WO2018062652A1

WO2018062652A1 - Photosensitive resin composition, cured film formed therefrom, and electronic device having cured film

Info

Publication number: WO2018062652A1
Application number: PCT/KR2017/003499
Authority: WO
Inventors: 백택진; 김태수; 박종희; 신동주; 안치원; 유홍정
Original assignee: 삼성에스디아이 주식회사
Priority date: 2016-09-28
Filing date: 2017-03-30
Publication date: 2018-04-05
Also published as: KR102032345B1; KR20180035075A; CN109791360B; CN109791360A; JP2019530900A; JP6826193B2

Abstract

Provided are a photosensitive resin composition, a cured film produced by curing the photosensitive resin composition, and an electronic device comprising the cured film, the photosensitive resin composition comprising (A) a polysiloxane polymer and (B) a solvent, wherein the (A) polysiloxane polymer is formed by subjecting at least one type of a silane compound, represented by chemical formula 1 below, to hydrolysis and a condensation reaction, wherein a prebaked film is insoluble in an aqueous 2.38 wt% tetramethylammonium hydroxide (TMAH) solution and has a dissolution rate of 100Å/sec or lower in an aqueous 5 wt% TMAH solution: [chemical formula 1] (R¹)_aSiX¹ _4-a, wherein R¹, X¹ and a are as defined in the specification.

Description

【Specification】

[Name of invention]

An electronic device having a photosensitive resin composition, a cured film formed therefrom, and the cured film

Technical Field

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

Background Art

In order to achieve more accurate and higher resolution in liquid crystal displays and organic EL displays, the aperture ratio of the display device must be increased. To this end, a transparent flattening film is provided as a protective film on the TFT substrate to overlap the C data line and the pixel electrode, thereby increasing the high aperture ratio. There is a way to make this possible.

As a material for forming the organic insulating film for the 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 to secure the conduction between the TFT substrate electrode and the IT0 electrode. It is necessary to form a hole pattern on the order of 50 to several mils.

Conventionally, the material which combined phenolic resin and a numone diazide compound, or the photosensitive resin composition which combined an acryl-type resin and a numone diazide compound has been mainly used. However, these materials are not rapidly deteriorated at a high temperature of 2 (xrc or higher, but are gradually decomposed ^at 230 ^° C or higher, and a problem of deterioration in film thickness or cracking occurs, or transparent treatment due to high temperature treatment of the substrate. There is a problem that the membrane is colored and the transmittance is lowered.

In addition, in recent years, touch panels have been adopted in liquid crystal displays and the like. However, in order to improve the transparency and functionality of the touch panels, attempts have been made to perform heat treatment or film formation at higher temperatures for the purpose of high transparency and high conductivity of the transparent electrode member ITO. Is being done. Along with this, heat resistance to high temperature treatment is also required for the protective film and the insulating film of the transparent electrode member. However, acrylic resins are unsatisfactory in heat resistance and chemical resistance, such as high temperature treatment of substrates and high temperature of transparent electrodes. There exists a problem that a cured film is colored by film forming or various etching chemical processing, and transparency falls, or electroconductivity of an electrode falls by degassing in high temperature film forming. Therefore, it cannot be used for the process of forming a film | membrane at high temperature using apparatuses, such as PE-CVD, on this transparent film material.

Also in an organic EL element, cracks and decomposition products generated from the above materials are not optimal materials for use because they adversely affect the luminous efficiency and lifetime of the organic EL element. In addition, the acrylic material imparted heat resistance may cause a crack phenomenon at 300 ^° C or more, otherwise the dielectric constant is generally high. Therefore, the parasitic capacitance caused by the insulating film is increased due to the high dielectric constant, which causes a problem in the quality of the image quality due to the increased power consumption or the delay of the liquid crystal element drive signal. In addition, in the case of an insulating material having a high 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 not preferable.

On the other hand, silsesquioxane is known as a high heat resistant and high transparency material. In particular, the photosensitive composition which consists of an acryl-type copolymer and the quinonediazide compound which copolymerized the silsesquioxane compound which provided the acryl group to specific silsesquioxane, the unsaturated compound containing unsaturated carboxylic acid and an epoxy group, and an olefinic unsaturated compound. And the like have been proposed. However, these compounds also have a high thermal content of organic compounds and decompose after high temperature curing ^at 250 ^° C. or higher, resulting in a heat resistance problem that is poor in permeability, and results in a residual film that is not developed to form a flat film, or NMP (N-methyl-). 2-pyrrol idone), tetramethylammonium hydroxide (TMAH) solution, 10% NaOH and other chemical resistance to the solvent is also reduced.

Moreover, the system which combined the quinonediazide compound in order to give positive photosensitive property to a siloxane polymer, The material which combined the siloxane polymer and quinonediazide compound which have a phenolic hydroxyl group at the terminal, and the phenolic hydroxyl group by cyclic heat addition reaction, Materials in which a siloxane polymer to which a carboxyl group or the like is added and a quinonediazide compound are combined are known. However, these materials contain large amounts of quinonediazide compounds, or because phenolic hydroxyl groups are present in the siloxane polymer, This coating film tends to occur whitening or coloring during heat curing, in the above 300 ^° C acrid high temperatures can cause the cracking and thus can not be utilized permeability ^'and due to the decrease as a transparent material according to. In addition, these materials have a problem of low sensitivity at the time of pattern formation because of their low transparency.

When the photosensitive composition material which consists only of polysiloxane and a quinone diazide compound is thermoset, crosslinking and high molecular weight generate | occur | produce by dehydration of the silanol group in polysiloxane. In this thermosetting process, before the thermosetting of the pattern proceeds sufficiently, the film is melted by the low viscosity of the film by high temperature, and the patterns such as holes and lines obtained after development flow. As a result, a crack does not occur, but a "pattern" deterioration occurs in which the resolution decreases, which must be prevented. In addition, a combination of the insoluble polysiloxane, the soluble polysiloxane system, and the quinone diazide compound is combined with the developer, and during heat curing, a pattern such as a hole or a line obtained after development collapses, resulting in a "pattern sagging" that results in a decrease in resolution. A photosensitive composition which prevents is proposed. However, when insoluble polysiloxane is used in the developing solution, it melts after development, but causes a development pattern defect to occur due to re-adhesion of residues or difficult-to-melt materials that start to melt. In addition, in order to prevent pattern deterioration, it is necessary to increase the molecular weight of siloxane sufficiently. As a result, the photosensitive material is low in sensitivity and high reaction energy is required. In addition, there is a drawback that the residual film ratio is also not divided, resulting in a large loss of material.

[Detailed Description of the Invention]

[Technical problem]

In some ^embodiments, for example, after high temperature curing is excellent in chemical resistance, and has high light transmittance and crack resistance, cracks margin is improved to provide a photosensitive resin composition which is easy to adjust the thickness.

Another embodiment is to provide a cured film obtained by curing the photosensitive resin composition.

Another embodiment is to provide an electronic device including the cured film. Technical Solution

In one embodiment, (A) a polysiloxane polymer formed by hydrolysis and condensation reaction of at least one silane compound represented by the following Chemical Formula 1, wherein at least 65% of all silicon atoms are substituted by a phenyl group, (B A photosensitive resin composition comprising a solvent, wherein the film after prebaking is insoluble in a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) and the dissolution rate in a 5% by weight solution of TMAH is 100 A / sec or less. do:

[Formula 1]

4 一 a

In Chemical Formula 1,

R ¹ is hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 Arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted Or an unsubstituted C2 to C30 alkynyl group, R0-, R (C = 0)-(where R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or Unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof,

X ¹ is a C1 to C6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or any combination thereof ⁰ igo,

a is 0 <a <4

In Formula 1, R ¹ is hydrogen, C1 to C10 alkyl group, C2 to C10 alkenyl group, C6 to C16 aryl group, or a combination thereof, X ¹ is C1 to C6 alkoxy group, hydroxy group, halogen, or a combination thereof May be a combination.

In Formula 1, R ¹ is a methyl group or a phenyl group, a may be 1.

The polysiloxane polymer (A) is a silane compound represented by the following formula (2) It may be further included hydrolyzed and condensation.

[Formula 2]

X ^ Si -Y ^ SiX ^ _.

In Chemical Formula 2,

Y ¹ is a single bond, oxygen, substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C3 to C30 cycloalkalene group, substituted or unsubstituted C6 to C30 arylene group, substituted or unsubstituted C2 to A C30 heteroarylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

X ² and X ³ are each independently a C1 to C6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof.

In Formula 2, Y ¹ may be a C1 to C10 alkylene group, a C3 to C10 cycloalkylene group, a C6 to C12 arylene group, or a combination thereof, and X ² and X ³ may be a C1 to C6 alkoxy group.

The film after prebaking of the photosensitive resin composition may be insoluble in a 2.38 wt% TMAH aqueous solution and the dissolution rate in the 5 wt% TMAH aqueous solution may be 50 A / sec or less.

The polysiloxane polymer (A) is prepared by hydrolyzing and condensing the silane compound represented by Formula 1 to 80 mol% to 97 mol¾> and 3 to 20 mol% of the silane compound represented by Formula 2 together. can do.

At least 70% of the total silicon atoms of the polysiloxane polymer (A) may be substituted by phenyl groups.

The photosensitive resin composition may further include (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 may be at least 1.50.

Another embodiment provides a cured film prepared by curing the photosensitive resin composition. The cured film may have a light transmittance of 98% or more at a 400 nm wavelength. Another embodiment provides an electronic device including the cured film. 【Effects of the Invention】

The photosensitive resin composition according to an embodiment may have excellent chemical resistance, have high light transmittance and crack resistance after high silver curing, and may provide a cured film having an improved crack margin.

The cured film may be usefully used for manufacturing a planarization film for a thin film transistor (TF) substrate, an interlayer insulating film of a semiconductor device, and the like.

[Best form for implementation of the invention]

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice. As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention.

Unless otherwise defined herein, 'substituted' means that a hydrogen atom in a compound is a halogen atom (F, Br, C1, or 1), a hydroxyl group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, an amino group Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or salt thereof, sulfonic acid group or salt thereof, phosphoric acid or salt thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 C20 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 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, It means substituted with a substituent selected from C6 to C15 cycloalkynyl group, C3 to C30 heterocycloalkyl group and combinations thereof.

In addition, unless otherwise defined herein, "hetero" means containing at least one hetero atom selected from N, 0, S and P.

Unless otherwise specified herein, 'combination' means a combination or copolymerization.

Hereinafter, a photosensitive resin composition according to an embodiment will be described. The photosensitive resin composition according to one embodiment is formed by (A) hydrolyzing and condensing at least one silane compound represented by Formula 1 below, and a polysiloxane polymer in which at least 65% of all silicon atoms are substituted by phenyl groups And (B) a solvent, wherein the membrane after prebaking is insoluble in a 2.38 wt% tetramethylammonium hydroxide (TMAH) water ^' solution and the dissolution rate in a 5 wt% TMAH aqueous solution is 100 A / sec or less:

[Formula 1]

4-a

In Chemical Formula 1,

R ¹ is hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 Arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, ^' substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group, Substituted or unsubstituted C2 to C30 alkynyl group, R0-, R (C = 0)-(where R is substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted Or an unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof,

X ¹ is a C1 to C6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof,

n is 0 <n <4.

The photosensitive resin composition according to the embodiment includes a polysiloxane polymer prepared by hydrolyzing and condensing at least one silane compound represented by Chemical Formula 1, thereby having excellent chemical resistance, and having a high tangerine index having a refractive index of 1.5 or more. It provides a resin composition. Accordingly, the photosensitive resin composition according to the embodiment has a high light transmittance at high temperature curing, the crack margin is improved to exhibit an easy thickness control of the insulating film. For example, R ¹ of Formula 1 may be hydrogen, C1 to C10 alkyl group, C2 to C10 alkenyl group, C6 to C16 aryl group, or a combination thereof, X ¹ is C1 to C6 alkoxy group, hydroxy group, halogen , Or a combination thereof, and n in Formula 1 may be 0 or 1.

In one embodiment, R ¹ is a methyl group or a phenyl group, a may be 1. The polysiloxane polymer (A) according to the embodiment may further be hydrolyzed and condensation-polymerized further comprising a silane compound represented by the following formula (2):

[Formula 2]

X ^ Si-Y ^ SiX ^

In 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 to C30 arylene group, substituted or unsubstituted C2 to C30 hetero An arylene group, a substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

For example, in Formula 2, Y ¹ may be C1 to C10 alkylene group, C3 to C10 cycloalkylene group, C6 to C12 arylene group, or a combination thereof, and X ² and X ³ may be C1 to C6 alkoxy. It may be a flag. In one embodiment, the photosensitive resin composition is hydrolyzed and condensed at least one type represented by the formula (1) and 80 mol% to 97 mol% of the silane compound, and 3 mol% to 20 mol% of the silane compound represented by Chemical Formula 2 It can be prepared by reaction. When the polysiloxane copolymer prepared by hydrolyzing and condensing the silane compound represented by Formula 1 and Formula 2 in the above range, the photosensitive resin composition has a refractive index of 1.50 or more, for example, 1.51 or more, for example For example, 1.52 or more, 1.53 or more, for example, 1.54 or more, for example, 1.55 or more. As the photosensitive resin composition according to the embodiment has a high refractive index of 1.50 or more, crack margin is improved to control the thickness of the insulating film. It shows an easy effect.

The molecular weight of the polysiloxane polymer (A) formed by hydrolysis and polycondensation has a weight average molecular weight of 1,000 to 500,000 in terms of polystyrene standard 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 to 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 ι, οοο or more, it is possible to implement the desired thickness of the cured film without causing cracks on the surface during curing. In addition, when the weight average molecular weight is 500,000 or less, it is possible to improve the surface planarity while maintaining the viscosity required for coating.

As described above, the polysiloxane polymer (A) according to one embodiment is a compound in which the membrane after prebaking is insoluble in an aqueous 2.38 wt% TMAH solution and has a dissolution rate of 100 A / sec or less in a 5 wt% TMAH aqueous solution. For example, the polysiloxane polymer (A) is a compound in which the film after prebaking is insoluble in a 2.38 wt% TMAH aqueous solution and has a dissolution rate of 50 A / sec or less in a 5 wt% aqueous TMAH solution. After prebaking the composition comprising the polysiloxane polymer and the dissolution rate in the TMAH aqueous solution of the film is within the above range, the cured film obtained by curing the composition has a crack free thickness margin of 3.0 or more, for example, 3.2 m or more. The cured film obtained by hardening the said photosensitive resin composition is very high crack resistance in silver.

In addition, after curing the photosensitive resin composition to produce a specimen on a 10 X 10 glass substrate so that the thickness is 2.5 sul 0.1 / ，, and after measuring the thickness of the center portion of the specimen and soaked in a chemical-resistant solvent for 5 minutes and the thickness change is confirmed , Exhibited a thickness change rate of less than 5%. Through this, it can be seen that the cured film prepared from the photosensitive resin composition according to the embodiment has a relatively excellent chemical resistance. The rate of change of thickness can be calculated from Equation 1:

[Equation 1]

Thickness change rate (w = (film thickness after chemical resistance evaluation-film thickness before chemical resistance evaluation) / film thickness before chemical resistance evaluation x ioo

On the other hand, as can be seen from the comparative examples described below, the content of phenyl groups substituted for all silicon atoms in the polysiloxane copolymer, or the membrane prepared from the composition comprising the copolymer does not meet the above dissolution rate range for TMAH. In this case, the cured film cured from such a composition does not have the above crack resistance and chemical resistance.

The content of a phenyl group substituted in the polysiloxane polymer (A) is at least 65%, for example at least 70%, based on the number of all Si atoms. The photosensitive resin composition comprising the polysiloxane polymer substituted with the phenyl group of the above content can significantly reduce the crack incidence upon curing at high temperature. If the content of phenyl groups 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 prepared therefrom is cured at high temperatures. The incidence of stacks may increase.

In general, in the case of a photosensitive resin composition, for example, a positive photosensitive resin composition, the curable film may be used as a protective film or an insulating film of a display display device. By the way, the conventional positive photosensitive resin composition is low in refractive index, and it became a cause which lowered the efficiency and thermal stability of an electronic device, for example, a 0LED light emitting element. The photosensitive resin composition includes a polysiloxane polymer formed by hydrolysis and polycondensation of a silane compound represented by Chemical Formula 1 and / or Chemical Formula 2 to form a surface protective film and an interlayer insulating film of a display device by increasing the refractive index. It can be usefully used.

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

Although there is no restriction | limiting in particular in the solvent which can be used, Preferably the compound which has an alcoholic hydroxyl group, and / or the cyclic compound which has a carbonyl group is used. When these solvents are used, the silane compound is uniformly dissolved to form a film after application of the composition. High transparency can be achieved without whitening of the temporal membrane.

Particularly limited, but the compound having an alcoholic hydroxyl group, can be preferably used for a boiling point of 110 ^° C to 250 ^° C under atmospheric pressure compound. If the boiling point is higher than 25CTC, the amount of remaining solvent in the film increases, and the film shrinks during curing, thereby making it impossible to obtain good flatness. If the boiling point is lower than 110 ^° C, the coating film becomes too dry and the film surface becomes rough, resulting in poor coating properties.

Specific examples of the compound having an alcoholic hydroxyl group include ace, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy-3-methyl-2—butanone and 5-hydroxy-2-pentanone. , 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate, butyl lactate, propylene glycol mono methyl ether, propylene glycol mono ethyl ether, propylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol, 3-methyl-3- methoxy-1-butanol, and the like. Among these, especially compounds having a carbonyl group are preferable, and diacetone alcohol is particularly preferably used. In addition, you may use the compound which has these alcoholic hydroxyl groups individually or in combination of 2 or more types.

In particular restriction on a cyclic compound having a carbonyl group, but, preferably may be under atmospheric pressure boiling point of the phosphorus compound to 150 ^° C 25CTC. If the boiling point is higher than 250 ^° C., the amount of residual solvent in the film increases, the film shrinkage during curing increases, and good elasticity cannot be obtained. If the boiling point is lower than 15 CTC, the coating film properties become poor due to too fast drying during coating.

Specific examples of the cyclic compound having a carbonyl group include _γ -butyrolactone, _γ -valerlactone, δ-valerolactone, propylene carbonate, Ν-methyl pyridone, cyclonucleanone, cycloheptanone, and the like. . In particular, _γ -butyrolactone may be preferably used. In addition, you may use these cyclic compounds which have a carbonyl group individually or in combination of 2 or more types.

The compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group may be used alone or in combination with each other. When used in combination, Although there is no restriction | limiting in particular in the weight ratio, Preferably, the ratio of the compound which has an alcoholic hydroxyl group, and the cyclic compound which has a carbonyl group is 99-50: 1-50, or, for example, 97-60: 3-40. When the compound having an alcoholic hydroxyl group is more than 99% by weight (the cyclic compound having a carbonyl group is less than 1% by weight), the compatibility of the silane compound of Formula 1 may be deteriorated, the cured film may be whitened, and transparency may be decreased. In addition, when the compound having an alcoholic hydroxyl group is less than 50% by weight (the cyclic compound having a carbonyl group is more than 50% by weight), the condensation reaction of unreacted silanol groups in the silane compound of Formula 1 may easily occur, leading to poor storage stability. have.

The photosensitive resin composition according to the above embodiment may further include other solvents in a range that does not impair the effects of the present invention. Other solvents include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol mono methyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-medium when 1-ester such as butyl acetate, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, ketones such as acetyl acetone, diethyl ether, diisopropyl ether, _di-n - butyl ether, diphenyl ether Ethers such as ^: c.

Although there is no restriction | limiting in particular in the addition amount of a solvent, Preferably it can be used in the range of 100-1, 000 weight% with respect to 100 weight% of said silane compounds of the said Formula (1). Alternatively, the solvent may be included so that the solid content is 10 to 50 wt% based on the total weight of the photosensitive resin composition. The said solid content means the composition component except a solvent in the resin composition of this invention.

In addition, the photosensitive resin composition according to the embodiment may contain an additive capable of generating an acid or a base with (C) heat or light. For example, it may be a thermal acid generator, a photoacid generator, a thermal base generator or a photoacid generator, for example, may be a thermal acid generator. Such (C) additive can improve the resolution by strengthening the shape of the pattern during the manufacture of the cured film, or by increasing the contrast of development,

Photosensitive resin composition according to an embodiment is the (A) polysiloxane polymer 100 With respect to parts by weight, the (C) additive may include 0.001 to 10.0 parts by weight, for example, 0.01 to 5.0 parts by weight.

In one embodiment, when the (C) additive is included in the above range, cracks and coloring does not occur when the cured film is manufactured.

Examples of the thermal acid generator include various aliphatic sulfonic acids and salts thereof, various aliphatic carboxylic acids such as citric acid, acetic acid and maleic acid, salts thereof, various aromatic carboxylic acids such as benzoic acid and phthalic acid, salts thereof, aromatic sulfonic acids and ammonium salts, and various amines. Salts, aromatic diazonium salts, phosphonic acids, and salts thereof; salts and esters for generating organic acids; For example, the thermal acid generator in one embodiment may be a salt consisting of an organic acid and an organic base, or a salt consisting of a sulfonic acid and an organic base, but is not limited thereto.

For example, a thermal acid generator containing sulfonic acid may be P-luenesulfonic acid, benzenesulfonic acid, P-dodecylbenzenesulfonic acid, 1,4-naphthalenedisulfonic acid, methanesulfonic acid _Γ, or a combination thereof. Can be.

Examples of the photoacid generator include diazomethane compounds, diphenyl iodonium salts, triphenylsulfonium salts, sulfonium salts, ammonium salts, phosphonium salts, sulfonimide compounds and the like. The structure of these photo-acid generators can be represented by General formula (3).

[Formula 3]

+ X ^"

In Formula 3, R ⁺ is hydrogen, substituted or unsubstituted alkyl group, aryl group, alkenyl group, acyl group, alkoxyl group, etc., X— is, BF ₄ ^" , PIV, Sbl, SCN-, (CF ₃ S0 ₂ ) ₂ N 1, carboxylic acid ions, sulfonium ions and the like.

Examples of the photobase generator may include a polysubstituted amide compound having an amide group, a lactam, an imide compound, and the like. Examples of the thermal base generator include N- (2-nitrobenzyloxycarbonyl) imidazole, N -(3-nitrobenzyloxycarbonyl) imidazole, N- (4-nitrobenzyloxycarbonyl) imidazole, N- (5-methyl-2-nitrobenzyloxycarbonyl) imidazole, N- (4- Imidazole derivatives such as chloro-2-nitrobenzyloxycarbonyl) imidazole, 1,8- Diazabicyclo (5, 4, 0) undecene-7, tertiary amines, quaternary ammonium salts, or combinations thereof.

The photosensitive resin composition according to the embodiment may include (D) a quinonediazide compound. (D) The photosensitive resin composition containing a mundone diazide compound forms the positive type by which an exposure part is removed with a developing solution. The quinonediazide compound which can be used is not particularly limited, but for example, a compound obtained by ester bonding of naphthozinone diazide sulfonic acid to a compound having a phenolic hydroxyl group can be used, and the ortho position of the phenolic hydroxyl group of the compound; and Each of the para positions may independently be hydrogen, or a compound having any one of substituents represented by the following general formula (5):

Formula

In Chemical Formula 5,

R ¹² , R ¹³ , and R ¹⁴ each independently represent any of C1 to C10 alkyl, carboxyl, phenyl and substituted phenyl groups, and R ¹² , R ¹³ , and R ¹⁴ together form a ring. You may.

In R ¹² , R ¹³ , and R ¹⁴ of the group represented by Formula ₅ , the alkyl group may be any of 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-nuclear group, cyclonuclear group, n-heptyl group and n-octyl group And trifluoromethyl group and 2-carboxyethyl group. In addition, the substituted phenyl group includes a phenyl group substituted with a hydroxy group. In addition, R ¹² , R ¹³ , and R ¹⁴ may form a ring together, and specific examples thereof include a cyclopentane ring, a cyclonucleic acid ring, an adamantane ring, and a fluorene ring.

Ortho position of a phenolic hydroxyl group, and a para position, the group of that excepting the above, for example For example, in the case of a metal group, oxidative decomposition occurs by thermosetting, and the conjugated compound represented by a quinoid structure is formed, a cured film is colored and colorless transparency falls. These quinonediazide compounds can be synthesized by a known esterification reaction of a compound having a phenolic hydroxyl group with naphthoquinone diazide sulfonic acid chloride. As a specific example of a compound which has a phenolic hydroxyl group, the following compounds are mentioned (all are the products of Unshu Chemical Co., Ltd.).

TrisP-HAP

BisOTBP-2 BisP-FL

TrisP-TC

4-naphthoquinone diazide sulfonic acid or 5-naphthoquinone diazide sulfonic acid can be used as a naphthoquinone diazide sulfonic acid. The 4-naphthoquinone diazide sulfone acid ester compound is suitable for i-ray exposure because it has absorption in the i-ray (wavelength 365 nm) region. In addition, the 5-naphthoquinone diazide sulfonic acid ester compound is suitable for exposure at a wide range of wavelengths because absorption occurs in a wide range of wavelengths. Depending on the exposure wavelength, 4-naphthozinone diazide sulfonic acid ester compound or 5-naphthoquinone diazide sulfonic acid ester compound can be selected. The 4-naphthoquinone diazide sulfonic acid ester compound and the 5-naphthoquinone diazide sulfonic acid ester compound can also be used in combination.

Although there is no restriction | limiting in particular in the addition amount of a quinonediazide compound, For example, 0.1-15 weight part, for example, 1-10 weight part can be used with respect to 100 weight part of said siloxane compounds of the said Formula (1). 0.1 weight part of addition amount of a quinonediazide compound When less, the melt | dissolution contrast of an exposure part and a non-exposure part is too low, and it does not have photosensitivity realistically. Moreover, 1 weight part or more is preferable in order to acquire more favorable melt contrast. When the amount of the quinone diazide compound is more than 15 parts by weight, the compatibility between the siloxane compound and the quinone diazide compound is deteriorated, so that whitening of the coating film occurs or coloring due to decomposition of the quinone diazide compound occurs during thermal curing. Since it becomes, the colorless transparency of a cured film falls. Moreover, in order to obtain a more transparent film, it is preferable to use a quinonediazide compound at 10 weight part or less.

The photosensitive resin composition according to the above embodiment may further include additional components conventionally used in the photosensitive resin composition, for example, a silane coupling agent, a surfactant, and the like, as necessary.

A silane coupling agent is added in order to improve the adhesiveness of the cured film formed and a board | substrate, As a well-known silane coupling agent, the functional silane compound which has a semi-aromatic substituent can be used. Examples of the semi-aromatic substituent include carboxyl group, methacryloyl group, isocyanate group, epoxy group and the like.

Specific examples of the silane coupling agent include trimethoxysilylbenzoic acid, Y-methacryloxypropyltrimethoxysilane, vinyltriacexoxysilane, vinyltrimethoxysilane, Y-isocyanatopropyltriethoxysilane, _Y One or more selected from -glycidoxypropyltrimethoxysilane, _γ -glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclonucleosil) ethyltrimethoxysilane can be used, preferably Glycidoxypropyltriethoxysilane and / or glycidoxypropyltrimethoxysilane having an epoxy group may be used in view of the residual film ratio and the adhesion between the substrate, but the present invention is not limited thereto.

^The silane coupling agent may be included in the range of 0.01 to 10 parts by weight, for example, 0.01 to 5 parts by weight, based on 100 parts by weight (based on the solid content) of the compound represented by Formula 1 in the photosensitive composition. When the content of the silane coupling agent is 0.01 parts by weight or more, the adhesion to the substrate is improved, when the content is less than 10 parts by weight, the thermal stability is improved at high temperatures, and staining after development can be prevented. have.

The photosensitive resin composition according to the present invention may further include a surfactant to improve coating performance. Such surfactants include fluorine-based surfactants, silicone-based surfactants, nonionic surfactants, and other surfactants. As the surfactant, for example, FZ2122 Dow Corning Toray Corporation), BM-1000, BM-

1100 (manufactured by BM CHEMIE Co., Ltd.), Mega Pack F142 D, Copper F172, Copper F173, Copper F183 (Dai Nippon Ink Chemical Co., Ltd.), Flora FC-135, Copper FC-170 C, Copper FC-430 , Copper FC-431 (manufactured by Sumitomo 3M Limited), Supron S-112, Copper S- 113, Copper S-131, Copper S- 141, Copper S-145, Copper S-382, Copper SC- 101, Copper SC-102, East SC-103, East SC-104, East SC-105, East SC-106 (manufactured by Asahi Glass Co., Ltd.), F-Top EF301, East 303, East 352 (manufactured by Shinagawa Kasei Co., Ltd.) ), Fluorine-based and silicone-based surfactants such as SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, DC-190 (manufactured by Toray Silicone Co., Ltd.); Polyoxyethylene aryl ethers such as polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether Nonionic surfactants such as polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) or (meth) acrylic acid-based copolymer polyflow Nos. 57, 95 (manufactured by Kyoeisha Chemical Co., Ltd.) is used alone or in combination. The above can be used in parallel.

The surfactant may be used in the range of 0.05 to 10 parts by weight, for example, 0.01 to 5 parts by weight, based on 100 parts by weight of the compound represented by Formula 1 (based on the solid content). When the content of the surfactant is 0.05 parts by weight or more, the applicability is improved and cracks do not occur on the coated surface, and when it is 10 parts by weight or less, it is advantageous in terms of price.

The photosensitive resin composition according to one embodiment, in addition to the components, is typically in the thermosetting resin composition and / or photosensitive resin composition, if necessary It may further comprise additional ingredients used. For example, the photosensitive resin composition according to the above embodiment may contain additives such as a dissolution accelerator, a dissolution inhibitor, a surfactant, a stabilizer, and an antifoaming agent, as necessary.

Hereinafter, the formation method of the cured film using the photosensitive resin composition which concerns on the said Example is demonstrated.

The photosensitive resin composition according to the above embodiment is applied onto the base substrate by a known method such as spinner, dipping, slit or the like, and prebaked with a heating device such as a hot plate or an oven. Prebaking is carried out in the range of 50 ^° C to 150 ^° C for 30 seconds to 30 minutes, the film thickness after prebaking can be 0.1 [M to 15. After prebaking, ultraviolet light exposure devices such as stepper, mirror projection mask aligner (MPA) and paratel light mask aligner (PLA) are used to detect 10 mJ / cin in the wavelength range of 2Q0 nm to 450 nm ^. The exposure may be performed at an exposure amount of from 500 mJ / cin ² . After the exposure, the exposed portion is dissolved by development, and a positive pattern can be obtained. As the developing method, it is preferably immersed in the developing solution for 5 seconds to 10 minutes by a method such as showering, dipping, paddle or the like. A well-known alkali developing solution can be used as a developing solution. Specific examples include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylamino ethanol, monoethanol amines and diethan amines, tetramethylammonium hydroxide and choline. The aqueous solution containing 1 type, or 2 or more types of ammonium salts is mentioned.

It is preferable to rinse with water after image development. In addition, if necessary, a drying bake may be performed in a range of 50 ^° C. to 150 ^° C. with a heating device such as a hot plate or an oven. '

If necessary, soft bake in a range of 50 ^° C to 150 ^° C with a heating apparatus such as a hot plate or an oven, and then in a range of 150 ^° C to 450 ^° C with a heating apparatus such as a hot plate, an oven, for example, 10 The desired cured film can be prepared by post-baking for minutes to 5 hours.

As mentioned above, the cured film has high crack resistance and chemical resistance and is excellent in light transmittance. Therefore, the cured film is a thin film transistor (TFT) substrate It can be effectively used for planarization film, interlayer insulation film of semiconductor element and the like.

For example, the cured film according to the embodiment manufactured as described above, in the case of a cured film of 2 urn thickness, high light of 90¾> or more, for example, 95% or more, for example, 98¾> or more in the 400 nm wavelength range Has transmittance.

Conventional acrylic insulating film has a problem that yellowing at 250 ^° C or more due to the low heat resistance characteristics, the transmittance is reduced and the polymer is decomposed to reduce the chemical resistance, silsesquioxane containing acrylic group or epoxy group is more heat resistant than acrylic insulating film This improved but the transmittance was still low at high temperatures and there was a problem of low residual film after development.

At least one silane compound represented by Formula 1 and a formula according to one embodiment

The photosensitive resin composition comprising a polysiloxane copolymer synthesized by hydrolyzing and condensing the silane compound represented by 2, and a solvent may be used as a cross l inker of a carbosilane structural unit in the siloxane compound to form a cured film prepared therefrom. The hardness can be easily adjusted to form a high hardness coating film, thereby improving the high temperature crack resistance. In addition, the organic solvent and the like can be effectively prevented from penetrating through the cured film. Accordingly, the cured film prepared by curing the composition solves the problem of the residual film rate, in which the film thickness is reduced after development, thereby failing to form a flat film, and also does not have a pattern collapse phenomenon due to excellent chemical resistance after curing. In addition, as compared to the conventional acrylic copolymer or silsesquioxane copolymerized with the organic compound has a high heat resistance, it does not discolor at a curing temperature of 300 ^° C or more.

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

According to another embodiment, an electronic device including the cured film is provided. The device is a liquid crystal comprising the cured film as a flattening film of a TFT substrate. It can be a display element, an organic EL element, a semiconductor device, a solid-state image sensor, etc., It is not limited to these.

[Form for implementation of invention]

Through the following examples will be described in more detail the embodiment of the present invention. However, the following examples are merely for illustrative purposes and do not limit the scope of the present invention.

(Example)

Synthesis Examples 1 to 8: Preparation of Polysiloxane Copolymer

Synthesis Example 1 Preparation of Polysiloxane Copolymer

In a 500 ml three-necked flask, 57.74 g (0.70 mol) of phenyltrimethoxysilane (silane compound 1), 14.17 g (0.25 mol) of methyltrimethoxysilane (silane compound 2), and 1, 2-bistrie 7.38 g (0.05 mol) of oxysilylethane (silane compound 3) and 168.78 g of propylene glycol monomethyl ether acetate (PGMEA) were added, and a nitric acid solution in which 180 ppm of nitric acid was dissolved in 48.54 g of water was stirred at room temperature for 10 minutes. Added. Thereafter, the flask was immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, and then the oil bath was heated to 110 ^° C over 60 minutes. From this, the mixture was heated and stirred for 8 hours to obtain a polysiloxane copolymer solution having an internal temperature of 100 to 11 (TC). A total of 43.6 g of methanol and water, which were by-products of the reaction product, was flowed out. The solid content concentration of the obtained polysiloxane copolymer solution was 40%. Weight ¾ The molecular weight (polystyrene equivalent) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3, 825. The obtained resin solution was applied to a silicon wafer so as to have a film thickness of 2 卿 after prebaking, 5 The dissolution rate in the% TMAH aqueous solution was measured and found to be 40 A / sec Synthesis Example 2 Preparation of Polysiloxane Copolymer

In a 500 ml three-necked flask, 61.72 g (0.75 mol) of phenyltrimethoxysilane, 11.31 g (0.20 mol) of methyltrimethoxysilane, and 7.36 g (0.05 mol) of 1,2-bistrisuccixysilylethane and PGMEA 168.38 g was added to 48.42 g of water with stirring at room temperature. An aqueous solution of nitric acid in which 180 ppm of nitric acid was dissolved was added over 10 minutes. The flask was then immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, and then the oil bath was heated to licrc over 60 minutes. It heated and stirred for 8 hours from this (internal temperature is ioo-iio ^° C), and obtained the polysiloxane copolymer solution. A total of 43.4 g of the byproduct methane and water were discharged. Solid content concentration of the obtained polysiloxane copolymer solution was 40 weight%. The molecular weight (polystyrene conversion) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,650. The obtained resin solution was applied to a silicon wafer so as to have a film thickness of 2 after prebaking, and the dissolution rate of the 5¾> TMAH aqueous solution was measured, and found to be 35 A / sec. Synthesis Example 3 Preparation of Polysiloxane Copolymer

In a 500 ml three-necked flask, 65.67 g (0.80 mol) of phenyltrimethoxysilane, 8.46 g (0.15 mol) of methyltrimethoxysilane, 7.34 g (0.05 mol) of 1,2-bistriethoxysilylethane, 167.97 g of PGMEA was added, and a nitric acid aqueous solution in which 180 ppm of nitric acid was dissolved in 48.31 g of water was added over 10 minutes while stirring at room temperature. The flask was then immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, and then the oil bath was heated to 110 ^° C. over 60 minutes. By heating and stirring for 8 hours (internal temperature is 100 ~ 110 ^° C) to obtain a polysiloxane copolymer solution. As a by-product, methanol and water in the reaction product flowed out in total 43.3 _g . Solid content concentration of the obtained polysiloxane copolymer solution was 40 weight>. The molecular weight (polystyrene equivalent) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3, 500. It was 45 A / sec when the obtained resin solution was apply | coated so that the film thickness might become 2 after prebaking on a silicon wafer, and the dissolution rate with respect to 5¾ »TMAH aqueous solution was measured. Synthesis Example 4 Preparation of Polysiloxane Copolymer In a 500 ml three-necked flask, 69.53 g (0.85 mol) of phenyltrimethoxysilane, 5.62 g (Omol) of methyltrimethoxysilane, 7.31 g (0.05 mol) of 1,2-bistriethoxysilylethane and PGMEA 167.36 g was added, and a nitric acid solution in which 180 ppm of nitric acid was dissolved in 48.13 g of water was added over 10 minutes while stirring at room temperature. The flask was then immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, after which the oil bath was heated to 110 ^° C. over 60 minutes. By heating and stirring for 8 hours (internal temperature is 100 ~ 110 ^° C) to obtain a polysiloxane copolymer solution. In total, 43.2 g of the byproduct methane and water were discharged. Solid content concentration of the obtained polysiloxane copolymer solution was 40 weight%. The molecular weight (polystyrene conversion) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,364. The obtained resin solution was applied to a silicon wafer so as to have a film thickness of 2 after prebaking, and the dissolution rate in the 5% TMAH aqueous solution was measured to be 32 A / sec. Synthesis Example 5 Preparation of Polysiloxane Copolymer

In a 500 ml three-necked flask, 73.44 g (0.90 mol) of phenyltrimethoxysilane, 2.8 g (0.05 mol) of methyltrimethoxysilane, 7.30 g (0.05 mol) of 1,2-bistrioxyoxysilylethane and 166.96 g of PGMEA Was added, and an aqueous nitric acid solution in which 180 ppm of nitric acid was dissolved in 48.01 g of water was added over 10 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, and then the oil bath was heated to 110 ^° C over 60 minutes. By heating and stirring for 8 hours (internal temperature is 100 ~ 110 ^° C) to obtain a polysiloxane copolymer solution. A total of 43. 1 g of methane and water were spilled in the byproduct. Solid content concentration of the obtained polysiloxane copolymer solution was 40 weight%. The molecular weight (polystyrene equivalent) of the obtained polysiloxane co-polymer was extended average molecular weight (Mw) = 3, 195. It was 25 A / sec when the obtained resin solution was apply | coated so that the film thickness might become 2 after prebaking to a silicon wafer, and the dissolution rate with respect to 5% TMAH aqueous solution was measured. Synthesis Example 6 Preparation of Polysiloxane Copolymer

Into a 500 ml three-necked flask, 77.29 g (0.95 mol) of phenyltrimethoxysilane, 7.27 g (0.05 mol) of 1,2-bistrioxyoxysilylethane and 166.47 g of PGMEA were added to 47.87 g of water with stirring at room temperature. A nitric acid solution in which 180 ppm of nitric acid was dissolved was added over 10 minutes. Thereafter, the flask was immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, and then the oil bath was heated to 1 K C over 60 minutes. The mixture was heated and stirred for 8 hours to obtain a polysiloxane copolymer solution having an internal temperature of 100 to 11 (C). A total of 43.0 g of methanol and water, which were by-products in the reaction product, were flowed out. The solid content concentration of the obtained polysiloxane copolymer solution 40 weight% ^' The molecular weight (polystyrene equivalent) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3170. The obtained resin solution was applied to a silicon wafer so as to have a film thickness of 2 after prebaking, and a TMAH aqueous solution. It was 20 A / sec as a result of measuring the dissolution rate with respect to Synthesis Example 7: Preparation of polysiloxane copolymer

In a 500 ml three-necked flask, 41.74 g (0.50 mol) of phenyltrimethoxysilane, 25.81 g (0.45 mol) of methyltrimethoxysilane, 7.46 g (0.05 mol) of 1,2-bistriethoxysilylethane and 170.81 g of PGMEA Was added, and an aqueous nitric acid solution in which 180 ppm of nitric acid was dissolved in 49.12 g of water was stirred for 10 minutes while stirring at room temperature. The flask was then immersed in an oil bath at 25 ^° C. and stirred for 120 minutes, and then the oil bath was heated to 1KTC over 60 minutes. By heating and stirring for 8 hours (internal temperature is 100 ~ 110 ^° C) to obtain a polysiloxane copolymer solution. In the reaction product, methane and water, a by-product, were discharged in total 44.1 g. Solid content concentration of the obtained polysiloxane copolymer solution was 40 weight%. The molecular weight (polystyrene conversion) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 3,150. It was 45 A / sec when the obtained resin solution was apply | coated so that the film thickness might become 2 after prebaking on a silicon wafer, and the dissolution rate with respect to 5% TMAH aqueous solution was measured. Synthesis Example 8 Preparation of Polysiloxane Copolymer

In a 500 ml three-necked flask, 41.74 g (0.50 mol) of phenyltrimethoxysilane, 25.81 g (0.45 mol) of methyltrimethoxysilane, 7.46 g (0.05 mol) of 1,2-bistriethoxysilylethane and 170.81 g of PGMEA Was added, and an aqueous nitric acid solution in which 180 ppm of nitric acid was dissolved in 49.12 g of water was stirred for 10 minutes while stirring at room temperature. After that, the flask was immersed in an oil bath at 25 ^° C and stirred for 120 minutes. After that, the oil bath was heated to 11 CTC over 60 minutes. By heating and stirring for 4 hours (internal temperature is 100-110 ^° C.) to obtain a polysiloxane copolymer solution. A total of 43. 1 g of the byproduct methane and water were spilled. Solid content concentration of the obtained polysiloxane copolymer solution was 40 weight%. The molecular weight (polystyrene conversion) of the obtained polysiloxane copolymer was weight average molecular weight (Mw) = 2,850. The obtained resin solution was applied to a silicon wafer so as to have a film thickness of 2 after prebaking, and the dissolution rate in the 2.38% TMAH aqueous solution was measured, which was 200 A / sec. The composition of the polysiloxane copolymer solution prepared in Synthesis Examples 1 to 8, the molecular weight, the refractive index measured under the wavelength Dl ine (589 nm) using an Abbe refractive index, and the dissolution rate for the TMAH aqueous solution after prebaking in Table 1 Indicated.

TABLE 1

Synthesis Example 5 90 5 5 1.57 3, 195 0 25 Synthesis Example 6 95-5 1.59 3, 170 0 20 Synthesis Example 7 50 45 5 1.45 3, 150 0 45 Synthesis Example 8 50 45 5 1.46 2, 850 200-

Referring to Table 1, according to one embodiment, phenyltrimethoxysilane and methyltrimethoxysilane, which are silane compounds represented by Chemical Formula 1, and 1,2-bistriethoxysilylethane represented by Chemical Formula 2, In the case of the polysiloxane copolymer formed by the decomposition and condensation reaction and 65% or more of the total silicon atoms substituted by the phenyl group, it was confirmed that the refractive index exhibits a high refractive index of 1.50 or more. On the other hand, the polysiloxane copolymer prepared in Synthesis Example 7 in which only 50% of the total silicon atoms in the polysiloxane copolymer were substituted with phenyl groups was insoluble in 2.38% aqueous TMAH solution and had a dissolution rate of 45 A / sec for 5.0% TMAH aqueous solution. Even, the refractive index was lower than 1.50. In addition, even in the case of the polysiloxane copolymer prepared in Synthesis Example 8 in which only 50% of the total silicon atoms in the polysiloxane copolymer were substituted with phenyl groups and the dissolution rate in the TMAH aqueous solution was also one embodiment, the refractive index was lower than 1.50.

Examples and Evaluations: Preparation of the photosensitive resin composition and the cured film. And evaluation Each of the polysiloxane copolymer, the thermal acid generator, and the solvent prepared in the above synthesis example were mixed and stirred to prepare a homogeneous solution, respectively, and filtered through a filter of 0.2. The photosensitive resin composition according to the following Examples and Comparative Examples To prepare.

10 X 10 to the photosensitive resin composition according to the Examples and Comparative Examples prepared above Spin-coated to a class using a spin coater (Mikasa Corporation), prebaked at 140 ^° C. for 120 seconds using a hot plate (SCW—636 from Dainippon Screen Mfg. Co., Ltd.), each of 2.7 mm 2 membranes. Adjust to thickness. Thereafter, plastic curing is carried out at 38 C C to measure the transmittance and to observe the shape of the film surface. Then, check the occurrence of cracks by performing a curing cycle in the thermal barrier chamber.

Each measurement was carried out by the following method, the results are shown in Table 2 below:

(1) Confirmation of crack generation After the hardening, prepare a specimen on a 10 X 10 glass substrate so that the thickness is 2.5 cm 0.1 IM. After curing, check the surface of the specimen with an optical microscope to determine the presence or absence of cracking.

(2) Light transmittance measurement

Using the MultiSpec-1500 (trade name, manufactured by SHIMADZU Corporation), first, the light transmittance of only the glass substrate was measured, and this ultraviolet visible absorption spectrum was used as a reference. Subsequently, a cured film of the photosensitive resin composition was formed (the pattern exposure was not performed) on the glass substrate, the sample was measured by a single beam, and a light transmittance having a wavelength of 400 nm per 1 was obtained to determine the difference from the reference. It was set as transmittance | permeability.

(3) Measurement of chemical resistance After the curing, the specimen was prepared on a 10 X 10 glass substrate so as to have a thickness of 2.5 / 皿皿 0.1, cut into 5 X 5 glass specimens. Subsequently, after measuring the thickness of the center part, it is immersed in chemical-resistant solvent for 5 minutes, and washed with water, and the thickness change is confirmed. Thickness change rate (%) = (film thickness after chemical resistance evaluation-film thickness before chemical resistance evaluation) / film thickness before chemical resistance evaluation X100. The following describes the photosensitive resin composition and the cured film produced therefrom according to each Example and Comparative Example, and the characteristics of the cured film. Example 1 Preparation and Evaluation of Cured Film 3 parts by weight of the thermal acid generator are added to 100 parts by weight of the polysiloxane copolymer obtained in Synthesis Example 1. After adding the solvent which mixed PGMEA and GBL to this, it mixed and stirred to make a homogeneous solution, and it filtered with the filter of 0.2 Pa, and prepared the resin composition. The composition was spin-coated with a spin coater (Mikasa Corporat ion) in a 10 × 10 class and then prebaked at 140 ^° C. for 120 seconds using a hot plate (SCW-636 from Dainippon Screen Mfg. Co., Ltd.). To adjust the film thickness to 2.7. After prebaking, plastic curing was carried out at 380 ^° C. to obtain an insulating film having improved high temperature crack resistance and chemical resistance with maintaining a transmittance of 98% and a crack free thickness of 3.2. Example 2: Preparation and Evaluation of Cured Film A resin composition was prepared 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, and a cured film was prepared in the same manner. As a result of hardening, an insulating film with high temperature crack resistance and chemical resistance maintained at a transmittance of 98% and a crack-free thickness margin of 3.2 zm was obtained. Example 3 Preparation and Evaluation of Cured Film A resin composition was prepared 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, and a cured film was prepared in the same manner. As a result of curing, an insulating film having high transmittance of 98% and a crack-free thickness margin of 3.5 kPa having high temperature crack resistance and chemical resistance was obtained. Example 4: Preparation of cured film prepared and evaluated, except that with the polysiloxane 100 parts by weight of copolymer obtained in Synthesis Example ₄ and Example 1 to produce the resin composition in the same manner, and using this, ^was' prepared cured film in the same manner . As a result of curing, an insulating film having improved high-temperature crack resistance and chemical resistance with a transmittance of 98% and a crack-free thickness margin of 3.5 was obtained. Example 5 Preparation and Evaluation of Cured Film A resin composition was prepared 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, and a cured film was prepared in the same manner. As a result of curing, an insulating film having a high permeability and chemical resistance of 98% in transmittance and no crack generation thickness margin of 4.0 was obtained. Example 6 Preparation and Evaluation of Cured Film A resin composition was prepared in the same manner as in Example 1, except that 100 weight% of the polysiloxane copolymer obtained in Synthesis Example 6 was used, and a cured film was prepared in the same manner. . As a result of curing, an insulating film having a high permeability and chemical resistance of 98% having a transmittance and no crack generation thickness margin of 4.5 was obtained. Comparative Example 1: Preparation and Evaluation of Cured Film A resin composition was prepared 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, and a cured film was prepared in the same manner. As a result of curing, an insulating film having a transmittance of 97% and a crack-free thickness margin of 2.5 / m was obtained. Comparative Example 2: Preparation and Evaluation of Cured Film A resin composition was prepared 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, and a cured film was prepared in the same manner. As a result of curing, an insulating film having a transmittance of 97% and a crack-free thickness margin of 2.5 was obtained.

TABLE 2

* 50 ^° C MEA: DMS0 (monoethanol amine: Dimethyl sul foxide) = 7: 3 in solution. Thickness change rate of cured film measured by washing after immersion for 5 minutes 0

** Thickness change rate of cured film measured by immersion in 50 ^° C NMP solution for 5 minutes and washed with water (¾>) As can be seen from Table 2, one embodiment for the decomposition of a silane compound represented by the silane compound and formula (2) represented by the general formula (1) according to artists, and condensation polymerization was made and the entire ^"65% or more based on the number of silicon atoms A polysiloxane copolymer substituted with this phenyl group, and the film after prebaking is 2. The cured film manufactured from the photosensitive resin composition which is insoluble in a 38 weight% TMAH aqueous solution and has a dissolution rate of 100 A / sec or less for a 5.0 weight% -TMAH aqueous solution has a thickness of 2. There is no cracking at 3 and no crack-free thickness margin that maintains a light transmittance of 98% for 400 nm wavelength. It can be seen that it has excellent anti-tacktack and a high light transmittance of 2 i or more. Moreover, the rate of change of the thickness of the cured film with respect to the chemical resistance evaluation solvent is 5% or less, and the chemical resistance is also very excellent. On the other hand, the photosensitive resin composition according to Comparative Example 1 and Comparative Example 2 comprising the polysiloxane co-polymer prepared 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, had a thickness after curing. Both cracks occurred, and the crack-free thickness margin maintaining 97% light transmittance for the 400 nm wavelength was 2. 5 j ^, it can be seen that it is significantly lower than the crack resistance of the cured film according to Examples 1 to 6. In addition, it can be seen that the thickness change rate measured after 5 minutes of immersion in a chemical resistant solution, that is, a MEA: DMS0 = 7: 3 solution and an NMP solution, respectively, is 5% or more, and the chemical resistance is also very low. In conclusion, the photosensitive resin composition according to the embodiment has excellent crack resistance and chemical resistance after curing of the cured film prepared therefrom, maintains high light transmittance, ^and can increase the crack margin to easily control the thickness of the cured film. It can be seen that. Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concept of the present invention defined in the following claims are also provided. It belongs to the scope of the present invention.

Claims

[Range of request]

[Claim 1]

(A) A polysiloxane polymer formed by hydrolysis and condensation reaction of at least one silane compound represented by the following formula (1), wherein at least 65% of all silicon atoms are substituted with a phenyl group, and (B) a solvent. As the photosensitive resin composition,

The photosensitive resin composition after the prebaking is insoluble in a 2.38 weight ¾> tetramethylammonium hydroxide (TMAH) aqueous solution and has a dissolution rate in a 5 weight% TMAH aqueous solution of 100 A / sec or less:

[Formula 1]

In Chemical Formula 1,

R ¹ is hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C30 alkyl group substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or ^' unsubstituted C6 to C30 aryl group, substituted or unsubstituted C7 to C30 Arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C1 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted Or an unsubstituted C2 to C30 alkynyl group R0-, R (C = 0)-(where R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted A substituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group, or a combination thereof,

a is 0≤a <4.

[Claim 2]

In paragraph 1,

R ¹ of Formula 1 is hydrogen, C1 to C10 alkyl group, C2 to C10 alkenyl group, C6 to C16 aryl group, or a combination thereof, X ¹ is a C1 to C6 alkoxy group, Photosensitive resin composition which is a hydroxyl group, a halogen, or a combination thereof.

[Claim 3]

In claim 1,

R ¹ of Formula 1 is a methyl group or a phenyl group, a is a photosensitive resin composition.

[Claim 4]

In paragraph 1,

The polysiloxane polymer (A) is a photosensitive resin composition that is further hydrolyzed and condensation polymerization comprising a silane compound represented by the following formula (2):

[Formula 2]

X ^ Si-Y ^ SiX ^

In 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 to C30 arylene group, substituted or unsubstituted C2 to C30 Heteroarylene group, substituted or unsubstituted C2 to C30 alkenylene group, substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

[Claim 5]

In paragraph 4,

Y ¹ of Formula 2 is a C1 to C10 alkylene group, C3 to C10 cycloalkylene group, C6 to C12 arylene group, or a combination thereof, X ² and X ³ are each independently a C1 to C6 alkoxy group, Photosensitivity. Resin composition.

[Claim 6]

In this μ term,

The film after prebaking of the photosensitive resin composition is insoluble in a 2.38 wt% ΤΜΑΗ aqueous solution, and the dissolution rate in the 5 wt% ΤΜΑΗ aqueous solution is 50 A / sec or less. Photosensitive resin composition.

[Claim 7]

In paragraph 4,

The polysiloxane polymer (A) is formed by hydrolysis and condensation reaction of 80 mol% to 97 mol% of the silane compound represented by Formula 1 and 3 mol% to 20 mol% of the silane compound represented by Formula 2 Photosensitive resin composition.

[Claim 8]

In paragraph 4,

Photosensitive resin composition in which 70% or more of all the silicon atoms of the said polysiloxane polymer (A) are substituted by the phenyl group.

[Claim 9]

In paragraph 1,

The photosensitive resin composition further comprises (C) an additive which generates an acid or a base with heat or light, (D) a nonone diazide compound, or a combination thereof.

[Claim 10]

In paragraph 1,

The refractive index of the said photosensitive resin composition is 1.50 or more. [Claim 111]

The cured film obtained by hardening | curing the photosensitive resin composition of any one of Claims 1-10.

[Claim 12]

In claim 11,

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

[Claim 13]

An electronic device comprising the cured film of claim 11.