JP6826193B2 - An electronic device having a photosensitive resin composition, a cured film formed from the photosensitive resin composition, and the cured film. - Google Patents

Description

The present invention relates to a photosensitive resin composition, a cured film formed from the photosensitive resin composition, and an electronic device including the cured film.

In liquid crystal displays, organic EL displays, etc., the aperture ratio of the display device must be increased in order to achieve higher precision and higher resolution. Therefore, there is a method of enabling a high aperture ratio by overlapping the data line and the pixel electrode by installing a transparent flattening film on the upper part of the TFT substrate as a protective film.

As a material for forming such an organic insulating film for a TFT substrate, a material having high heat resistance, high transparency, high temperature crack resistance, low dielectric constant, chemical resistance and the like is required, and the TFT substrate is required. In order to ensure the continuity between the electrode and the ITO electrode, it is necessary to form a hole pattern of about several μm to 50 μm.

Conventionally, a material in which a phenol-based resin and a quinone-diazide compound are combined, or a photosensitizing resin composition in which an acrylic-based resin and a quinone-diazide compound are combined has been mainly used. However, although the material properties of these materials do not deteriorate rapidly at a high temperature of 200 ° C. or higher, decomposition starts gradually at a high temperature of 230 ° C. or higher, causing a problem of film thickness reduction or cracking phenomenon, or a high temperature of the substrate. There is a problem that the transparent film is colored by the treatment and the transmittance is lowered.

Recently, touch panels have been adopted in liquid crystal displays and the like, but in order to improve the transparency and functionality of the touch panel, the temperature is higher for the purpose of high transparency and high conductivity of ITO, which is a transparent electrode member. Attempts have been made to perform heat treatment and film formation in. Along with this, the protective film and insulating film of the transparent electrode member are also required to have heat resistance to high temperature treatment. However, acrylic resin has insufficient heat resistance and chemical resistance, and the cured film is colored by high-temperature treatment of the substrate, high-temperature film formation of transparent electrodes, or various etching chemical treatments, or the transparency is lowered. There is a problem that the conductivity of the electrode is lowered due to degassing during high-temperature film formation. Therefore, it cannot be used in a process of forming a film on the transparent film material at a high temperature by using an apparatus such as PE-CVD.

Further, even in the organic EL element, cracks and decomposition products generated from the material adversely affect the luminous efficiency and the life of the organic EL element, so that it cannot be said to be the optimum material for use. Further, the acrylic material to which heat resistance is imparted also causes a crack phenomenon at 300 ° C. or higher, and if not, the dielectric constant generally increases. Therefore, due to the high dielectric constant, the parasitic capacitance due to the insulating film increases, which causes a problem in the quality of image quality due to an increase in power consumption and a delay in the liquid crystal element drive signal. Further, even with an insulating material having a large dielectric constant, for example, the capacity can be reduced by increasing the film thickness, but it is generally difficult to form a uniform thick film, and the amount of material used is also large, which is not preferable.

On the other hand, silsesquioxane is known as a material having high heat resistance and high transparency. In particular, an acrylic copolymer obtained by copolymerizing a silsesquioxane compound obtained by imparting an acrylic group to a specific silsesquioxane, an unsaturated compound containing an unsaturated carboxylic acid and an epoxy group, and an olefin-based unsaturated compound. And a photosensitive composition composed of a quinone diazide compound and the like have been proposed. However, these compounds also have a problem of heat resistance, which has a high content of organic compounds and is decomposed after curing at a high temperature of 250 ° C. or higher and is colored yellow to reduce the permeability, and the residual film ratio after development is reduced to be a flat film. However, there is a problem that the chemical resistance to a solvent such as NMP (N-methyl-2-pyrrolidone), tetramethylammonium hydroxide (TMAH) solution, and 10% NaOH is also reduced.

Further, as a system in which a quinone diazide compound is combined to impart positive photosensitivity to the siloxane polymer, a material in which a siloxane polymer having a phenolic hydroxyl group at the terminal and a quinone diazide compound are combined, and phenol is subjected to a cyclization heat addition reaction. Materials such as a combination of a siloxane polymer to which a sex hydroxyl group or a carboxyl group is added and a quinone diazide compound are known. However, since these materials contain a large amount of quinonediazide compounds or have phenolic hydroxyl groups in the siloxane polymer, whitening of the coating film and coloring during thermosetting are likely to occur, and the temperature is severe at 300 ° C. or higher. Cracks occur under high temperature conditions, and the material cannot be used as a highly transparent material due to the accompanying decrease in permeability. Further, since these materials have low transparency, there is also a problem that the sensitivity at the time of pattern formation is low.

When a photosensitive composition material composed of only a polysiloxane and a quinonediazide compound is thermoset, cross-linking and high molecular weight are caused by dehydration condensation of silanol groups in the polysiloxane. In this thermosetting process, the pattern is melted due to the low viscosity of the film due to high temperature before the pattern is sufficiently thermoset, and the pattern such as holes and lines obtained after development flows. As a result, the crack phenomenon does not occur, but "pattern" deterioration that reduces the resolution occurs, which must be prevented.

In addition, a system of polysiloxane insoluble in a developing solution, a soluble polysiloxane system, and a quinonediazide compound are combined, and when this is heat-cured, the patterns such as holes and lines obtained after development are destroyed, resulting in a decrease in resolution. Photosensitive compositions that prevent "pattern dripping" have been proposed. However, if insoluble polysiloxane is used in the developing solution, the undissolved residue after development and the difficult-to-dissolved substance reattached, which causes a development pattern defect. Further, in order to prevent pattern deterioration, it is necessary to sufficiently increase the molecular weight of siloxane. As a result, the photosensitive material has low sensitivity and requires high reaction energy. In addition, there is a drawback that the residual film ratio is not sufficient and the material loss is large.

The present invention provides a photosensitive resin composition having excellent chemical resistance, high light transmittance and crack resistance after high-temperature curing, improved crack margin, and easy thickness adjustment. ..

The present invention also provides a cured film obtained by curing the photosensitive resin composition.

The present invention also provides an electronic device including the cured film.

One embodiment of the present invention is formed by (A) hydrolysis and condensation reaction of at least one silane compound represented by the following chemical formula 1, and 65% or more of all silicon atoms are substituted with phenyl groups. A photosensitive resin composition containing the polysiloxane polymer and the solvent (B), and after prebaking, the film is insoluble in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution and is 5 wt%. Provided is a photosensitive resin composition having a dissolution rate of 100 Å / sec or less in an aqueous TMAH solution:

In the chemical formula 1,
R ¹ is hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted. C7 to C30 arylalkyl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heterocycloalkyl groups, substituted or unsubstituted C1 to C30 heteroaryl groups, substituted Alternatively, an unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, RO-, R (C = O)-(where R is a substituted or unsubstituted C1-C30 alkyl group. , Substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, or substituted or unsubstituted C7 to C30 arylalkyl groups), or a combination thereof.
X ¹ is an alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof of C1 to C6.
a is 0 ≦ a <4.

In the chemical formula 1, R ¹ is hydrogen, an alkyl group of C1 to C10, an alkenyl group of C2 to C10, an aryl group of C6 to C16, or a combination thereof, and X ¹ is an alkoxy group of C1 to C6 and a hydroxy group. , Halogen, or a combination thereof.

In the chemical formula 1, R ¹ may be a methyl group or a phenyl group, and a may be 1.

The polysiloxane polymer (A) may be hydrolyzed and condensed polymerized by further containing a silane compound represented by the following chemical formula 2.

In the chemical formula 2,
Y ¹ is a single bond, oxygen, substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted. C2-C30 heteroarylene group, substituted or unsubstituted C2-C30 alkenylene group, substituted or unsubstituted C2-C20 alkynylene group, or a combination thereof.
X ² and X ³ are independently C1 to C6 alkoxy groups, hydroxy groups, halogens, carboxyl groups, or combinations thereof.

In the chemical formula 2, Y ¹ is an alkylene group of C1 to C10, a cycloalkylene group of C3 to C10, an arylene group of C6 to C12, or a combination thereof, and X ² and X ³ are alkoxy groups of C1 to C6. Can be a group.

After prebaking the photosensitive resin composition, the film is insoluble in 2.38 wt% TMAH aqueous solution, and the dissolution rate in 5 wt% TMAH aqueous solution can be 50 Å / sec or less.

The polysiloxane polymer (A) is hydrolyzed and condensed with 80 mol% to 97 mol% of the silane compound represented by the chemical formula 1 and 3 mol% to 20 mol% of the silane compound represented by the chemical formula 2. Can be manufactured.

More than 70% of the total silicon atoms of the polysiloxane polymer (A) can be substituted with phenyl groups.

The photosensitive resin composition may further contain (C) an additive capable of generating an acid or a base with heat or light, (D) a quinonediazide compound, or a combination thereof.

The refractive index of the photosensitive resin composition can be 1.50 or more.

Another embodiment provides a cured film produced by curing the photosensitive resin composition.

The cured film may have a light transmittance of 98% or more at a wavelength of 400 nm.

Another embodiment provides an electronic device that includes the cured film.

The photosensitive resin composition according to one embodiment of the present invention has excellent chemical resistance, high light transmittance and crack resistance after high-temperature curing, improved crack margin, and easy thickness adjustment. Can be provided.

The cured film can be usefully used for manufacturing a flattening film for a thin film transistor (TFT) substrate, an interlayer insulating film for a semiconductor element, and the like.

Hereinafter, embodiments of the present invention will be described in detail so that those having ordinary knowledge in the technical field to which the present invention belongs can easily carry out the embodiments. However, the present invention can be embodied in various different forms and is not limited to the embodiments described herein.

Unless otherwise defined herein,'substitution' means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group. , Azido group, amidino group, hydrazino group, hydrazono group, carbonyl group, carbamoyl group, thiol group, ester group, carboxyl group and its salt, sulfonic acid group and its salt, phosphoric acid and its salt, alkyl group of C1 to C20. , C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 hetero It was substituted with an arylalkyl group, a cycloalkyl group of C3 to C30, a cycloalkenyl group of C3 to C15, a cycloalkynyl group of C6 to C15, a heterocycloalkyl group of C3 to C30 and a substituent selected from a combination thereof. Means that.

Also, unless otherwise defined herein,'hetero' means one containing at least one heteroatom selected from N, O, S and P.

Unless otherwise specified herein,'combination' means mixing or copolymerizing.

Hereinafter, the photosensitive resin composition according to one embodiment will be described.

The photosensitive resin composition according to one embodiment is formed by hydrolyzing and condensing at least one silane compound represented by (A) the following chemical formula 1, and 65% or more of the total silicon atoms are phenyl groups. The polysiloxane polymer substituted with (B) and the solvent (B) are contained, and after prebaking, the film is insoluble in a 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution and dissolved in a 5 wt% TMAH aqueous solution. The speed is less than 100 Å / sec:

In the chemical formula 1,
R ¹ is hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted. C7 to C30 arylalkyl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heterocycloalkyl groups, substituted or unsubstituted C1 to C30 heteroaryl groups, substituted Alternatively, an unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, RO-, R (C = O)-(where R is a substituted or unsubstituted C1-C30 alkyl group. , Substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, or substituted or unsubstituted C7 to C30 arylalkyl groups), or a combination thereof.
X ¹ is an alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof of C1 to C6.
a is 0 ≦ a <4.

The photosensitive resin composition according to the above embodiment has excellent chemical resistance by containing a polysiloxane polymer produced by hydrolyzing and condensing at least one silane compound represented by the chemical formula 1. Provided is a photosensitive resin composition having a high refractive index of 1.5 or more. Therefore, the photosensitive resin composition according to one embodiment has a high light transmittance when cured at a high temperature, has an improved crack margin, and exhibits a property that the thickness of the insulating film can be easily adjusted.

As an example, R ^{1 of the} chemical formula 1 may be hydrogen, an alkyl group of C1 to C10, an alkoxy group of C2 to C10, an aryl group of C6 to C16, or a combination thereof, and X ¹ is of C1 to C6. It may be an alkoxy group, a hydroxy group, a halogen, or a combination thereof, and n in the chemical formula 1 may be 0 or 1.

In one embodiment, the R ¹ may be a methyl or phenyl group and a may be 1.

The polysiloxane polymer (A) according to one embodiment may further contain a silane compound represented by the following chemical formula 2 and be hydrolyzed and condensation polymerized:

In the chemical formula 2,
Y ¹ is a single bond, oxygen, substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted. C2-C30 heteroarylene group, substituted or unsubstituted C2-C30 alkenylene group, substituted or unsubstituted C2-C20 alkynylene group, or a combination thereof.
X ² and X ³ are independently C1 to C6 alkoxy groups, hydroxy groups, halogens, carboxyl groups, or combinations thereof.

In Formula 2, wherein ^{Y 1} is an alkylene group of C1 -C10, cycloalkylene C3 -C10, arylene group C6~C12 or may be a combination thereof, wherein ^{X 2} and ^{X 3} C1~ It may be an alkoxy group of C6. In one embodiment, the photosensitive resin composition comprises 80 mol% to 97 mol% of one or more silane compounds represented by the chemical formula 1 and 3 mol% to 20 mol% of the silane compound represented by the chemical formula 2. % Can be produced by hydrolysis and condensation reaction. When the photosensitive resin composition contains a polysiloxane copolymer produced by hydrolyzing and condensing the silane compounds represented by the chemical formulas 1 and 2 in the above range, the photosensitive resin composition has a refractive index of 1.50 or more. For example, it can be 1.51 or more, for example 1.52 or more, for example 1.53 or more, for example 1.54 or more, for example 1.55 or more. When the photosensitive resin composition according to one embodiment has a high refractive index of 1.50 or more, the crack margin is improved and the thickness of the insulating film can be easily adjusted.

The molecular weight of the polysiloxane polymer (A) formed by hydrolysis and decomposition is 1,000 to 500,000 in terms of weight average molecular weight converted to a polystyrene standard sample measured by gel permeation chromatography (GPC). For example, 1,000 to 100,000, for example, 1,000 to 50,000, for example, 1,000 to 30,000, for example, 1,000 to 20,000, for example, 1,000 to 15,000, for example, 1,000. It may be ~ 10,000, for example 1,000 to 8,000, for example 1,000 to 6,000, for example 1,000 to 5,000, for example 2,000 to 5,000.

When the weight average molecular weight of the compound is 1,000 or more, cracks do not occur on the surface during curing, and a preferable cured film thickness can be realized. Further, when the weight average molecular weight is 500,000 or less, the flatness of the surface can be improved while maintaining the viscosity required for coating.

As described above, the polysiloxane polymer (A) according to one embodiment has a film insoluble in a 2.38 wt% TMAH aqueous solution after prebaking, and has a dissolution rate of 100 Å / sec or less in a 5 wt% TMAH aqueous solution. It is a compound. For example, the polysiloxane polymer (A) is a compound whose membrane is insoluble in a 2.38 wt% TMAH aqueous solution after prebaking and whose dissolution rate is 50 Å / sec or less in a 5 wt% TMAH aqueous solution.

When the dissolution rate of the film in the TMAH aqueous solution after prebaking the composition containing the polysiloxane polymer is within the above range, the cured film obtained by curing the composition is 3.0 μm or more, for example, 3. The cured film obtained by curing the photosensitive resin composition has a thickness margin of 2 μm or more without cracks, and has very high crack resistance at high temperatures.

Further, a sample is produced on a 10 × 10 glass substrate so that the thickness of the photosensitive resin composition becomes 2.5 ± 0.1 μm after curing, and after measuring the thickness of the intermediate portion of the sample, resistance is achieved. After immersing in a chemical solvent for 5 minutes, the change in thickness was confirmed, and the thickness change rate was less than 5%. From this, it can be seen that the cured film produced from the photosensitive resin composition according to one embodiment has relatively excellent chemical resistance. The thickness change rate can be calculated from Equation 1 below:

On the other hand, as can be seen from the comparative example described later, the content of the phenyl group substituted with all the silicon atoms in the polysiloxane copolymer or the film produced from the composition containing the copolymer is relative to the TMAH. If the dissolution rate range is not met, the cured film cured from such a composition does not have the crack resistance and chemical resistance.

The content of the phenyl group substituted with the polysiloxane polymer (A) is 65% or more, for example 70% or more, based on the number of all Si atoms. The photosensitive resin composition containing the polysiloxane polymer substituted with the phenyl group having the above content can significantly reduce the crack generation rate when cured at a high temperature. When the content of the phenyl group in the polysiloxane polymer (A) is less than 65%, for example, less than 60%, for example, less than 55% based on the number of all Si atoms, the photosensitive resin composition produced from the phenyl group is: The crack generation rate will increase during curing at high temperatures.

Generally, in the case of a photosensitive resin composition, for example, a positive photosensitive resin composition, it can be used as a protective film or an insulating film of a display display element through the production of a cured film. However, the conventional positive photosensitive resin composition has a low refractive index, which causes a decrease in efficiency and thermal stability of electronic devices such as OLED light emitting devices. The photosensitive resin composition according to one embodiment has an increased refractive index by containing a polysiloxane polymer formed by hydrolyzing and polycondensing the silane compound represented by the chemical formula 1 and / or the chemical formula 2. It can be usefully used for forming a surface protective film, an interlayer insulating film, and the like of a display device.

The photosensitive resin composition according to one embodiment contains (B) a solvent.

The solvent that can be used is not particularly limited, but a compound having an alcoholic hydroxyl group and / or a cyclic compound having a carbonyl group is preferably used. When these solvents are used, the silane compound is uniformly dissolved, and after the composition is applied, the film does not become cloudy during film formation, and high transparency can be achieved.

The compound having an alcoholic hydroxyl group is not particularly limited, but a compound having a boiling point of 110 ° C. to 250 ° C. under atmospheric pressure is preferably used. If the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, the film shrinkage rate during curing increases, and good flatness cannot be obtained. If the boiling point is lower than 110 ° C., the coating film is dried too quickly and the film surface is roughened, resulting in poor coating film properties.

Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2-butanone, 5-hydroxy-2-pentanone, 4-. Hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono Examples thereof include t-butyl ether, 3-methoxy-1-butanol, 3-methyl-3-methoxy-1-butanol and the like. Among these, a compound having a carbonyl group is particularly preferable, and diacetone alcohol is particularly preferably used. Further, these compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

The cyclic compound having a carbonyl group is not particularly limited, but a compound having a boiling point of 150 ° C. to 250 ° C. under atmospheric pressure is preferably used. If the boiling point is higher than 250 ° C., the amount of residual solvent in the film increases, the film shrinkage during curing becomes large, and good elasticity cannot be obtained. If the boiling point is lower than 150 ° C., the coating film is dried too quickly and the film surface is roughened, resulting in poor coating film properties.

Specific examples of the cyclic compound having a carbonyl group include γ-butyrolactone, γ-valerolactone, δ-valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone, cycloheptanone and the like. Of these, γ-butyrolactone is particularly preferably used. Further, these cyclic compounds having a carbonyl group may be used alone or in combination of two or more.

The above-mentioned compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group may be used alone or in admixture with each other. When used in combination, the weight ratio is not particularly limited, but preferably the ratio of the compound having an alcoholic hydroxyl group to the cyclic compound having a carbonyl group is 99 to 50: 1 to 50, or, for example, 97 to 60: 3. ~ 40. When the amount of the compound having an alcoholic hydroxyl group is more than 99% by weight (the amount of the cyclic compound having a carbonyl group is less than 1% by weight), the compatibility of the silane compound of Chemical Formula 1 is deteriorated, the cured film is whitened, and the transparency is lowered. Will be done. Further, when the amount of the compound having an alcoholic hydroxyl group is less than 50% by weight (the amount of the cyclic compound having a carbonyl group is more than 50% by weight), the condensation reaction of the unreacted silanol group in the silane compound of Chemical Formula 1 is likely to occur, and the compound is stored. Poor stability.

The photosensitive resin composition according to the above-described embodiment may further contain other solvents as long as the effects of the present invention are not impaired. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-methoxy-1- Examples thereof include esters such as butyl acetate, ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetylacetone, and ethers such as diethyl ether, diisopropyl ether, din-butyl ether and diphenyl ether.

The amount of the solvent added is not particularly limited, but is preferably used in the range of 100 to 1,000% by weight with respect to 100% by weight of the silane compound of the above chemical formula 1. Alternatively, the solvent may be contained so that the solid content is 10 to 50% by weight based on the total weight of the photosensitive resin composition. The solid content means a composition component excluding a solvent in the resin composition of the present invention.

Further, the photosensitive resin composition according to the above-described embodiment may also contain (C) an additive that generates an acid or a base by heat or light. For example, it may be a thermoacid generator, a photoacid generator, a thermobase generator or a photoacid generator, and may be, for example, a thermoacid generator. Such an additive (C) can improve the resolution by strengthening the pattern shape or increasing the development contrast during the production of the cured film.

The photosensitive resin composition according to one embodiment has 0.001 to 10.0 parts by weight of the (C) additive, for example 0.01 to 5.0 parts by weight, based on 100 parts by weight of the (A) polysiloxane polymer. It can include parts by weight.

In one embodiment, when the additive (C) is contained within the above range, cracks and coloring do not occur during the production of the cured film.

Examples of the thermoacid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid and maleic acid and salts thereof, and various aromatic carboxylic acids such as benzoic acid and phthalic acid. Examples thereof include salts and esters that generate organic acids, such as salts thereof, aromatic sulfonic acids and ammonium salts thereof, various amine salts, aromatic diazonium salts and phosphonic acids and salts thereof. For example, the thermoacid generator in one embodiment may be, but is not limited to, a salt composed of an organic acid and an organic base, or a salt composed of a sulfonic acid and an organic base.

For example, the thermoacid generator containing sulfonic acid may be p-toluenesulfonic acid, benzenesulfonic acid, p-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid, or a combination thereof. ..

Examples of the photoacid generator include diazomethane compounds, diphenyliodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds and the like. The structure of these photoacid generators can be represented by Chemical Formula 3.

In Formula 3, ^{R +} is hydrogen, substituted or unsubstituted alkyl group, an aryl group, an alkenyl group, an acyl group, and the like alkoxyl group, X ^{- _{is, BF 4 -, PF 6 -}} , SbF 6 -, SCN _{^{-, (CF 3 SO 2)}} 2 N -, carboxylic acid ion, and the like sulfonium ions.

Examples of the photobase generator may be a polysubstituted amide compound having an amide group, lactam, an imide compound, etc., and examples of the thermobase generator may be N- (2-nitrobenzyloxycarbonyl). Imidazole, N- (3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4-chloro-2) It can be an imidazole derivative such as −nitrobenzyloxycarbonyl) imidazole, 1,8-diazabicyclo (5,4,0) undecene-7, tertiary amines, a quaternary ammonium salt, or a combination thereof.

The photosensitive resin composition according to the above-described embodiment can contain (D) a quinonediazide compound. (D) The photosensitive resin composition containing the quinone diazide compound forms a positive type in which the exposed portion is removed with a developing solution. The quinonediazide compound used is not particularly limited. For example, a compound in which a naphthoquinonediazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group is used, and the ortho-position and the para-position of the phenolic hydroxyl group of the compound are independent of each other. A compound that is either hydrogen or a substituent represented by the chemical formula 5 below is used:

In the chemical formula 5,
R ¹² , R ¹³ , and R ¹⁴ independently represent any one of the alkyl group, carboxyl group, phenyl group, and substituted phenyl group of C1 to C10, and R ¹² , R ¹³ , And R ¹⁴ may form a ring.

In R ¹² , R ¹³ , and R ¹⁴ of the groups represented by the chemical formula 5, the alkyl group may be used either unsubstituted or substituted. Specific examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-hexyl group, cyclohexyl group and n-heptyl group. Examples thereof include an n-octyl group, a trifluoromethyl group and a 2-carboxyethyl group. Moreover, the substituted phenyl group includes a phenyl group substituted with a hydroxy group. Further, a ring may be formed by R ¹² , R ¹³ , and R ¹⁴ , and specific examples thereof include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

When the ortho-position and para-position of the phenolic hydroxyl group are groups other than the above, for example, a methyl group, oxidative decomposition occurs by thermosetting, a conjugated compound represented by a quinoid structure is formed, and the cured film is colored and colorless and transparent. The sex is reduced. These quinone diazide compounds can be synthesized by a known esterification reaction of a compound having a phenolic hydroxyl group and naphthoquinone diazido sulfonic acid chloride. Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all manufactured by Honshu Chemical Industry Co., Ltd.).

As the naphthoquinone diazide sulfonic acid, 4-naphthoquinone diazido sulfonic acid or 5-naphthoquinone diazido sulfonic acid can be used. The 4-naphthoquinone diazide sulfonic acid ester compound has absorption in the i-line (wavelength 365 nm) region and is therefore suitable for i-line exposure. Further, the 5-naphthoquinonediazide sulfonic acid ester compound is suitable for exposure in a wide range of wavelengths because absorption occurs in a wide range of wavelengths. A 4-naphthoquinone diazide sulfonic acid ester compound or a 5-naphthoquinone diazido sulfonic acid ester compound can be selected depending on the exposure wavelength. A 4-naphthoquinone diazide sulfonic acid ester compound and a 5-naphthoquinone diazido sulfonic acid ester compound can also be mixed and used.

The amount of the quinonediazide compound added is not particularly limited, and for example, 0.1 to 15 parts by weight, for example, 1 to 10 parts by weight can be used with respect to 100 parts by weight of the siloxane compound of the chemical formula 1. When the amount of the quinonediazide compound added is less than 0.1 parts by weight, the dissolution contrast between the exposed part and the unexposed part is too low, and there is practically no photosensitivity. Further, in order to obtain a better dissolution contrast, 1 part by weight or more is preferable. When the amount of the quinonediazide compound added is more than 15 parts by weight, the compatibility between the siloxane compound and the quinonediazide compound deteriorates, so that the coating film is whitened or the coloring due to the decomposition of the quinonediazide compound that occurs during thermosetting becomes remarkable. , The colorless transparency of the cured film is reduced. Further, in order to obtain a more transparent film, it is preferable to use the quinone diazide compound in an amount of 10 parts by weight or less.

If necessary, the photosensitive resin composition according to the above-described embodiment may further contain additional components usually used in the photosensitive resin composition, such as a silane-based coupling agent and a surfactant.

The silane-based coupling agent is added to improve the adhesion between the formed cured film and the substrate, and a functional silane compound having a reactive substituent can be used as a known silane-based coupling agent. Examples of the reactive substituent include a carboxyl group, a methacryloyl group, an isocyanate group, an epoxy group and the like.

Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanoxidetriethoxysilane, and γ-glycid. One or more selected from xypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane can be used, preferably a residual film. In terms of rate and adhesion to the substrate, γ-glycidoxypropyltriethoxysilane and / or γ-glycidoxypropyltrimethoxysilane having an epoxy group can be used, but the present invention is limited thereto. Not done.

The silane coupling agent is in the range of 0.01 to 10 parts by weight, for example, 0.1 to 100 parts by weight, based on 100 parts by weight (based on solid content) of the compound represented by Chemical Formula 1 in the photosensitive resin composition. Included in the range of 5 parts by weight. If the content of the silane coupling agent is 0.01 parts by weight or more, the adhesiveness to the substrate is improved, and if it is 10 parts by weight or less, the thermal stability is improved at high temperature, and unevenness occurs after development. Can be prevented.

The photosensitive resin composition according to the present invention may further contain a surfactant in order to improve coating performance. Examples of such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants.

As surfactants, for example, FZ2122 (manufactured by Toray Dow Corning), BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafuck F142D, F172, F173, F183 (Dainippon Ink and Chemicals Co., Ltd.) , Florad FC-135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M Limited), Surfron S-112, S-113, S-131, S-141, same S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF301, same 303, 352 (manufactured by Shin-Akita Kasei Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.), etc. And silicone-based surfactants; polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether, and polyoxys such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether. Nonionic surfactants such as polyoxyethylene dialkyl esters such as ethylene aryl ethers, polyoxyethylene dilaurates, and polyoxyethylene distearate; organic siloxane polymer KP341 (manufactured by Shinetsu Chemical Industry Co., Ltd.), or (meth). Acrylic acid-based copolymer Polyflow No. 57 and 95 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) can be used alone or in parallel of two or more.

The surfactant can be used in the range of 0.05 to 10 parts by weight, for example, 0.1 to 5 parts by weight, based on 100 parts by weight (based on solid content content) of the compound represented by the chemical formula 1. .. If the content of the surfactant is 0.05 parts by weight or more, the coatability is improved and cracks do not occur on the coated surface, and if it is 10 parts by weight or less, it is advantageous from the aspect of price.

In addition to the above components, the photosensitive resin composition according to one embodiment may further contain additional components usually used in the thermosetting resin composition and / or the photosensitive resin composition, if necessary. For example, the photosensitive resin composition according to the above-described embodiment may contain additives such as a dissolution accelerator, a dissolution inhibitor, a surfactant, a stabilizer, and an antifoaming agent, if necessary.

Hereinafter, a method for forming a cured film using the photosensitive resin composition according to the above embodiment will be described.

The photosensitive resin composition according to the above embodiment is applied onto a base substrate by a known method such as spinner, dipping, slit, etc., and prebaked by a heating device such as a hot plate or an oven. Prebaking is performed in the range of 50 ° C. to 150 ° C. for 30 seconds to 30 minutes, and the film thickness after prebaking can be 0.1 μm to 15 μm.

After prebaking, stepper, a mirror projection mask aligner (MPA), using an ultraviolet-visible exposure machine, such as a parallel light mask aligner (PLA), an exposure amount of 10mJ ^/ cm ² ~500mJ ^/ cm 2 at a wavelength of 200nm~450nm Exposure can be performed.

After exposure, the exposed part is melted by development, and a positive pattern can be obtained. As a developing method, it is preferable to immerse the developer in a developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, or paddle. As the developing solution, a known alkaline developing solution can be used. Specific examples include alkali metal hydroxides, carbonates, phosphates, silicates, inorganic alkalis such as borate, amines such as 2-diethylaminoethanol, monoethanolamine, and diethanolamine, and tetra hydroxides. Examples thereof include an aqueous solution containing one or more quaternary ammonium salts such as methylammonium and choline.

After development, it is preferable to rinse with water. Further, if necessary, drying baking can be performed in the range of 50 ° C. to 150 ° C. with a heating device such as a hot plate or an oven.

If necessary, soft bake in the range of 50 ° C to 150 ° C with a heating device such as a hot plate or oven, and then use a heating device such as a hot plate or oven in the range of 150 ° C to 450 ° C for 10 minutes to. The desired cured film can be produced by curing after 5 hours (post-bake).

As described above, the cured film has high crack resistance and chemical resistance, and has excellent light transmittance. Therefore, the cured film can be effectively used as a flattening film for a thin film transistor (TFT) substrate, an interlayer insulating film of a semiconductor element, and the like.

For example, the cured film according to one embodiment produced as described above has a high light transmittance of 90% or more, for example 95% or more, for example 98% or more in the 400 nm wavelength range in the case of a cured film having a thickness of 2 μm.

The existing acrylic insulating film has a problem that it turns yellow at 250 ° C. or higher due to its low heat resistance, the transmittance decreases, the polymer decomposes, and the chemical resistance decreases. A sill containing an acrylic group or an epoxy group Although sesquioxane has higher heat resistance than the acrylic insulating film, it has a problem that the transmittance still decreases at high temperature and the residual film ratio after development is low.

A photosensitive resin composition containing one or more silane compounds represented by the chemical formula 1 according to one embodiment, a polysiloxane copolymer synthesized by hydrolyzing and condensing the silane compound represented by the chemical formula 2, and a solvent. Through the role of the crosslinker of the carbosilane structural unit in the siloxane compound, the product can easily adjust the hardness of the cured film produced from it and form a high-hardness coating film, and thus high-temperature crack resistance. Is improved. In addition, it is possible to effectively prevent the invasion of an organic solvent or the like through the cured film. As a result, the cured film produced by curing the composition solves the problem of the residual film ratio that the film thickness after development is reduced and does not become a flat film, and is excellent in chemical resistance after curing. There is no pattern drooling phenomenon. Further, since it has higher heat resistance than silsesquioxane copolymerized with an existing acrylic copolymer or organic compound, it exhibits a property of not discoloring even at a curing temperature of 300 ° C. or higher.

The cured film is a flattening film for thin film transistor (TFT) substrates such as liquid crystal display elements and organic EL display elements, a protective film or insulating film for touch panel sensor elements, an interlayer insulating film for semiconductor elements, and a flattening film for solid-state imaging devices. It can be used as a core or clad material for an optical waveguide such as a microlens array pattern or an optical semiconductor device.

Further, according to another embodiment, an electronic device including the cured film is provided.

The electronic device may be a liquid crystal display device, an organic EL device, a semiconductor device, a solid-state imaging device, or the like including the cured film as a flattening film of a TFT substrate, and is not limited thereto.

Hereinafter, embodiments of the present invention described above will be described in more detail through Examples. However, the examples below are for purposes of illustration only and do not limit the scope of the invention.

(Example)
Synthesis Example 1-8: Production of polysiloxane copolymer Synthesis Example 1: Production of polysiloxane copolymer 57.74 g (0.70 mol) of phenyltrimethoxysilane (silane compound 1) and methyltri in a 500 ml 3-port flask. 14.17 g (0.25 mol) of methoxysilane (silane compound 2), 7.38 g (0.05 mol) of 1,2-bistriethoxysilylethane (silane compound 3) and 168.78 g of propylene glycol monomethyl ether acetate (PGMEA). Was added, and an aqueous nitrate solution prepared by dissolving 180 ppm of nitrate in 48.54 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.6 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,825. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 40 Å / sec.

Synthesis Example 2: Production of polysiloxane copolymer 61.72 g (0.75 mol) of phenyltrimethoxysilane, 11.31 g (0.20 mol) of methyltrimethoxysilane, and 1,2-bistriethoxy in a 500 ml three-necked flask. 7.36 g (0.05 mol) of silylethane and 168.38 g of PGMEA were added, and an aqueous nitric acid solution prepared by dissolving 180 ppm of nitrate in 48.42 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.4 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,650. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 35 Å / sec.

Synthesis Example 3: Production of Polysiloxane Copolymer 65.67 g (0.80 mol) of phenyltrimethoxysilane, 8.46 g (0.15 mol) of methyltrimethoxysilane, 1,2-bistriethoxysilyl in a 500 ml three-necked flask. 7.34 g (0.05 mol) of ethane and 167.97 g of PGMEA were added, and an aqueous nitrate solution prepared by dissolving 180 ppm of nitrate in 48.31 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.3 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was a weight average molecular weight (Mw) = 3,500. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 45 Å / sec.

Synthesis Example 4: Production of Polysiloxane Copolymer 69.53 g (0.85 mol) of phenyltrimethoxysilane, 5.62 g (0.10 mol) of methyltrimethoxysilane, 1,2-bistriethoxysilyl in a 500 ml three-necked flask. 7.31 g (0.05 mol) of ethane and 167.36 g of PGMEA were added, and an aqueous nitrate solution prepared by dissolving 180 ppm of nitrate in 48.13 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.2 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,364. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 32 Å / sec.

Synthesis Example 5: Production of polysiloxane copolymer 73.44 g (0.90 mol) of phenyltrimethoxysilane, 2.8 g (0.05 mol) of methyltrimethoxysilane, 1,2-bistriethoxysilyl in a 500 ml three-necked flask. 7.30 g (0.05 mol) of ethane and 166.96 g of PGMEA were added, and an aqueous nitrate solution prepared by dissolving 180 ppm of nitrate in 48.01 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.1 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,195. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 25 Å / sec.

Synthesis Example 6: Production of Polysiloxane Copolymer 77.29 g (0.95 mol) of phenyltrimethoxysilane, 7.27 g (0.05 mol) of 1,2-bistriethoxysilylethane and PGMEA 166.47 g in a 500 ml three-necked flask. Was added, and an aqueous nitric acid solution prepared by dissolving 180 ppm of nitric acid in 47.87 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.0 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,170. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 20 Å / sec.

Synthesis Example 7: Production of polysiloxane copolymer 41.74 g (0.50 mol) of phenyltrimethoxysilane, 25.81 g (0.45 mol) of methyltrimethoxysilane, 1,2-bistriethoxysilyl in a 500 ml three-necked flask. 7.46 g (0.05 mol) of ethane and 170.81 g of PGMEA were added, and an aqueous nitrate solution prepared by dissolving 180 ppm of nitrate in 49.12 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 8 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 44.1 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was a weight average molecular weight (Mw) = 3,150. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 5% TMAH aqueous solution was measured and found to be 45 Å / sec.

Synthesis Example 8: Production of polysiloxane copolymer 41.74 g (0.50 mol) of phenyltrimethoxysilane, 25.81 g (0.45 mol) of methyltrimethoxysilane, 1,2-bistriethoxysilyl in a 500 ml three-necked flask. 7.46 g (0.05 mol) of ethane and 170.81 g of PGMEA were added, and an aqueous nitrate solution prepared by dissolving 180 ppm of nitrate in 49.12 g of water was added over 10 minutes while stirring at room temperature. Then, the flask was immersed in an oil bath at 25 ° C. and stirred for 120 minutes, and then the temperature of the oil bath was raised to 110 ° C. over 60 minutes. From there, the mixture was heated and stirred for 4 hours (internal temperature was 100 to 110 ° C.) to obtain a polysiloxane copolymer solution. A total of 43.1 g of methanol and water, which are by-products, were distilled from the reaction product.

The solid content concentration of the obtained polysiloxane copolymer solution was 40% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 2,850. The obtained resin solution was applied to a silicon wafer so that the film thickness after prebaking was 2 μm, and the dissolution rate in a 2.38% TMAH aqueous solution was measured and found to be 200 Å / sec.

The composition, molecular weight, refractive index measured at D-line (589 nm) wavelength using an Abbe refractometer, and TMAH aqueous solution after prebaking, and the composition and molecular weight of the polysiloxane copolymer solution prepared in Synthesis Examples 1 to 8. The dissolution rate with respect to is shown in Table 1 below.

Referring to Table 1 above, according to one embodiment, phenyltrimethoxysilane and methyltrimethoxysilane, which are silane compounds represented by the chemical formula 1, and 1,2-bistriethoxysilylethane represented by the chemical formula 2 are added. In the case of the polysiloxane copolymer produced in Synthesis Examples 1 to 6 formed by decomposition and condensation reaction in which 65% or more of all silicon atoms are substituted with phenyl groups, the refractive index is 1.50 or more and high refraction. It was confirmed that the rate was shown.

On the other hand, the polysiloxane copolymer produced in Synthesis Example 7 in which only 50% of all silicon atoms in the polysiloxane copolymer was substituted with a phenyl group was insoluble in a 2.38% TMAH aqueous solution, and was 5.0. It was shown that the refractive index was lowered to less than 1.50 even when the dissolution rate in the% TMAH aqueous solution was 45 Å / sec.

Further, also in the case of the polysiloxane copolymer produced in Synthesis Example 8 in which only 50% of the total silicon atoms in the polysiloxane copolymer are substituted with phenyl groups and the dissolution rate in the TMAH aqueous solution also deviates from one embodiment. It was shown that the refractive index was lowered to less than 1.50.

Examples and Evaluation: Production and Evaluation of Photosensitive Resin Composition and Cured Film Each polysiloxane copolymer produced in the above synthesis example, a thermoacid generator, and a solvent are mixed and stirred to prepare a uniform solution. Then, the mixture is filtered through a 0.2 μm filter to produce a photosensitive resin composition according to the following Examples and Comparative Examples.

The photosensitive resin compositions according to the manufactured Examples and Comparative Examples were spin-coated on a 10 × 10 glass substrate using a spin coater (manufactured by Mikasa Corporation) and hot plates (manufactured by Dainippon Screen Mfg. Co., Ltd.). Pre-bake at 140 ° C. for 120 seconds using SCW-636), and adjust each to a thickness of 2.7 μm. Then, it is calcined by firing at 380 ° C., the transmittance is measured, and the shape of the film surface is observed. Then, a curing cycle is performed with a thermal shock chamber to check for cracks.

Each of the above measurements was performed by the following method, and the results are shown in Table 2 below:
(1) Confirmation of crack occurrence A sample is manufactured on a 10 × 10 glass substrate so that the thickness after curing is 2.5 ± 0.1 μm. After curing, the surface of the specimen is checked with an optical microscope to determine the presence / absence of cracks.

(2) Measurement of Light Transmittance Using the MultiSpec-1500 (trade name, SHIMADZU Corporation), the light transmittance of only the glass substrate was first measured, and the ultraviolet-visible absorption spectrum thereof was used as a reference. Next, a cured film of the photosensitive resin composition was formed on the glass substrate (no pattern exposure was performed), and this sample was measured with a single beam to determine the light transmittance at a wavelength of 400 nm per μm, which was used as a reference. The difference was defined as the light transmittance of the cured film.

(3) Measurement of chemical resistance A sample is manufactured on a 10 × 10 glass substrate so that the thickness after curing is 2.5 μm ± 0.1 μm, and this is 5 × 5 with a glass sample. Disconnect. Next, after measuring the thickness of the intermediate portion, it is immersed in a chemical resistant solvent for 5 minutes and then washed with water to confirm the change in thickness.

The photosensitive resin compositions according to each Example and Comparative Example, the cured film produced from the photosensitive resin composition, and the characteristics of the cured film are described below.

Example 1: Production and evaluation of cured film 3 parts by weight of a thermoacid generator is added to 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 1. A solvent in which PGMEA and GBL were mixed was added thereto, and the mixture was mixed and stirred to prepare a uniform solution, and then filtered through a 0.2 μm filter to prepare a resin composition.

The composition was spin-coated on a 10 × 10 glass substrate using a spin coater (manufactured by Mikasa Corporation), and then spun-coated at 140 ° C. using a hot plate (Dainippon Screen Mfg. Co., manufactured by Ltd. SCW-636). It was prebaked for 120 seconds and adjusted to a film thickness of 2.7 μm. After prebaking, firing curing was carried out at 380 ° C. to obtain an insulating film having an improved transmittance of 98% and a thickness margin of 3.2 μm without cracks and improved high temperature crack resistance and chemical resistance. ..

Example 2: Production and Evaluation of Hardened Film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 2 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having an improved transmittance of 98% and a thickness margin of 3.2 μm without cracks and improved high temperature crack resistance and chemical resistance was obtained.

Example 3: Production and Evaluation of Hardened Film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 3 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having an improved transmittance of 98% and a thickness margin of 3.5 μm without cracks and improved high temperature crack resistance and chemical resistance was obtained.

Example 4: Production and Evaluation of Hardened Film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 4 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having an improved transmittance of 98% and a thickness margin of 3.5 μm without cracks and improved high temperature crack resistance and chemical resistance was obtained.

Example 5: Production and evaluation of cured film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 5 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having an improved transmittance of 98% and a thickness margin of 4.0 μm without cracks and improved high temperature crack resistance and chemical resistance was obtained.

Example 6: Production and Evaluation of Hardened Film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 6 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having an improved transmittance of 98% and a thickness margin of 4.5 μm without cracks and improved high temperature crack resistance and chemical resistance was obtained.

Comparative Example 1: Production and Evaluation of Hardened Film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 7 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having a transmittance of 97% and a thickness margin of 2.5 μm without cracks was obtained.

Comparative Example 2: Production and Evaluation of Hardened Film A resin composition was produced in the same manner as in Example 1 except that 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 8 was used. A cured film was produced using the same method.

When the curing was carried out, an insulating film having a transmittance of 97% and a thickness margin of 2.5 μm without cracks was obtained.

As can be seen from Table 2 above, it is produced by hydropolymerizing and polycondensing a silane compound represented by the chemical formula 1 and a silane compound represented by the chemical formula 2 according to one embodiment, and 65% based on the total number of silicon atoms. The above contains a polysiloxane copolymer substituted with a phenyl group, the film is insoluble in a 2.38 wt% TMAH aqueous solution after prebaking, and the dissolution rate is 100 Å / sec in a 5.0 wt% TMAH aqueous solution. The cured film produced from the following photosensitive resin composition has a thickness of 2 μm and does not cause cracks, and has a thickness margin of 3.2 μm or more without cracks that maintains a light transmittance of 98% for a wavelength of 400 nm and is resistant to cracks. It can be seen that it is excellent in cracking property and has a high light transmittance. Further, the rate of change in the thickness of the cured film with respect to the evaluation solvent for chemical resistance is 5% or less, and the chemical resistance is also very excellent.

On the other hand, the photosensitivity according to Comparative Example 1 and Comparative Example 2 containing the polysiloxane copolymer produced in Synthesis Example 7 and Synthesis Example 8 in which only 50% of all silicon atoms in the polysiloxane copolymer were substituted with phenyl groups. In each of the sex resin compositions, cracks were generated at a thickness of 2 μm after curing, and crack-free thickness margins for maintaining a light transmittance of 97% for a wavelength of 400 nm were 2.5 μm, respectively, according to Examples 1 to 6. It can be seen that the crack resistance of the cured film is significantly lower than that of the cured film. Further, it can be seen that after immersing in a chemical resistant solution, that is, MEA: DMSO = 7: 3 solution and NMP solution for 5 minutes, the measured thickness change rates are all 5% or more, and the chemical resistance is also very low. ..

In conclusion, the photosensitive resin composition according to one embodiment has excellent crack resistance and chemical resistance after curing of the cured film produced from the photosensitive resin composition, maintains high light transmittance, increases crack margin and cures. It can be seen that the thickness of the film can be easily adjusted.

Although the preferred embodiment of the present invention has been described in detail above, the scope of rights of the present invention is not limited to this, and those skilled in the art using the basic concept of the present invention defined in the following claims. Various modifications and improvements also belong to the scope of the invention.

Claims (12)

(A) Formed by hydrolyzing and condensing at least one silane compound represented by the following chemical formula 1 and a silane compound represented by the following chemical formula 2, 65% or more of all silicon atoms are phenyl groups. A photosensitive resin composition containing the polysiloxane polymer substituted with (B) and the solvent (B).
A polysiloxane polymer solution composed of the component (A) and the component (B) in the photosensitive resin composition is applied to a silicon wafer so that the film thickness after prebaking is 0.1 μm to 15 μm, and the temperature is 50 ° C. film after prebaking 30 seconds to 30 minutes at to 150 DEG ° C. is the 2.38 wt% tetramethylammonium hydroxide (TMAH) aqueous solution is insoluble, dissolution rate at 5 wt% TMAH aqueous solution is 100 Å / sec Photosensitive resin composition:
In the chemical formula 1,
R ¹ is hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6-C30 aryl groups, substituted or unsubstituted. C7 to C30 arylalkyl groups, substituted or unsubstituted C1 to C30 heteroalkyl groups, substituted or unsubstituted C2 to C30 heterocycloalkyl groups, substituted or unsubstituted C1 to C30 heteroaryl groups, substituted Alternatively, an unsubstituted C2-C30 alkenyl group, a substituted or unsubstituted C2-C30 alkynyl group, RO-, R (C = O)-(where R is a substituted or unsubstituted C1-C30 alkyl group. , Substituted or unsubstituted C3 to C30 cycloalkyl groups, substituted or unsubstituted C6 to C30 aryl groups, or substituted or unsubstituted C7 to C30 arylalkyl groups), or a combination thereof.
X ¹ is an alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof of C1 to C6.
a is 0 ≦ a <4 :

In the chemical formula 2,
Y ¹ is a single bond, oxygen, substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C3 to C30 cycloalkylene group, substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted. C2-C30 heteroarylene group, substituted or unsubstituted C2-C30 alkenylene group, substituted or unsubstituted C2-C20 alkynylene group, or a combination thereof.
X ² and X ³ are independently C1 to C6 alkoxy groups, hydroxy groups, halogens, carboxyl groups, or combinations thereof . In the chemical formula 1, R ¹ is hydrogen, an alkyl group of C1 to C10, an alkenyl group of C2 to C10, an aryl group of C6 to C16, or a combination thereof, and X ¹ is an alkoxy group of C1 to C6, a hydroxy group, and the like. The photosensitive resin composition according to claim 1, which is a halogen or a combination thereof. Wherein R ¹ in Chemical Formula 1 is a methyl group or a phenyl radical, a is 1, the photosensitive resin composition of claim 1. In the chemical formula 2, the Y ¹ is an alkylene group of C1 to C10, a cycloalkylene group of C3 to C10, an arylene group of C6 to C12, or a combination thereof, and X ² and X ³ are independent of each other. an alkoxy group of C1 -C6, the photosensitive resin composition of claim 1. A polysiloxane polymer solution composed of the component (A) and the component (B) in the photosensitive resin composition is applied to a silicon wafer so that the film thickness after prebaking is 0.1 μm to 15 μm, and the temperature is 50 ° C. The first aspect of claim 1 , wherein the film after prebaking at ~ 150 ° C. for 30 seconds to 30 minutes is insoluble in a 2.38 wt% TMAH aqueous solution and has a dissolution rate of 50 Å / sec or less in a 5 wt% TMAH aqueous solution. Photosensitive resin composition. The polysiloxane polymer (A) hydrolyzes and condenses 80 mol% to 97 mol% of the silane compound represented by the chemical formula 1 and 3 mol% to 20 mol% of the silane compound represented by the chemical formula 2. The photosensitive resin composition according to claim 1 , wherein the photosensitive resin composition is formed. The photosensitive resin composition according to claim 1 , wherein 70% or more of the total silicon atoms of the polysiloxane polymer (A) are substituted with phenyl groups. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition further comprises (C) an additive that generates an acid or a base by heat or light, (D) a quinonediazide compound, or a combination thereof. .. The photosensitive resin composition according to claim 1, wherein the refractive index of the photosensitive resin composition measured under the D-line (589 nm) wavelength is 1.50 or more. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 9 . The cured film according to claim 10 , wherein the cured film has a light transmittance of 98% or more at a wavelength of 400 nm per 1 μm of thickness . An electronic device comprising the cured film according to claim 10 .