TW202214714A - Photosensitive resin composition, photosensitive resin film, patterned resin film, cured product, patterned cured product, method for producing electronic device and electronic device - Google Patents

Abstract

This photosensitive resin composition contains a photosensitizer and a polyamide having a structural unit represented by general formula [1]. In general formula [1], R1 is a tetravalent organic group represented by general formula [2], and R2 is a divalent organic group. In general formula [2], the two numbers denoted by n are each independently an integer between 0 and 3, and R3 is a monovalent substituent group. In a case where multiple R3 groups are present, these groups may be the same as, or different from, each other. Of the two OH groups bonded to R1, one bonds to *1 or *2 and one bonds to *3 or *4.

Description

Photosensitive resin composition, photosensitive resin film, patterned resin film, cured product, patterned cured product, manufacturing method of electronic device, and electronic device

The present invention relates to a photosensitive resin composition, a photosensitive resin film, a patterned resin film, a cured product, a patterned cured product, a method for producing an electronic device, and an electronic device.

Conventionally, a polyimide resin having excellent heat resistance, electrical properties, mechanical properties, and the like has been used for surface protective layers and interlayer insulating films of semiconductor elements. In recent years, also for the purpose of simplification of the process, a positive-type photosensitive resin composition has been developed by combining a quinonediazide compound as a photosensitizer, etc., to impart photosensitivity to the resin itself.

"Patent Documents" "Patent Document 1": Japanese Patent Laid-Open No. H1-46862 "Patent Document 2": Japanese Patent Laid-Open No. H6-12449 "Patent Document 3": Japanese Patent Laid-Open No. 2014-111718

However, since polyimide, which is a precursor of polyimide resin, has a very high solubility in an alkaline developing solution, even if a quinonediazide compound is added, the dissolution rate of the exposed part and the unexposed part is poor (dissolution rate). contrast) is still small, and there is a problem that a good pattern cannot be obtained.

The addition of the quinonediazide compound can obtain a relatively good dissolution comparison, because the compound having a phenolic hydroxyl group, among which the polybenzoxazole precursor is suitable for this application from the viewpoint of being excellent in heat resistance and electrical properties. (Patent Document 1).

In addition, from the viewpoint of transparency and the like, a polybenzoxazole precursor containing a fluorine atom in its structure is often used (Patent Document 2). In the case of introducing fluorine atoms into the polybenzoxazole precursor, it is conceivable that those skilled in the art generally use "-C(CF ₃ ) ₂ -" in terms of the price of the raw material and the ease of acquisition. structure.

On the other hand, in recent years, there has been a molding first method in which rewiring is formed after the wafer is sealed with a sealant. For example, materials cured at 220°C). In general, resin compositions containing polybenzoxazole precursors do not sufficiently undergo cyclization at low temperatures, and many have problems in mechanical properties such as heat resistance, chemical resistance, and elongation of cured products. As such improvement measures, a method of adding a crosslinking agent such as an epoxy compound to a photosensitive resin composition containing a polybenzoxazole precursor having a "-C(CF ₃ ) ₂ -" structure has been proposed (patent Reference 3). However, it is difficult to say that the performance is sufficient in terms of alkali solubility and the like.

In recent years, the demand for a photosensitive resin composition has been increasing, and a photosensitive resin composition that can achieve a high exposure portion dissolution rate while maintaining the residual film ratio at a high value has been demanded.

The present invention has been made in view of such circumstances. One of the objects of the present invention is to provide a photosensitive resin composition capable of forming a photosensitive resin film which is excellent in an alkaline dissolution rate and exhibits a relatively high dissolution contrast.

The inventors of the present invention, as a result of repeated intensive studies to achieve the above-mentioned problems, found that a photosensitive resin composition comprising a polyamide having a specific structural unit and a photosensitizer can form a photosensitive resin composition that is excellent in an alkaline dissolution rate and has a relatively high appearance. A photosensitive resin film with high dissolution contrast was obtained, and the present invention was completed.

（上述通式［1］中，R ¹為由下述通式［2］所示之4價的有機基，R ²為2價的有機基。） ［化2］

（上述通式［2］中，2個n分別獨立為0～3的整數，R ³為1價的取代基。R ³在係為多個的情況下可相同亦可相異。鍵結於R ¹的2個OH基分別鍵結於＊1或＊2之一者且鍵結於＊3或＊4之一者。） That is, the present invention is a photosensitive resin composition comprising a polyamide having a structural unit represented by the following general formula [1] and a photosensitizer. [Change 1]

(In the above general formula [1], R ¹ is a tetravalent organic group represented by the following general formula [2], and R ² is a divalent organic group.) [Chemical 2]

(In the above-mentioned general formula [2], two n's are each independently an integer of 0 to 3, and R ³ is a monovalent substituent. When there are multiple R ³ s, they may be the same or different. Bonded to The two OH groups of R ¹ are respectively bonded to one of *1 or *2 and to one of *3 or *4.)

Moreover, this invention is a photosensitive resin film which made the said photosensitive resin composition into a coating material which apply|coated on a support base material, and dried this coating material.

Moreover, this invention is the hardened|cured material of the said photosensitive resin composition or the said photosensitive resin film.

Moreover, this invention is a patterned resin film which subjected the above-mentioned photosensitive resin film to pattern exposure and development.

Moreover, this invention is a pattern hardened|cured material, and is the hardened|cured material of the said pattern resin film.

Furthermore, the present invention is a method of manufacturing an electronic device, comprising: The coating process of coating the above-mentioned photosensitive resin composition on the support substrate, A drying step of obtaining a photosensitive resin film containing polyamide by removing the solvent contained in the coated photosensitive resin composition, an exposure step of subjecting the above-mentioned photosensitive resin film to pattern exposure to obtain a resin film, a developing process of developing the above-mentioned resin film using an alkaline aqueous solution to obtain a patterned resin film, and A heating step in which the patterned resin film described above is heat-treated to form a patterned cured product.

Moreover, this invention is an electronic device containing the said pattern hardened|cured material.

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive resin composition which can form the photosensitive resin film which is excellent in the alkali dissolution rate and shows a comparatively high dissolution contrast can be provided.

Embodiments of the present invention will be described in detail below.

In this specification, the expression "x to y" in the description of the numerical range means x or more and y or less unless otherwise noted. For example, "1-5 mass %" means "1 mass % or more and 5 mass % or less".

In the expression of a group (group) in the present specification, the expression not describing whether or not there is substitution includes both those having no substituent and those having a substituent. For example, the so-called "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups), but also substituted alkyl groups (substituted alkyl groups).

The term "organic group" in this specification means a group from which one or more hydrogen atoms are removed from an organic compound unless otherwise noted. For example, the "monovalent organic group" means a group from which one hydrogen atom is removed from any organic compound.

In the chemical formulas in this specification, the expression "Me" represents a methyl group (CH ₃ ).

In this specification, the term "trifluoroacetaldehyde" means trifluoroacetaldehyde.

<Photosensitive resin composition>

（上述通式［1］中，R ¹為由下述通式［2］所示之4價的有機基，R ²為2價的有機基。） ［化4］

（上述通式［2］中，2個n分別獨立為0～3的整數，R ³為1價的取代基。R ³在係為多個的情況下可相同亦可相異。鍵結於R ¹的2個OH基分別鍵結於＊1或＊2之一者且鍵結於＊3或＊4之一者。） The photosensitive resin composition concerning this embodiment is a photosensitive resin composition containing a polyamide (polyhydroxyamide) having a structural unit represented by the following general formula [1], and a photosensitizer. [Change 3]

(In the above general formula [1], R ¹ is a tetravalent organic group represented by the following general formula [2], and R ² is a divalent organic group.) [Chem. 4]

(In the above-mentioned general formula [2], two n's are each independently an integer of 0 to 3, and R ³ is a monovalent substituent. When there are multiple R ³ s, they may be the same or different. Bonded to The two OH groups of R ¹ are respectively bonded to one of *1 or *2 and to one of *3 or *4.)

<Polyamide>

The polyamide (polyhydroxyamide) according to this embodiment has a structural unit represented by the above-mentioned general formula [1], and has a tetravalent organic group represented by the above-mentioned general formula [2] in the structural unit. The tetravalent organic group contains a fluorine atom. That is, a fluorine atom exists in the "-C( _CF3 )H-" part in general formula [2]. In the present invention, the "Ph-C(CF ₃ )H-Ph" structure having the general formula [2] is referred to as a Bis-EF structure. Here, Ph is a phenyl group, and Ph can be polyvalently substituted. It is presumed that the photosensitive resin composition according to the present embodiment can form a photosensitive resin film having an excellent alkaline dissolution rate and a relatively high dissolution contrast by having a "-C(CF ₃ )H-" moiety. In addition, it is conceivable that the relative permittivity and the dielectric loss tangent can be reduced through the "-C(CF ₃ )H-" part.

In addition, the polybenzoxazole obtained by cyclizing the polyamide of the present embodiment, which will be described later, may have high heat resistance due to the rigid cyclic skeleton.

The structural unit represented by the general formula [1] may also be a repeating unit. In addition, the polyamide may be a homopolymer or a copolymer. The type of the copolymer is not particularly limited, for example, it can also be an alternating copolymer, a block copolymer, a random copolymer, and a graft copolymer.

In the case of introducing fluorine into polyamide, it is conceivable that a person with ordinary knowledge in the art would generally adopt a "-C(CF ₃ ) ₂ -" structure in terms of the price of the raw material and the ease of acquisition. It is conceivable that the "-C(CF ₃ )H-" structure of this embodiment has poor symmetry (increased asymmetry) compared to the "-C(CF ₃ ) ₂ -" structure, so a softer polymerization can be obtained chain, which then enables the cyclization reaction at lower temperatures. In addition, the increase in asymmetry can conceivably loosen the packing of the polymer chains, and as a result, it is involved in the reduction of the density of the polymer, the reduction of the dielectric constant, and the improvement of the alkaline dissolution rate.

That is, in the "-C(CF ₃ )H-" structure, although there are fewer fluorine atoms than the "-C(CF ₃ ) ₂ -" structure which is conceivably common to those with ordinary knowledge in the art, It is presumed that due to the loose packing of the polymer chains, the alkaline dissolution rate is improved and the low-temperature curability is excellent.

In the general formula [2], the monovalent substituent of R ³ is not particularly limited, but examples thereof include an alkyl group, an alkoxy group, a cycloalkyl group, an aryl group, an alkenyl group, an alkynyl group, an aryloxy group, Amine group, alkylamine group, arylamine group, cyano group, nitro group, silicon group and halogen group (such as fluorine group), etc. These may further have substituents, such as a fluorine atom or a carboxyl group.

As the monovalent substituent of R ³ , an alkyl group, an alkoxy group, a fluoroalkyl group (for example, a trifluoromethyl group), a halogen group (for example, a fluoro group) and a nitro group are preferable.

Specific examples of the alkyl group in R ³ include straight-chain or branched alkyl groups having 1 to 6 carbon atoms. Among them, n-butyl, tertiary butyl, isobutyl, tertiary butyl, n-propyl, isopropyl, ethyl and methyl are preferred, and ethyl and methyl are preferred.

Specific examples of the alkoxy group in R ³ include straight-chain or branched alkoxy groups having 1 to 6 carbon atoms. Among them, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, n-propoxy, isopropoxy, ethoxy and methoxy are preferred, and ethoxy and Methoxy is particularly preferred.

An alkyl or alkoxy group in ^R3 can also be substituted on any carbon thereof with, for example, a halogen atom, an alkoxy group, and a haloalkoxy group in any number and in any combination. Furthermore, when the number of R ³ is 2 or more, these 2 or more R ³ may be linked together to form a saturated or unsaturated monocyclic or polycyclic cyclic group having 3 to 10 carbon atoms.

In the general formula [2], n is preferably 0-2, more preferably 0-1, more preferably 0.

As particularly preferable R ¹ , the following groups having a Bis-EF structure are exemplified. In the following, methyl groups are distinguished from mere atomic bonds by marking them as Me.

[Chemical 5]

In the general formula [1], the divalent organic group of R ² is not particularly limited, but from the viewpoints of the heat resistance required for the photosensitive resin composition and the relatively good alkaline dissolution rate, the organic group containing benzene is used. A divalent organic group of an aromatic ring such as a ring is preferable. More specifically, the divalent organic group of R ² may be "-Phe-", "-Phe-Z-Phe-", or the like. Here, Phe is a substituted or unsubstituted phenylene group, and Z is a single bond or a divalent linking group other than a phenylene group (such as a straight-chain or branched alkylene group with 1 to 3 carbon atoms, an ether group, thioether group, carbonyl group, sulfanyl group, carbonyloxy group, oxycarbonyl group, etc.).

The following are mentioned as especially preferable R< ² >.

[Chemical 6]

Preferred examples of the structural unit represented by the general formula [1] are disclosed below.

[Chemical 7]

[Chemical 8]

[Chemical 9]

In this case, the above-mentioned polyamide according to the present embodiment is preferably a copolymer having a structural unit represented by the following general formula [3] and a structural unit represented by the following general formula [4].

（上述通式［3］中，R ²、R ³如上所述。並且，m分別獨立為0～3的整數。） [Chemical 10]

(In the above general formula [3], R ² and R ³ are as described above. In addition, m is each independently an integer of 0 to 3.)

（上述通式［4］中，R ⁵為2價的有機基，p為1或2，R ⁴為由下述通式［5］～［8］之任一者所示之3價或4價的有機基。） [Chemical 11]

(In the above general formula [4], R ⁵ is a divalent organic group, p is 1 or 2, and R ⁴ is a trivalent or 4 represented by any one of the following general formulas [5] to [8] valent organic radicals.)

（上述通式［5］中，X為單鍵或2價的連結基，2個q分別獨立為0～3的整數。R ⁶為1價的取代基。R ⁶在係為多個的情況下可相同亦可相異。） [hua 12]

(In the above general formula [5], X is a single bond or a divalent linking group, and the two qs are each independently an integer of 0 to 3. R ⁶ is a monovalent substituent. When there are multiple R ^6s can be the same or different.)

（上述通式［6］中，R ⁷表示1價的取代基。） [hua 13]

(In the above general formula [6], R ⁷ represents a monovalent substituent.)

[Chemical 14]

[Chemical 15]

If the above-mentioned polyamide is a copolymer having a structural unit represented by the general formula [3] and a structural unit represented by the general formula [4], it is possible to maintain a high exposure dissolution rate after exposure, and further A photosensitive resin composition showing a high residual film ratio in the unexposed portion was obtained.

In addition to the first polymer (polyamide) having a structural unit represented by the following general formula [9], the photosensitive resin composition of the present embodiment may further include the first polymer (polyamide) having the following general formula [ The second polymer of the structural unit shown in 10].

In short, in the photosensitive resin composition of the present embodiment, the structural unit containing a "-C(CF ₃ ) ₂ OH" group as represented by the general formula [4] or [10] may also be included in the structure having Bis In the polyamide of the -EF structure, it may be contained in the photosensitive resin composition in the form different from the resin of the polyamide which has a Bis-EF structure.

（上述通式［9］中，R ²、R ³如上所述。並且，2個r分別獨立為0～3的整數。） [Chemical 16]

(In the above general formula [9], R ² and R ³ are as described above. In addition, two r's are each independently an integer of 0 to 3.)

（上述通式［10］中，R ⁹為2價的有機基，s為1或2，R ⁸為由下述通式［11］～［14］之任一者所示之3價或4價的有機基。） [hua 17]

(In the above general formula [10], R ⁹ is a divalent organic group, s is 1 or 2, and R ⁸ is a trivalent or 4 represented by any one of the following general formulas [11] to [14] valent organic radicals.)

（上述通式［11］中，X為單鍵或2價的連結基，2個t分別獨立為0～3的整數。R ¹⁰為1價的取代基。R ¹⁰在係為多個的情況下可相同亦可相異。） [Chemical 18]

(In the above general formula [11], X is a single bond or a divalent linking group, and the two t's are each independently an integer of 0 to 3. R ¹⁰ is a monovalent substituent. When there are multiple R ^10s can be the same or different.)

（上述通式［12］中，R ¹¹表示1價的取代基。） ［化19］

(In the above general formula [12], R ¹¹ represents a monovalent substituent.)

[hua 20]

[hua 21]

Even if the polyamide according to the present embodiment includes the first polymer and the second polymer, it can maintain a high exposure dissolution rate after exposure, and at the same time, furthermore, a high residual amount appears in the unexposed part. The photosensitive resin composition of film ratio.

In this case, R ⁴ of the general formula [4] is preferably a trivalent or tetravalent organic group selected from at least one of the following. Furthermore, R ⁸ of the general formula [10] is preferably a trivalent or tetravalent organic group selected from at least one of the following. With the organic group having the Bis-EF structure, since the asymmetry increases, it is involved in the improvement of the alkaline dissolution rate. Moreover, if it is an organic group which does not have a Bis-EF structure, it is excellent in cost and easiness of acquisition.

[hua 22]

Furthermore, R ² in the above general formula [3] and R ⁵ in the above general formula [4] are preferably divalent organic groups independently selected from at least one of the following. Furthermore, it is preferable that R ² in the above general formula [9] and R ⁹ in the above general formula [10] are each independently a divalent organic group selected from at least one of the following. The availability of these organic groups is excellent, and a relatively favorable alkaline dissolution rate can be imparted by the photosensitive resin composition.

[hua 23]

As a specific structural unit represented by the said general formula [3] or the said general formula [9], the following structural unit is mentioned, for example.

[hua 24]

[hua 25]

[hua 26]

Moreover, as a specific structural unit represented by the said general formula [4] or the said general formula [10], the following structural unit is mentioned, for example.

[hua 27]

[hua 28]

[hua 29]

The monomer corresponding to the structural unit represented by the above-mentioned general formula [4] or the above-mentioned general formula [10] can be synthesized, for example, in the following manner.

Amines having hexafluoroisopropanol (—C(CF ₃ ) ₂ OH) groups are obtained by reacting amine-substituted R ⁴ or R ⁸ with hexafluoroacetone or hexafluoroacetone trihydrate. Here, R ⁴ and R ⁸ are as described above.

The amount of hexafluoroacetone or hexafluoroacetone trihydrate used in this reaction is preferably 2 mol or more and 10 mol or less, preferably 2.5 mol or more and 5 mol or less, relative to 1 mol of amine-substituted R ⁴ or R ⁸ for better. By doing so, an amine having a hexafluoroisopropanol group can be obtained in high yield.

In addition, this reaction is usually carried out in the range of 20°C or higher and 180°C or lower, preferably 50°C or higher and 150°C or lower, and particularly preferably 90°C or higher and 140°C or lower. In this way, the reaction proceeds well.

This reaction may be carried out without using a catalyst, but it is preferable to promote the reaction by using an acid catalyst. Examples of the acid catalyst used include Lewis acids such as aluminum chloride, iron (III) chloride, and boron fluoride, and organic acids such as benzenesulfonic acid, camphorsulfonic acid (CAS), and methanesulfonic acid. The amount of the catalyst is expressed in mol% relative to the amine-substituted R ⁴ or R ⁸ , preferably 1 mol% or more and 50 mol% or less, and preferably 3 mol% or more and 40 mol% or less. By doing so, the reaction can be carried out with high efficiency.

This reaction may be carried out using a solvent, or may be carried out without using a solvent. In the case of using a solvent, the solvent is not particularly limited as long as it does not participate in the reaction, and for example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, and water can be used. The amount of the solvent used is not particularly limited.

When this reaction is carried out in a sealed reaction vessel such as an autoclave, the operation differs depending on which of hexafluoroacetone and hexafluoroacetone trihydrate is used. In the case of using hexafluoroacetone, first place R ⁴ or R ⁸ substituted with an amine and an acid catalyst and a solvent as required into the reaction vessel, and then the temperature is raised in such a way that the pressure in the reaction vessel does not exceed the specified pressure, and at the same time Hexafluoroacetone was added successively to make it react.

In the case of using hexafluoroacetone trihydrate, firstly, the amine-substituted R ⁴ or R ⁸ and the necessary amount of hexafluoroacetone trihydrate can be placed in the reaction vessel, and then the acid catalyst and solvent can be placed into the reaction vessel as required. inside the vessel, thereby allowing the reaction to proceed.

The reaction time of this reaction is preferably 8 hours or more and 48 hours or less, and within this range, a favorable reaction time varies depending on the temperature, the amount of the solvent used, and the like. Therefore, it is preferable to carry out the reaction while confirming the progress of the reaction by analytical means such as gas chromatography, and to complete the reaction after confirming that the raw material compound is sufficiently consumed in the reaction. After completion of the reaction, an amine having a hexafluoroisopropanol group can be obtained by means such as extraction, distillation, or precipitation. In addition, it can be purified by column chromatography or recrystallization as required.

The structural unit represented by the general formula [4] or the general formula [10] can be obtained by using the above-mentioned amine having a hexafluoroisopropanol group and reacting it with, for example, dimethyl chloride or the like.

The molar ratio of the above-mentioned polyamide related to this embodiment is not particularly limited, but the molar ratio of the structural unit represented by the general formula [3] and the structural unit represented by the general formula [4] (generally Formula [3]: general formula [4]) is preferably 99.9:0.1-10:90, more preferably 90:10-30:70. In addition, the molar ratio of the structural unit represented by the general formula [9] and the structural unit represented by the general formula [10] (general formula [9]: general formula [10]) is 99.9: 0.1 to 10 : 90 is better, and 90:10～30:70 is better.

The weight average molecular weight of the polyamide of this embodiment is not particularly limited. However, the weight average molecular weight of the polyamide is preferably 1,000 or more and 1,000,000 or less, and more preferably 10,000 or more and 100,000 or less, in terms of performance when forming a cured film and ease of film formation on a substrate.

The weight average molecular weight and the number average molecular weight can be measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

In addition, the terminal structure of the above-mentioned polyamide is preferably a terminal structure obtained by reacting with a terminal blocking agent. That is, it can be formed from a capped structure comprising a reactant with a capping agent. If it is such a photosensitive resin composition, the time-dependent change of molecular weight and the fall of the sensitivity by coloring of resin can be suppressed.

As the end-capping agent, well-known end-capping agents can be used, or monoamines such as hydroxyaniline, aminobenzoic acid, dihydroxyaniline, carboxyhydroxyaniline, and dicarboxyaniline; Diacid anhydrides such as dianhydride, ethynylphthalic anhydride, hydroxyphthalic anhydride; monocarboxylic acids such as benzyl acid, ethynylbenzyl acid, hydroxybenzyl acid, naphthoic acid, ethynylnaphthoic acid; and the hydroxyl groups of these monocarboxylic acids with chlorine Atomically substituted monoformyl chlorides and through the reaction of these monocarboxylic acids or monoformyl chlorides with 1-hydroxybenzotriazole or N-hydroxy-5-noralkene-2,3-dimethylimide The obtained active ester compound and other carboxylic acid derivatives are blocked. Among them, carboxylic acid derivatives are preferred, monoformyl chloride is more preferred, and benzyl chloride is more preferred. In the case of a carboxylic acid derivative, monomethyl chloride or benzyl chloride, the polyamide can be terminated with higher efficiency.

In the case of using an end-capping material, when the amount of the diamine compound (monomer) or derivative thereof used to obtain the polyamide of the present embodiment is 100 parts by mass, the amount of the end-capping material is 0.1-50 mass parts is preferable, and 10-35 mass parts is preferable.

<Organic solvents>

It is preferable that the photosensitive resin composition of this embodiment further contains an organic solvent. The organic solvent is preferably at least one selected from the group consisting of amide-based solvents, ether-based solvents, aromatic-based solvents, halogen-based solvents, and lactone-based solvents. These solvents will dissolve the polyamide of this embodiment well. Specific examples of these solvents include the same organic solvents used for the reaction (polycondensation) as described in the later-mentioned <Method for producing polyamides>. Incidentally, when preparing the polyamide solution, it is preferable to use the same organic solvent as the organic solvent used for the reaction (polycondensation), from the viewpoint of simplification of the production process and the like.

The concentration of polyamide may be appropriately set according to the application and purpose. From the viewpoint of good film-forming properties, etc., the concentration of the polyamide in the photosensitive resin composition containing an organic solvent is preferably 0.1% by mass or more, more preferably 1% by mass or more, and preferably 50% by mass or less Preferably, it is preferably 30 mass % or less.

In addition to the organic solvent, the photosensitive resin composition of this embodiment may contain 1 type or 2 or more types of additives. For example, additives such as surfactants can be used for the purpose of improving coating properties, leveling properties, film-forming properties, storage stability, defoaming properties, and the like.

Commercially available surfactants include: DIC Co., Ltd. trade name MEGAFACE, product number F142D, F172, F173 or F183; Sumitomo 3M Co., Ltd. trade name FLUORAD, product number FC-135, FC -170C, FC-430 or FC-431; trade name SURFLON manufactured by AGC SEIMI CHEMICAL Co., Ltd., product number S-112, S-113, S-131, S-141 or S-145; or Dow Corning Toray Co. ., Ltd.'s trade name DOWSIL, product number SH-28PA, SH-190, SH-193, SZ-6032 or SF-8428 (MEGAFACE is a fluorine-based additive (surfactant/surface modification) made by DIC Co., Ltd. FLUORAD is the trade name of fluorine-based surfactant manufactured by Sumitomo 3M Co., Ltd., SURFLON is the trade name of fluorine-based surfactant manufactured by AGC SEIMI CHEMICAL Co., Ltd., and DOWSIL is the trade name of Dow Corning Toray Trade names of silicone-based additives manufactured by Co., Ltd., each of which is a registered trademark).

When a surfactant is used, the amount thereof is usually 0.001 to 10 parts by mass relative to 100 parts by mass of polyamide.

<The production method of polyamide>

The polyamide (having a structural unit represented by the general formula [1]) of this embodiment can be typically obtained by reacting a diamine compound (monomer) or a derivative thereof with another compound (monomer) (polycondensation). ) to manufacture. The reaction usually involves the reaction of a diamine compound (monomer) or its derivatives with other compounds (monomers) in an organic solvent.

As a diamine compound or its derivative(s), the diamine represented by the following general formula [DA] or its salt is mentioned preferably.

Incidentally, the diamine represented by the general formula [DA] has both an amino group and a phenolic hydroxyl group. From this, the "salt of diamine" can be assumed to be a salt in which an amine group is cationized under acidic conditions, and a salt in which a phenolic hydroxyl group is anionized under basic conditions. In the present specification, both of them correspond to "salts of diamines". As the salt of the diamine, a salt in which the amine group is cationized is preferable.

（通式［DA］中，n及R ³的定義及具體態樣與在通式［2］中之n及R ³相同。） [hua 30]

(In the general formula [DA], the definitions and specific aspects of n and R ³ are the same as those of n and R ³ in the general formula [2].)

The diamine represented by the general formula [DA] can be obtained, for example, by making (i) 2-aminophenol or a derivative thereof (specifically, 2-aminophenol in the general formula [2] and [DA]) The substituent R ³ substituted) is obtained by reacting with (ii) trifluoroacetaldehyde. The molar ratio of the reaction of (i) and (ii) is usually 2:1.

In addition, the diamine represented by the general formula [DA] can also be obtained by reducing the corresponding nitro group-containing compound (in which the amine group in the general formula [DA] is substituted with a nitro group).

Then, by reacting the diamine obtained as described above with an acid, a salt of the diamine can be obtained. Examples of specific reaction conditions and trifluoroacetaldehyde will be described in detail later.

As the diamine represented by the general formula [DA], the following can be preferably mentioned. Of course, the diamines that can be used are not limited to these.

[hua 31]

From the viewpoint of cost and performance adjustment, the diamine compound represented by the general formula [DA] or its salt and other diamine compounds or its salts may be used in combination. As a diamine compound that can be used in combination, 5-(trifluoromethyl)-1,3-phenylenediamine, 2-(trifluoromethyl)-1,3-phenylenediamine, 4-(trifluoromethyl) Methyl)-1,3-phenylenediamine, 2-(trifluoromethyl)-1,4-phenylenediamine, 2,2'-bis(trifluoromethyl)benzidine, 2,2'-diphenylamine Fluoro-4,4'-diaminobiphenyl, 2,2'-dichloro-4,4'-diaminobiphenyl, 2,2'-dibromo-4,4'-diaminobiphenyl , 2,4-diaminotoluene, 2,5-diaminotoluene, 2,4-dimethyl-1,3-phenylenediamine, 2,5-dimethyl-1,3-phenylenediamine , 2,3-dimethyl-1,4-phenylenediamine, 2,5-dimethyl-1,4-phenylenediamine, 2,6-dimethyl-1,4-phenylenediamine, 2 ,3,5,6-Tetramethyl-1,4-phenylenediamine, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethoxy-4 ,4'-diaminobiphenyl, 2,2'-ethoxy-4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4'-diamine diphenyl ether, 4,4'-diaminodiphenylene, 4,4'-diaminodiphenyl ketone, 1,3-bis(3-aminophenoxy)benzene, 1,3 -Bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis[4 -(3-Aminophenoxy)phenyl]sine, bis[4-(4-aminophenoxy)phenyl]ssene, 2,2-bis[4-(4-aminophenoxy) Phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(3-aminophenoxy)phenyl]propane , 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(4-(4-aminophenyl)hexafluoropropane, 2,2-bis (4-aminophenyl)hexafluoropropane, 2,2-bis(3-aminophenyl)hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-Bis(3-amino-4-methylphenyl)hexafluoropropane, 4,4'-diaminobenzylbenzene, salts of these (e.g. hydrochloride, sulfate, nitric acid) However, from the viewpoint of obtaining extremely sufficient properties, it is preferable to use 50 mol% or more of all diamine compounds used in polymer production—more preferably 75 mol% or more, and 92 mol% or more. More preferably, it is a diamine compound represented by the general formula [DA] or a salt thereof (the upper limit of the value can be 100%). That is, in the polyamide of this embodiment, all structures The ratio of the structural unit represented by the general formula [1] in the unit is preferably 50 mol% or more, preferably 75 mol% or more, more preferably 92 mol% or more (the upper limit of this value can be 100% ).The ratio of the structural unit represented by the general formula [1] in all the structural units is preferably known by spectral analysis such as nuclear magnetic resonance, and can also be estimated from the incorporation ratio of the starting material.

In the production of polyamides, (i) only one diamine compound or a salt thereof corresponding to the general formula [DA] may be used, or (ii) two or more diamine compounds corresponding to the general formula [DA] or a salt thereof may be used in combination (ii) For its salts, (iii) one or two or more kinds of diamine compounds or their salts conforming to the general formula [DA] and one or two or more kinds of diamine compounds not conforming to the general formula [DA] or their salts may be used in combination. Salt.

As another compound (monomer) which is made to react with a diamine compound (monomer) or its salt, a dicarboxylic acid or its derivative(s) (a diester, a dihalide, an active ester compound, etc.) etc. are mentioned preferably. As a dicarboxylic acid or its derivative(s), the compound represented by the following general formula [DC1] or [DC2] is mentioned.

（通式［DC1］中，R ²與在通式［1］中之R ²同義，2個A分別獨立表示氫原子、碳數1～10之烷基或碳數6～10之芳烴基。） [hua 32]

(In the general formula [DC1], R ² is synonymous with R ² in the general formula [1], and the two A's each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aromatic hydrocarbon group having 6 to 10 carbon atoms. )

（通式［DC2］中，R ²與在通式［1］中之R ²同義，2個Y分別獨立表示氟原子、氯原子、溴原子、碘原子或活性酯基。） [hua 33]

(In the general formula [DC2], R ² is synonymous with R ² in the general formula [1], and two Ys independently represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or an active ester group.)

A compound in which Y is an "active ester group" can be obtained, for example, by reacting a dicarboxylic acid with an active esterifying agent in the presence of a dehydrating condensing agent. As a good dehydration condensing agent, for example, dicyclohexylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1'-carbonyldioxy [Bis(1,2,3-benzotriazole)], carbonic acid-N,N'-dibutanediimidate, and the like. Examples of good active esterification agents include N-hydroxybutanediimide, 1-hydroxybenzotriazole, N-hydroxy-5-norene-2,3-dimethylimide, 2- Hydroxyimino-2-cyanoacetate, 2-hydroxyimino-2-cyanoacetamide, etc.

Specific examples of the dicarboxylic acid itself or the dicarboxylic acid that is the source of the dicarboxylic acid derivative include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid or sebacic acid; phthalic acid, isophthalic acid, terephthalic acid, 3,3'-dicarboxydiphenyl ether, 3,4- Dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl ether, 3,3'-dicarboxydiphenylmethane, 3,4-dicarboxydiphenylmethane, 4,4'-dicarboxydiphenyl Phenylmethane, 3,3'-dicarboxydiphenyldifluoromethane, 3,4-dicarboxydiphenyldifluoromethane, 4,4'-dicarboxydiphenyldifluoromethane, 3,3'- Dicarboxydiphenylene, 3,4-dicarboxydiphenylene, 4,4'-dicarboxydiphenylene, sulfide-3,3'-dicarboxydiphenyl, sulfide-3,4-dicarboxydiphenyl base, sulfur-4,4'-dicarboxydiphenyl, 3,3'-dicarboxydiphenyl ketone, 3,4-dicarboxydiphenyl ketone, 4,4'-dicarboxydiphenyl ketone, 2,2-bis(3-carboxyphenyl)propane, 2,2-bis(3,4'-carboxyphenyl)propane, 2,2-bis(4-carboxyphenyl)propane, 2,2-bis (3-Carboxyphenyl)hexafluoropropane, 2,2-bis(3,4'-carboxyphenyl)hexafluoropropane, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,3- Bis(3-carboxyphenoxy)benzene, 1,4-bis(3-carboxyphenoxy)benzene, 1,4-bis(4-carboxyphenoxy)benzene, 3,3′-[1,4 -phenylene bis(1-methylethylene)]bisbenzyl acid, 3,4′-[1,4-phenylenebis(1-methylethylene)]bisbenzyl acid, 4,4 '-[1,4-phenylene bis(1-methylethylene)]bisbenzoic acid, 2,2-bis[4-(3-carboxyphenoxy)phenyl]propane, 2,2- Bis[4-(4-Carboxyphenoxy)phenyl]propane, 2,2-bis[4-(3-carboxyphenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4 -Carboxyphenoxy)phenyl]hexafluoropropane, sulfide-2,2-bis[4-(3-carboxyphenoxy)phenyl], sulfide-2,2-bis[4-(4-carboxybenzene] oxy)phenyl], 2,2-bis[4-(3-carboxyphenoxy)phenyl]sine or 2,2-bis[4-(4-carboxyphenoxy)phenyl]ssene; as 4-(Perfluorononenyloxy)phthalic acid, 5-(perfluorononenyloxy)isophthalic acid, 2-(perfluorononenyloxy)terephthalic acid containing perfluorononenyloxydicarboxylic acid acid or 4-methoxy-5-(perfluorononenyloxy)isophthalic acid; as perfluorohexenyloxydicarboxylic acid containing 4-(perfluorohexenyloxy)phthalic acid, 5-( perfluorohexenyloxy)isophthalic acid, 2-(perfluorohexenyloxy)terephthalic acid or 4-methoxy-5-(perfluorohexenyloxy)isophthalic acid.

A dicarboxylic acid or its derivative may be used alone or in combination of two or more.

As a preferable example of a dicarboxylic acid or a dicarboxylic acid derivative, an aromatic dicarboxylic acid or its derivative(s) can be mentioned. The following are mentioned as especially preferable examples of a dicarboxylic acid or a dicarboxylic acid derivative. In the following, the definition and specific aspects of A are the same as those of the general formula [DC1], and the definition and specific aspects of Y are the same as those of the general formula [DC2].

［化34］

[hua 35]

As the organic solvent used for the reaction (polycondensation), one that dissolves the raw material compound can be used without particular limitation. Specifically, amide-based solvents, ether-based solvents, aromatic-based solvents, halogen-based solvents, lactone-based solvents, and the like can be mentioned. More specifically, as an amide-based solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylformamide, and triamide hexamethylphosphate can be exemplified. Amine or N-methyl-2-pyrrolidone; as an ether solvent, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, cyclopentyl methyl ether, diethyl ether Phenyl ether, dimethoxyethane, diethoxyethane, tetrahydrofuran, dioxane or trioxane; as aromatic solvents, exemplified: benzene, methoxybenzene, nitrobenzene or benzonitrile ; As a halogen-based solvent, chloroform, dichloromethane, 1,2-dichloroethane, or 1,1,2,2-tetrachloroethane can be exemplified; as a lactone-based solvent, γ-butyrolactone can be exemplified γ-valerolactone, ε-valerolactone, γ-caprolactone, ε-caprolactone or α-methyl-γ-butyrolactone. The organic solvent may be used alone or in combination of two or more.

The temperature at the time of the reaction may be appropriately set, for example, between -100°C and 100°C. In addition, the reaction may be performed in an atmosphere of an inert gas such as nitrogen or argon.

In the production of polyamide, terminal modification with addition-reactive groups, which is often carried out with well-known polyamide resins, can also be carried out.

The addition-reactive group is not particularly limited as long as it undergoes an addition polymerization reaction (curing reaction) through heat or light, and examples thereof include groups including double bonds such as acryl groups and triple bonds such as ethynyl groups.

The addition-reactive group is introduced into the polymer terminal by reacting a dicarboxylic acid anhydride, carboxylic acid derivative or monoamine having an addition-reactive group in the molecule with an amine group, a carboxyl group or a derivative thereof at the polymer terminal. Examples of such compounds include 4-ethynylaniline, 4-(2-phenylethynyl)aniline, 4-ethynylphthalic anhydride, 4-(2-phenylethynyl)phthalic anhydride, and phenylethynyl-1 , 2,4-Mellitic anhydride, normethylene dioic anhydride, maleic anhydride, acryl chloride.

In addition, in the production of polyamide, the terminal can also be terminated with monoamines such as hydroxyaniline, aminobenzoic acid, dihydroxyaniline, carboxyhydroxyaniline, and dicarboxyaniline; maleic anhydride, phthalic anhydride, Dicarboxylic anhydrides such as enedioic anhydride, ethynyl phthalic anhydride, hydroxyphthalic anhydride; monocarboxylic acids such as benzyl acid, ethynyl benzyl acid, hydroxy benzyl acid, naphthoic acid, ethynyl naphthoic acid; Chlorine atom-substituted monoformyl chloride and by such monocarboxylic acid or monoformyl chloride with 1-hydroxybenzotriazole or N-hydroxy-5-noralkene-2,3-dimethylimide A carboxylic acid derivative such as an active ester compound obtained by the reaction is blocked.

After the polycondensation reaction is completed, for the purpose of removing residual monomers and low molecular weight compounds, it is preferable to add the reaction solution to a poor solvent (such as water, alcohol, etc.) to precipitate the polyamide, and separate and purify it separately. Thereby, a polyamide with reduced impurities can be produced. In addition, the polyamide having reduced impurities may be dissolved in an organic solvent again.

<Diamine or its salt and its production method>

A diamine or a salt thereof having one trifluoromethyl group represented by the following general formula [DA] can be used as a monomer used for the synthesis of the polyamide according to the present invention, for example, the following reaction can be performed The formula represented by the formula is obtained by reduction (specifically, reduction using hydrogenation or hydrazine, etc.) of bisnitrophenol represented by the following general formula [DN]. And the salt of a diamine can be obtained by making the diamine represented by general formula [DA] react with an acid, for example. The kind of salt is not particularly limited, but examples thereof include hydrochloride, sulfate, nitrate, and the like.

（通式［DN］中，2個n及R ³的定義及具體態樣與通式［DA］相同（亦即，與在通式［2］中之n及R ³相同）。） ［化36］

(In the general formula [DN], the definitions and specific aspects of the two n and R ³ are the same as in the general formula [DA] (that is, the same as n and R ³ in the general formula [2]).)

Dinitrophenol represented by the general formula [DN] can be obtained by reacting a trifluoroacetaldehyde/hydrogen fluoride mixture with nitrophenol as shown in the following reaction formula.

（在上述反應式中，n及R ³的定義及具體態樣與通式［DN］相同（亦即，與在通式［2］中之n及R ³相同）。） ［化37］

(In the above reaction formula, the definitions and specific aspects of n and R ³ are the same as in the general formula [DN] (that is, they are the same as n and R ³ in the general formula [2]).)

For the preparation of trifluoroacetaldehyde as the starting material, a hydrate of a commercial product (product of Tokyo Chemical Industry Co., Ltd.) or a hemiacetal form of trifluoroacetaldehyde can be used as its equivalent. The hydrate of trifluoroacetaldehyde or the hemiacetal compound of trifluoroacetaldehyde is prepared by the method described in Japanese Patent Laid-Open No. H5-97757 and other documents.

In general, trifluoroacetaldehyde is mostly used as a hydrate or a hemiacetal. Accordingly, when trifluoroacetaldehyde is used under anhydrous conditions, anhydrous trifluoroacetaldehyde can be prepared by dehydrating a hydrate or hemiacetal form of trifluoroacetaldehyde.

On the other hand, according to the method described in Japanese Patent Laid-Open No. H3-184933, it is possible to convert into trifluoroacetaldehyde almost quantitatively through the gas phase fluorination reaction of an inexpensive trichloroacetaldehyde catalyst. The method can prepare anhydrous trifluoroacetaldehyde.

As described in Japanese Patent Laid-Open No. 2019-026628, trifluoroacetaldehyde is a low-boiling compound, and is generally a compound with high self-reactivity and is difficult to handle. However, trifluoroacetaldehyde can operate very stably in a hydrogen fluoride solution and Can be used appropriately. When trifluoroacetaldehyde is operated in hydrogen fluoride, as shown in the following diagram, 1,2,2,2-tetrafluoroethanol which is an adduct of trifluoroacetaldehyde and hydrogen fluoride is produced.

［化38］

In this way, it is presumed that 1,2,2,2-tetrafluoroethanol forms an equilibrium state between the trifluoroacetaldehyde and the adduct, and the equilibrium state is maintained by the presence of excess hydrogen fluoride in the reaction system. As a result, The decomposition of trifluoroacetaldehyde was inhibited. Trifluoroacetaldehyde in the aforementioned hydrogen fluoride not only improves the stability of the compound, but also confirms that the boiling point rises, and trifluoroacetaldehyde, which is a low-boiling compound, is converted into an adduct of hydrogen fluoride, even at room temperature. Also easy to operate.

In the case of operating the prepared trifluoroacetaldehyde as a mixture with hydrogen fluoride, the amount of hydrogen fluoride used is 1 mol relative to the prepared trifluoroacetaldehyde, usually 0.1 to 100 mol. 1 to 75 mol is preferred, and 2 to 50 mol is more preferred. When the amount of hydrogen fluoride added is more than 0.1 mol, it is easy to obtain a sufficient stabilization effect. In addition, although the same stabilizing effect can be expected by adding more than 100 moles of hydrogen fluoride, it is not desirable in terms of productivity and economy. In addition, the trifluoroacetaldehyde/hydrogen fluoride mixture used in this step may contain an excess amount of hydrogen fluoride, but since it has the function as an acid substance that hydrogen fluoride itself possesses, it may also be used as an acid catalyst or as an acid catalyst. The dehydrating agent is used effectively as an additive that promotes the reaction. In short, it is advantageous to operate the trifluoroacetaldehyde as a trifluoroacetaldehyde/hydrogen fluoride mixture.

The usage-amount of the nitrophenol compound which is a raw material of bisnitrophenol may be 1 mol or more with respect to 1 mol of trifluoroacetaldehyde. Usually, when 2-10 mol is used, the reaction will proceed smoothly, so it is better. If the post-processing operation is further considered, 2-5 mol is particularly preferred.

The step of obtaining bisnitrophenol represented by the general formula [DN] can be carried out in the presence of a reaction solvent. Examples of the reaction solvent include aliphatic hydrocarbon-based, aromatic hydrocarbon-based, halogenated hydrocarbon-based, ether-based, ester-based, amide-based, nitrile-based, sulfite-based, and the like. Specific examples include n-hexane, cyclohexane, n-heptane, benzene, toluene, ethylbenzene, xylene, 1,3,5-trimethylbenzene, methylene chloride, chloroform, 1,2-dichloroethyl Alkane, diethyl ether, tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, N,N-dimethylformamide Acetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, propionitrile, dimethylsulfoxide, etc. These reaction vehicles can be used alone or in combination.

In this step, adding a Lewis acid or a Brinell acid together with a mixture of trifluoroacetaldehyde/hydrogen fluoride and nitrophenol to the reaction system can improve the conversion rate of the condensation reaction, so it is considered as one of the good aspects.

The Lewis acid that can be used is selected from the group consisting of boron (III: represents an oxidation number. The same applies hereinafter), tin (II), tin (IV), titanium (IV), zinc (II), aluminum A metal halide of at least one metal of the group consisting of (III), antimony (III) and antimony (V). Further, as the metal halide to be used, a halide of a metal having the highest valence usually has the best halide.

Among the metal halides using these metals, boron trifluoride (III), aluminum trichloride (III), zinc dichloride (II), titanium tetrachloride (IV), tin tetrachloride (IV) ), antimony pentachloride (V) is particularly preferred.

To function as an additive, the Lewis acid is used in an amount of 0.001 mol or more per 1 mol of trifluoroacetaldehyde, and usually 0.01 to 2.0 mol can be used. In this way, it is excellent also in terms of cost.

Brinell acid is an inorganic acid or organic acid. Specific examples of inorganic acids include phosphoric acid, hydrogen chloride, hydrogen bromide, concentrated nitric acid, concentrated sulfuric acid, fuming nitric acid, and fuming sulfuric acid. Specific examples of organic acids include: formic acid , acetic acid, oxalic acid, benzyl acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.

In order to function as an additive of brucella's acid, the usage-amount is 0.001 mol or more with respect to 1 mol of trifluoroacetaldehyde, and 0.01-2.0 mol can be used normally. In this way, it is excellent also in terms of cost.

The temperature conditions can be carried out in the range of -20 to +200°C, usually -10 to +180°C is preferable, and 0 to +160°C is particularly preferable.

The pressure conditions can be carried out in the range of atmospheric pressure to 4.0 MPa (absolute pressure, the same below), usually atmospheric pressure to 2.0 MPa is preferred, especially atmospheric pressure to 1.5 MPa is preferred.

Examples of reaction vessels that can be used include stainless steel, monel (trademark), Herstel (trademark), nickel and other metal containers, tetrafluoroethylene resin, chlorotrifluoroethylene resin, difluorovinylene resin, PFA resin, acrylic resin, and polyethylene resin are lined inside, etc. It is preferable to use a reactor capable of sufficiently carrying out the reaction under normal pressure or increased pressure.

The reaction time is usually within 24 hours. It can be appropriately adjusted according to the difference of the reaction conditions caused by the combination of the trifluoroacetaldehyde/hydrogen fluoride mixture and the aromatic compound and the amount of Lewis acid or Brookfield acid used as an additive. The progress of the reaction is tracked by gas chromatography, thin layer chromatography, liquid chromatography, nuclear magnetic resonance and other analytical methods, and it is better to take the point at which the starting matrix almost disappears as the end point of the reaction.

As a post-treatment after the reaction, for example, the reaction-ending liquid is subjected to a usual purification operation, such as injecting the reaction-ending liquid into water or an inorganic base of an alkali metal (such as sodium hydroxide, potassium hydroxide, sodium bicarbonate, carbonic acid, etc.). potassium hydrogen carbonate, sodium carbonate or potassium carbonate, etc.) and extracted with an organic solvent (such as ethyl acetate, toluene, 1,3,5-trimethylbenzene, dichloromethane, etc.). By doing so, the target monomer of the bisnitrophenol compound represented by the general formula [DN] can be easily obtained. The target product can be further purified to high chemical purity through activated carbon treatment, distillation, recrystallization, column chromatography, etc. as required.

In addition, the step of obtaining the diamine represented by the general formula [DA] can be carried out using a general reduction method for reducing a nitro group to an amine group. As the reducing agent, for example, one of hydrogen, hydrazine, tin, zinc, iron, lithium aluminum hydride, lithium borohydride, sodium aluminum hydride, sodium borohydride, diisobutyl aluminum hydride, borane, aluminum hydride and the like can be used or two or more. As the cyclizing agent, hydrogen and hydrazine are particularly preferred.

Specific examples of the reduction method are listed below.

(1) Reduction by hydrogenation using a metal catalyst

As the reaction solvent that can be used, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, halogenated hydrocarbon-based, ether-based, ester-based, amide-based, sulfite-based, and the like are exemplified. Specific examples include n-hexane, cyclohexane, n-heptane, benzene, toluene, ethylbenzene, xylene, 1,3,5-trimethylbenzene, methylene chloride, chloroform, 1,2-dichloroethyl Alkane, diethyl ether, tetrahydrofuran, diisopropyl ether, methyl tert-butyl ether, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, ethyl acetate, n-butyl acetate Esters, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethylidene Mushroom and so on. The reaction vehicles can be used alone or in combination. The usage-amount is 10-2000 mass parts with respect to 100 mass parts of bisnitrophenol compounds, Preferably it is 100-1000 mass parts.

The metal catalyst is at least one metal (transition metal) selected from the group consisting of, for example, ruthenium, palladium, rhodium, and platinum, or a metal compound-supporting catalyst in which a metal compound containing the metal is supported on a carrier. Specifically, ruthenium (0 valence), palladium metal (0 valence), rhodium metal (0 valence), or platinum metal (0 valence), or a ruthenium compound, palladium compound, rhodium compound, and platinum compound supported on a carrier can be used. The compound carries the catalyst.

As the carrier, activated carbon or metal oxide can be preferably used. Specifically, activated carbon, alumina, zirconia, silica, zeolite, magnesia, titania, etc. are mentioned. The metal compound in the supported catalyst includes various compounds such as transition metal acetate, sulfate, nitrate, chloride, bromide, oxide, and hydroxide.

The supported catalyst for the transition metal compound can be prepared by a conventionally well-known method such as an impregnation method, and a commercially available product can also be used. Among the catalysts supported on transition metal compounds, those supported on carbon or alumina are preferred in terms of availability, economy, reactivity, and selectivity. For example, N.E. CHEMCAT company's 5% palladium carbon STD type, 5% alumina rhodium powder and 2% platinum carbon powder (water-containing product) can be suitably used.

The amount of the transition metal catalyst used is usually 0.0001 to 10.00 parts by mass, preferably 0.001 to 5.00 parts by mass, and more preferably 0.01 to 2.50 parts by mass in terms of metal content relative to 100 parts by mass of the bisnitrophenol compound. In this way, productivity and economical efficiency are excellent.

The temperature conditions are usually in the range of -20 to +200°C, preferably -10 to +180°C, and more preferably +20 to +90°C.

The hydrogen pressure is usually in the range of 0.2 to 4.0 MPa (absolute pressure, the same below), preferably 0.2 to 2.0 MPa, more preferably 0.4 to 1.0 MPa. Examples of the reaction container include metal containers such as stainless steel, Monel (trademark), Hearst Alloy (trademark), nickel, etc., or containers made of tetrafluoroethylene resin, chlorotrifluoroethylene resin, difluorovinylene resin, PFA resin, Acrylic resin, polyethylene resin, etc. lining the interior, etc. It is preferable to use a reactor capable of sufficiently carrying out the reaction under normal pressure or increased pressure.

The reaction time is usually within 24 hours. According to the different reaction conditions caused by the use of dinitrophenol, reaction solvent or metal catalyst, and hydrogen pressure, the appropriate reaction time will vary accordingly. The progress of the reaction is tracked by thin-layer chromatography, liquid chromatography, nuclear magnetic resonance and other analytical means, and it is better to take the point at which the starting material almost disappears as the end point of the reaction.

In the post-treatment after the reaction, for example, the reaction completion liquid can be filtered to remove the metal catalyst, and then the solvent can be distilled off, whereby the target diamine monomer represented by the general formula [DA] can be easily obtained. The target product can be further purified to high chemical purity through activated carbon treatment, distillation, recrystallization, column chromatography, etc. as required.

(2) Reduction using hydrazine

Examples of hydrazine that can be used include hydrazine, hydrazine monohydrate, methylhydrazine, hydrazine salt, hydrazine hydrochloride, hydrazine sulfate, and the like. These reducing agents can also be used as solutions in the form of, for example, aqueous, alcoholic, ethereal solutions.

The amount of hydrazine used is 1.0-20.0 mol per 1 mol of dinitrophenol, preferably 2.0-5.0 mol.

As the reaction solvent that can be used, water-based, alcohol-based, nitrile-based, ester-based, amide-based, sulfite-based, and the like are exemplified. Specific examples include: water, methanol, ethanol, 1-propanol, 2-propanol, tetrahydrofuran, 1,4-dioxa, 1,2-dimethoxyethane, diethylene glycol dimethyl Ethyl ether, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl- 2-imidazolidinone, dimethyl sulfoxide, etc. These reaction vehicles can be used alone or in combination. The usage-amount is 50-2000 mass parts with respect to 100 mass parts of bisnitrophenols, Preferably it is 100-1000 mass parts.

Examples of catalysts that can be used include iron halides, Reinhardt nickel, palladium carbon, ruthenium carbon, and the like, and among them, iron halides are particularly preferred. Examples of the iron halide catalyst include ferrous chloride, ferric chloride, ferrous bromide, hydrate and anhydrous of ferric bromide. The usage-amount of an iron halide is 0.01-100 mass parts with respect to 100 mass parts of bisnitrophenols, Preferably it is 0.10-20.0 mass parts.

For temperature conditions, it is usually -20 to +200°C, preferably -10 to +150°C, and more preferably +20 to +100°C.

The reaction time is usually within 24 hours. The reaction conditions vary depending on the dinitrophenol, the reaction solvent, the amount of metal catalyst used, and the amount of hydrazine. The progress of the reaction is tracked by thin-layer chromatography, liquid chromatography, nuclear magnetic resonance and other analytical methods, and it is better to set the point at which the starting matrix almost disappears as the end point of the reaction.

In the post-treatment after the reaction, the monomer of the diamine represented by the general formula [DA] can be easily obtained by simply distilling off the solvent. The target product can be further purified to high chemical purity through activated carbon treatment, distillation, recrystallization, column chromatography, etc. as required. After the reaction, if it is in a uniform state, it can also be purified by adding a poor solvent to the solution and reprecipitating it.

In the synthesis of diamines accompanied by hydrogenation or nitro reduction with hydrazine, dehalogenation of the trifluoromethyl group is usually unavoidable as a side reaction. Usually, the fluoride ion concentration contained in the diamine contained after the reduction reaction is 50 ppm or more. When it is used for polymerization as it is, it often has a bad influence on the quality such as coloring. Accordingly, it is preferable to perform a treatment for reducing the concentration of fluorine ions contained in the monomer raw material. The concentration of fluoride ions contained in the diamine is preferably less than 20 ppm, more preferably less than 10 ppm, more preferably less than 2 ppm. The concentration of fluoride ions is preferably as low as possible, but in reality, it is, for example, 0.1 ppm or more.

According to the manufacturing method of this embodiment, the diamine or its salt which has one trifluoromethyl group represented by general formula [DA] can be manufactured easily. As a favorable diamine, the diamine represented by following formula [DA-1], or its salt is mentioned, for example.

［化39］

In addition, as the diamine represented by the general formula [DA] or a salt thereof, from the viewpoint of the cost of the raw material, the easiness of synthesis, and the like, those represented by the following general formula [DA-2] or [DA-3] are exemplified the diamine or its salt.

（通式［DA-2］中，2個R分別獨立表示碳數1～6之烷基或鹵原子。） [Chemical 40]

(In the general formula [DA-2], two Rs each independently represent an alkyl group having 1 to 6 carbon atoms or a halogen atom.)

[hua 41]

In particular, among the compounds represented by the general formula [DA], the compounds represented by the following formulae [DA-4] to [DA-7] or their salts can be produced with high purity and high yield by the above-mentioned method.

The compound name of the diamine represented by the formula [DA-4] is 1,1,1-trifluoro-2,2-bis(3-amino-5-methyl-4-hydroxyphenyl)ethane.

The compound name of the diamine represented by the formula [DA-5] is 1,1,1-trifluoro-2,2-bis(3-amino-5-fluoro-4-hydroxyphenyl)ethane.

The compound name of the diamine represented by the formula [DA-6] is 1,1,1-trifluoro-2,2-bis(3-amino-5-isopropyl-4-hydroxyphenyl)ethane .

The compound name of the diamine represented by the formula [DA-7] is 1,1,1-trifluoro-2,2-bis(3-amino-6-methyl-4-hydroxyphenyl)ethane.

［化42］

[hua 43]

［化44］

[Chemical 45]

<Photosensitive agent>

The photosensitive resin composition related to this embodiment contains a photosensitizer. As the sensitizer, a well-known sensitizer can be used, and it can be a negative type that can be cured by transmitting light at an exposure location, or a positive type that can be solubilized by transmitting light at the exposed location. As a photosensitizer, a photoinitiator and a quinonediazide compound are mentioned, for example. In this case, a quinonediazide compound can be particularly suitably used.

The photopolymerization initiator generates radicals by irradiating light in the visible to ultraviolet region to initiate polymerization of the polymerizable unsaturated compound and the like. As a light source, a general-purpose light source can be used, for example, a high-pressure mercury lamp can be used. Specifically, acetophenone derivatives, diphenyl ketone derivatives, benzoin ether derivatives, etc. are mentioned, and good photopolymerization initiators include diethoxyacetophenone, 2-hydroxy- 2-Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, isobutylbenzoin ether, methylbenzoin Ether, 9-oxothio, isopropyl-9-oxothio, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-𠰌linyl)propan-1-one, 2-benzyl-2-dimethylamino-1-[4-(N-𠰌olinyl)phenyl]-1-butanone and the like, but not limited thereto.

As a polymerizable unsaturated compound, the compound which has double bonds, such as a vinyl group, an allyl group, an acryl group, and a methacryloyl group, and triple bonds, such as a propargyl group, is mentioned, for example. Specifically, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, diethylene glycol dimethacrylate, and triethylene glycol dimethacrylate may be mentioned. , tetraethylene glycol dimethacrylate, trimethylolpropane diacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 1,3-dipropenyloxy-2- Hydroxypropane, 1,3-Dimethacryloyloxy-2-hydroxypropane, N,N-Dimethacrylamide, N-Methylacrylamide, Methacrylic acid-2,2,6, 6-Tetramethylpiperidine ester, N-vinylpyrrolidone, N-vinylcaprolactam, etc. may be used alone or in combination of two or more. In addition, the polyamide contained in the photosensitive resin composition can be reacted with these polymerizable unsaturated compounds by terminal modification with an addition-reactive group, so that curing can be performed more efficiently.

The photopolymerization initiator generates radicals by irradiating light in the visible light to ultraviolet light region to initiate polymerization. As a light source, a general-purpose light source can be used, for example, a high-pressure mercury lamp can be used. Specifically, acetophenone derivatives, diphenyl ketone derivatives, benzoin ether derivatives, etc. are mentioned, and good photopolymerization initiators include diethoxyacetophenone, 2-hydroxy- 2-Methyl-1-phenylpropan-1-one, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, isobutylbenzoin ether, methylbenzoin Ether, 9-oxothio, isopropyl-9-oxothio, 2-methyl-1-[4-(methylthio)phenyl]-2-(N-𠰌linyl)propan-1-one, 2-benzyl-2-dimethylamino-1-[4-(N-𠰌olinyl)phenyl]-1-butanone and the like, but not limited thereto.

The quinonediazide compound is a compound having a quinonediazide group such as a 1,2-quinonediazide group. As the 1,2-quinonediazide compound, for example, 1,2-naphthoquinone-2-diazide-4-sulfonic acid and 1,2-naphthoquinone-2-diazide-5-sulfonic acid can be mentioned. , 1,2-naphthoquinone-2-diazide-4-sulfonyl chloride and 1,2-naphthoquinone-2-diazide-5-sulfonyl chloride. When a quinonediazide compound is used, a positive-type photosensitive resin can be obtained that is sensitive to i-line (wavelength 365 nm), h-line (wavelength 405 nm), and g-line (436 nm) of a mercury lamp, which is a general ultraviolet light composition.

In this embodiment, it is particularly preferable to use a quinonediazide compound. By using the quinonediazide compound to make the photosensitive resin composition positive, it is possible to exhibit particularly good alkaline dissolution rate and dissolution contrast.

Commercially available products of the quinonediazide compound include NT series, 4NT series, PC-5, and TKF series and PQ-C manufactured by Toyo Gosei Kogyo Co., Ltd., and Sanbo Chemical Research Institute Co., Ltd.

<Photosensitive resin film>

The photosensitive resin composition related to this embodiment can be coated on the support substrate. Thereby, a coating material can be obtained. In particular, it is preferable to apply the photosensitive resin composition by dissolving it in the above-mentioned organic solvent, and it is preferable to dry the coating material of the photosensitive resin composition dissolved in the above-mentioned organic solvent to form a photosensitive resin film.

The supporting substrate is not particularly limited, but an inorganic substrate or an organic substrate is suitable. Specifically, glass, silicon wafer, stainless steel, alumina, copper, nickel, etc.; polyethylene terephthalate, polyethylene terephthalate, polyethylene naphthalate, polycarbonate Ester, polyimide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polyether, polyphenylene, polyphenylene sulfide, etc.

Among these, from the viewpoint of heat resistance, it is preferable to use an inorganic base material, and it is preferable to use an inorganic base material such as glass, silicon wafer, and stainless steel.

In addition, the coating method is not particularly limited, and a well-known coating method can be employed. Depending on the thickness of the coating film or the viscosity of the solution, a spin coater, a bar coater, a blade coater, an air knife coater, a roll coater, a rotary coater, a flow coater, a die coater, A well-known coating device such as a lip coater.

And the said photosensitive resin film can be pattern-exposed and developed. The formation or exposure of the pattern is not particularly limited, but for example, the mask of the intervening lattice pattern can be exposed with a high pressure mercury lamp. In addition, it is preferable to develop the photosensitive resin film after exposure with an alkaline aqueous solution such as a tetramethylammonium hydroxide (TMAH) aqueous solution. By doing so, a patterned resin film can be formed.

In addition, the photosensitive resin film may be made to advance the cyclization reaction part in advance by heating at the temperature described in the heating process mentioned later.

<Solidified product>

Moreover, the photosensitive resin composition concerning this embodiment, the said photosensitive resin film, or pattern resin film can be made into a hardened|cured material. It can be cured by heat-treating the photosensitive resin composition, the photosensitive resin film or the patterned resin film at a high temperature. By heating, the cyclization reaction of the polyamide of the photosensitive resin composition or the resin film proceeds, and the structural unit represented by the general formula [1] becomes a polybenzoxazole represented by the following general formula [15]. of the cured product. Thereby, the photosensitive resin composition and the photosensitive resin film can be made into a cured product, and the patterned resin film can be made into a patterned cured product.

In addition, when the general formula [4] and the general formula [10] are included, the hydroxyl group in the general formula [4] and the general formula [10] reacts with the carbonyl group of the amide amide, and finally water is removed, thereby forming closed loop structure.

（上述通式［15］中，R ¹及R ²如前所述。） ［化46］

(In the above general formula [15], R ¹ and R ² are as described above.)

The photosensitive resin composition, the photosensitive resin film, the patterned resin film, and the cured products thereof according to the present embodiment can be suitably used for electronic devices. Herein, the so-called electronic device refers to the technology applied in electronic engineering including semiconductor chips, semiconductor elements, MEMS, printed wiring boards, electrical circuit display devices, information communication terminals, light emitting diodes, physical batteries, chemical batteries, etc. Used by humans in the sense of components, equipment, final products, etc.

<Manufacturing method of electronic device>

The electronic device using the photosensitive resin composition according to this embodiment is preferably manufactured as follows. That is, it can be manufactured by a method including the following steps: The coating process of coating the photosensitive resin composition on the support substrate, A drying step of obtaining a photosensitive resin film containing polyamide by removing the solvent contained in the coated photosensitive resin composition, an exposure step of subjecting the above-mentioned photosensitive resin film to pattern exposure to obtain a resin film, a developing process of developing the above-mentioned resin film using an alkaline aqueous solution to obtain a patterned resin film, and A heating step in which the patterned resin film described above is heat-treated to form a patterned cured product.

(coating process)

The photosensitive resin composition to be applied may be dissolved in a solvent. In addition, the coating method in the coating step is the same as the above, and a well-known coating method can be used. In addition, the thickness of the finally obtained pattern cured product can be adjusted by adjusting the coating amount per unit area in the coating process and the concentration of the polyamide used in the photosensitive resin composition to be coated.

The thickness of the finally obtained pattern cured product can be set to 1 μm or more, preferably 5 μm or more. When the thickness is 1 μm or more, the strength of the cured product can be sufficient. In addition, the thickness can be made 1000 μm or less, preferably 500 μm or less. When the thickness is 1000 μm or less, defects such as cratering, crawling, and breakage can be suppressed.

(drying process)

In the drying process, the solvent in the applied photosensitive resin composition is usually volatilized by heating using a hot plate. The heating temperature in the drying step also depends on the type of solvent, but the drying temperature can be set to 50°C or higher, preferably 80°C or higher. In addition, the drying temperature may be set to 150°C or lower, preferably 120°C or lower.

When the drying temperature is set to 50° C. or higher, drying becomes easy and sufficient. In addition, when the drying temperature is set to 150° C. or lower, defects such as shrinkage cavities, dents, and breakages due to rapid solvent evaporation can be suppressed, and a uniform photosensitive resin film can be formed.

The temperature in the drying step is usually lower than the temperature in the heating step described later.

(exposure process)

In the exposure process, the photosensitive resin film obtained in the drying process is exposed. The exposure is not particularly limited as long as it is pattern exposure, but as described above, it can be exposed through a mask in a lattice pattern. In addition, the type of light source is not particularly limited, for example, semiconductor lasers, high-pressure mercury lamps (g-line (wavelength 436 nm), h-line (405 nm), i-line (365 nm)), excimer lasers, etc. .

(Development process)

In the developing process, the above-mentioned resin film exposed in a pattern is developed with an alkaline aqueous solution. If it is an alkaline aqueous solution, it is not particularly limited, and a developer that does not contain TMAH other than the aqueous solution containing TMAH described above can be used. As a developer which does not contain TMAH, the TMK series of Kanto Chemical Co., Ltd. etc. are mentioned, for example.

By developing using an alkaline aqueous solution, a patterned resin film can be obtained.

(heating process)

In the heating process, the patterned resin film obtained in the developing process is cured by heat-treating at high temperature. The cyclization reaction of the polyamide in the patterned resin film proceeds by heating, and a patterned cured product containing the polybenzoxazole represented by the above-mentioned general formula [15] is obtained. In addition, when the general formula [4] and the general formula [10] are included, the hydroxyl group in the general formula [4] and the general formula [10] reacts with the carbonyl group of the amide amide, and finally dehydrates the water. Patterned cured product of closed-loop structure.

In the heating step, in addition to removing the residual solvent that was not removed in the drying step, it can be expected that the cyclization rate can be improved and the physical properties can be improved. The temperature of the heating step can be set to 150°C or higher, preferably 200°C or higher. By doing so, the cyclization reaction can be sufficiently advanced. In addition, the temperature of the heating step can be set to 400°C or lower, preferably 350°C. In this way, the occurrence of defects such as cracks can be suppressed.

The heating process is preferably carried out using an inert gas oven or a heating plate, a box-type dryer, and a conveyor-type dryer, but it is not limited to the use of these devices. The heating step is preferably performed under an inert gas flow from the viewpoints of preventing oxidation of the resin film and removing the residual solvent. As an inert gas, nitrogen gas, an argon gas, etc. are mentioned, for example. By reducing the oxygen concentration contained in the inert gas, the coloring and performance degradation due to the oxidation of the resin film during heating can be suppressed, so the oxygen concentration in the inert gas can be set to 500 ppm or less, and set to 100 ppm The following is better, and it is better to set it as 20 ppm or less.

Depending on the purpose and use, a peeling process obtained by peeling the pattern cured product from the supporting base material after the heating process to use the pattern cured product as a substrate may also be performed. The peeling process can be performed after heating and cooling to room temperature (25° C.) to about 40 degrees. In order to facilitate peeling, a release agent may be applied to the support substrate in advance. The release agent is not particularly limited, and for example, a silicone-based or fluorine-based release agent can be used.

The patterned cured product according to the present embodiment contains polybenzoxazole having a structural unit represented by the above-mentioned general formula [15]. In addition, the patterned cured product may further include a polyamide having a structural unit represented by the general formula [1].

The pattern cured product related to this embodiment can be suitably used in the above-mentioned electronic device. Therefore, it is preferable to make an electronic device including the pattern cured product related to this embodiment.

The pattern cured product related to this embodiment may be suitable for use as, for example, a redistribution layer (RDL) due to its low relative permittivity and low dielectric loss tangent originating from the "-C(CF ₃ )H-" portion. interlayer insulating film. In addition, it may be suitably used as a surface protective film such as a buffer coat due to the heat resistance or the like derived from the rigid structure.

Embodiments of the present invention have been described above in detail, but these are examples of the present invention. In addition, various configurations other than those described above may be employed. In addition, the present invention is not limited to the above-mentioned embodiments.

"Example"

Embodiments of the present invention will be described in detail based on examples and comparative examples, but the present invention is not limited to these.

<Synthesis of diamine (polyamide precursor)>

[Example of catalyst preparation]

896 g of special-grade reagent CrCl ₃ . 6H ₂ O was dissolved in pure water to prepare a 3.0 L solution. 400 g of granular alumina was immersed in this solution and left to stand for one day and one night. After standing, the solution was filtered to take out alumina, kept at 100°C in a hot air circulation dryer, and dried for one day and one night. By doing so, chromium-supported alumina is obtained.

The obtained chromium-supporting alumina was filled in a cylindrical SUS316L reaction tube having a diameter of 4.2 cm and a length of 60 cm equipped with an electric furnace. Then, nitrogen gas was circulated in the reaction tube at a flow rate of about 20 mL/min, and the temperature was raised to 300°C. When the outflow of water was not observed, hydrogen fluoride was accompanied with nitrogen gas, and the concentration of hydrogen fluoride was gradually increased. When the hot spot caused by the fluorination of the filled chromium-supported alumina reached the outlet end of the reaction tube, the temperature of the reactor was raised to 350°C, and this state was maintained for 5 hours. The catalyst was prepared through the above operation.

[Preparation Example 1: Preparation of trifluoroacetaldehyde shown in the following diagram]

[hua 47]

125 mL of the catalyst prepared in the above catalyst preparation example was filled in a gas-phase reaction apparatus (made of SUS316L, diameter 2.5 cm, length 40 cm) consisting of a cylindrical reaction tube equipped with an electric furnace as a catalyst.

Air was circulated in the reaction tube filled with the catalyst at a flow rate of about 100 mL/min, while the temperature of the reaction tube was raised to 280° C. and hydrogen fluoride was introduced at a rate of about 0.32 g/min for 1 hour. Then, trichloroacetaldehyde (trichloroacetaldehyde) as a raw material was started to be supplied to the reaction tube at a rate of about 0.38 g/min (contact time 15 seconds). Since the reaction was stabilized 1 hour after the start of the reaction, the gas flowing out of the reactor was collected in a cylinder made of SUS304 with a blow pipe cooled with a refrigerant of -15°C over 18 hours.

With respect to 484.8 g of the collected liquid containing trifluoroacetaldehyde obtained above, the hydrogen fluoride content, the hydrogen chloride content, and the organic matter content were calculated by titration. As a result, hydrogen fluoride was 40 mass %, hydrogen chloride was 11 mass %, and organic matter content was 49 mass %, and the recovery rate of organic matter was 88% (based on molar number of supplied raw material chloroacetal). When a part of the recovered organic matter was collected into a resin-made NMR tube, and the degree of fluorination was confirmed by ¹⁹ F-NMR, almost no lower fluoride was detected, and it was confirmed that fluorination was quantitatively progressing.

Next, 450 g of a part of the collected trifluoroacetaldehyde-containing mixture (hydrogen fluoride: 40 mass %, hydrogen chloride: 11 mass %, organic matter: 49 mass %) was put into a cooling pipe equipped with a refrigerant of -15°C, A 500 mL SUS-made reactor of a thermometer and a stirrer was used, and the reactor was heated at 25°C. Under normal pressure, hydrogen fluoride is refluxed with a cooling pipe, and at the same time, the hydrogen chloride passing through the top of the cooling pipe is absorbed and removed by water. After 5 hours of reflux, samples were taken from the reactor and the sampled mixture was titrated. By titration, the hydrogen fluoride content, the hydrogen chloride content, and the organic matter content were calculated. At this time, hydrogen fluoride: 44 mass %, hydrogen chloride: 1 mass %, and organic matter: 55 mass %. Then, a part of the mixture was collected in a resin-made NMR tube, and ¹⁹ F-NMR was measured. From the integral ratio calculated from the obtained graph, it was confirmed that trifluoroacetaldehyde in anhydrous hydrogen fluoride was converted into 1,2,2,2-tetrafluoroethanol which is a composition of trifluoroacetaldehyde/hydrogen fluoride. On the other hand, when the water used for the absorption of hydrogen chloride was subjected to titration, it was partially confirmed that the hydrogen fluoride accompanying the droplet was contained, but almost no organic matter was contained.

[NMR data]

1,2,2,2-Tetrafluoroethanol: ¹⁹ F-NMR (400 MHz, CFCl ₃ ) δ (ppm): -85.8 (3F, s), -137.8 (1F, d, J=54.9 Hz)

Hydrogen fluoride: ¹⁹ F-NMR (400 MHz, CFCl ₃ ) δ (ppm): -193.4 (1F, s)

(Synthesis Example 1: Synthesis of bisnitrophenol shown in the following diagram)

［化48］

In a 200 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, an insertion tube, and a stirring motor, the trifluoroacetaldehyde-containing mixture (hydrogen fluoride: 44% by mass, hydrogen chloride) obtained in Preparation Example 1 was placed. : 1 mass %, organic matter: 55 mass %) 39.2 g (trifluoroacetaldehyde: 220 mmol, hydrogen fluoride: 862 mmol), 74.3 g (3.72 mol) of hydrogen fluoride, 60.1 g (432 mmol) of 2-nitrophenol, 120 It was heated in an oil bath at ℃ and reacted for 18 hours under an absolute pressure of 1.2 MPa. After the reaction, the reaction solution was poured into a mixture of 200 g of ice water and 270 g of ethyl acetate. The separated organic layer was washed with 240 g of 10 mass % potassium carbonate water and 120 g of water, and then the organic layer was recovered by two-layer separation. The recovered organic layer was concentrated in an evaporator, and then recrystallized through 67 g of ethyl acetate and 155 g of n-heptane to obtain 1,1,1-trifluoro-2,2- which is the target product as a yellow solid. Bis(3-nitro-4-hydroxyphenyl)ethane 47.0 g, 61% yield, 99.8% (GC).

[NMR data]

1,1,1-Trifluoro-2,2-bis(3-nitro-4-hydroxyphenyl)ethane: ¹ H-NMR (400 MHz, CDCl ₃ ) δ (ppm): 4.69 (1H, q , J=9.4 Hz), 7.20 (2H, d, J=8.9 Hz), 7.55 (2H, dd, J=8.7, 2.3 Hz), 8.09 (2H, d, J=2.3 Hz), 10.57 (2H, s) ) ¹⁹ F-NMR (400 MHz, CDCl ₃ ) δ (ppm): -66.9 (3F, d, J=8.7 Hz)

(Synthesis Example 2: Synthesis of diamine shown in the following scheme)

［化49］

In a 200 mL stainless steel autoclave reactor equipped with a pressure gauge, a thermometer protection tube, a gas introduction tube connected to a hydrogen cylinder, and a stirring motor, the 1,1,1-trifluoro- 22.1 g (61.7 mmol) of 2,2-bis(3-nitro-4-hydroxyphenyl)ethane, 221 mg of 50% water by mass of N.E. CHEMCAT company, 5% by mass palladium on carbon, and 119 g of ethyl acetate were mixed with 70 The mixture was heated in an oil bath at °C, and hydrogen was continuously introduced at 0.6 MPa, while the reaction was allowed to proceed for 9 hours. The fluoride ion concentration in the reaction solution was measured with an ion electrode method, and the result was 80 ppm.

After completion of the reaction, the catalyst was removed by pressure filtration, and the obtained filtrate was then concentrated by an evaporator until it became 70 g. To this concentrate, 80 g of toluene was dropped into a drop to precipitate crystals, thereby obtaining 1,1,1-trifluoro-2,2-bis(3-amino-4-hydroxyphenyl) as a white solid which is the target product Ethane 15.4 g, yield 84%, purity 99.6% (LC). In addition, the fluoride ion concentration of the target product obtained by purification was less than 1 ppm.

[NMR data]

1,1,1-Trifluoro-2,2-bis(3-amino-4-hydroxyphenyl)ethane: ¹ H-NMR (400 MHz, CD ₃ CN) δ (ppm): 4.03 (4H, br-s), 4.45 (1H, q, J=10.2 Hz), 6.51 (2H, d, J=8.1 Hz), 6.63 (2H, d, J=8.7 Hz), 6.67 (2H, s), 6.88 ( 2H, br-s) ¹⁹ F-NMR (400 MHz, CD ₃ CN) δ (ppm): -66.1 (3F, d, J=8.7 Hz)

<Production of polyamide (polybenzoxazole (PBO) precursor)>

(Synthesis Example 3)

Synthesis of Polyamide (A-1)

In a 300 mL glass three-necked flask equipped with a stirrer and a thermometer, 87 g of N-methyl-2-pyrrolidone was placed under a nitrogen atmosphere to make 1,1,1-trifluoro-2,2-bis (3-amino-4-hydroxyphenyl)ethane 8.95 g (30.0 mmol) was stirred and dissolved. Then, after adding 5.22 g (66.0 mmol) of pyridine as a base, the flask was immersed in an ice bath, and the temperature was kept at 0 to 10°C, while adding 7.53 g (25.5 mmol) of 4,4′-diphenyl ether dimethyl chloride ) and stir for 30 minutes. After warming up to room temperature (25°C), 1.27 g (9.00 mol) of benzyl chloride was added, followed by stirring for 2 hours. The obtained reaction solution was put into 1 L of methanol aqueous solution, the precipitated solid was recovered, washed three times with methanol aqueous solution, and dried under reduced pressure to obtain polyamide (A-1). The weight average molecular weight determined by gel permeation chromatography (GPC) described later was 21,400, and the degree of dispersion was 2.89.

[Chemical 50]

(Synthesis Example 4)

Synthesis of Polyamide (A-2)

In a 300 mL glass three-necked flask equipped with a stirrer and a thermometer, 104 g of N-methyl-2-pyrrolidone was placed in a nitrogen atmosphere to make 1,1,1-trifluoro-2,2-bis (3-Amino-4-hydroxyphenyl)ethane 4.47 g (15.0 mmol) and 3,3′-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl) -4,4'-oxydianiline 7.98 g (15.0 mmol) was stirred and dissolved. Then, after adding 5.22 g (66.0 mmol) of pyridine as a base, the flask was immersed in an ice bath, and the temperature was kept at 0 to 10°C, while adding 7.53 g (25.5 mmol) of 4,4′-diphenyl ether dimethyl chloride ) and stir for 30 minutes. After warming up to room temperature (25°C), 1.27 g (9.00 mol) of benzyl chloride was added, followed by stirring for 2 hours. The obtained reaction solution was put into 1 L of methanol aqueous solution, and the precipitated solid was recovered, washed three times with methanol aqueous solution, and dried under reduced pressure to obtain polyamide (A-2). The weight average molecular weight determined by GPC was 25,500, and the degree of dispersion was 4.34.

[hua 51]

(Synthesis Example 5: Comparison)

Synthesis of Polyamide (R-1)

In a 300 mL glass three-neck flask equipped with a stirrer and a thermometer, 97 g of N-methyl-2-pyrrolidone was placed in a nitrogen atmosphere to make 1,1,1,3,3,3-hexafluoro. -2,2-bis(3-amino-4-hydroxyphenyl)propane 11.0 g (30.0 mmol) was stirred and dissolved. Then, after adding 5.22 g (66.0 mmol) of pyridine as a base, the flask was immersed in an ice bath, and the temperature was kept at 0 to 10°C, while adding 7.53 g (25.5 mmol) of 4,4′-diphenyl ether dimethyl chloride ) and stir for 30 minutes. After warming up to room temperature (25°C), 1.27 g (9.00 mol) of benzyl chloride was added, followed by stirring for 2 hours. The obtained reaction solution was put into 1 L of methanol aqueous solution, the precipitated solid was recovered, washed three times with methanol aqueous solution, and dried under reduced pressure to obtain polyamide (R-1). The weight average molecular weight determined by GPC was 25,200, and the degree of dispersion was 2.60.

[hua 52]

(weight average molecular weight (Mw) and number average molecular weight (Mn))

The weight average molecular weight and the number average molecular weight were measured using gel permeation chromatography (GPC, HLC-8320 manufactured by Tosoh Corporation) using polystyrene as a standard substance. N,N-dimethylformamide (DMF) was used as the mobile phase, and TSKgel SuperHZM-H was used as the column.

(Example 1)

<Preparation of photosensitive resin composition>

The polyamide (A-1) obtained in Synthesis Example 3, a naphthoquinonediazide compound (TKF-528 manufactured by Sanbao Chemical Research Institute Co., Ltd.) as a sensitizer (B-1), and a solvent (*1) ) of N-methyl-2-pyrrolidone was blended in the ratio (mass ratio) shown in Table 1.

<Production of patterned resin film>

The obtained photosensitive resin composition was coated on a silicon wafer using a spin coater, and dried at 110° C. for 7 minutes to obtain a photosensitive resin film with a film thickness of about 3 μm. The obtained photosensitive resin film was irradiated with an i-line of 450 mJ/cm ² for exposure using a mask designated by a high-pressure mercury lamp. After exposure, it was developed with a 2.38% tetramethylammonium hydroxide (TMAH) aqueous solution and rinsed with water to obtain a patterned resin film.

<Manufacture of pattern cured product>

The obtained patterned resin film was heated at 130°C/30 minutes, 200°C/1 hour, and 320°C/2 hours in a nitrogen atmosphere using an oven to obtain a patterned cured product.

<Evaluation of the dissolution rate of the exposed part and the residual film rate of the unexposed part>

Development was started, and the elapsed time when the film thickness of the exposed portion became 0 was defined as the development time, and the film thickness of the unexposed portion was defined as the film thickness after development, and was calculated by the following equation. Exposure part dissolution speed (nm/s) = film thickness before development (nm) / development time (s) Unexposed part residual film rate (%) = [film thickness after development (μm) / film thickness before development (μm)] × 100

The results are shown in Table 1 together.

(Example 2)

The same operation as in Example 1 was carried out, except that the polyamide (A-1) obtained in Synthesis Example 3 was changed to the polyamide (A-2) obtained in Synthesis Example 4. The blending and results of Example 2 are disclosed in Table 1 together.

(Comparative example)

The same operation as in Example 1 was carried out, except that the polyamide (A-1) obtained in Synthesis Example 3 was changed to the polyamide (R-1) obtained in Synthesis Example 5. The blending and results of the comparative examples are shown in Table 1 together.

[Table 1] Example 1 Example 2 Comparative example Polyamide (PBO precursor) A-1 100 - - A-2 - 100 - R-1 - - 100 sensitizer B-1 30 30 30 solvent *1 400 400 400 Exposure part dissolution rate (nm/s) 422 221 157 Unexposed part residual film rate 96 99 99

The resin film of Example 1 comprising the polyamide having the "-C(CF ₃ )H-" structure is compared with the resin film of the comparative example comprising the polyamide having the "-C(CF ₃ ) ₂ -" structure , the exposure part of the dissolution rate is excellent. For example, the development time can be shortened, which is advantageous in terms of productivity improvement. In addition, even if the dissolution rate of the exposed part is high, the residual film ratio of the unexposed part is excellent. Therefore, it can be seen that there is a relatively high dissolution contrast.

In general, resin films with high solubility such as polyamic acid cannot obtain sufficient dissolution inhibition effect even if a photosensitive agent is added, or even if obtained, problems such as scum generation still occur. On the other hand, the resin film of Example 1 has a high dissolution rate in the exposed part and excellent residual film ratio in the unexposed part, and can obtain a pattern of L/S=20/20 (μm) without scum generation. Although the reason is unclear, it is conceivable that the resin film containing the polyamide having the "-C(CF ₃ )H-" structure has excellent compatibility with the photosensitizer and the like.

In addition, even though the resin film of Example 2 contains the structure of "imide having hexafluoroisopropyl at the ortho-position of the aromatic ring" with extremely low alkali solubility, it can obtain a higher dissolution rate than that of the comparative example. That is, the polyamide and its composition having the "-C(CF ₃ )H-" structure of Example 1 can maintain relatively good alkalinity even if other components (alkaline insoluble polymers, etc.) are combined Solubility. For example, it is advantageous in that the alkaline dissolution rate can be adjusted to a desired range and physical properties derived from the components to be combined can be imparted.

Although the reason for the high alkaline dissolution rate of the resin film containing the polyamide having the "-C(CF ₃ )H-" structure of the embodiment is unclear, it is presumably due to Generally speaking, it is a polyamide with a general "-C(CF ₃ ) ₂ -" structure, which has poor symmetry (increased asymmetry). That is, it is conceivable that as the asymmetry increases, the stacking of the polymer chains becomes loose, and as a result, it is involved in the improvement of the solubility of the polymer in the alkaline developer.

This application claims priority based on Japanese Patent Application No. 2020-133130 filed on August 5, 2020, the disclosure of which is incorporated herein by reference.

none.

none.

none.

Claims (29)

A photosensitive resin composition comprising a polyamide having a structural unit represented by the following general formula [1] and a photosensitizer, [Chemical 1]

(In the above general formula [1], R ¹ is a tetravalent organic group represented by the following general formula [2], and R ² is a divalent organic group) [Chemical 2]

(In the above-mentioned general formula [2], the two n's are each independently an integer of 0 to 3, R ³ is a monovalent substituent, and when there are multiple R ³ s, they may be the same or different, and are bonded to The two OH groups of R ¹ are respectively bonded to one of *1 or *2 and to one of *3 or *4). The photosensitive resin composition according to claim 1, wherein R ¹ is a tetravalent organic group selected from at least one of the following, [Chem. 3]

. The photosensitive resin composition according to claim 1 or 2, wherein R ² is a divalent organic group selected from at least one of the following, [Chem. 4]

. The photosensitive resin composition according to claim 1 or 2, wherein the polyamide has a structural unit represented by the following general formula [3] and a structural unit represented by the following general formula [4] Copolymer, [Chem. 5]

(In the above-mentioned general formula [3], the definitions of R ² and R ³ are the same as those of the above-mentioned general formulas [1] and [2], and the two m are each independently an integer of 0 to 3.) [Formula 6]

(In the above general formula [4], R ⁵ is a divalent organic group, p is 1 or 2, and R ⁴ is a trivalent or 4 represented by any one of the following general formulas [5] to [8] valence organic group) [Chem. 7]

(In the above-mentioned general formula [5], X is a single bond or a divalent linking group, two qs are each independently an integer of 0 to 3, R ⁶ is a monovalent substituent, and R ⁶ is a plurality of series. can be the same or different) [化8]

(In the above general formula [6], R ⁷ represents a monovalent substituent) [Chemical 9]

[Chemical 10]

. The photosensitive resin composition according to claim 4, wherein R ⁴ is a trivalent or tetravalent organic group selected from at least one of the following, [Chem. 11]

. The photosensitive resin composition according to claim 4, wherein R ² in the general formula [3] and R ⁵ in the general formula [4] are each independently a divalent value of at least one selected from the following The organic group of , [Chem. 12]

. The photosensitive resin composition according to claim 4, wherein the molar ratio of the structural unit represented by the general formula [3] and the structural unit represented by the general formula [4] in the polyamide is: 99.9:0.1～10:90. The photosensitive resin composition according to claim 1 or 2, wherein the polyamide is a first polymer having a structural unit represented by the following general formula [9], and the photosensitive resin composition further comprises a The second polymer of the structural unit represented by the following general formula [10], [Chem. 13]

(In the aforementioned general formula [9], the definitions of R ² and R ³ are the same as those of the aforementioned general formulas [1] and [2], and the two r's are each independently an integer of 0 to 3.) [Chem. 14]

(In the above general formula [10], R ⁹ is a divalent organic group, s is 1 or 2, and R ⁸ is a trivalent or 4 valence represented by any one of the following general formulas [11] to [14] valence organic group) [Chem. 15]

(In the above-mentioned general formula [11], X is a single bond or a divalent linking group, two t's are each independently an integer of 0 to 3, R ¹⁰ is a monovalent substituent, and there are multiple R ^10s in the series can be the same or different) [化16]

(In the above general formula [12], R ¹¹ represents a monovalent substituent) [Chemical 17]

[Chemical 18]

. The photosensitive resin composition according to claim 8, wherein R ⁸ is selected from at least one of the following trivalent or tetravalent organic groups, [Chem. 19]

. The photosensitive resin composition according to claim 8, wherein R ² in the general formula [9] and R ⁹ in the general formula [10] are each independently a divalent value of at least one selected from the following The organic group of ［Chem.20］

. The photosensitive resin composition according to claim 8, wherein the molar ratio of the structural unit represented by the general formula [9] and the structural unit represented by the general formula [10] is 99.9:0.1-10: 90. The photosensitive resin composition according to claim 1 or 2, wherein the weight average molecular weight of the polyamide is 1,000 or more and 100,000 or less. The photosensitive resin composition according to claim 1 or 2, wherein the polyamide includes one having a capped structure obtained by reacting with a capping agent. The photosensitive resin composition according to claim 13, wherein the blocking agent is a carboxylic acid derivative. The photosensitive resin composition according to claim 14, wherein the carboxylic acid derivative is acyl chloride. The photosensitive resin composition according to claim 15, wherein the acyl chloride is benzyl chloride. The photosensitive resin composition according to claim 1 or 2, wherein the photosensitive agent is a quinonediazide compound. The photosensitive resin composition according to claim 1 or 2, further comprising an organic solvent. The photosensitive resin composition according to claim 18, wherein the organic solvent is at least one selected from the group consisting of amide-based solvents, ether-based solvents, aromatic-based solvents, halogen-based solvents, and lactone-based solvents kind. The photosensitive resin composition according to claim 18, wherein the concentration of the polyamide is 0.1 mass % or more and 50 mass % or less. A photosensitive resin film obtained by forming the photosensitive resin composition according to any one of Claims 18 to 20 as a coating on a support substrate and drying the coating. A cured product, which is a cured product of the photosensitive resin composition according to any one of claims 1 to 20 or the photosensitive resin film according to claim 21. A patterned resin film obtained by subjecting the photosensitive resin film according to claim 21 to pattern exposure and development. A patterned cured product obtained by curing the patterned resin film described in claim 23. A method of manufacturing an electronic device, comprising: a coating process of coating the photosensitive resin composition as described in any one of claims 18 to 20 on a support substrate, by allowing the coated photosensitive resin composition to be A drying step of removing the contained solvent to obtain a photosensitive resin film containing polyamide, an exposure step of subjecting the aforementioned photosensitive resin film to pattern exposure to obtain a resin film, and an alkaline aqueous solution developing the aforementioned resin film to obtain a patterned resin film The development process of , and the heating process of heat-treating the above-mentioned patterned resin film to form a patterned cured product. The method for manufacturing an electronic device according to claim 25, wherein the thickness of the pattern cured product is set to be 1 μm or more and 1000 μm or less. The manufacturing method of the electronic device of Claim 25 or 26 whose temperature of the said drying process is made into 50 degreeC or more and 150 degrees C or less. The manufacturing method of the electronic device of Claim 25 or 26 whose temperature of the said heating process is made into 150 degreeC or more and 400 degrees C or less. An electronic device comprising the pattern cured product as claimed in claim 24.