JPH03233457A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a higher sensitivity, the stable viscosity at the time of preservation and the better heat resistance of films by using a specific polyamide acid compd., acrylic acid, methacrylic acid or acrylate having 1 or 2 acrylic groups or methacrylic groups in one molecule, and a sensitizer as essential components. CONSTITUTION:The polyamide acid compd. expressed by formula I, the acrylate having 1 or 2 acrylic groups or methacrylic groups and expressed by formula II and the sensitizer having 330 to 555nm absorption max. wavelength (lambda max) are used as the essential components. In the formula I, R1, R2 denote the same or different arom. cylic group; R3 denotes -C2H4N (CH3)2 or -C2H4N(C2H5)2; m denotes >=6 and <=200 integer. In the formula II, x denotes -H or -CH3 group; Y denotes a phenyl group; Z denotes -C2H4-, -C3H6-; O, P denote 1 or 2. The higher sensitivity, the stable viscosity at the time of preservation and the better heat resistance of the films are obtd. in this way.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention provides a photosensitive resin i! which has excellent optical properties such as sensitivity to visible light or ultraviolet light, and development properties, as well as excellent heat resistance. It is something that is thrown into the Ji precepts.

(Prior art) Conventionally, surface protection films of semiconductor elements, glabellar insulating films, etc.
Polyimide is used because it has excellent heat resistance, as well as excellent electrical insulation and mechanical strength, but recently technology has been developed to impart photosensitivity to polyimide itself in order to simplify the complicated process of creating polyimide patterns. It is attracting attention.

For example, a polyimide precursor with a photosensitive group added with an ester group as shown in the following formula (Japanese Unexamined Patent Publication No. 55-30207), or a polyamic acid with carbon that can be dimerized or polymerized by actinic radiation. - Compositions containing a compound containing a carbon double bond and an amino group or a quaternized salt thereof (for example, JP-A No. 145794/1984) are known.

All of these are dissolved in an appropriate organic solvent, applied as a varnish, dried, exposed to ultraviolet light through a photomask, developed and rinsed to obtain the desired pattern, and further heat-treated to form a polyimide. It is a coating.

Using polyimide with photosensitization not only simplifies the pattern creation process, but also eliminates the need to use highly toxic etching solutions, making it safer and less polluting. It is expected that this technology will become an important technology in the future.

However, when such conventional photosensitization technology is applied, the polyamide ξ-do precursor parabolite to which a photosensitive group is added with an ester group,
Since the photosensitive groups are difficult to scatter during heat curing, only films with low heat resistance after curing can be obtained, making it difficult to use in the semiconductor industry.

In addition, compounds containing carbon-carbon double bonds and amino groups that can be dimerized or polymerized by actinic radiation, or quaternized salts thereof are added to polyamic acids, and the sensitivity is extremely low even when irradiated with infrared rays. The viscosity of the varnish was low and the viscosity of the varnish changed greatly during storage, making it insufficient for use in manufacturing processes commonly used in the semiconductor industry.

(Problems to be Solved by the Invention) The object of the present invention is to have high sensitivity photocurability by blending an acrylate compound having a carboxyl group and a photosensitizer in a polyamic acid compound. Another object of the present invention is to provide a photosensitive resin composition in which the viscosity of the compound does not change during storage, and the film after curing has excellent heat resistance, heat cycle resistance, heat shock resistance, moisture resistance, etc.

<Means for solving tJ, H) The present inventors have conducted extensive studies to solve these problems that could not be overcome with conventional techniques. (A) As a result of the following formula (1) (1) (wherein R+, Rt is the same or different aromatic cyclic group,
R8 is -CJ4N(CH+)z or -CJaN(CJs
) 2, m is an integer of 6 or more and 200 or less) An acrylate of the following formula (ff) having one or two acrylic or methacrylic groups (■) (wherein X is - H or -CH co group, Y is phenyl group, Z is -CJ4-, -Csll1.O, P is 1 or 2)
(C) Maximum absorption wavelength (λwax) is 330 to 555n
The present invention was completed based on the finding that it is possible to obtain a highly reliable photosensitive resin composition by using the sensitizer No. 11 as an essential component.

(Function) The boria straw acid compound (A) in the present invention is a polyamide acid compound (A) that preferably becomes an aromatic polyimide after thermosetting in order to improve the heat resistance of the boria straw acid coating. is T-butyrolactone, N-methyl-2
- The bottom is formed by condensation of a diester of a tetracarboxylic acid obtained by reacting an aromatic tetracarboxylic anhydride with an amino alcohol in a polar solvent such as pyrrolidone or N,N-dimethylacetamide, and a diamine. In order to improve sensitivity, it is preferable that the polyamic acid compound (A) has a high molecular weight, so the reaction temperature is -20°
The temperature is preferably from C to 50°C, more preferably from -10°C to 30°C, and the molarization of the dicarboxylic acids and diamisos is preferably from 0.8 to 1.1.

The aromatic cyclic groups R1 and R2 in the following formula (1) are, for example, a benzene ring, (I) (in the formula, R+ and Rz are the same or different aromatic cyclic groups, and R3 is -CJaN(CI+)z or - CJ4N (
C2H4) where z is an integer of 6 or more and 200 or more) naphthalene ring, etc. Moreover, it is preferable that m is 6 or less and 200 or less. If it is less than 6, the sensitivity will decrease and 20
Those exceeding 0 are difficult to synthesize industrially. The above formula (1
Examples of the aromatic tetracarboxylic dianhydride used to synthesize the polyamic acid compound (2) include the following acid anhydrides. Pyromellitic dianhydride, 3,3°, 4.4
'-benzophenonetetracarboxylic dianhydride, 2.3
, 6.7-naphthalenetetracarboxylic dianhydride, 3.
3', 4.4°-diphenyltetracarboxylic dianhydride, 2.2', 3,3. '-Diphenyltetracarboxylic dianhydride, 1,2,5,6. -Naphthalenetetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxydiphenyl)ether dianhydride, naphthalene-1,2,4,5tetracarboxylic dianhydride, naphthalene-1,4,58 , -tetracarboxylic dianhydride, 4.
8-dimethyl-1°2.3,5.6,7. -hexahydronaphthalene-1,2,5,6 tetracarboxylic dianhydride, 2.6. -dichloronaphthalene, 1.4,5.8-
Tetracarboxylic dianhydride, 2,7-cyclonaphthalene-1,4,5,8-tetracarboxylic dianhydride, phenanthrene-1,2,9,10-7-tracarboxylic dianhydride, pyrrolidine -2,3,4,5,-tetracarboxylic dianhydride, pyrazine-2,3,5,6,-tetracarboxylic dianhydride, 2,2-bis(2,5-dicarboxyphenyl)propani Anhydrous, 1. l-bis(2゜3
-dicarboxyphenyl)ethane dianhydride, l,1-bis(3,4-dicarboxyphenyl)ethane dianhydride,
Bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)sulfone dianhydride, benzene-1,2,3,4-butanetetracarboxylic dianhydride, thiophene-2, 3,4,5-tetracarboxylic dianhydride and the like.

In addition to the aromatic tetracarboxylic dianhydride mentioned above, silicone tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride can of course be used in combination to impart various properties.

In addition, examples of amino alcohols used in the synthesis of polyamic acid compounds include, but are not limited to, 2-dimethylaminoethanol, 2-diethylaminoethanol, 3-dimethylamitubrobanol, and 3-diethylaminopropanol.

Further, the aromatic diamine component used in the synthesis of the polyamic acid compound may be one type or a mixture of two or more types, but the aromatic diamines used include phenylene diamine, p-phenyl diamine, 4.4' -diaminodiphenylpropane, 4,4'-diaminodiphenylmethane, benzidine, 4.4°diaminodiphenyl sulfide, 4,4°-diaminophenyl sulfone, 3.3'
- Diaminodiphenyl specifications sulfone, 4,4'-diaminodiphenyl ether, 3
．． 3°-diaminodiphenyl ether, 4,4'-diamino-p-terphenyl, 2,6-diamitupyridine,
Bis(4-aminophenyl)phosphine oxyto, bis(4-aminophenyl)-N-methylamine, 1゜5-
Diaminonaphthalene, 3.3"-dimethyl-4,4°-
Diaminobiphenyl, 3.3'-dimethoxybenzidine, 2.4-bis(β-amino-(-butyl)-toluene, bis(p-β-amino-L-butylphenyl)ether, p-bis(2-methyl) -4-aminopentyl)benzene, p-bis(l,1-dimethyl-5-aminopentyl)benzene, 2,4-diaminotoluene, toxylylenediamine, p-xylylenediamine, and the like.

As the diamine component used in the present invention, in addition to the above-mentioned aromatic diamines, silicone diamines and aliphatic diamines can also be used in combination to impart various properties.

The polyamic acid compound thus obtained does not have a carboxyl group unlike polyamic acid, so there is no intermolecular interaction and the varnish has excellent viscosity stability during storage.

The acrylate (B) in the present invention has the following formula % formula % () (wherein X is -H or -CL group, Y is phenyl group, Z is -
C, l+, -, ~Cs1la-, ○, P indicates 1 or 2) It is an acrylate compound having one or two acrylic or methacrylic groups and a carboxylic acid group in one molecule. The acrylates include acrylic acid, methacrylic acid, ethyl phthalate-2-acrylate, ethyl phthalate-2-methacrylate, propyl phthalate-2-acrylate, propyl phthalate-2-methacrylate, trimerin-1-ethyl-2-acrylate, Ethyl trimellitate-2-methacrylate Diethyl pyromellitate-2
- diacrylate, diethyl pyromellitate-2-dimethacrylate, etc., but are not limited to these.

The sensitizer (C) in the present invention is a compound having a maximum absorption wavelength (λmax) of 330 to 500 nm.

If l wax is less than 33Or+m, light will be absorbed by the polyamic acid compound and no photoreaction will occur, which is undesirable.If it exceeds 500nm, photoreaction will occur with visible light, making the work place an abandoned room. Examples of the sensitizer of the present invention, which are not preferable because the handling thereof is deteriorated, include, but are not limited to, sensitizers of the present invention.

The method of using the Mi Kaiboku of the present invention will be described below.

The composition of the present invention, the composition of all the IJl precepts?
The solution is dissolved in a medium that can be dissolved in water and applied onto a predetermined substrate.

The solvent is preferably a polar solvent, such as N-methyl-pyrrolidone, dimethiacetamide, γ-butyrolactone, or dimethylformamide.

Further, in order to enhance adhesion to a substrate such as a silicon wafer, a silane coupling agent such as triethoxyvinylsilane, tri(methoxyethquin)vinylsilane, T-glycidquinpropyltrimethoxysilane is added.

As a method for coating the substrate, the solution obtained as described above is coated on the substrate using a spin coater, a bar coater, a screen printing method, or the like. Substrates include metal, glass,
These include silicone and glass epoxy.

Next, the coating film obtained in this way is air-dried, heat-dried,
After drying by vacuum drying etc., exposure is performed.At this time, the active light used is, for example, visible light, ultraviolet light, X-rays, etc.
Rays, electron beams, etc. may be mentioned, with visible light and ultraviolet light being preferred.

After exposure in this way, development is performed using a dipping method or a spray method to remove the unirradiated areas. Examples of developing solutions used for this removal include N-methylpyrrolidone, N,
Aprotic polar solvents such as N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide may be used alone, or they may be supplemented with alcohols such as ethanol, isopropanol, hexane, etc. as a secondary component. , aliphatic hydrocarbons such as cyclohexane, and aromatic hydrocarbon compounds such as toluene and xylene may be mixed and used.Furthermore, immediately after development, rinsing with a solvent such as that shown as the second component may be used. is preferred.

The thus obtained image containing polyamide as a main component is used for applications such as a resist, an insulating film, and a protective film after being cured.

At this time, treatments such as removing unnecessary components by heating and converting the chemical structure of the polyamide are performed as necessary.

Example Next, the present invention will be explained in more detail using examples.

Example 1 Pyromellitic anhydride 21.8g (0,1+of)
, 2-dimethylaminoethanol 36.8 g (0
, 207ao-poor) p-toluenesulfonic acid hydrate 19
．． 41.2 g (0,2 + wof) of N
-Methyl-2-pyrrolidone solution was slowly added dropwise and allowed to react for 75 minutes.

Next, 4,4°-diaminodiphenyl ether18. (
After 4 hours of reaction, the precipitate was filtered, and the filtrate was added to ethanol (52) to obtain a yellow-white polyimide oxide compound. 100 parts by weight of this polyimide acid compound was dissolved in 400 parts by weight of N-methyl-2-pyrrolidone, 80 parts by weight of methyl methacrylate and 5 parts by weight of photosensitizer Michler's ketone were stirred at room temperature for 3 hours, and dissolved.
Mixed.

The obtained solution was applied onto an aluminum plate using a spinner and dried using a drier for 80'CI hours to obtain a film.

This film is coated with a Kodak Photographic Step Tablet N112, 21 Step (with the blur scale mentioned above, each step increase in the number of steps increases the amount of transmitted light by 1/2 of that of the previous step).
f2, so the larger the number of remaining stages of the film after development, the higher the sensitivity. ) were stacked and irradiated with 500 mJ/cj of ultraviolet rays, then developed using a developer containing 60 parts by weight of N-methylpyrrolidone and 40 parts by weight of methanol, and further rinsed with isopropyl alcohol to produce a result of 200 mJ/cj.
- It was found that the sensitivity was high.

Next, exposure and development were performed in the same manner as in the buttering experiment described above using a resolution measurement mask manufactured by Toppan Printing (Toppan Test Chart NcLl), and no cranking occurred and almost no decrease in film thickness was observed. .

The pattern also had a resolution of 10 μm.

Furthermore, when the polyimide film was measured for thermal decomposition, there was no change in viscosity for 30 days under storage conditions of +5°C.

The photosensitive resin thus obtained had the following effects: high sensitivity, high heat resistance, and excellent varnish storage stability.

The evaluation results are shown in Table 1.

32.2 g of anhydride (0.1 mof), 20.6 g of 2-diethylaminoethanol (0.2 moI!,
) p-7z elm 7 diamine 10.8g (0.1ff
1al) in the same manner as in Example 1 to obtain a polyamic acid compound.

100 parts by weight of this polyamic acid compound was dissolved in 300 parts by weight of T-phthyrolactone, and further 90 parts by weight of diethyl-2-diacrylate pyromellitate and 5 parts by weight of the photosensitizer Michler's ketone were dissolved and mixed. The resulting photosensitive resin & hardware was evaluated in the same manner as in Example 1. The results are shown in Table 1.

The resulting photosensitive resin IJl had high sensitivity and excellent heat resistance.

Example 3 2.3*3'+4'-diphenyltetracarboxylic dianhydride 18.4g (0.1moj!)
, 35.8 g of 2-dimethylaminoethanol (0,20
1mof), p-7z elm 7 diamine 8.6g (0
,08mo j! ) was carried out in the same manner as in Example 1 to obtain a polyamic acid compound.

100 parts by weight of this polyamic acid compound was dissolved in 200 parts by weight of N,N-dimethylacetamide, and further 70 parts by weight of ethyl trimellitate-2-acrylate and parts by weight of the photosensitizer Bay Hiller Ketone IO were dissolved for evaluation by a mixed method. I did it. The results are shown in Table 1.

The resulting photosensitive resin composition has high sensitivity, heat resistance, and varnish storage stability.

Comparative Example 1 290 g of 3.3;4.4'-benzophenone tetracarboxylic dianhydride (0.9 oi!), 200 g of 4,4°-diaminodiphenyl ether (0.1 mon) in N-methylpyrrolidone. The reaction was carried out to obtain a polyamic acid solution.

To 100 parts by weight of the obtained polyamic acid solution (solid content of polyamic acid), 80 parts by weight of N,N-dimethylaminoethyl methacrylate and 5 parts by weight of Michler's ketone were stirred at room temperature for 3 hours to dissolve and react, resulting in a photosensitive resin. &[l
I got a parabola.

The obtained photosensitive resin & 11 precepts has carboxyl groups in the molecule, so there is strong intermolecular interaction, and when it is affected by moisture etc. during storage, the viscosity changes greatly, making it impractical. I found it to be low.

Comparative Example 2 Pyromellitic anhydride 21.8 g, 2-hydroxyethyl methacrylate 21.0 g, r-butyrolactone 1
00d, add 17.0g of pyridine while stirring under water cooling.
added. After stirring at room temperature for 8 hours, 41.2 g of dicyclohexylcarbodiimide and 40 g of γ-butyrolactone were added.
A solution of Jd was added over 10 minutes under water cooling, followed by 4.4'
16.0 g of -diaminodiphenyl ether was added over 15 minutes, and the mixture was stirred for 3 hours under water cooling. After filtering the precipitate, the resulting solution was added to 101 ethanol to obtain a yellowish white powder. 100 parts by weight of this powder, 40 g of ethylene glycol di-acrylate, 0 Michler's ketone
．． 4g of benzophenone, 2.0g of benzophenone, and 4.0g of benzyldimethylkecoel were dissolved in 200g of N-methylpyrrolidone to obtain a photosensitive resin composition.

An elm pattern was formed using the obtained photosensitive resin &IIt2 product in the same manner as in Example 1. The thermal decomposition initiation temperature of this polyimide film was 330°C.

Since the photosensitive resin &II thus obtained has a polyimide compound and a photosensitive group bonded to each other through a covalent bond, the photosensitive group is difficult to scatter and has poor heat resistance.

The evaluation results are shown in Table 1.

(Effect of the invention) Photosensitive polyamic acid, which is made by blending an acrylic compound with an amino group, has strong intermolecular interactions, so it is easily affected by moisture and the viscosity may change significantly during storage. Furthermore, even when irradiated with light for patterning, the sensitivity was low, making it unsuitable for the semiconductor industry.

However, in the present invention, since the polyimide acid compound (A) does not contain a carboxy group, there is no intermolecular interaction, and the viscosity during storage is stable. In addition, mono- to di-functional acrylate (B
) and maximum absorption wavelength (λ-ax) of 330 to 500 rrm
Since the sensitizer (C) is blended, as a result, crosslinking occurs with an extremely small amount of light irradiation, resulting in high sensitivity.

Furthermore, the heat resistance of the polyimide film after thermosetting is determined by the heat resistance during curing, since the acrylate (B) is simply blended into the polyimide compound (A), and the acrylate is not introduced into the polyimide skeleton through covalent bonds. easily disperses,
The heat resistance inherent to aromatic polyimide is maintained, and the very excellent effect of exhibiting high heat resistance can be obtained at the same time.

Claims (1)

[Claims] (1) (A) The following formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R_1 and R_2 are the same or different aromatic cyclic groups, and R_3 is -C_2H_4N(CH_3)_2 or - C
_2H_4N(C_2H_5)_2, m is 6 or more 20
polyamide acid compound (B) represented by acrylic acid, methacrylic acid (representing an integer of 0 or less), or the following formula (I
Acrylate of I) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, X is -H or -CH_3 group, Y is phenyl group, Z
-C_2H_4-, -C_3H_6-, O and P indicate 1 or 2) (C) Maximum absorption wavelength (λmax) is 330
A photosensitive resin composition comprising as an essential component a sensitizer having a wavelength of 500 nm.