JPS61148233A - Photo-sensitive heat-resistant resin - Google Patents

Abstract

PURPOSE:To provide the titled resin having excellent alkali-resistance, long potlife, and enabling a fine processing, by reacting a specific polybenzimidazole polymer with a specific acid halide compound, and using the reaction product as a component. CONSTITUTION:The objective resin can be produced by reacting (A) a polybenzimidazole polymer of formula III (R<1> is bivalent organic group; R<2> is 4-valent organic group; n is integer) synthesized by the polycondensation of a tetraamino compound having 4 amino groups (e.g. the compound of formula I) with a dicarboxylic acid phenyl ester (e.g. the compound of formula II) with (B) an acid halide compound of formula IV or V (R<3> and R<4> are group having double bond dimerizable or polymerizable with light or ionizing radiation, a group containing -N2-, or N3 group; X1 and X2 are halogen).

Description

[Detailed description of the invention] (Industrial application field 1 The present invention relates to a novel photosensitive heat-resistant resin.

[Prior Art 1] In the semiconductor industry, the use of sentient materials as insulating layers and passivation layers of solid-state devices provides excellent properties such as low stress and smoothness, so they have been put to practical use in some semiconductor devices. Manufacturing solid-state devices involves a lot of heating work, such as the Guibonden process.
It is necessary to use a heat-resistant material, and therefore polyimide, which has excellent heat resistance, has been widely considered.

In recent years, photosensitive polyimide, which is a polyimide with resist) If function, has been put into practical use, making microfabrication possible and shortening the process.

[Problem to be solved by the invention 1 However, conventional photosensitive polyimide is
It must be processed at high temperatures of 0 to 400°C, and the film thickness is significantly reduced during this process.It is easily hydrolyzed by alkali, water, etc., so it cannot be applied to electroless plating baths.
It had many drawbacks, including poor stability of the photosensitive polyimide precursor solution and difficulty in patterning on steel because polyamic acid and copper tend to form composites.

Therefore, there has been a desire for a photosensitive heat-resistant material that does not require heat treatment after patterning, has excellent alkali resistance, has a long pot life, is easy to butter on steel, and can be microfabricated.

Means 1 for Solving Problem E and α The present invention was made to solve the above-mentioned conventional drawbacks, and has the general formula (I): (wherein, R1 is a divalent organic group, R2 is a tetravalent organic group, organic group, n
represents an integer), the general formula (■): Xl5O□-R3(II) or the general formula (■): X2CO-R' (I[I
) (In the formula, both R3 and R4 are 2 with light or radiation.
A group having a quantifiable or polymerizable double bond, -N2-
or N3 group, and Xl and N2 each represent one of F, C1, I, Br)
Regarding the photosensitive heat-resistant resin containing the one obtained by reacting the acid halogen compound shown in , it does not require high heat treatment after patterning, has excellent alkali resistance, has a long pot life, and is photosensitive that can be microfabricated. The purpose of this invention is to provide a heat-resistant resin with high properties.

[Example 1] The polybenziimiguzole polymer of the present invention has a structure represented by the general formula (1), and usually has four amino acids.
It is synthesized by condensation polymerization of a tetraamino compound having a group and a dicarboxylic acid phenyl ester. Specific examples of the tetraamino compound include the following, and at least one of these is used.

Further, there are examples of dicarboxylic acid phenyl esters, and at least one of these is used. ■ Using these tetraamino compounds and dicarboxylic acid phenyl esters.

Vogel, C.S. Marvel (J. Polym.
Polycondensation is carried out according to the method described in , Sci., 50, 511 (1964)) to form a polybenciimigsol polymer.

In addition, there is a method of polycondensing the hydrochloride of the tetraamino compound and a dicarboxylic acid using polyphosphoric acid as a dehydrating agent, and a method of polycondensing the tetraamino compound and a dicarboxylic acid halogen compound, both of which are well known. ing.

Next, R'' and R4 of the acid halogen compounds represented by general formulas (II) and (III) according to the present invention are as follows:
For example, (in the formula, 85 is hydrogen or a 7enyl group, R6 is hydrogen, an alkyl group or an ara7 group, R7 is an alkyl group or a substituted alkyl group, x5 is CL H3O, C17, nC1□ or (SO4)+ /2ZnSO< ), etc., are used.

The reaction between these acid halogen compounds and polybenziimigusol polymers is preferably carried out using a compound having an epoxy group such as propylene oxide or styrene oxide as a dehalogenating agent, or without a catalyst, and the amount of the dehydrochlorinating agent used is , preferably 1.0 to 5.0 equivalents to the acid halogen compound. Tertiary amines, which are common dehalogenating agents, are not preferred because they have a negative effect on pot life and dielectric constant.

The viscosity of the polybenzimigsol polymer solution used is 500 cps to 4000 cps, preferably 1
000 cps - 2000 cps, it is difficult to form a uniform film with a large percentage of this, but if the film is still too small, a sufficient film thickness cannot be obtained when using a spinner, which is disadvantageous.

Further, the amount of the acid halogen compound to be added is suitably 2.0 to 0.4 equivalents relative to -i- in the polybenciimigsol.

The solvent used as the reaction solution and the photosensitive heat-resistant resin material (hereinafter referred to as photosensitive material) is mainly a polar solvent due to the solubility of the polymer, such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone. , hexamethylphosphoramide, etc. are preferred, and are used in an amount of 2 to 10 times that of the polybenzimidazole polymer.

In the reaction, equivalent amounts of the tetraamide/compound and dicarboxylic acid are mixed, heated to 220°C in a nitrogen atmosphere, and once melted, the temperature is raised to 250-300°C and reacted for 30 minutes. Next, switch the reaction system to vacuum (0,1ivh), continue the reaction at the same temperature for 20-40 minutes, and then continue the reaction for 30-40 minutes.
Raise the temperature to 500'C, preferably 350-400"C,
The reaction is carried out for 1 to 10 hours, preferably 4 to 9 hours.

The resulting product has most of the impurities removed.
However, if it is reprecipitated with methanol, ethanol, water, etc., a highly pure product can be obtained.

In the infrared absorption spectrum of the obtained photosensitive polymer, absorption of the peptide bond in -N- was observed around 1675 cz-'.

One typical example of a photosensitive polymer obtained by the above method is as follows.

[Margin 1 below] The photosensitive material thus obtained is usually put to practical use in the form of a solution. In addition to the photosensitive polymer, this solution may also contain a photoinitiator, a sensitizer, a copolymer monomer, a photocrosslinking agent, a stabilizer for improving pot life, or an adhesion improver with the substrate. However, the types of these additives are highly dependent on the photosensitive groups grafted onto the photosensitive polymers of the present invention. ” - The additives include diazide,
Polyazides, tetrazonium salts, polynoazonium salts, falls, polyols, siloxanes, compounds with anthraquinone rings, compounds with naphthalene rings,
Byrylium salts, Thiapyrylium salts, Takahiro Tsunoda [New photosensitive resin] (Printing Society Publishing Department Tokyo 1981) 65-6
Photoinitiators, benzoquinones, as described in 8 PENO,
Thiols, chloranil, epoxies, etc. are used, and the amount used is 50% or less of the total solute amount.

The novel photosensitive material of the present invention is patterned using conventional 7-photoresist technology. The substrate can be ceramic, lath epoxy, BT resin, glass polyimide, epoxy, paper 7-ninol, metal, etc. Coating to the substrate can be done using a spinner, screen printing or bar coater, for example, with a coating of 1 to 30%.
The coating is applied so as to form a film with a thickness of 5 to 15 microns, preferably 5 to 15 microns. This coating film is heated at 50 to 80°C, preferably 60 to 75°C for 15 to 60 minutes, preferably 2
Dry for 0-40 minutes.

Next, a mask is placed on this coating film and actinic radiation is irradiated.

Actinic radiation varies greatly depending on the type and power of the radiation source, so it is difficult to specify the irradiation conditions, but as a type of actinic radiation, X#! , electron beams, ultraviolet rays, visible light, laser beams, etc., with ultraviolet rays being particularly desirable. Then, by developing with a developer, a relief 7 pattern is obtained. The developer is usually a mixture of a polar solvent that dissolves the photosensitive material, such as dimethyl sulfoxide, dimethylformamide, trimethylacetamide, N-, /thylpyrrolidone, or hexamethylene phosphoramide, and methanol, ethanol, water, or other poor solvent. Preferably used, the ratio of polar solvent to poor solvent is 9:1 to 3, preferably 7.5:2.
．． The ratio is 5 to 6:4 (weight ratio).

After development, by rinsing with a poor solvent such as isopropyl alcohol and evaporating the pattern by heating or blowing air, which is conventionally used, it is possible to create a pattern with excellent heat resistance and sharp edges.

As described above, by using the photosensitive material of the present invention, patterns having heat resistance, chemical resistance, insulation properties, and mechanical properties can be created.
It can be processed without the high-temperature baking process required for conventional polyimide-based photosensitive materials.

Next, the photosensitive heat-resistant resin of the present invention will be explained based on Examples.

Example I HoVogel, COS Marvel (J, Po
lym, Sci., 50° 511 (1964)) was dissolved in 86 g of dimethyl sulfoxide, and 2.6 g of propion oxide was added. Add and mix;
Once completely dissolved, add 5 toluene while cooling in an ice bath.
．． 0. 3.83 ml of cinnamic acid chloride dissolved in was added, and the mixture was reacted at 10 to 15° C. for 3 hours. To this solution, 0.2 g of benzo7ene and 1.2 fI of Michler's ketone were added, uniformly dissolved, and filtered to obtain a sample solution (1). This sample solution 1(1) was applied onto a ceramic plate using a spinner.

Next, when dried at 65℃ for 30 minutes, the thickness of the coating film was 2.
It was μ. On top of this, I put on a mask with a square-shaped test pattern written on it, and applied 500W from a distance of 23ci+.
After irradiating it with a high-pressure mercury lamp for 10 minutes, it was developed with a mixed solvent of trimethyl sulfoxide (7 parts) and methanol (3 parts) while applying ultrasonic waves, rinsed with an inproper tool, blown out with air, and dried. As a result, a negative pattern with good heat resistance, sharp alkali resistance, and dry etching resistance was obtained, and there was no film burr due to development or drying. In addition, sample solution (1) can be patterned on copper, and although it was stored in a cool, dark place at 4℃ and opened and returned to room temperature after each use, the viscosity decreased even though it was used once a day for a total of 8 times. No deterioration was observed.

Example 2 Polybenzimidazole 14 used in Example 1 was converted to 861? of dimethyl sulfoxide, and further propion oxide 2.61? Add dimethyl sulfoxide and mix, and when completely dissolved, add 5. dimethyl sulfoxide while cooling with an ice path. Add 2 g of 1,2-7toquinone-2-diazide-5 sulfonic acid chloride dissolved in O.
After reacting at ~15°C for 3 hours, remove the sample solution (2) by filtration. This sample solution (2) was applied onto a ceramic plate using a spinner.

Next, when it was dried at 65° C. for 30 minutes, the thickness of the coating film was about 2 μm. A mask with a positive test pattern written on it was placed on top of this, and a voltage of 23011 [500 W from a distance] was applied.
Irradiated with a high-pressure mercury lamp for 7 minutes, hexamethylphosphoramide (7 parts) and sodium hydroxide 5% methanol solution (3 parts)
Developed with ultrasonic waves in the mixed solvent of part), rinsed with isopropanol, blown with air, and dried, resulting in sharp alkali resistance with good heat resistance.
A positive pattern with dry etching resistance is obtained,
There was almost no film 9 due to development and drying. In addition, the sample solution [(2) was also capable of patterning on copper, and no deterioration such as a decrease in viscosity was observed even though it was stored in a cool, dark place at 4°C and used 8 times as in Example 1. .

Example 3 Polybenci imiguzol used in Examples 1 and 2 14. was dissolved in dimethyl sulfoxide of 869, and propion oxide 2,6. When completely dissolved, add 2 g of rose-azidocinnamic acid chloride dissolved in 5.0 g of dimethyl sulfoxide while cooling in an ice bath, react at 10 to 15°C for 3 hours, and then filter. A sample solution (3) was thus obtained. This solution was applied onto a ceramic plate using a spinner. Next 6
When dried at 5° C. for 30 minutes, the film thickness was 2 μm. A mask with a negative test pattern written on it was placed on top of the mask, and a 500W high-pressure mercury lamp was used to immediately remove the 2BCI.
irradiated for minutes, and developed while applying ultrasound with a mixed solvent of dimethyl sulfoxide (7 parts) and methanol (3 parts).
) Rinse with isoproper tool and blow air,
As a result of drying, the pattern was changed to a sharp one having good heat resistance, alkali resistance, and dry etching resistance, and there was almost no film burring due to development and drying. Sample solution (3) was also capable of patterning on copper, and no deterioration such as a decrease in viscosity was observed even though it was stored in a cool, dark place at 4°C and used 8 times as in Examples 1 and 2. - E Comparative Example 1] Based on Example 2 in Japanese Patent Publication No. 54-116217, a photosensitive polyimide solution was prepared to obtain a comparative sample solution (1). When this solution was patterned in the same manner as in Examples 1 and 3, a similar pattern of polyamic acid was completed. In order to imidize this
When heat-treated according to No. 17, a pattern of heat-resistant polyimide was obtained. However, the film thickness was reduced to 60% of the pre-treatment thickness by heat treatment, the aspect ratio was worse than in Examples 1 to 3, and patterning on copper was not possible. The pattern that has been raised in the process is hydrolyzed in an aqueous alkaline solution and deteriorates, so it is difficult to immerse the pattern in an electroless plating solution for a long period of time. Comparative sample solution (1) is easily hydrolyzed by moisture in the air, and even if it is stored in a cool, dark place at 4°C, the viscosity will only decrease after opening 3 to 4 times.

[Effect of the invention 1] According to the photosensitive heat-resistant resin of the present invention, a photosensitive group is grafted onto the -NH portion of the polyimiguzole-based polymer by utilizing a reaction with an acid halide compound. It eliminates the need for high-temperature treatment at temperatures as high as 0.9°C, improves pot life, and allows for a pattern change that has good heat resistance, sharp alkali resistance, and dry etching resistance. Further, the photosensitive material obtained by the present invention can be patterned on copper, and does not suffer from deterioration such as a decrease in viscosity due to storage in a cool and dark place.

Claims (3)

[Claims] (1) General formula (I): ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 is a divalent organic group, R^2 is a tetravalent organic group, and n is an integer. ), general formula (II): X^1SO_2-R^3(II) or general formula (III): X^2CO-R^4(III) (in the formula, R Both ^3 and R^4 are 2 with light or radiation.
Group having a quantifiable or polymerizable double bond, -N_2
Indicates either a group containing - or a N_3 group, X^1,
A photosensitive heat-resistant resin containing a compound obtained by reacting an acid halogen compound represented by X^2 (all of which represent one of F, Cl, I, and Br). (2) The divalent organic group represented by R^1 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼
, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, ▲ Mathematical formulas, chemical formulas,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, -(CH_2)_
4- The photosensitive heat-resistant resin according to claim (1), which is one of the following: ▲There are mathematical formulas, chemical formulas, tables, etc.▼. (3) The tetravalent organic group represented by R^2 has ▲mathematical formula, chemical formula, table, etc.▼, ▲mathematical formula, chemical formula,
There are tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X^4 represents one of CH_2, O, S, SO_2, CO, and NHCO.) A photosensitive heat-resistant resin according to claim (1).