed with hydrochloric acid / saturated saline to give 2-hexyl-6-hydroxybenzo [d] [1,3] dioxol-5-carbaldehyde (2-hexyl-6-hydroxybenzo). 0.52 g of [d] [1,3] dioxole-5-carbaldehyde) was obtained.

Subsequently, 0.50 g of potassium carbonate was added to 10 mL of methanol in a 100 mL flask. In a 100 mL flask, 0.86 g (2.0 mmol) of ethoxycarbonylmethyl (triphenyl) phosphonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.), 2-hexyl-6-hydroxybenzo [d] [1,3] dioxole-5 -Carbaldehyde (0.5 g, 2.0 mmol) was dissolved in 25 mL of methanol and slowly added dropwise to a well-stirred potassium carbonate solution. After stirring for 3 hours, the completion of the reaction was confirmed by thin layer chromatography, followed by filtration to remove potassium carbonate and concentration under reduced pressure. After concentration, 30 mL of 1N aqueous sodium hydroxide solution was added and stirred overnight. 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 0.45 g of cinnamic acid derivative A.
Subsequently, 0.40 g (1.37 mmol) of cinnamic acid derivative A was dissolved in 10 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask under a nitrogen atmosphere, and 1-ethyl-3- (3-dimethylaminopropyl) was dissolved in an ice bath. Carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.30 g (1.64 mmol, 1.2 eq) was added. After 30 minutes, 0.16 ml (1.64 mmol, 1.2 eq) of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. After extraction with chloroform, the mixture was washed with an aqueous hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, and dried over sodium sulfate. By purifying by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 50/1), 32 mg of a thermal base generator (5) represented by the following chemical formula (10) was obtained.

(Production Example 6: Synthesis of thermal base generator (6))
In a 100 mL flask, ethyl (triphenylphosphoranylidene) acetate (Tokyo Chemical Industry Co., Ltd.) 2.56 (7.34 mmol), 2'-hydroxyacetophenone (Tokyo Chemical Industry Co., Ltd.) 2.56 g (7 .34 mmol, 1.0 eq) was dissolved in 20 mL of toluene and stirred at 80 ° C. for 3 hours. After confirming the completion of the reaction by thin layer chromatography, a saturated aqueous ammonium chloride solution was added, extracted with chloroform, washed with water and a saturated aqueous ammonium chloride solution, and then dried over anhydrous magnesium sulfate. After concentration, the residue was purified by silica gel column chromatography (developing solvent hexane / ethyl acetate 2/1 (volume ratio)).
Subsequently, 15 mL of 1N aqueous sodium hydroxide solution was added and stirred overnight. After completion of the reaction, the precipitate was removed by filtration, concentrated hydrochloric acid was added dropwise to acidify the reaction solution, extracted with chloroform and concentrated to obtain 580 mg (3.25 mmol) of cinnamic acid derivative B.
Subsequently, 0.50 g (2.80 mmol) of cinnamic acid derivative B was dissolved in 10 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask under a nitrogen atmosphere, and 1-ethyl-3- (3-dimethylaminopropyl) was dissolved in an ice bath. 0.64 g (3.4 mmol, 1.2 eq) of carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.33 ml, 3.4 mmol, 1.2 eq) was added, followed by stirring overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. Extraction with chloroform, washing with an aqueous hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, drying over sodium sulfate, and concentration are performed to concentrate a thermal base generator (6) represented by the following chemical formula (11) 272 mg (1.04 mmol) was obtained.

（製造例７：熱塩基発生剤（７）の合成）
１００ｍＬフラスコ中、(トリフェニルホスホラニリデン)酢酸エチル（東京化成工業（株）製）２．５６（７．３４ｍｍｏｌ）、２’−ヒドロキシ−４’−メトキシアセトフェノン（東京化成工業（株）製）１．２２ｇ（７．３４ｍｍｏｌ、１．０ｅｑ）をトルエン２０ｍＬに溶解し、８０℃で３時間撹拌した。薄層クロマトグラフィーにより反応の終了を確認したうえで、飽和塩化アンモニウム水溶液を加え、クロロホルムで抽出した後、水、飽和塩化アンモニウム水溶液にて洗浄した後、無水硫酸マグネシウムを用い乾燥した。濃縮後、シリカゲルカラムクロムトグラフィー（展開溶媒 ヘキサン／酢酸エチル ２／１（体積比））により精製した。
続いて、１Ｎの水酸化ナトリウム水溶液を１５ｍＬ加え終夜で撹拌した。反応終了後、沈殿物をろ過により除き、濃塩酸を滴下し反応液を酸性にしたのち、クロロホルムで抽出し濃縮し、桂皮酸誘導体Ｃを５２０ｍｇ得た。
続いて、窒素雰囲気下、１００ｍＬ三口フラスコ中、桂皮酸誘導体Ｃ０．４９ｇ（２．８０ｍｍｏｌ）を脱水テトラヒドロキシフラン１０ｍＬに溶解し、氷浴下で１−エチル−３−（３−ジメチルアミノプロピル）カルボジイミド塩酸塩（東京化成工業（株）製）０．６４ｇ（３．４ｍｍｏｌ、１．２ｅｑ）を加えた。３０分後、ピペリジン（東京化成（株）製）０．３３ｍｌ（３．４ｍｍｏｌ、１．２ｅｑ）を加えたのち終夜で攪拌した。反応終了後、反応溶液を濃縮し、水に溶解した。クロロホルムで抽出した後、炭酸水素水溶液、１Ｎ塩酸、飽和食塩水で洗浄し、硫酸ナトリウムにて乾燥を行ったのち、濃縮することで下記化学式（１２）で表される熱塩基発生剤（７）を１５２ｍｇ得た。

(Production Example 7: Synthesis of thermal base generator (7))
In a 100 mL flask, ethyl (triphenylphosphoranylidene) acetate (Tokyo Chemical Industry Co., Ltd.) 2.56 (7.34 mmol), 2′-hydroxy-4′-methoxyacetophenone (Tokyo Chemical Industry Co., Ltd.) 1.22 g (7.34 mmol, 1.0 eq) was dissolved in 20 mL of toluene and stirred at 80 ° C. for 3 hours. After confirming the completion of the reaction by thin layer chromatography, a saturated aqueous ammonium chloride solution was added, extracted with chloroform, washed with water and a saturated aqueous ammonium chloride solution, and then dried over anhydrous magnesium sulfate. After concentration, the residue was purified by silica gel column chromatography (developing solvent hexane / ethyl acetate 2/1 (volume ratio)).
Subsequently, 15 mL of 1N aqueous sodium hydroxide solution was added and stirred overnight. After completion of the reaction, the precipitate was removed by filtration, concentrated hydrochloric acid was added dropwise to acidify the reaction solution, extracted with chloroform and concentrated to obtain 520 mg of cinnamic acid derivative C.
Subsequently, 0.49 g (2.80 mmol) of cinnamic acid derivative C was dissolved in 10 mL of dehydrated tetrahydroxyfuran in a 100 mL three-necked flask under a nitrogen atmosphere, and 1-ethyl-3- (3-dimethylaminopropyl) was dissolved in an ice bath. 0.64 g (3.4 mmol, 1.2 eq) of carbodiimide hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added. After 30 minutes, piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) (0.33 ml, 3.4 mmol, 1.2 eq) was added, followed by stirring overnight. After completion of the reaction, the reaction solution was concentrated and dissolved in water. Extraction with chloroform, washing with an aqueous hydrogen carbonate solution, 1N hydrochloric acid and saturated brine, drying over sodium sulfate, and concentration are performed to concentrate a thermal base generator (7) represented by the following chemical formula (12) 152 mg was obtained.

（製造例８：塩基発生剤（８）の合成）
製造例７において、２’−ヒドロキシ−４’−メトキシアセトフェノンを用いる代わりに、１’−ヒドロキシ−２’−アセトナフトン（東京化成工業（株）製）を用いて、製造例７と同様にして、ケイ皮酸の合成を行うことで桂皮酸誘導体Ｄを得た。続いて、製造例７において、桂皮酸誘導体Ｃの代わりに桂皮酸誘導体Ｄを用いることでアミド化反応を行い、シリカゲルカラムクマトグラフィー（展開溶媒：クロロホルム／メタノール１００／１〜５０／１）により精製することにより下記化学式（１３）で表される塩基発生剤（８）を得た。

(Production Example 8: Synthesis of base generator (8))
In Production Example 7, instead of using 2′-hydroxy-4′-methoxyacetophenone, 1′-hydroxy-2′-acetonaphthone (manufactured by Tokyo Chemical Industry Co., Ltd.) was used in the same manner as in Production Example 7, Cinnamic acid derivative D was obtained by synthesizing cinnamic acid. Subsequently, in Production Example 7, an amidation reaction was performed using cinnamic acid derivative D instead of cinnamic acid derivative C, and purification was performed by silica gel column chromatography (developing solvent: chloroform / methanol 100/1 to 50/1). As a result, a base generator (8) represented by the following chemical formula (13) was obtained.

[Evaluation of thermal base generator]
The synthesized thermal base generators (1) to (8) were evaluated by measuring the thermal decomposition starting temperature as follows.
(1) Solid-state 5% weight loss temperature Thermal base generators (1) to (8) Using Shimadzu Corp., simultaneous differential heat / thermogravimetric measuring device DTG-60, temperature rising rate 10 ° C The 5% weight loss temperature was measured under the conditions of / min. The results of the 5% weight loss temperature of each thermal base generator are shown in Table 1.
(2) 10 mol% base generation temperature in the solution 1 mg of each of the hot base generators (1) to (8) was dissolved in 0.5 μL of heavy dimethyl sulfoxide in an NMR tube, and a 2 mg / mL solution for NMR measurement Were prepared respectively. Each of the prepared samples was heated for 10 minutes using a warmed oil bath, and then subjected to NMR measurement. The oil bath was raised every 10 ° C., and NMR measurement was performed every 10 ° C.
The 10 mol% base generation temperature of each thermal base generator was determined as the thermal decomposition start temperature of each thermal base generator.

(Example 1: Preparation of polymer precursor composition (1))
A polymer precursor composition (1) having the composition shown below was prepared.
Polyimide precursor (1): 100 parts by weight Thermal base generator (1): 15 parts by weight Solvent (NMP (N-methylpyrrolidone)): 843 parts by weight

(Examples 2 to 8: Preparation of polymer precursor compositions (2) to (8))
In Example 1, polymer precursor compositions (2) to (8) were prepared using thermal base generators (2) to (8) instead of the thermal base generator (1).

(Comparative Example 1: Preparation of comparative polymer precursor composition (1))
A comparative polymer precursor composition (1) was prepared in the same manner as in Example 1 except that the thermal base generator (1) was not added in Example 1.

(Creation of coating film)
The polymer precursor compositions (1) to (8) and the comparative polymer precursor composition (1) were each spin-coated on a chrome-plated glass so as to have a final film thickness of 4 μm. It was made to dry for 10 minutes on a hotplate, and the coating film of polymer precursor composition (1)-(8) and comparative polymer precursor composition (1) was obtained 1 sheet at a time. Thereafter, each coating film was heated at 160 ° C. for 10 minutes.

<Evaluation of polymer precursor composition>
An infrared absorption spectrum measurement was performed on the sample after heating to obtain an imidization ratio. In the coating films of the polymer precursor compositions (1) to (8) to which the thermal base generator was added, the imidization rate was high as shown in Table 2 below, whereas the thermal base generator was added. The coating film of the comparative polymer precursor composition (1) that did not have an imidation ratio of 0.40 clearly shows that the conversion of the polymer precursor to the polymer is promoted by the addition of the thermal base generator. became.
Note that the imidization rate appears when the polyimide precursor is converted to polyimide by dehydration cyclization, the absorption intensity of 1774 cm ⁻¹ derived from C═O stretching motion, and the C of the benzene ring that does not change after imidization. using absorption intensity of 1500 cm ^-1 derived from -C stretching movement, it is calculated from the absorption intensity ratio of 1774 cm ^-1 and 1500 cm ^-1.

（実施例９：高分子前駆体組成物（９）の調製）
本発明に係る熱塩基発生剤（７）を用いて、下記に示す組成の高分子前駆体組成物（９）を調製した。
・エポキシ樹脂（ＹＰ５０ＥＫ３５（フェノキシ樹脂）、３５重量％メチルエチルケトン溶液 新日鐵化学社製）：１００重量部
・熱塩基発生剤（７）：３５重量部

(Example 9: Preparation of polymer precursor composition (9))
Using the thermal base generator (7) according to the present invention, a polymer precursor composition (9) having the following composition was prepared.
Epoxy resin (YP50EK35 (phenoxy resin), 35% by weight methyl ethyl ketone solution manufactured by Nippon Steel Chemical Co., Ltd.): 100 parts by weight Thermal base generator (7): 35 parts by weight

  The polymer precursor composition (9) was spin-coated on 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 to obtain a coating film of a resin composition. . Then, it heated at 150 degreeC for 60 minutes. When the heated coating film was immersed in a mixed solution of isopropanol and chloroform (isopropanol: chloroform = 4: 1 (volume ratio)) for 10 minutes at room temperature, it was revealed that the epoxy resin was cured without dissolving in the mixed solution. became.

(Comparative Example 2: Preparation of comparative polymer precursor composition (2))
A comparative polymer precursor composition (2) was prepared in the same manner as in Example 9, except that the thermal base generator (7) was not added in Example 9.

  Using the prepared comparative polymer precursor composition (2), a coating film was prepared in the same manner as the polymer precursor composition (9), and spin-coated on glass to a final film thickness of 0.5 μm. The film was dried on a hot plate at 80 ° C. for 15 minutes to obtain a coating film of the comparative polymer precursor composition (2). Then, it heated at 150 degreeC for 60 minutes. When 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, the coating film was dissolved.

(Example 10: Preparation of polymer precursor composition (10))
Highly composed of 100 parts by weight of hexamethylene diisocyanate (manufactured by Kanto Chemical) as an isocyanate resin, 150 parts by weight of polytetrahydrofuran (manufactured by Aldrich) as a resin having a hydroxyl group, 10 parts by weight of a base generator (7), and 500 parts by weight of tetrahydrofuran. A molecular precursor composition (10) was prepared.

  The polymer precursor composition (10) was spin-coated on chrome-plated glass so that the final film thickness was 0.5 μm, and dried on a hot plate at 60 ° C. for 5 minutes to obtain a polymer precursor composition. One coating film was obtained. When the obtained coating film was heated at 120 ° C. for 10 minutes and cooled to room temperature, a low-elasticity solid was obtained, and it was confirmed that curing of the isocyanate group and the hydroxyl group had proceeded.

(Synthesis Example 2: Synthesis of metal alkoxide condensate)
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 using 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)).

(Example 11: Preparation of polymer precursor composition (11))
After mixing 100 parts by weight of the alkoxysilane condensate (1) obtained in Synthesis Example 2 above and 10 parts by weight of the base generator (7), the polymer precursor is dissolved in 500 parts by weight of tetrahydrofuran as a solvent. Composition (11) was prepared.

The polymer precursor composition (11) was spin-coated on two chrome-plated glasses so that the final film thickness was 0.5 μm, and dried on an 80 ° C. hot plate for 5 minutes, A coating film of the polymer precursor composition was obtained. Then, it heated at 120 degreeC for 30 minutes. Infrared absorption spectrum measurement was performed on each sample before and after heating. As a result, for the sample after heating, a peak of 1020 cm ^-1 attributed to the Si-O-Si bond indicating polymerization appeared, and 2850 cm ^-1 and 850 cm attributed to Si-OCH ₃ indicating the raw material. The peak at ^-1 decreased from the sample before heating. Thus, it has been clarified that, when the heating is performed using the thermal base generator of the present application, a base is generated and the polymerization of the alkoxysilane condensate is promoted.

(Comparative Example 3: Preparation of comparative polymer precursor composition (3))
A comparative polymer precursor composition (3) was prepared in the same manner as in Example 11 except that the thermal base generator (7) was not added in Example 11.

Using the prepared comparative polymer precursor composition (3), a coating film was prepared in the same manner as the polymer precursor composition (11), and spin-coated on glass to a final film thickness of 0.5 μm. The film was dried on an 80 ° C. hot plate for 5 minutes to obtain a coating film of the comparative polymer precursor composition (3). Then, it heated at 120 degreeC for 30 minutes. Infrared absorption spectrum measurement was performed on each sample before and after heating. As a result, it does not appear that the peak of the of 1020 cm ^-1 attributed to Si-O-Si bond indicates the polymerization was, the peak intensity of 2850 cm ^-1 and 850 cm ^-1 attributed to Si-OCH ₃ showing the raw material There was almost no change from before heating.

Claims (8)

A thermal base generator represented by the following chemical formula (1) and generating a base by heating.

(In Formula (1), R ¹ and R ² are each independently hydrogen or an organic group and may be the same or different. R ¹ and R ² are bonded to form a cyclic structure. may form a, may contain a binding heteroatom. However, the organic group in .R ¹ and R ² at least one of R ¹ and R ² is an organic group, a hydrocarbon group And at least one selected from the group consisting of a bond other than a hydrocarbon group or a substituent on the hydrocarbon group, and the bond other than the hydrocarbon group is an ether bond, a thioether bond, It is at least one selected from the group consisting of a carbonyl bond, a thiocarbonyl bond, an ester bond, an amide bond, a urethane bond, an imino bond, a carbonate bond, a sulfonyl bond, a sulfinyl bond, and an azo bond. Substituents other than the hydrocarbon group are halogen atom, hydroxyl group, mercapto group, sulfide group, cyano group, isocyano group, cyanato group, isocyanato group, thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl Group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group, phosphono group, phosphonate group, hydroxy It is at least one selected from the group consisting of an imino group, a saturated or unsaturated alkyl ether group, a saturated or unsaturated alkyl thioether group, an aryl ether group, an aryl thioether group, an amino group, and an ammonio group (provided that R ¹ And At least one of the ends of R ² is - at (C = NH) -C (R ) = CH 2 ( wherein R is hydrogen or a substituent) - (C = O) -C (R) = CH 2 or Except in some cases).
R ³ is hydrogen or a hydrocarbon group.
R ⁴ , R ⁵ , R ⁶ and R ⁷ are hydrogen, halogen, hydroxyl group, mercapto group, sulfide group, silyl group, silanol group, nitro group, nitroso group, sulfino group, sulfo group, sulfonate group, phosphino group, phosphinyl group. Group, phosphono group, phosphonate group, amino group, ammonio group or organic group, which may be the same or different. Two or more of R ⁴ , R ⁵ , R ^6, and R ⁷ may be bonded to form a cyclic structure, and the cyclic structure may include a hetero atom bond. However, when R ³ is hydrogen, two or more of R ⁴ , R ⁵ , R ⁶ and R ⁷ are bonded to form a cyclic structure, and the cyclic structure is a hetero atom bond. May be included.
The organic group in R ⁴ , R ⁵ , R ⁶ and R ⁷ is a saturated or unsaturated alkyl group, a saturated or unsaturated cycloalkyl group, an aryl group, an aralkyl group, a cyano group, a cyanato group, an isocyanato group, a thiocyanato group, Containing a bond or substituent other than an isothiocyanato group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, carboxyl group, carboxylate group, acyl group, acyloxy group, hydroxyimino group, and hydrocarbon group Any group is at least one selected from the group consisting of, and the bond other than the hydrocarbon group is an ether bond, thioether bond, carbonyl bond, thiocarbonyl bond, ester bond, amide bond, urethane bond, imino bond Bond, carbonate bond, sulfonyl bond, sulfini A substituent selected from the group consisting of a bond and an azo bond, and the substituent other than the hydrocarbon group is a halogen atom, a hydroxyl group, a mercapto group, a sulfide group, a cyano group, an isocyano group, a cyanato group, an isocyanato group , Thiocyanato group, isothiocyanato group, silyl group, silanol group, alkoxy group, alkoxycarbonyl group, carbamoyl group, thiocarbamoyl group, nitro group, nitroso group, carboxyl group, carboxylate group, acyl group, acyloxy group, sulfino group, sulfo Groups, sulfonate groups, phosphino groups, phosphinyl groups, phosphono groups, phosphonate groups, hydroxyimino groups, saturated or unsaturated alkyl ether groups, saturated or unsaturated alkyl thioether groups, aryl ether groups, aryl thioether groups, amino groups, and ammo groups. It is at least one selected from the group consisting of O group. )   The thermal base generator according to claim 1, wherein the thermal decomposition starting temperature is 40 ° C. or higher and 350 ° C. or lower. The thermal base generator according to claim 1 or 2, wherein the structure of the generated base is a thermal base generator represented by the following formula (2).

(In the formula (2), ^{R 1} and ^{R 2} are each independently an alkyl group having 1 to 20 carbon atoms which may have a substituent, or a substituent of carbon atoms which may 4-22 of having A cycloalkyl group, 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; May be included.)   A polymer precursor whose reaction to a final product is accelerated by heating in the presence of a basic substance or in the presence of a basic substance, and the thermal base generator according to any one of claims 1 to 3. A polymer precursor composition containing the polymer precursor composition.   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 polymer precursor composition according to claim 4, comprising the above.   The polymer precursor composition according to claim 4 or 5, wherein the polymer precursor is a polyimide precursor or a polybenzoxazole precursor.   It is used as a forming material for paints, printing inks, sealants or adhesives, or display devices, semiconductor devices, electronic components, microelectromechanical systems, optical members or building materials. A polymer precursor composition as described in 1. above.   Printed matter, paint, sealant, adhesive, display device, semiconductor device, electronic component, at least part of which is formed of the polymer precursor composition according to any one of claims 4 to 7 or a cured product thereof. An article of any of the electromechanical systems, optical components or building materials.