JPH03271272A - Polymerizable imide monomer, production thereof and photo-setting composition - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I (R is H or methyl). USE:Used as a photo-setting composition. Said composition is made to a hardened material of heat-resistant and photo-sensitive resin useful as a coating material or heat resistant photoresist, etc., in electric or electronic industrial field having excellent adhesiveness to base material, photo-setting property and heat resistance after hardening. PREPARATION:Imidealcohol expressed by formula II is reacted with acrylic acid or methacrylic acid in a solvent such as sulforane-toluene at 50-200 deg.C for 3-20hr and preferably using a catalyst such as p-toluene sulfonate to afford the aimed compound expressed by formula I. Molar ratio of imidealcohol to acrylic acid or methacrylic acid is used as 1 :2-1 :10 and the catalyst is used in 0.01-30wt.% to imidealcohol.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a polymerizable imide monomer, a method for producing the same, and a photocurable composition containing the monomer.

[Conventional technology]

In recent years, heat-resistant photosensitive resins have been widely used as coating materials, heat-resistant photoresists, and the like in the electrical and electronic industries.

This type of heat-resistant photosensitive resin has the following inherent characteristics:
It is desired that the material has excellent photocurability and heat resistance after photocuring.

However, few of the conventionally known heat-resistant photosensitive resins satisfy all of these requirements. - In general, many of the materials that have excellent photocurability have poor heat resistance after photocuring.

[Problem to be solved by the invention]

The present invention was made in order to solve the above-mentioned problems, and provides a novel and useful polymerizable imide monomer capable of forming a heat-resistant photosensitive resin cured product satisfying the above-mentioned required properties, and a polymerizable imide monomer thereof. The purpose is to provide a manufacturing method.

Another object of the present invention is to provide a photocurable composition that forms a cured heat-resistant photosensitive resin as described above.

[Means to solve the problem]

The present invention relates to a polymerizable imide monomer represented by the general formula (I) in which R represents a hydrogen atom or a methyl group.

Further, the present invention provides the above general formula (n) characterized by reacting an imide alcohol represented by -Momonana (n) with acrylic acid or methacrybilic acid.
The present invention relates to a method for producing a polymerizable imide monomer represented by I).

This reaction is an esterification reaction, and is carried out by a conventional method. The molar ratio of imide alcohol represented by formula (II) to acrylic acid or methacrylic acid is 1=2 to 1:10, preferably 1:3 to 1:6, particularly preferably 1:4 to 1:
Prepare so that it becomes 5.

When using an organic solvent for the reaction, the starting material of the formula (
An organic solvent capable of dissolving any of the imide alcohol and acrylic acid or methacrylic acid of n) and the reaction product, the polymerizable imide monomer represented by the general formula (1), can be used as appropriate. , generally polar organic solvents are preferred. Examples of such polar organic solvents include sulfolane, N,N-dimethylacetamide, N,N-dimethylformamide, N-methyl-2-pyrrolidone, and N-dimethylacetamide.
, N-dimethylpropyleneurea, N,N-dimethylethyleneurea, and the like. From the viewpoint of solubility and reactivity, it is preferable to use sulfolane.

In addition, an organic solvent having a boiling point of 30-150"C that easily forms an azeotrope with water can be used in combination with such a polar organic solvent. Examples of such organic solvents include EVA, benzene, toluene, xylene, and ethylbenzene. , hexane,
Heptane, cyclohexane, octane, isopropyl ether, ethyl ether, butyl ether, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone,
Examples include organic solvents such as carbon tetrachloride and trichlorethylene.

The reaction temperature of the reaction between the imide alcohol represented by the above general formula (I[) and acrylic acid or methacrylic acid is 50
-200°C, preferably 100-180°C, particularly preferably 120-150°C. The time required for the reaction is 3 to 20 hours, preferably 4 to 10 hours,
Particularly preferably, the time is 5 to 6 hours.

The reaction between the imide alcohol represented by the above general formula (n) and acrylic acid or methacrylic acid can be promoted by using a catalyst.

Examples of catalysts include known ester catalysts such as sulfuric acid, J)-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, zinc chloride, phosphoric acid, antimony oxide, titanate ester, and methoxyphenol. Can be mentioned. The amount of catalyst used is 0.0 relative to the imide alcohol represented by -Momona (Il).
The amount is 1 to 30% by weight or 0.05 to 20% by weight, particularly preferably 0.1 to 10% by weight.

After the reaction is completed, a non-solvent for the reaction product, such as tetrahydrofuran, acetone, methyl alcohol, ethyl alcohol, isopropyl alcohol, butyl alcohol, etc. is mixed into the reaction solution, and the resulting precipitate is separated by =P,
By washing the reaction product, the above-mentioned hole (I
) can be obtained as a powdery substance.

The imide alcohol represented by the above formula (n) used as a starting material in the present invention is prepared by adding monoethanol to benzophenone tetracarboxylic anhydride (HtN-CH, -C
H2-0H) in an organic solvent. The molar ratio of hensifhenonetetracarboxylic anhydride and ethanolamine is 1:2 to 1:1O
1 preferably 1:2 to 1:5, particularly preferably 1
:2 to 1:3.

Further, as the organic solvent used in the production of this imide alcohol, a polar organic solvent that can dissolve both benzophenone tetracarboxylic anhydride and monoethanolamine is used. Such polar organic solvents include:
For example, sulfolane, N,N-dimethylacetamide,
N,N-dimethylformamide, N-methyl-2-pyrrolidone, N,N-dimethylpropylene urea and N,N-
Examples include dimethylethylene urea. From the viewpoint of solubility and reactivity, it is preferable to use sulfolane. Also,
An organic solvent having a boiling point of 30 to 150°C that easily forms an azeotrope with water can also be used in combination with such a polar organic solvent. Examples of such organic solvents include benzene, toluene, xylene, ethylbenzene, hexane, heptane, cyclohexane, octane, isopropyl ether, ethyl ether, butyl ether, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, carbon tetrachloride, and trichloroethylene. Organic solvents such as

The above reaction between benzophenone tetracarboxylic anhydride and monoethanolamine is carried out at a temperature of 50 to 200°C, preferably 100 to 180°C, particularly preferably 140 to 160°C.
Perform at a temperature of °C. The time required for the reaction is 2 to 20 hours.
Preferably 4 to 10 hours, particularly preferably 5 to 7 hours.
It's time.

The above reaction between benzophenone tetracarboxylic anhydride and monoethanolamine can be promoted using a catalyst. As the catalyst, for example, known catalysts such as sulfuric acid, p-)luenesulfonic acid, zinc chloride, phosphoric acid, antimony oxide, titanate ester, and methoxyphenol can be used. The amount of the catalyst used is 0.01 to 30% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 10% by weight, based on the benzophenone tetracarboxylic anhydride.

The imide compound represented by the general formula (r) obtained as described above can be polymerized in the presence of a photoinitiator, and can be used as a photocurable composition together with a photosensitive polymer.

Moreover, the present invention (A) Polymerizable imide monomer represented by general formula (I) (B) Photosensitive polymer and (C) photoinitiator The present invention relates to a photocurable composition comprising:

Examples of the photosensitive polymer (B) include known photosensitive polyamic acids, photosensitive polyimides, and photosensitive polyamideimides that have high heat resistance.

(C) Photoinitiators include, for example, benzophenone, diethylaminobenzophenone, diethylthioxanthone, benzoin methyl ether, 2-1-butylanthraquinone, anthraquinone, Michler's ketone, phenanthrenequinone, camphorquinone, benzoin, 2-methylhendiin, Known photoinitiators include methylanthraquinone, acetophenone, diacetyl, benzyl, anthracene and the like.

The above (A) and (B) components are preferably used in a range of (A)/(B) (weight ratio) of 20/80 to 50,150. If it is less than 20/80, sensitivity and heat resistance tend to decrease, and if it exceeds 50,150, developer resistance tends to decrease and it becomes difficult to obtain a desired pattern.

The amount of component (C) to be used is preferably 0.01 to 30 parts by weight, and preferably 0.05 to 10 parts by weight per 100 parts by weight of components (A) and (B). More preferably, it is used in an amount of 0.1 to 2.7 parts by weight. If this amount is too small, sensitivity tends to decrease, and if this amount is too large, stability tends to decrease.

The photocurable composition of the present invention can be used by dissolving it in an appropriate amount of an organic solvent.
) that can dissolve the polymerizable imide monomer represented by () and the photoinitiator used, and that does not impede workability such as coating, is appropriately used. Specific examples include those exemplified as organic solvents. When an organic solvent is used, the amount used is usually 50 to 500 parts by weight per 100 parts by weight of components (A) and (B).

In preparing the photocurable composition of the present invention,
There are no particular restrictions on the order and method of mixing the imide monomer represented by I), the photosensitive polymer, and the photoinitiator, and the mixing may be carried out in the same manner as conventionally known methods.

The photocurable m-parabolite of the present invention can be applied to copper-clad laminates, silicone wafers, etc. by dipping, spraying, screen, spinner coating, bar coater coating, etc. after dissolving it in an appropriate amount of organic solvent. It is applied to a base material, and after drying, it becomes a coating film.

By irradiating this coating film with actinic light from above a mask with a desired pattern, polymerization occurs in the irradiated areas, and the solubility of the irradiated areas in a developer is greatly reduced compared to the non-irradiated areas.

As the actinic light, ultraviolet rays are usually used, but in some cases, the same effect can be given to the coating film by irradiating the coating with ionizing radiation such as electron beams or radiation.

If an appropriate developer is applied to the coating film treated as described above, the non-irradiated areas that maintain high solubility will be developed and removed, and the solubility will be reduced by irradiation with actinic light. The irradiated area remains, and a desired resin pattern can be obtained.

The developer is preferably one that can completely dissolve and remove the non-irradiated area within an appropriate time.

The photocurable composition of the present invention not only has excellent adhesiveness to a substrate, but also forms a cured heat-resistant photosensitive resin having high heat resistance by heat treatment after photocuring.

〔Example〕

Next, the present invention will be explained in more detail by examples.
The present invention is not limited to these Examples.

Reference Example 1 Synthesis of photosensitive polyamic acid PI-A 50 equipped with a stirring device, a cooler, a thermometer and a dropping funnel
Diaminodiphenyl ether 4 in a 0d four-loaf flask
0.05g (0.2 mol), dimethylacetamide/acetone 126g/126g (1/l), completely dissolved, and after cooling to 5℃, Ebicuron B-440
0 (manufactured by Dainippon Ink Co., Ltd., 5-(2,5-dioxotetrahydrofuryl)3-methyl-3-cyclohexene-1,
2-dicarboxylic anhydride) 52.85 g (0.2 mol)
was added and reacted for 8 hours while keeping the temperature below 40°C to obtain polyamic acid.

Furthermore, n-butyl dilaurate is added as a catalyst,
Isocyanate ethyl methacrylate 15 while stirring
．． 52 g (0.1 mol) was gradually added dropwise from the dropping funnel. After the completion of the dropwise addition, the reaction was allowed to proceed for about 6 hours to obtain a solution of photosensitive polyagodic acid PI-A.

Reference Example 2 Synthesis of photosensitive polyamic acid PI-B 50 equipped with a stirrer, a cooler, a thermometer and a dropping funnel
Diaminodiphenyl ether 4 in a 0d four-loaf flask
0.05g (0.2 mol) and 295g of N-methyl-2-pyrrolidone were charged, completely dissolved, and cooled to 5°C.
11g (0.14 mol), 5XDA (1,3-bis(3,4-dicarboxyphenyl)-1,L3,3tetramethyldisiloxane dianhydride manufactured by Organic Synthetic Pharmaceutical Industry ■)
Add 25.59g (0.06 mol) and lower the temperature to 40°C.
The reaction was carried out for 8 hours while maintaining the following conditions to obtain boriagodic acid.

Furthermore, n-butyl dilaurate is added as a catalyst,
While stirring, add isocyanate (ethyl methacrylate) 15
．． 52 g (0.1 mol) was gradually added dropwise from the dropping port. After completion of the dropwise addition, the reaction was carried out for about 6 hours to obtain a solution of photosensitive polyamic acid PI-B.

Example 1 30 with stirrer, cooler, thermometer and dropping funnel
40 g (0,124 mol) of benzophenone tetracarboxylic dianhydride and sulfolane/toluene (30 g/20 g) were placed in a four-bottle flask with a capacity of 0+Id.
15.2 g of monoethanolamine (15.2 g (0,
248 mol) was added dropwise over about 30 minutes. Furthermore, 150
The reaction was carried out at a temperature of .degree. C. for 6 hours, and the benzophenonetetracarboxylic dianhydride was completely reacted. Then, 35.75 g (0,496 mol) of acrylic acid was added to the reaction solution.
, p-1 luenesulfonic acid 5.07 g (10% by weight),
After charging 0.05 g (0.1% by weight) of methoxyphenol and 50 g of toluene and attaching a water separator, an esterification reaction was carried out under reflux. The reaction took 5 hours at 130°C.

After the reaction, the precipitated crystals were collected, washed with tetrahydrofuran, and vacuum dried to obtain yellow crystals. The infrared absorption spectrum of this crystal (measured by the KBr method using a Hitachi Model 260-30 infrared spectrophotometer manufactured by Hitachi, Ltd.) is shown in Figure 1, and its I3C-NMR and 'H-N
The results of analysis by MR (both Hitachi R250 Nuclear Magnetic Resonance Spectrometer manufactured by Hitachi, Ltd.) were
It is shown in Fig. 3 and Fig. 3. In Figure 2, 9.62 p
Absorption based on 0=C-H of pm and 8.25-9.0
Absorption based on ppm benzene rings, 6.15-6.2
Absorption based on ppm C=C and 1.85-3.05p
Absorption based on CH of pm was observed. In addition, in Fig. 3, absorption of 8.1 to 8.2 ppm and absorption of 5.8 to 6 ppm are shown.
．． The integrated intensity ratio of absorption at 4 ppm and absorption at 4.0 to 4.5 ppm is 6:6:8 (=3:3:4), respectively.
), which corresponded to the theoretical value, and it was confirmed that a polymerizable imide monomer represented by the desired general formula (r) (R is a hydrogen atom) was obtained.

Comparative Example 1 30 equipped with a stirrer, cooler, thermometer and dropping funnel
40 g (0,124 mol) of benzophenone tetracarboxylic dianhydride and sulfolane/toluene (30 g/20 g) were placed in a four-bottle flask with a capacity of 0 d, and heated at 150°C.
25.58 g (0,24
8 mol) was added dropwise over about 40 minutes. Furthermore, 150°C
The reaction was carried out at a temperature of 6 hours, and the benzophenonetetracarboxylic dianhydride was completely reacted. Then, 35.75 g (0,496 mol) of acrylic acid was added to the reaction solution,
After charging 4.83 g (10% by weight) of P-toluenesulfonic acid, 0.05 g (0.1% by weight) of methoxyphenol, and 50 g of toluene and attaching a water separation device, an esterification reaction was carried out under reflux. , could not obtain crystals.

Comparative Example 2 30 equipped with a stirrer, cooler, thermometer and dropping funnel
B-4400 (5-(2,5-dioxotetrahydrofuryl) manufactured by Dainippon Ink Co., Ltd.) was placed in a four-bottle flask with a capacity of 0 d.
-3-Methyl-3-cyclohexene-1,2-dicarboxylic anhydride) 40g (0,151 mol) and methyl isobutyl ketone/toluene (30g/20g) were charged, heated to a temperature of 150°C, and left as it was. Add neopentanolamine 31.16 from the dropping funnel while stirring vigorously.
g (0,302 mol) was added dropwise over about 50 minutes. Furthermore, a reaction was carried out at a temperature of 150"C for 6 hours, and B-440
0 was completely reacted. Next, 43.53 g (0,604 mol) of acrylic acid, 5.0 g (10% by weight) of p-)luenesulfonic acid, 0.1 g (0.2% by weight) of methoxyphenol, and toluene were added to the reaction solution. After charging 50 g and attaching a water separator, the esterification reaction was carried out under reflux. The reaction was carried out at 130°C for about 5 hours. Reaction-
After a week, the resulting material had partially gelled.

Example 2 50 parts by weight of the monomer obtained in Example 1, 50 parts by weight of the photosensitive polyamic acid PI-A (solid content) obtained in Reference Example 1, 2.7 parts by weight of benzophenone as a photoinitiator, and 0.1 part by weight of diethylaminobenzophenone was dissolved in dimethylacetamide/acetone (1/1 weight ratio) and the solid content was adjusted to 30% by weight to obtain a photocurable composition.

The photocurable composition thus obtained was applied onto a copper-clad laminate and dried at 80°C for 10 minutes (thickness: 3
0 μm), irradiated with ultraviolet rays at 500+J/cd (negative film including a part where the amount of light transmission changes stepwise (first stage is optical density 0.05, and optical density 0.05 for each stage)
Irradiation was carried out through step tablets (SD) in increments of 15. Furthermore, by developing with 1% sodium carbonate aqueous solution at 23°C for 1 minute, the sensitivity S
A good pattern with 4.7 steps, resolution of 200 μm, and adhesion of 125 μm was obtained.

In addition, when the monomer was applied to a glass plate, heated at 80'C for 3 minutes, and then heat-treated at 250°C for 1 hour, 10
The % weight loss temperature was 380°C.

Example 3 20 parts by weight of the monomer obtained in Example 1, photosensitive boriadic acid PI-A (solid content) 8031i obtained in Reference Example 1
1 part by weight, 2.7 parts by weight of benzophenone as a photoinitiator and 0.1 part by weight of diethylaminobenzophenone are dissolved in dimethylacetamide/acetone (l/1 by weight),
The solid content was adjusted to 30% by weight to obtain a photocurable composition.

The photocurable composition thus obtained was applied onto a copper-clad laminate and dried at 80°C for 10 minutes (thickness: 3
0 μm) and irradiated with ultraviolet light at 500 o+J/dl. Furthermore, using a 1% aqueous sodium carbonate solution at 23°C
By developing for 1 minute at
A good pattern with a resolution of 200 μm and an adhesion of 150 μm could be obtained.

Example 4 50 parts by weight of the monomer obtained in Example 1, 850 parts by weight of the photosensitive polyamic acid PI-obtained in Reference Example 2, 2.7 parts by weight of benzophenone and 0.1 part by weight of diethylaminobenzophenone as photoinitiators. Part by weight was dissolved in N-methyl-2-pyrrolidone to obtain a photocurable composition.

The photocurable m-acid thus obtained was applied onto a copper-clad laminate, dried at 80°C for 15 minutes, and then irradiated with ultraviolet rays at 500 J/cil. Furthermore, by developing for 1 minute at 23°C using a 1% aqueous sodium carbonate solution, the sensitivity S T 4.5 steps and the resolution 200 am were obtained.
A good pattern with adhesion of 125 μm could be obtained.

Example 5 20 parts by weight of the monomer obtained in Example 1, 880 parts by weight of the photosensitive polyamic acid PI-obtained in Reference Example 2, 2.7 parts by weight of benzophenone and 0.1 part by weight of diethylaminobenzophenone as photoinitiators. Parts by weight were dissolved in N-methyl-2-pyrrolidone to obtain a photocurable composition.

The photocurable composition thus obtained was applied onto a copper-clad laminate, dried at 80''C for 15 minutes, and then irradiated with ultraviolet light at 500 sJ/d. By developing at 23° C. for 1 minute using the above-mentioned film, a good pattern with a sensitivity S T of 4.5 steps, a resolution of 200 μm, and an adhesion of 150 μm could be obtained.

〔Effect of the invention〕

The photocurable composition containing the novel polymerizable imide monomer of the present invention produces a photosensitive resin cured product that has excellent adhesion to a substrate and has excellent photocurability and heat resistance after curing. .

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of the crystal obtained in Example 1, FIG. 2 shows the 13(,-NMR spectrum) of the crystal, and FIG. 3 shows the 'H-NMR spectrum of the crystal.

Claims (1)

[Claims] 1. A polymerizable imide monomer represented by the general formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼(I) [In the formula, R represents a hydrogen atom or a methyl group]. 2. Formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) The general formula (I) according to claim 1, characterized in that the imide alcohol represented by (II) is reacted with acrylic acid or methacrylic acid. A method for producing the polymerizable imide monomer shown. 3. A photocurable composition comprising (A) a polymerizable imide monomer represented by the general formula (I) according to claim 1, (B) a photosensitive polymer, and (C) a photoinitiator.