JPH0148942B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a polyamide-imide-based curable material that cures in response to radiation such as light or electron beams, and is particularly photosensitive and easily soluble in organic solvents.

In recent years, there has been a high demand for curable materials that can be cured by light, electron beams, etc. to provide heat-resistant substances, and are mainly used as protective materials, insulating materials, solder resists, adhesives, coating materials, etc. in the electrical and electronic fields. It is also being applied as a heat-resistant photoresist in semiconductor devices.

This type of curable material not only requires good radiation sensitivity properties and excellent heat resistance after sensitive curing, but also exhibits good adhesion to adherends. Also, insulation properties,
It is also desired that the material satisfies various properties such as moisture resistance and chemical resistance. On the other hand, it is desired that the material has excellent storage stability without problems such as gelation over time in a solvent-free or organic solvent-containing state before sensitive curing with radiation.

However, there are few conventionally known curable materials that satisfy all of these required properties. Generally, materials with excellent radiation sensitivity tend to have poor storage stability, and many also lack adhesive strength to adherends.

For example, as a photocurable heat-resistant photoresist, one is known that is made by blending dichromic hydrochloric acid with polyamic acid that has not been completely imidized by reacting a polyimide precursor, that is, an aromatic tetracarboxylic acid component with a diamine. It is being However, this type of material has extremely poor storage stability and must be used immediately after mixing the polyimide precursor and dichromate, which has major limitations on industrial application. Furthermore, since inorganic ions are included in the curing material, reliability will be impaired when this is applied to semiconductor applications.

In addition, as another known heat-resistant photoresist, 2 mol of aromatic tetracarboxylic dianhydride is used.
There is a polyimide precursor made by reacting moles of allyl alcohol, then chlorinating two free carboxyl groups, and then condensing it with a diamine. However, this type of material also has problems in terms of storage stability, and the above condensation reaction removes chlorine ions, which are then included in the cured resist, so its reliability is still high for semiconductor applications. There was a risk of damage to sex.

Furthermore, in addition to the above drawbacks, the conventional photocurable heat-resistant photoresists described above have poor solubility in organic solvents, and when developed by dissolving the uncured portions in an organic solvent after being cured by masking irradiation, N - Because special and hygroscopic organic solvents such as methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide must be used, it is not practical from an economic standpoint, and the workability during development is poor. I was filled with regret.

From this point of view, the present invention is a radiation-sensitive polyamide that satisfies all of the above-mentioned required properties and has improved solubility in organic solvents, as being essentially different from the conventionally known curable materials as described above. The aim is to provide an imide-based curable material, the gist of which is to provide a) an aromatic tricarboxylic acid or its derivative, b) a double bond having at least one radiation-sensitive carbon-carbon double bond. It is a radiation-sensitive polyamide-imide-based curable material mainly composed of a polyamide-imide easily soluble in organic solvents obtained by reacting a basic acid or a derivative thereof, c) a lactam, and d) an organic diisocyanate compound.

By the way, it is already known that as a method for producing a heat-resistant resin, a resin having improved properties such as heat stability and heat deterioration resistance is produced by reacting the a component, c component, and d component used in the above-mentioned present invention. It is being
The heat-resistant resin obtained by this method mainly has the following structural formulas (1) and (2); (In the formula, Y is a trivalent aromatic group, _R1 is a divalent organic group, _R2 and _R3 are a hydrogen atom or a monovalent organic group, and n is an integer from 2 to 20.) 1 with repeating structural elements as shown.

In this invention, the reaction product is a four-component system in which a b component is added in addition to the above a, c, and d components, and in addition to the above structural formulas (1) and (2), the following structural formula ( 3), (4); (However, in the formula, X is radiation-sensitive carbon
A divalent organic group having at least one carbon double bond, R ₁ is a divalent organic group, R ₂ and R ₃ are hydrogen atoms or monovalent organic groups, n is an integer from 2 to 20)
It has been found that this polyamide-imide is extremely suitable as a radiation-sensitive curable material.

That is, the above polyamideimide has the structural formula
Because the X group of the amide structure represented by (3) and (4) contains at least one radiation-sensitive carbon-carbon double bond, it is extremely sensitive to radiation-sensitive electron beams. Can be cured well,
Further, depending on the type of the above-mentioned X group, photocuring can be carried out in a short time using light such as ultraviolet rays, with or without using a photosensitizer.

In addition, the product cured in this way exhibits excellent heat resistance due to the amide bonds and imide bonds contained in the molecular skeleton of polyamide-imide, and also has good adhesion to adherends, for example, compared to conventional Curable materials require etching of the surface of the adherend to improve adhesive strength, but practical adhesive strength can be obtained without such treatment, and in addition, absolute properties and Various properties such as moisture resistance and chemical resistance can also be fully satisfied.

On the other hand, as mentioned above, polyamide-imide before being cured by radiation is a very good material that does not gel in a short period of time even if it is left at room temperature in a solvent-free or organic solvent-containing state. It exhibits storage stability, and in this respect also has the advantage that, unlike the conventionally known photocurable heat-resistant photoresists, there are no major restrictions on industrial application.

Moreover, it has extremely good solubility in organic solvents,
Since ordinary solvents such as halogenated hydrocarbons and ketones can be used, it is easy to use, and it also greatly improves the workability when removing and developing the photo-cured portions by masking irradiation with solvents. Ru.

In the present invention, in order to synthesize a polyamideimide easily soluble in an organic solvent having the above-mentioned characteristics, a) aromatic tricarboxylic acid or a derivative thereof is particularly prepared by the following general formula; (However, in the formula, Y represents a trivalent aromatic group)
Using an aromatic monoanhydride represented by this and b) the following general formula; HOOG-X-COOH...(6) where, (representing one divalent organic group) or a derivative thereof;
c) the following general formula; (However, in the formula, R ₂ and R ₃ are hydrogen atoms or monovalent organic groups, and n is an integer of 2 to 20.) and d) the following general formula; ON-R ₁ - What is necessary is to react with an organic diisocyanate compound represented by NCO...(8) (wherein R ₁ represents a divalent organic group).

Typical aromatic monoanhydrides as component a represented by the above general formula (5) include trimellitic anhydride and hemimellitic anhydride, but other aromatic monoanhydrides It's okay to be hot. Furthermore, in place of the above-mentioned monoanhydride, it is also possible to use aromatic tricarboxylic acid itself or other derivatives such as lower alkyl esters.

Furthermore, in this invention, an aromatic or aliphatic dianhydride may be used together with the monoanhydride as described above to form a heat-resistant structural part in the molecular skeleton. In addition to the amide-imide structure represented, the following structural formulas (9) and (10) derived from dianhydride; (However, in the formula, R ₄ is a tetravalent organic group, R ₁ ,
It is also possible to introduce an imide structure represented by (R ₂ , R ₃ and n are the same as above). However, the proportion used should be 5% by weight or less based on the total amount with the aromatic monoanhydride; if it is too large, it may adversely affect storage stability and other properties, which is not desirable.

Specific examples of the aromatic or aliphatic dianhydrides include pyromellitic anhydride, benzophenone-3,4,3',4'-tetracarboxylic dianhydride, naphthalene-2,3,6,7 -Tetracarboxylic dianhydride, perylene-2, 3, 9, 10-tetracarboxylic dianhydride, 3, 3', 4, 4'-diphenyltetracarboxylic dianhydride, 2, 2', 3・
3′-diphenyltetracarboxylic dianhydride, 2.
2'-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride , ethylenetetracarboxylic dianhydride, 1,2,3,4-butanetetracarboxylic dianhydride, and the like.
These can be used alone or in combination of two or more.

The dibasic acid as component b represented by general formula (6) has a radiation-sensitive carbon-carbon double bond that is highly sensitive to radiation, particularly to light such as ultraviolet rays. Dibasic acids (hereinafter referred to as
They can be broadly classified into dibasic acids (hereinafter referred to as group a dibasic acids) and dibasic acids with high photosensitivity (hereinafter referred to as group b dibasic acids).

Examples of the group a dibasic acids include maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, and diphenylmethane-di-γ-ketocrotonic acid-4.4'. Also b
Group dibasic acids include 4-carboxycinnamic acid, 3-carboxycinnamic acid, cinnamylidenemalonic acid, m-phenylene diacrylic acid, 0-phenylene diacrylic acid, and P-phenylene diacrylic acid. Examples include acids.

Further, in the present invention, derivatives of the various dibasic acids mentioned above, such as lower alkyl esters, can also be used as component b. These dibasic acids or derivatives thereof may be used alone or in combination of two or more. When two or more types are used in combination, they may be selected from either group a dibasic acids or their derivatives and group b dibasic acids or their derivatives, or from both groups dibasic acids or their derivatives. They can also be used in combination.

The b component consisting of the dibasic acid represented by the general formula (6) or its derivative is the a component, that is, the above-mentioned aromatic monoanhydride (or this and an aromatic or aliphatic dianhydride). Usually 5 out of the total amount of
It is used in a proportion of ~80 mol%, preferably 10-40 mol%. If this amount is too large, it becomes difficult to synthesize polyamide-imide with a high degree of condensation through a polycondensation reaction with a diisocyanate compound, resulting in a loss of film-forming ability, and in some cases, gelation, and heat resistance etc. On the other hand, if the amount decreases too much, the radiation sensitivity characteristics will deteriorate.

Note that the dibasic acid represented by general formula (6) or its derivative has a content of up to 95 mol%, preferably 50% by mole.
There is no problem in replacing up to mol% with other dibasic carboxylic acids. When such a dibasic carboxylic acid is used in combination, the above structural formula is present in the molecular skeleton.
In addition to the amide structures represented by (3) and (4), an amide bond based on the dibasic carboxylic acid mentioned above will be introduced.

As the other dibasic carboxylic acids mentioned above, aromatic ones are preferred, but aliphatic or alicyclic carboxylic acids can also be used in combination within a range of 50 mol% or less. Specific examples of aromatic dibasic carboxylic acids include isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, methylisophthalic acid, and methyl. Terephthalic acid, biphenyl-2,2'-dicarboxylic acid, biphenyl-2-
3'-dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, etc. can be mentioned. Examples of aliphatic or alicyclic dibasic carboxylic acids include succinic acid, glutanic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, malonic acid,
3.9-bis(2-carboxyethyl)-2.
Examples include 4,8,10-tetraoxaspiro[5,5]undecane.

The above general formula (7) as component c in this invention
A lactam represented by R ₂ and
R ₃ may be the same or different, and may be a hydrogen atom as well as various organic groups such as an alkyl group, an aryl group, an aralkyl group, or a substituent thereof. Representative examples include ε-caprolactam, butyrolactam, δ-valerolactam, 2-propyl-piperidone-(6), 3-ethyl-piperidone-(2), ω
-Includes laurin lactam. Most preferred is ε-caprolactam.

One or more of these lactams can be used, and the proportion used is in the total amount of component a and component b, that is, in the total amount of the three components a, b, and c (the above-mentioned dianhydride or general dibasic acids (in the total amount including these), usually 55~
The content is 10 mol%, preferably 50 to 30 mol%. If this ratio is too large, unreacted lactam remains, making it difficult to obtain good results in heat resistance and other properties. On the other hand, if the amount is too small, the solubility in organic solvents will be poor, and when developing by dissolving uncured parts in an organic solvent after being cured by masking irradiation,
Because special and hygroscopic organic solvents such as N-methyl-2-pyrrolidone, dimethylformamide, and dimethylacetamide must be used,
This results in drawbacks such as impracticality in terms of workability and economy.

The above general formula (8) as the d component in this invention
The organic diisocyanate compound represented by is preferably an aromatic one, but an aliphatic or alicyclic one may be used in combination in an amount of 10 mol % or less. Specific examples of aromatic diisocyanate compounds include dianiridine diisocyanate, bistolylene diisocyanate, naphthalene diisocyanate, m-(or P-)phenylene diisocyanate, 2,4-(or 2,6-)tolylene diisocyanate, and diphthalene diisocyanate. Examples include enyl ether diisocyanate, diphenylmethane diisocyanate, and m-(or P-)xylidene diisocyanate. Examples of aliphatic or alicyclic diisocyanate compounds include methylcyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isopropylidene bis(4-cyclohexyl isocyanate), dicyclohexyl ether diisocyanate, and hexamethylene diisocyanate.

The usage ratio of these organic diisocyanate compounds is determined based on the amount of reactive acid groups and isocyanate groups contained in the above-mentioned components a and b (including dianhydrides and general dibasic acids when used). It is desirable that the proportions be approximately equivalent. However, the isocyanate group per equivalent of reactive acid group
Some excess or deficiency is acceptable as long as the ratio is about 0.9 to 1.1 equivalent.

In this invention, the reactions of the components a, b, c, and d are preferably carried out by heating in an organic solvent. The organic solvent used here is preferably one that does not react with each component at all under the reaction conditions or only forms a loosely bonded adduct or a compound that further reacts, and is also capable of dissolving all the components and eliminating reaction products. It is desirable that the material be able to dissolve the polyamideimide.

Among the preferred solvents are, for example, hydrocarbons,
halogenated hydrocarbons, phenols, esters, ketones, ethers, substituted amides,
Includes sulfoxides and sulfones.
Specific examples of these include benzene, toluene,
Xylene, chlorobenzene, naphtha, 0-cyclobenzene, phenol, cresol, xylenol, acetophenone, ethylene glycol monomethyl ether acetate, N-methyl-2-pyrrolidone, dimethylacetamide, dimethylformamide, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl Examples include sulfone, hexamethylsulfolamide, methylforamide, formamide, and N-acetyl-2-pyrrolidone.
Among these, the most preferred are those containing phenols such as cresol, phenol, and xylenol as a main component. Note that these solvents may be used alone or in combination of two or more.

The amount of organic solvent used is not particularly limited as long as polyamideimide having film-forming ability is obtained, but generally, the concentration of polyamideimide is 10 to 60%.
It may be used in a proportion of % by weight.

In the reaction of the components a, b, c, and d, a suitable catalyst may be used to promote the reaction. Catalysts include those commonly used in isocyanate reactions, such as boron fluoride, its adducts, mineral acids, carboxylic acids, zinc chloride, and triethylamine, N-alkylmorpholine, triethylenediamine, 1,8-diamine, etc. There are tertiary amines such as azabicyclo(5.4.0) undecene-7 (including salts with acids such as phenol, hexanoic acid, and oleic acid), trialkylphosphines, and acetic acid. Dialkyltin diacylates such as potassium, zinc octoate, and dibutyltin dilaurate; alkali metal salts such as lithium linoleate, sodium oleate, rhidium methoxide, and potassium ethoxide; and heavy metal salts such as cobalt acetate and cobalt naphthenate. be. Further, there are titanium-based catalysts such as titanium tetraalkoxides such as titanium isopropoxide, titanium tetrabutoxide, and titanium tetraphenolate, or their chelate compounds, tetraalkyl titanium acylate compounds, and titanium bischelate compounds.

Among these, preferred are tertiary amines, tin-based compounds, and titanium-based compounds, and particularly preferred are titanium-based catalysts, 1,8-diazabicyclo(5.4.0) undecene-7 (for example,
(including salts with acids such as phenol, hexanoic acid, and oleic acid).

The reaction temperature and reaction time vary depending on the type of polybasic acid component, diisocyanate compound, and organic solvent used, but usually the reaction is carried out by heating sequentially from room temperature to a temperature of 150 to 250 °C,
The reaction can be carried out for several hours. When a catalyst is used, the reaction can be carried out at a lower temperature or in a shorter time than when a catalyst is not used.

The intrinsic viscosity of the produced polyamideimide is N
-C=0.5 at 30°C in methyl-2-pyrrolidone
The viscosity ηinh in g/100ml is usually in the range of 0.1 to 1.5, particularly preferably in the range of 0.2 to 1.0. If the intrinsic viscosity is too low, the film-forming ability will be poor and practicality will be poor.

The curable material of the present invention is mainly composed of polyamideimide easily soluble in organic solvents synthesized by the method described above, and when cured using an electron beam as radiation, it is expressed by the general formula (6). Regardless of the type of dibasic acid or its derivative expressed, that is, the dibasic acid having at least one radiation-sensitive carbon-carbon double bond, or its derivative, without intentionally using a sensitizer, etc. It has the characteristic of being able to be rapidly cured by irradiation with electron beams.

In addition, even when curing is performed using light such as ultraviolet rays as the radiation, the dibasic acid represented by the general formula (6) or its derivative contains primarily a group B dibasic acid or its derivative. In this case, it can be sufficiently cured by ultraviolet irradiation without using a photosensitizer as described above. It should be noted that many of the conventionally known photosensitive materials cannot achieve a practical curing speed unless a photosensitizer is used. On the other hand, according to the above aspect of the present invention, since no photosensitizer is required, it is possible to provide a highly significant photosensitive material that is unprecedented in this respect.

On the other hand, the above dibasic acid or its derivative is a
When the composition is mainly composed of a group dibasic acid or a derivative thereof, a practical curing speed can usually be obtained by blending a photosensitizer with the polyamideimide.

A wide range of conventionally known photosensitizers can be used as such photosensitizers, such as benzoin, benzoin methyl ether, benzoin ethyl ether,
Carbonyl compounds such as benzoin isopropyl ether, benzyl, benzyl dimethyl ketal,
Examples include organic sulfur compounds such as benzyl sulfide, halogen compounds, and photoreducible dyes. When using a photosensitizer, the amount used may be 10 parts by weight or less per 100 parts by weight of polyamideimide. In addition,
Of course, such a photosensitizer may be incorporated when curing with electron beams or when using a group b dibasic acid.

In addition to the above-mentioned photosensitizer, a peroxide can be added to the curable material of the present invention, if necessary. Specific examples include organic peroxides such as benzoyl peroxide, methyl ethyl ketone peroxide, tert-butyl perbenzoate, and dicumyl peroxide. When such a peroxide is used, heat resistance after curing can be further improved by further post-heating treatment after radiation curing. The amount used may be about 0.5 to 5 parts by weight per 100 parts by weight of polyamideimide.

In addition, as another optional component, monofunctional or polyfunctional monomers having double bonds, which are reactive diluents for ultraviolet curable or electron beam curable resins, may be added within a range that does not reduce heat resistance. You may. Even if the various optional components mentioned above are added, the storage stability characteristic of this type of material will not be impaired.

As mentioned above, the curable material of this invention has excellent storage stability, but when storing it for a long period of time, it must be stored in a dark room or in a cold room, taking into account its photosensitivity. It is advisable to save it.

On the other hand, in use, the above-mentioned material is applied to an adherend using a bar coater, applicator, spinner, etc., dried under appropriate conditions, and then cured by irradiation with radiation. If necessary, by performing post-heat treatment to further improve heat resistance and adhesion, we can create a cured film with excellent properties such as heat resistance, adhesion, insulation properties, moisture resistance, and chemical resistance. Can be formed. Also, when masking irradiation is performed during this curing work,
After the above-mentioned curing, a desired pattern in which only the cured portion remains can be formed by developing with a solvent that dissolves the uncured polymer. Cresol and other inexpensive organic solvents can be used as the solvent, and the workability during dissolution and development is also good.

Next, examples of this invention will be described. In the following, parts and % mean parts by weight and % by weight, respectively.

Example 1 13.44 g (0.07 mol) of trimellitic anhydride, 3.48 g (0.03 mol) of fumaric acid, ε-caprolactam
11.31 g (0.1 mol), 25.53 g (0.102 mol) of diphenylmethane diisocyanate, and 38 g of m-cresol were placed in a 200 ml four-necked flask, heated to 120-125°C to start the reaction, and then heated to 120-125°C to start the reaction. It was held for 3 hours. During this time, the generation of carbon dioxide gas was remarkable. Next, change the temperature from 120-125℃ to 210℃
The temperature was raised over 1 hour until the temperature reached 1 hour, and the reaction was continued at this temperature for an additional 20 hours. At the beginning of the reaction, the solution was opaque and cloudy, but as the reaction progressed, it became a reddish-brown, clear solution.

The viscosity ηinh (C=0.5g/100ml, in N-methyl-2-pyrrolidone at 30°C) of the polyamideimide thus obtained was 0.26. 3 parts of benzoin isobutyl ether was blended with 100 parts of this polyamideimide, and N-methyl-
A 2-pyrrolidone solution was prepared to form the curable material of this invention.

This material was subjected to the following storage stability test and photocurability test.

A. Storage stability test The curable material was left at room temperature to examine changes in properties over time. As a result, no gelation occurred even after 3 months, and no changes in properties were observed visually.

B. Photo-curing test A curable material was coated onto an adherend using a bar coater to a dry thickness of 10 μm, and dried by heating at 100° C. for 30 minutes. Next, pattern mask the above coating surface, and the input per unit length is 80W/cm.
Using two high pressure mercury lamps with a lamp output of 1KW,
Light curing was performed by irradiating at a speed of 1 m/min from a position 15 cm away. After photocuring, the coating was immersed in trichlorethylene at room temperature for 30 minutes, and the masked portions were dissolved and disappeared, but the unmasked cured portions remained intact, forming a clear pattern.

On the other hand, in the above test, the entire coating film was photocured without a pattern mask, and the photocured film was subjected to a thermal decomposition test in nitrogen at a heating rate of 10°C/min, and the weight loss was determined from the thermal decomposition curve. When we investigated the temperature when the amount of water becomes 10%, it was 305℃.
Further, the following heat resistance and adhesion tests were conducted and the results were as follows.

<Heat resistance> For those using copper foil as the adherend, 100
℃ and 150℃ for 120 hours, and the cured film was examined to see if there were any abnormalities such as deterioration or peeling, but no abnormalities were observed at either temperature.

<Adhesion> For adherends such as copper foil, polyester film, glass, aluminum plate, stainless steel plate, Kapton film, nickel plated plate, aluminum plated plate, etc., cross-cut the cured film into a 2 mm square and apply Nitto Electric Co., Ltd. After pressing No. 29 cellophane tape manufactured by Kogyo Co., Ltd., it was rapidly peeled off and the number of peeled pieces in 100 cross-cuts was determined. The results were all 0/100 except for the stainless steel plate which was 50/100.

Note that the stainless steel plate was reduced to 5/100 pieces by further post-heating at 200°C for 30 minutes after photocuring.

Example 2 The polyamideimide obtained in Example 1 was prepared as a 30% solution of N-methyl-2-pyrrolidone without adding benzoin isobutyl ether, and used as the curable material of the present invention without adding benzoin isobutyl ether. A linear hardenability test was conducted.

<Electron beam curing test> The above material was coated onto the adherend using a bar coater to a dry thickness of 10 μm, and after heating and drying at 100°C for 30 minutes, an electron beam was applied at an accelerating voltage.
It was irradiated and cured at 1.3 MeV with an absorbed dose of 10 Mrad. Below, various properties were investigated using the same procedure as the photocuring test described in Example 1, and all of the properties of pattern development, heat resistance, and adhesion were as good as when photocuring. It was hot.

Example 3 To 100 parts of the polyamideimide obtained in Example 1,
N・N′-diphenylmethane-bismaleimide 30
1 part and 5 parts of benzoin isopropyl ether were added, and these were dissolved in N-methyl-2-pyrrolidone by heating to a solid content of 30% to obtain the curable material of the present invention.

When this material was subjected to the same storage stability test as in Example 1, no changes in properties such as an increase in viscosity were visually observed even after 3 months had passed. Furthermore, when the same photocuring test as in Example 1 was conducted, a clear cured pattern could be formed and the heat resistance was good, the 10% weight loss temperature was 333°C and the adhesion was 5/100. .

Example 4 The number of moles of trimellitic anhydride used was 0.06 mole,
While reducing the number of moles of fumaric acid used to 0.037 moles,
A polyamideimide was synthesized in the same manner as in Example 1, except that 0.003 mol of pyromellitic anhydride was used as a polybasic acid component other than these. ηinh of this polyamideimide (C=0.5g/100ml, N-
(30°C) in methyl-2-pyrrolidone was 0.22. 5 parts of benzoin isobutyl ether was blended with 100 parts of this polyamideimide, and N with a solid content of 30% was added.
-Methyl-2-pyrrolidone solution was prepared as the curable material of this invention.

When this material was subjected to the same photocuring test as in Example 1, it was possible to form a clear curing pattern, and the heat resistance was also good, with a 10% weight loss temperature of 311
℃, adhesion was 0/100.

Example 5 Diphenyl ether diisocyanate instead of 0.102 mol of diphenylmethane diisocyanate
Polyamideimide was synthesized in the same manner as in Example 1 except that 0.102 mol was used. The ηinh (same as above) of this polyamideimide was 0.29.
5 parts of benzoin isobutyl ether was blended with 100 parts of this polyamide-imide to prepare an N-methyl-2-pyrrolidone solution with a solid content of 30%, which was used as the curable material of the present invention.

When this material was subjected to the same photocuring test as in Example 1, it was possible to form a clear cured pattern, and the heat resistance was also good, with a 10% weight loss temperature of 310
℃, adhesion was 0/100.

Example 6 The number of moles of trimellitic anhydride used was 0.05 mole,
While the number of moles of fumaric acid used is 0.03 mole, 0.02 mole of adipic acid is used as a polybasic acid component other than these.
Polyamideimide was synthesized in the same manner as in Example 1, except that 0.107 mol of diphenyl ether diisocyanate was used instead of 0.102 mol of diphenylmethane diisocyanate. ηinh of this polyamideimide (same as above)
was 0.27. To 100 parts of this polyamideimide,
Add 5 parts of benzoin isopropyl ether and add this to N-methyl-2-pyrrolidone to a solids content of 30%.
The curable material of the present invention was obtained by heating and melting to obtain the following.

When this material was subjected to the same photocuring test as in Example 1, it was possible to form a clear cured pattern, and the heat resistance was also good, with a 10% weight loss temperature of 298
℃, adhesion was 0/100.

Example 7 Trimellitic anhydride 13.44 g (0.07 mol), p-
6.54 g (0.03 mol) of phenylene diacrylic acid, ε
-Caprolactam 11.31g (0.1mol), diphenylmethane diisocyanate 25.53g (0.102mol),
38 g of m-cresol and 0.2 g of dibutyltin dilaurate were placed in a 200 ml four-necked flask, heated to 120-125°C to start the reaction, and maintained at the same temperature for 3 hours. During this time, the generation of carbon dioxide gas was remarkable. Next, change the temperature from 120-125℃ to 210℃
The temperature was raised for 1 hour until the temperature reached 1 hour, and the reaction was further continued at this temperature for 22 hours. At the beginning of the reaction, it was opaque and cloudy, but
As the reaction progressed, it became a bluish brown opaque liquid, and gradually turned into a reddish brown transparent liquid.

The viscosity of the polyamideimide thus obtained is ηinh (C=0.5g/100ml, N-methylol-2
- 30℃ in pyrrolidone) was 0.28. A 30% solution of this polyamideimide in N-methyl-2-pyrrolidone was prepared as a curable material of the present invention.

When this material was subjected to the same storage stability test as in Example 1, no changes in properties such as an increase in viscosity were visually observed even after 3 months had elapsed. In addition, when a photocuring test similar to that in Example 1 was conducted, a clear cured pattern could be formed.
Heat resistance was also good, with a 10% weight loss temperature of 322°C and adhesion of 0/100 on all surfaces except for the stainless steel plate. For stainless steel plates, add 200 yen to light curing.
By post-heating at ℃ for 30 minutes, 5/
There were 100 pieces. Furthermore, when an electron beam curing test was carried out in the same manner as in Example 2, the properties of pattern development, heat resistance, and adhesion were all as good as in the case of photocuring.

Example 8 To 100 parts of the polyamideimide obtained in Example 7,
N・N′-diphenylmethane-bismaleimide 30
1 part and 5 parts of benzoin isopropyl ether were added, and these were dissolved in N-methyl-2-pyrrolidone by heating to a solid content of 30% to obtain the curable material of the present invention.

When this material was subjected to the same storage stability test as in Example 1, no changes in properties such as an increase in viscosity were visually observed even after 3 months had passed. Furthermore, when a photocuring test similar to that in Example 1 was conducted, a clear cured pattern could be formed, and the heat resistance was also good, the 10% weight loss temperature was 344°C, and the adhesion was 5/100. .

Example 9 The number of moles of trimellitic anhydride used was 0.06 mole,
The number of moles of P-phenylene diacrylic acid used is
A polyamideimide was synthesized in the same manner as in Example 7, except that 0.037 mol of pyrrolimethic anhydride was used as a polybasic acid component other than these. ηinh of this polyamideimide
(C=0.5g/100ml in N-methyl-2-pyrrolidone at 30°C) was 0.24. 5 parts of benzoin isobutyl ether was blended with 100 parts of this polyamide-imide to prepare an N-methyl-2-pyrrolidone solution with a solid content of 30%, which was used as the curable material of the present invention.

When this material was subjected to the same photocuring test as in Example 1, it was possible to form a clear cured pattern, and the heat resistance was also good, with a 10% weight loss temperature of 326
℃, adhesion was 0/100.

Example 10 Diphenyl ether diisocyanate instead of 0.102 mol of diphenylmethane diisocyanate
Polyamideimide was synthesized in the same manner as in Example 7 except that 0.102 mol was used. The ηinh (same as above) of this polyamideimide was 0.31.
5 parts of benzoin isobutyl ether was blended with 100 parts of this polyamide-imide to prepare an N-methyl-2-pyrrolidone solution with a solid content of 30%, which was used as the curable material of the present invention.

When this material was subjected to the same photo-curing test as in Example 1, it was possible to form a clear curing pattern, and the heat resistance was also good, with a 10% weight loss temperature of 321
℃, adhesion was 0/100.

Example 11 The number of moles of trimellitic anhydride used was 0.05 mole,
The number of moles of P-phenylene diacrylic acid used is 0.03
Example 7 was carried out in the same manner as in Example 7, except that 0.02 mol of adipic acid was used as a polybasic acid component other than these, and 0.107 mol of diphenyl ether diisocyanate was used instead of 0.102 mol of diphenylmethane diisocyanate. Polyamideimide was synthesized. The ηinh (same as above) of this polyamideimide was 0.31. To 100 parts of this polyamide-imide, 5 parts of benzoin isopropyl ether was added, and this was heated and dissolved in N-methyl-2-pyrrolidone to a solid content of 30% to obtain the curable material of the present invention.

When this material was subjected to the same photocuring test as in Example 1, it was possible to form a clear cured pattern, and the heat resistance was also good, with a 10% weight loss temperature of 305
℃, adhesion was 0/100.

Example 12 Polyamideimide was synthesized in the same manner as in Example 7, except that 0.03 mol of 4-carboxycinnamic acid was used instead of 0.03 mol of P-phenylene diacrylic acid. The ηinh (same as above) of this polyamide-imide was 0.28, and the reaction solution containing this polyamide-imide was used as the curable material of the present invention.

When this material was subjected to the same photocuring test as in Example 1, it was possible to form a clear cured pattern, and the heat resistance was also good, with a 10% weight loss temperature of 319
℃, adhesion was 0/100.

Example 13 The number of moles of trimellitic anhydride used was 0.05 moles, and P-phenylene diacrylic acid was 0.03 moles.
Polyamideimide was synthesized in the same manner as in Example 7 except that 0.03 mol of m-phenylene diacrylic acid was used instead of mol. The ηinh (same as above) of this polyamide-imide was 0.33, and a reaction solution containing this polyamide-imide was used as the curable material of the present invention.

When this material was subjected to the same photo-curing test as in Example 1, it was possible to form a clear cured pattern, and the heat resistance was also good, with a 10% weight loss temperature of 315
℃, adhesion was 0/100.

Claims (1)

[Scope of Claims] 1 a) an aromatic tricarboxylic acid or a derivative thereof, b) a radiation-sensitive carbon-carbon double bond that accounts for 5 to 80 mol% in the total amount of component a above. c) a lactam that accounts for 10 to 55 mol% in the total amount of components a and b above, and d) a dibasic acid or derivative thereof having at least one of components a and b above. A polyamide-imide easily soluble in an organic solvent obtained by reacting an organic diisocyanate compound in a proportion of 0.9 to 1.1 equivalents of isocyanate groups per equivalent of reactive acid groups, and a polyamide-imide having a proportion of 0 to 10 parts by weight based on 100 parts by weight of the polyamide-imide. A radiation-sensitive polyamideimide-based curable material containing a photosensitizer in the weight part. 2. The dibasic acid having at least one radiation-sensitive carbon-carbon double bond or its derivative is maleic acid, fumaric acid, mesaconic acid, citraconic acid, itaconic acid, chlorinated maleic acid, diphenylmethane di- The radiation-sensitive polyamideimide-based curable material according to claim 1, which comprises a dibasic acid having relatively low photosensitivity such as γ-ketocrotonic acid-4,4' or a derivative thereof. 3. The dibasic acid having at least one radiation-sensitive carbon-carbon double bond or its derivative is 4-carboxycinnamic acid, 3-carboxycinnamic acid, cinnamylidenemalonic acid, m-phenylidene diacrylic acid, o-phenylene diacrylic acid,
The radiation-sensitive polyamideimide-based curable material according to claim 1, which comprises a dibasic acid with high photosensitivity such as p-phenylene diacrylic acid or a derivative thereof. 4. The radiation-sensitive polyamide-imide according to any one of claims 1 to 3, which is obtained by blending a peroxide with a polyamide-imide that is easily soluble in an organic solvent or a mixture of this and a photosensitizer. curable material.