JP2823104B2 - Photosensitive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention generally comprises a photosensitive aromatic polyamide, a photopolymerization initiator, a dicarboxylic acid compound (A), and an alkoxysilane compound containing an epoxy group or an amino group (B), the molar ratio of (a) and (B) (a / B) is 2: 9-5: 2 der Rigen
Are those related to Ru better der photosensitive composition adhesion during the image.

The photosensitive composition of the present invention is obtained by forming a coating film (film) of the composition on a substrate, irradiating the coating film with light, and photo-curing in a pattern. By performing a developing operation of removing an unexposed portion (uncured portion) of the coating film, an insulating protective film (overcoat film) of an electronic member is formed, a transparent protective film, an etching resist,
A member having a fine photo-curing pattern such as a spacer can be manufactured.

[0003]

2. Description of the Prior Art Conventionally, a photosensitive composition generally comprises a photosensitive resin and a photopolymerization initiator, and if necessary, a silane coupling agent or the like is added to enhance the adhesion to a substrate. Was. These silane coupling agents have an alkoxysilane group and an organic reactive group, and impart adhesion by bonding the alkoxysilane group to the base material and the organic reactive group to an organic compound such as a photosensitive resin. ing. However, a photosensitive resin having poor reactivity with the organic reactive group,
For example, photosensitive polyimide, photosensitive polyamide, and the like did not provide sufficient adhesion. In particular, the adhesion at the time of development is not sufficient. Therefore, unless the photocuring is sufficiently performed to the bottom of the coating film, the development cannot be efficiently performed, and as a result, the sensitivity is low.

[0004]

[Problems to be Solved by the Invention] The present invention has excellent adhesion between a coating film and a substrate, and particularly has high adhesion during development.
The purpose is to provide a photosensitive composition that increases the apparent sensitivity and improves the operability of development because a stable photocurable pattern can be obtained even when the degree of photocuring at the bottom of the coating film is low. is there.

[0005]

SUMMARY OF THE INVENTION The present invention provides a photosensitive aromatic polyamide having a carbon-carbon unsaturated bond, a photopolymerization initiator, a dicarboxylic acid compound (A), and an epoxy or amino group. Consisting of an alkoxysilane compound (B), the molar ratio of (A) to (B) (A / B)
There 2: 9-5: 2 der Ri adhesion between the coating film and the substrate during development
About the photosensitive composition characterized by good der Rukoto.

The photosensitive composition of the present invention includes, for example, a photosensitive aromatic resin having a carbon-carbon double bond (photosensitive group).
"Photopolymerization initiators" such as amides , bisazide compounds , benzyls, benzoin ethers, thioxanthones, "dicarboxylic acid compounds" such as oxalic acid, maleic acid, succinic acid and phthalic acid; and γ-glycidoxypropyl tri A photosensitive composition in which “an alkoxysilane compound having an epoxy group or an amino group” such as methoxysilane and γ-aminopropyltriethoxysilane is uniformly blended and mixed, or a solution composition thereof is preferable.

The photosensitive resin having a carbon-carbon unsaturated bond includes ( meth) acrylated photosensitive resin.
Aromatic polyamides can be mentioned.

The photosensitive resin described above is disclosed in
Carbon is described in 37808 No. Gazette - photosensitive aromatic polyamide de soluble carbon unsaturated bond, photosensitivity, in terms of heat resistance, which is preferable.

The photosensitive resin has an average molecular weight of 100.
It is preferably from 0 to 1,000,000, particularly preferably from about 5000 to 500,000. The photosensitive resin has a boiling point of 50.
Is soluble in an organic solvent at a temperature of at least
It is preferable to use it by dissolving it uniformly at a concentration of 0% by weight.

Examples of the photopolymerization initiator compounded in the photosensitive composition of the present invention include bisazide compounds, Michler's ketone, benzoin, benzoin methyl ether,
Benzoin ethyl ether, benzoin isopropyl ether, 2-t-butylanthraquinone, 1,2-benzo-9,10-anthraquinone, benzyl, anisyl,
Photopolymerization initiators such as 4,4'-bis (diethylamino) benzophenone, acetophenone, benzophenone, 1,5-acenaphthene, thioxanthone or derivatives thereof, and dimethylaminobenzoate anthranilate can be given.

The bisazide compound used as the photopolymerization initiator includes 4,4'-diazidochalcone,
4,4'-diazidobenzalacetone, 2,6-di-
(4′-azidobenzal) methylcyclohexanone,
4,4′-diazidostilbene and the like can be preferably mentioned. Examples of the thioxanthones used as the photopolymerization initiator include 2,4-diethylthioxanthone and 2-chlorothioxanthone.

The amount of the photopolymerization initiator is based on 100 parts by weight of the photosensitive resin such as the photosensitive polyamide.
The amount is preferably 0.2 to 40 parts by weight, particularly 0.5 to 30 parts by weight. If the amount is too small, the sensitivity of the resulting composition will be low, and if it is too large, the heat resistance of the film formed by the resulting composition will be undesirably reduced.

The dicarboxylic acid compound used in the photosensitive composition of the present invention has a molecular weight of 300 or less,
When it has a high acidity (pKa <5) and is soluble in an organic polar solvent by 2% by weight or more, the compounding amount of the dicarboxylic acid compound can be reduced, or sublimation from the pattern portion after heat treatment. It is preferred because it is substantially removed by evaporation, decomposition and the like. The amount of the dicarboxylic acid is 0.1 to 100 parts by weight of the photosensitive resin.
It is preferably 15 parts by weight, particularly preferably 0.2 to 10 parts by weight.

The alkoxysilane compound containing an epoxy group or an amino group used in the photosensitive composition of the present invention includes, for example, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and γ-glycidoxy. Propyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β
(Aminoethyl) γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, N-
Phenyl-γ-aminopropyltrimethoxysilane and the like can be mentioned. The compounding amount of the alkoxysilane compound is 1 to 2 with respect to 100 parts by weight of the photosensitive resin.
It is preferably 5 parts by weight, particularly preferably 2 to 20 parts by weight.

In the present invention, the dicarboxylic acid compound is used in combination with an epoxysilane or amino group-containing alkoxysilane compound, and the molar ratio thereof is 2: 9 to 9: 1.
5: 2 is a particularly characteristic requirement.

In a photosensitive composition in which both are used in combination, one of the carboxyl groups of the dicarboxylic acid reacts with the epoxy group or amino group of the alkoxysilane compound to form a reaction product of both, and the photosensitive composition At the interface between the coating film and the substrate, it is estimated that the alkoxysilane groups are bonded to the substrate, and the unreacted carboxyl groups of the dicarboxylic acid form hydrogen bonds with the photosensitive resin to enhance the adhesion between the coating film and the substrate. During development, the developer does not easily penetrate into the interface between the coating film and the base material, so that the pattern of the photocured portion does not peel off. Since the pattern is maintained and the sensitivity becomes apparently high, the operability of development is dramatically improved, and a fine pattern can be effectively formed.

When the molar ratio of the dicarboxylic acid to the alkoxysilane compound is less than 2: 9 and the amount of the alkoxysilane compound used is large, polycondensation of the alkoxysilane groups is apt to occur, and the developability of the unexposed portion becomes poor. And the resolution of the pattern deteriorates. When the molar ratio is 5: 2
As the amount of dicarboxylic acid increases and becomes larger,
The mechanical adhesion of the final pattern after development deteriorates. Further, when the solution of the photosensitive composition of the present invention is stored for a long period, the above molar ratio is 1: 2 to 3: 2, particularly 2: 3 to 2.
It is preferably about 3: 2.

Also, the solution of the photosensitive composition of the present invention comprises:
It can be prepared by various blending procedures, and the method of preparing the solution is not particularly limited.For example, a solution in which a photosensitive resin is uniformly dissolved in the organic solvent is prepared, and It is preferable to add an acid compound and an alkoxysilane compound, and finally add a photopolymerization initiator. However, as for the method of adding the dicarboxylic acid and the alkoxysilane compound, they may be added alone, or may be added after preparing a mixed solution of both.

The solution of the photosensitive composition of the present invention has a concentration of the composition of 2 to 40% by weight, especially about 3 to 30% by weight, and a solution viscosity of the solution (rotational viscosity, 25%).
C) is preferably from 0.1 to 1000 poise, particularly preferably from 0.2 to 500 poise. The photosensitive composition (solution) of the present invention contains hydroquinone, 2,6-di-t
A thermal polymerization inhibitor such as -butyl-4-methylphenol (BHT), methyl ether hydroquinone, and phenothiazine may be blended.

The photosensitive composition of the present invention is, for example, coated on a substrate at a temperature of 0 to 60 ° C. and dried at a temperature of 180 ° C. or less to form a photosensitive thin film (dry coating film). And
Next, the photosensitive thin film is irradiated with a parallel light beam of an ultra-high pressure mercury lamp through a pattern mask, and the photosensitive thin film is photo-cured in each pattern, and then immersed in a developing solution.
The photo-cured film can be formed on the substrate by performing development to elute and remove unexposed portions (uncured portions) of the coating film.

The solution of the photosensitive composition can be applied to the surface of a substrate by, for example, a spin coating method, a roll coating method, an immersion method, a spray method, or the like. The coating film is dried at a temperature of 180 ° C. or less, particularly at a temperature of 50 to 150 ° C., using a hot air drier or a hot plate.
It is preferable to form the photosensitive thin film by substantially removing the organic solvent for about 60 minutes, especially about 2 to 30 minutes. The drying may be performed under reduced pressure. Also,
The thickness of the photosensitive thin film (the coating film after drying) is usually about 0.1 to 20.0 μm, preferably about 0.2 to 10.0 μm.

As described above, the substrate on which the light-cured thin film (light-cured film) formed by irradiation with light through the pattern mask is immersed in the developing solution to remove the uncured portion of the photosensitive thin film. When performing “development”, ultrasonic waves may be applied to the uncured portion. As the developer, a developer composed of “an organic solvent A capable of dissolving a photosensitive resin” or a mixed solution of the organic solvent A and an “organic solvent B that does not dissolve the photosensitive resin” is used. A developer can be used.

After the above-mentioned development, the substrate on which the photocured film photocured in a pattern is formed is rinsed with an organic solvent or water which does not dissolve the photosensitive resin, and then a hot air drier, a hot plate For example, at a temperature of about 250 ° C. or less, particularly 230 ° C. or less, for 1 to 60 minutes, particularly 2 to 30 minutes.
It is preferable to heat-treat (post-bake) for minutes.

In the method for forming a photo-cured film of the present invention,
For example, the thickness of a photosensitive thin film (coating film) after drying a coating film on a substrate (one side length: about 10 to 50 cm) of rectangular glass or the like sufficiently degreased and dried with a detergent or the like is 0%. .1 to
The photosensitive composition (solution composition) is applied by spin coating (coating) so as to have a thickness of 10 μm, particularly 0.5 to 5 μm to form a coating film.
It is preferable to dry at a temperature of 100 ° C. for 0.1 to 50 minutes, particularly 1 to 30 minutes, to substantially remove the organic solvent to form a dried photosensitive thin film (coating).

Next, a high-pressure mercury lamp (5 mW / c) was applied to the photosensitive coating film formed as described above through a pattern having a stripe pattern of 4 to 100 μm.
m ² ) to form a photocured film, the substrate is immersed in a developing solution as described above, and a developing operation of applying high-frequency ultrasonic waves is performed to substantially remove the unexposed portions. To obtain a substrate on which a patterned photocured film is formed.

[0026]

EXAMPLES Reference examples relating to the production of a photosensitive aromatic polyamide having a carbon-carbon unsaturated bond as a photosensitive resin, the preparation of a photosensitive polyamide composition of the present invention, and a method of forming a photocured film. Illustrating an example for
The present invention will be described in more detail.

Reference Example 1 [Production of Photosensitive Aromatic Polyamide] After passing dry air through a three-necked flask to replace the gas in the flask,
119.98 g of ethyl 3,5-diaminobenzoate methacrylate were added thereto, and then N-methyl-2 was added thereto.
-720 ml of pyrrolidone (NMP) was added and dissolved. After cooling this solution, 91.16 g of terephthalic acid dichloride was added little by little while cooling to 0 ° C. and stirring. At this time, heat was generated, and the temperature of the reaction solution tended to increase, but was kept at about 10 ° C. or lower. This reaction solution was further stirred in ice water for 2 hours to carry out a polymerization reaction.

Next, 500 ml of NMP was added to the reaction solution to dilute it, and this solution was added to a mixture of 1 liter of NMP and 10 liters of water to precipitate an aromatic polyamide, and the precipitate was filtered, collected, dried and dried. 167.8 g of Group III polyamide white powder was obtained. The resulting photosensitive aromatic polyamide powder has a logarithmic viscosity (concentration: 0.5 g /
100 ml solvent, solvent; NMP, measurement temperature; 3
(0 ° C.) was 0.88.

Example 1 [Preparation of photosensitive polyamide composition (solution composition)] N-methyl-2-pyrrolidone (NMP) 9 as an organic solvent
To 0 g, 120 mg of hydroquinone monomethyl ether (MEHQ) was added as a thermal polymerization inhibitor to prepare a uniformly dissolved solution. Then, the photosensitive aromatic polyamide produced in Reference Example 1 (logarithmic viscosity: 0.8
8) 10 g was added, and the mixture was sufficiently stirred and uniformly dissolved to prepare a viscous solution.

Then, diethylthioxanthone 400 as a photopolymerization initiator was added to the solution prepared as described above.
mg, benzyl 150 mg, diethylaminobenzoic acid ethyl ester 300 mg, and γ-glycidoxypropyltrimethoxysilane 39 as an adhesion promoter.
0 mg (1.65 × 10 ⁻³ mol) and 150 mg (1.66 × 10 ⁻³ mol) of oxalic acid as a dicarboxylic acid were added and stirred. Finally, the solution was filtered with a 1 μm fluororesin filter ( The mixture was filtered under pressure using a Teflon filter to prepare a photosensitive aromatic polyamide composition (solution composition).

[Formation of Patterned Photocured Film] A photosensitive aromatic polyamide composition (solution composition) was rotated on a glass substrate so that the film thickness of the dried film was 2.0 μm. A coating film is formed by coating (spin coating), and the coating film is dried at 80 ° C. for 10 minutes to substantially remove the organic solvent, and a 2.0 μm-thick photosensitive thin film ( (Dried film, coating film).

Next, for the photosensitive thin film (coating),
100 mJ / cm for 20 seconds with a light source of an ultra-high pressure mercury lamp through a 4-100 μm stripe pattern mask
^The photosensitive thin film was light-cured in a pattern by irradiating light with the exposure amount of No. ² .

Next, a substrate on which a thin film (photocured film) photocured in a pattern is formed is mixed with a mixed solution of γ-butyrolactone and ethylcellosolve (the volume ratio of γ-butyrolactone to ethylcellosolve is 30:70). Is)
At the same time as immersion in a developer consisting of 90 to 90 W while applying 15 W ultrasonic waves (frequency of 27 KHz).
A developing operation was performed for 240 seconds to produce a substrate with a patterned photocurable film. The uncured portion of the photosensitive thin film was dissolved and removed in a developing solution 60 seconds after the start of development, and the patterned photocured film was not peeled off at all, and a good patterned photocured film was formed.

Finally, the substrate is rinsed with ethyl cellosolve, and then the substrate is heat-treated at 200 ° C. for 30 minutes to form a photocured film (2.0 μm thick) having a stripe pattern of 4 to 100 μm. Was formed on the substrate. The substrate having the patterned photocurable film obtained as described above was subjected to an adhesion test. As a result, no peeling of the photocurable film was found.

Examples 2 to 5 and Comparative Examples 1 to 4 [Preparation of photosensitive polyamide composition (solution composition)] The types, added amounts and molar ratios of the dicarboxylic acid and the alkoxysilane compound were as shown in Table 1. Otherwise in the same manner as in Example 1, a photosensitive aromatic polyamide composition (solution composition) was prepared.

[Formation of Patterned Photocured Film] A photocured film (patterned) was formed on a substrate in the same manner as in Example 1 except that each photosensitive aromatic polyamide composition (solution composition) was used. Formed. Table 1 shows the pattern state immediately after development and the results of the adhesion test of the photocured film after post-baking for each substrate formed as described above.

[0037]

[Table 1]

[0038]

The present invention is generally based on a photosensitive resin such as a photosensitive aromatic polyamide, a photopolymerization initiator, a dicarboxylic acid compound (A), and an epoxysilane or amino group-containing alkoxysilane compound (B). Wherein the molar ratio of (A) and (B) is from 2: 9 to 5: 2, wherein (A) and (B) are contained in the photosensitive composition.
With the reaction, the adhesion of a coating film (photosensitive resin) formed on a substrate such as glass is greatly improved, and as a result, the coating film of the photosensitive composition of the present invention is exposed in a pattern,
At the time of development, the photocured pattern portion does not peel off, and the development operation is extremely easy. Further, if sufficient post-heat treatment (post-bake) is sufficiently performed after the above-described development, the pattern is finally formed. It has an excellent function and effect that the adhesion between the photocurable film and the substrate can be made extremely high.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/038 504 G03F 7/038 504 7/075 501 7/075 501 (56) References JP-A-2-5062 (JP, A) JP-A-2-68 (JP, A) JP-A-63-284213 (JP, A) JP-A-63-27834 (JP, A) JP-A-63-15847 (JP, A) JP-A-49 -123323 (JP, A) JP-B-46-21246 (JP, B1) Patent 2770894 (JP, B2) (58) Fields investigated (Int. Cl. ⁶ , DB name) G03F 7/085 G03F 7/075 G03F 7/027 G03F 7/031 G03F 7/038 C08K 5/09 C08K 5/54

Claims (1)

(57) [Claims] 1. A carbon - photosensitive fang having a carbon-carbon unsaturated bond
It comprises an aromatic polyamide , a photopolymerization initiator, a dicarboxylic acid compound (A), and an epoxysilane or amino group-containing alkoxysilane compound (B), and has a molar ratio (A / B) between (A) and (B). ) 2: 9-5: 2 der Rigen
Coating a photosensitive composition adhesion to the base material and said good der Rukoto during image.