WO2017073935A1 - Photosensitive resin composition, cured film produced from same, and device having cured film - Google Patents

Abstract

The present invention relates to a photosensitive resin composition comprising (Α) a siloxane compound represented by chemical formula 1 as below; (B) a quinonediazide compound, and (C) a solvent, wherein the siloxane compound represented by chemical formula 1 comprises a mixture of one or more of siloxane compounds (i) and (ii) and the siloxane compound (iii) as below: [Chemical formula 1] (R¹R²R³SiO_1/2)_M(R⁴R⁵SiO_2/2)_D(R⁶SiO_3/2)_T1(O_3/2Si-Y-SiO_3/2)_T2(SiO_4/2)_Q (in chemical formula 1, the definitions regarding R¹ to R⁶, Y, M, D, T1, T2, and Q are the same as described in the description of the present invention.) The siloxane compound comprises (i) a siloxane compound having a polystyrene standard sample-converted weight average molecular weight of 3,000 g/mole or less, measured by means of gel permeation chromatography (GPC), and having a dissolution rate of 1,500 Å/ sec or more for 2.38 wt%. TMAH aqueous solution of a film after prebaking; (ii) a siloxane compound having a polystyrene standard sample-converted weight average molecular weight of 3,000 g/mole to 6,000 g/mole, measured by gel permeation chromatography (GPC), and having a dissolution rate of 200 Å/sec to 1,500 Å/sec for 2.38 wt% TMAH aqueous solution of a film after prebaking; and (iii) a siloxane compound having a polystyrene standard sample-converted weight average molecular weight of 6,000 g/mole or more, measured by gel permeation chromatography (GPC), and having a dissolution rate of 200 Å/sec to 3,000 Å/sec for 5.0 wt% TMAH aqueous solution of a film after prebaking.

Description

 【Specification】

 [Name of invention]

 Photosensitive resin composition, the cured film formed therefrom, and the element which has a cured film

 It relates to a photosensitive resin composition, a cured film formed therefrom, and an element having the cured film.

 Background Art

 In order to realize more precise and high resolution in liquid crystal display or organic EL display, the aperture ratio of the display device should be increased. This is achieved by providing a transparent flattening film as a protective film on the TFT substrate to overlap the data line and the pixel electrode to achieve high opening ratio. It is a way to make it.

 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 ΠΌ electrode. It is necessary to form a hole pattern of 50 to 1 / several / m or so.

Conventionally, the material which combined the phenolic resin and the quinonediazide compound, or the photosensitive resin composition which combined the acrylic resin and the quinonediazide compound has been mainly used. However, these materials are not rapidly deteriorated at the high temperature of 200 ^° C., but the decomposition starts slowly ^at 230 ^° C. or higher, and the film thickness decreases or cracks occur, or the substrate is transparent by high temperature treatment. There is a problem that the membrane is colored and the transmittance is lowered.

 Moreover, although a touch panel is employ | adopted in liquid crystal displays etc. in recent years, in order to improve transparency and a function of a touch panel, the attempt of heat-processing and film forming at higher temperature for the purpose of high transparency and high conductivity of the transparent electrode member ITO is carried out. Is being done. Along with this, the protective film of the transparent electrode member

Heat resistance to high temperature treatment is also required for the insulating film. However, acrylic resins are inferior in heat resistance and chemical resistance, and the cured film is colored by high temperature treatment of a substrate, high temperature film formation, such as a transparent electrode, or various etching chemical liquid treatments, resulting in reduced transparency, or degassing in high temperature film formation. This causes a problem that the conductivity of the electrode is lowered. Therefore, the film is formed at a high temperature by using a device such as PE-CVD on the transparent film material. It cannot be used for processes like forming.

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, an acrylic material imparting heat resistance may cause cracking at 300 ^° C. or higher, and otherwise, 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 formation of a uniform thick film is generally difficult, and the amount of material used is large, which 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 a silsesquioxane compound which provided the acryl group to specific silsesquioxane, the unsaturated compound containing unsaturated carboxylic acid and an epoxy group, and the acryl-type copolymer and quinonediazide compound which copolymerized the olefinic unsaturated compound And the like have been proposed. However, these compounds also have high organic content and decompose after high temperature curing of 250 ^° C. or higher, resulting in yellowish yellowing and poor permeability. After development, the residual film rate is poor and does not form a flat film or NMP (N-methyl- 2-pyrrolidone), tetramethylammonium hydroxide (TMAH) solution, there is a problem that the chemical resistance to a solvent such as 10% NaOH is also reduced.

Moreover, as a 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 Materials which combine the siloxane polymer and the quinonediazide compound which added the carboxyl group etc. are known. However, these materials contain a large amount of quinonediazide compounds, or because phenolic hydroxyl groups are present in the siloxane polymer, it is liable to cause coloration during whitening or thermal curing of the coating film, and cracks may occur under severe high temperature conditions of 300 ^° C or higher. It may occur, and thus cannot be used as a highly transparent material due to the decrease in permeability. In addition, these materials have a problem of low sensitivity at the time of pattern formation because of low transparency.

The photosensitive composition material which consists only of a polysiloxane and a quinonediazide compound When thermally cured, crosslinking and high molecular weight occur due to dehydration of the silanol groups in the 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 the 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 a system of a soluble polysiloxane and a soluble polysiloxane and a quinone diazide compound in a developing solution, and upon heating and curing, a pattern such as a hole or a line obtained after development collapses, resulting in a decrease in resolution, resulting in "pattern sagging". There has been proposed a photosensitive composition that prevents this. But it is soluble in developer

When polysiloxane is used, it melts after development, but causes recurrence of development pattern defects due to re-adhesion of residues or difficult-to-melt solubles. Moreover, in order to prevent pattern deterioration, it is necessary to fully raise the molecular weight of siloxane. As a result, as a photosensitive material, a sensitivity is low and high reaction energy is needed. In addition, there is a drawback that the residual film ratio is not divided and the loss of material is large.

 [Detailed Description of the Invention]

 [Technical problem]

 In one embodiment, there is provided a photoresist composition having high heat resistance, high temperature crack resistance, high permeability, and high resolution, in which a pattern flow at a high temperature and post-developing scum do not occur.

 Another embodiment provides a cured film obtained by curing the composition.

 Another embodiment provides a device including the cured film.

 Technical Solution

 One embodiment, (A) a siloxane compound represented by the formula (1); A photosensitive resin composition comprising (B) a quinone diazide compound and (C) a solvent, wherein the siloxane compound represented by the formula (1) is one or more of siloxane compounds of the following (i) and (ii), and (iii) Provided is a photosensitive resin composition comprising a mixture of siloxane compounds:

 [Formula 1]

^{(R 1 R 2 R 3 SiOi} / 2) M (R 4 R 5 Si0 2/2) D (R 6 Si0 3/2) Ti (0 3 / 2Si-Y-Si0 3/2) T2 (Si0 4 / ₂ ) Q

(In Formula 1, R ¹ to R ⁶ are each independently hydrogen, hydroxy, halogen, substituted or unsubstituted C1 to C3 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted Or an unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C1 to C30

Heteroaryl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, RO-, R (C = 0)-(where R is a substituted or unsubstituted C1 to C30 alkyl group) Substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof,

 Y 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,

 0 <M <0.5, 0 <D <0.5, 0.5 <TK1, 0 <T2 <0.2, 0 <Q <0.5,

 M + D + T1 + T2 + Q = 1,

 The structural units represented by M, D, T1, T2, and Q may each include one or more different structural units.)

 (i) a polystyrene standard sample weight average molecular weight of 3,000 g / mole or less, as determined by gel permeation chromatography (GPC);

Siloxane compounds having a dissolution rate of 2.38 weight ⁰ / o TMAH aqueous solution of the film after prebaking in at least 1,500 A / sec;

 (ii) The weight average molecular weight in terms of polystyrene standard sample measured by gel permeation chromatography was 3,000 g / mole or more and 6,000 g / mole or less

2.38 weight ⁰ / o siloxane compound having a dissolution rate in an aqueous solution of TMAH in the range of 200 A / sec to 1,500 A / sec; And

(iii) The weight average molecular weight in terms of polystyrene standard sample measured by gel permeation chromatography is 6,000 g / mole or more, and the dissolution rate of the membrane after prebaking in a 5.0 weight ⁰ / o TMAH aqueous solution is 200 A / sec or more and 3,000 A / sec. The siloxane compound which is the following. In Formula 1, M, D, and Q are all 0 and may be 0.8 <T1 <1, and 0 <Τ2 <(). 2.

 In Formula 1, M, D, and Q are all 0, and 0.85 ≦ T1 <1, and 0 <Τ2 ≦ 0.15.

In Chemical Formula 1, at least one of R ¹ to R ⁶ includes a substituted or unsubstituted C6 to C30 aryl group, and at least one of R ¹ to R ⁶ is substituted or

It may include an unsubstituted C 1 to C 30 alkyl group.

 In Formula 1, γ may be a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.

Based on the total weight of the siloxane compound represented by Formula 1, the siloxane compound of (i) may be included in 20 weight ⁰ /.

 Based on the total weight of the siloxane compound represented by Formula 1, the siloxane compound of (H) may be included 20 to 80% by weight.

Based on the total weight of the siloxane compound represented by Formula 1, the siloxane compound of (iii) may be included in 10 weight ⁰ /.

 In another embodiment, a cured film obtained by curing the photosensitive resin composition according to the embodiment is provided.

 The cured film is a thin film of a liquid crystal display device or an organic EL display device.

A planarization film for a transistor (TFT) substrate, a protective sphere film or an insulating film for a touch panel sensor element _: an interlayer insulating film for a semiconductor device, a planarization film for a solid-state imaging device, a micro lens array pattern, or a core or clad material of an optical waveguide of an optical semiconductor device have.

The cured film exhibits a hole characteristic of less than 7 dB at 200 ^° C. or more, and has a light transmittance of 90% or more at 400 nm wavelength at a thickness of 2.5 IM.

 The cured film is `` (film thickness after development ÷ film thickness after prebaking) X

The residual film rate defined by 100 j is 85% or more.

 According to another embodiment, a device including the cured film is provided.

 【Effects of the Invention】

Photosensitive resin composition according to one embodiment has high heat resistance, high temperature crack resistance, high permeability, and high resolution that does not cause scum after pattern collapse or development at high temperature The branch is a positive photosensitive resin composition, and the cured film prepared by curing the same may be usefully used in the manufacture of a planarization film for a thin film transistor (TFT) 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 I), 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, thi 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 that C6 to C15 cycloalkynyl is substituted with a substituent selected from C3 to C30 heterocycloalkyl group and combinations thereof.

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

 Unless otherwise specified in this specification, the term "combination" means a mixture or copolymerization.

 Hereinafter, a photosensitive resin composition according to one embodiment will be described. The photosensitive resin composition according to one embodiment may include (A) a siloxane compound represented by Formula 1 below; (B) a quinonediazide compound, and (C) a solvent, Comprising:

The siloxane compound represented by 1 includes a mixture of at least one of the siloxane compounds of (i) and (ii) with the siloxane compound of (iii):

 [Formula 1]

^{(R l R 2 R 3 Si0} 1/2) M (R 4 R 5 Si0 2/2) D (6 Si03 / 2) Ti (0 3/2 Si-Y-Si0 3/2) T2 (Si0 4 / ₂ ) Q

(In Formula 1, R ¹ to R ⁶ are each independently 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, RO-, R (C = 0)-(where R is a substituted or unsubstituted C1 to C30 alkyl group) Substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof,

 Y 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,

 0 <M <0.5, 0 <D <0.5, 0.5 <TK1, 0 <T2 <0.2, 0≤Q <0.5,

 M + D + T1 + T2 + Q = 1,

 The structural units represented by M, D, T1, T2, and Q may each include one or more different structural units.)

 (i) polystyrene standard sample measured by gel permeation chromatography (GPC), average molecular weight increase of 3,000 g / mole or less;

Siloxane compounds having a dissolution rate of 2.38 weight ⁰ / o TMAH aqueous solution after prebaking in an aqueous solution of TMAH of at least 1,500 A / sec;

 (ii) The weight average molecular weight in terms of polystyrene standard sample measured by gel permeation chromatography was 3,000 g / mole or more and 6,000 g / mole or less

2.38 weight ⁰ / o siloxane compound having a dissolution rate in an aqueous solution of TMAH in the range of 200 A / sec to 1,500 A / sec; And

(iii) The weight average molecular weight in terms of polystyrene standard sample measured by gel permeation chromatography is 6,000 g / mole or more, and the dissolution rate of the membrane after prebaking in a 5.0 weight ⁰ / o TMAH aqueous solution is 200 A / sec or more and 3,000 A / sec. The siloxane compound which is the following. As represented by Formula 1, the siloxane compound contains at least 0.5 or more as a mole fraction of a structural unit represented by (R ⁶ Si0 _3/2 ) in the compound, and (0 _3/2 Si-Y-Si0 ₃ / It may contain less than 0.2 structural units represented by ₂ ).

When the structural unit represented by (0 _3/2 Si-Y-Si0 _3/2 ) is included in the above range, the photosensitive resin composition comprising the compound represented by Chemical Formula 1 may be dense through fine crosslinking during curing. By including the structure, it has high mechanical strength, chemical resistance, and high residual film.

In addition, the structural unit represented by (0 _3/2 Si-Y-Si0 _3/2 ) serves as a crosslinking agent in the compound represented by the formula (1), and thus, by including the structural unit appropriately adjusted within the above range It is easy to adjust the hardness to form a high hardness coating film, and the high hardness coating film produced has high crack resistance at high temperature and at the same time effectively prevents the penetration of organic solvents, thereby reducing the film thickness after development and flattening. An organic insulating film excellent in solving the problem of the remaining film which cannot form a film and excellent in chemical resistance, high temperature crack resistance, and etching resistance after curing can be realized.

 As described above, the siloxane compound represented by Chemical Formula 1 may be converted to (i) polystyrene standard sample measured by gel permeation chromatography.

A compound having a weight average molecular weight of 3,000 g / mole or less and a dissolution rate of the membrane after prebaking in an aqueous 2.38 weight ⁰ / o TMAH solution of 1,500 A / sec or more, (ii)

Conversion of polystyrene standard sample measured by gel permeation chromatography

The weight average molecular weight is 3,000 g / mole or more and 6,000 g / mole or less

2.38 one or more of the siloxane compounds having a dissolution rate of 200 A / sec or more and 1,500 A / sec or less in an aqueous solution of weight ⁰ / o TMAH; And (iii) the polystyrene standard sample weight average molecular weight measured by gel permeation chromatography is 6,000 g / moie or more and the rate of dissolution of the membrane after prebaking in a 5.0 weight ⁰ / o TMAH aqueous solution is 200 A / sec or more and 3,000 A / sec. It is used as a mixture containing the siloxane compound which is less than the second.

 The siloxane compound represented by the formula (1) is the specific molecular weight range, and

By using a combination of siloxane compounds having a specific dissolution rate for the TMAH aqueous solution of the film after prebaking, the cured film obtained by curing the photosensitive resin composition exhibits hole characteristics of less than 7 IM at a high temperature of 200 ^° C. or higher, and “(after development residual film ratio, which is defined as a film thickness after ^pre-o-baking film thickness of the unexposed area) x l00j 85% As described above, it is possible to provide a high heat resistance, a high transmittance, and a high-resolution photosensitive resin composition having a light transmittance of 90% or more at a wavelength of 400 nm at a cured film thickness of 2.5 kPa.

 When the hall characteristic is less than 7 rn, it can be considered that the cured film obtained from the said composition has sufficiently high resolution.

 In addition, when the residual film ratio which multiplied 100 by the value which divided the film thickness after prebaking from the film thickness of the non-exposure part after image development is 85% or more, it can be considered to have sufficient residual film rate to be used for a photosensitive resin composition.

 On the other hand, as can be seen from the comparative examples to be described later, the compound represented by the formula (1) is the molecular weight range of the above, and / or

The cured film cured from a composition comprising a combination of compounds in which the dissolution rate range for TMAH does not satisfy the above range does not exhibit the above-described hole characteristics and residual film rate.

 In one embodiment, T1 of the structural unit constituting the compound represented by Chemical Formula 1 is 0.6 <TK1, for example, 0.65 ≦ Τ1 <1, for example, Ό.7 ≦ Τ1 <1, for example, 0.75 ≦ Τ1 <1, for example, 0.8 ≦ Τ1 <1.

When the structural unit represented by T1 of the compound represented by Formula 1, that is, (R ⁶ Si0 _3/2 ) is present within the above range in the compound,

Conversion of polystyrene standard sample measured by gel permeation chromatography

A siloxane compound having a weight average molecular weight of 3,000 g / mole or more and 6,000 g / mole or less and simultaneously having a dissolution rate of 2.38 weight ⁰ / o TMAH aqueous solution of the membrane after prebaking is 200 A / sec or more and 1,500 A / sec or less can be easily prepared. Can be.

Further, in one embodiment, the structural unit represented by T2 of the structural units constituting the compound represented by the formula (1), that is, (0 _3/2 Si-Y-Si0 _3/2 ) is 0 <T2 <0.2, For example, 0 <Τ2 <0.17, for example 0 <Τ2 ≦ 0.15, for example 0 <Τ2 ≦ 0.13, for example 0 <Τ2 ≦ 0.12.

 In the case of including the structural unit represented by Τ2 in the compound represented by the formula (1) in the above range, the photosensitive resin composition containing the compound has a high surface hardness, residual film ratio, and chemical resistance improvement effect after curing.

 In one embodiment, M, D, and Q in Formula 1 are all 0, 0 · 8 <Τ1 <1, and

0 <Τ2 <0.2. In another embodiment, MJD of Formula 1, and Q are both 0, 0.85 ≦ T1 <1, and 0 <Τ2 <0.15.

Based on the total weight of the siloxane compound represented by Formula 1, the siloxane compound of (i) may be included in the 20 to 80% by weight ⁰ /.

Within this range, the siloxane compound of the above (i) is, based on the total weight of the siloxane compound represented by the formula (1), for instance, for 25 wt% to 75 wt _^0/0, for example, 25 parts by weight ⁰ / ₀ to 70 parts by weight ⁰ /., e.g., 30 may include _^0/0 wt.% to 65 wt.

 Based on the total weight of the siloxane compound represented by Formula 1, the siloxane compound of (ii) may be included in 20 to 80% by weight.

The siloxane compound of the above (ii) within this range, is, based on the total weight of the siloxane compound represented by the formula (1), for example, 30 parts by weight _^0/0 to 75 parts by weight _^0/0, for example, 35 the weight _^0/0 to 70% by weight, for example, may include _^0/0 40% to about 70 wt., based on the total weight of the siloxane compound represented by formula 1, above. Silicone compound of (iii) may contain _^0/0 10% by weight to 70 parts by weight.

 Within the above range, the siloxane compound of (iii) is represented by Chemical Formula 1

Based on the total weight of the siloxane compound represented, for example, 15% by weight to 65 parts by weight ⁰ /., E.g., 15 wt. ⁰ /. To 60 parts by weight ⁰ /., For example, 20 parts by weight _^0/0 to 60 it can be included by weight _^0/0.

In Formula 1, at least one of R ¹ to R ⁶ may include a substituted or unsubstituted C6 to C30 aryl group, and at least one of Ι ¹ to R ⁶ may include a substituted or unsubstituted C1 to C30 alkyl group. have.

 In Formula 1, Υ may be a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.

The compound represented by the formula (1) is, for example, a monomer represented by R '^ I ^ SiZ ¹ , a monomer represented by R ⁴ R ⁵ SiZ ² Z ³ , a monomer represented by R ⁶ SiZ ⁴ Z ⁵ Z ⁶ , Z ^{7 Z 8 Z 9 Si-Y-} SiZ 10 ^ ^ 12 monomer represented by, Z ¹⁴ and Z ¹⁵ to Z ¹³ SiZ least one of monomers represented by ¹⁶ kinds can be obtained the combined hydrolysis and condensation. Here, the definitions of R ¹ to R ⁶ are as described above, and X ¹ to X ¹⁶ each independently represent a C ¹ to C 6 alkoxy group, Hydroxyl group, halogen, carboxyl group, or a combination thereof.

The hydrolysis and polycondensation reaction for preparing the compound represented by Formula 1 may use a general method well known to those skilled in the art. For example, a solvent, water, and a catalyst, if necessary, are added to the mixture of monomers, and 0.5 to 100 hours at a temperature of 50 ^° C to 150 ^° C, for example, 90 ^° C to 130 ^° C. Stirring to a degree. In addition, during stirring, distillation and removal of a hydrolysis by-product (alcohol, such as methanol), and a condensation by-product, etc. can also be performed by distillation as needed.

 Although there is no restriction | limiting in particular as said reaction solvent, Usually, the same solvent as the solvent contained in the photosensitive resin composition which concerns on the said embodiment can be used.

 The amount of the solvent added may be 10 to 1000 parts by weight based on 100 parts by weight of the total weight of the monomer. In addition, the addition amount of the water used for a hydrolysis reaction can be used in the range of 5 mol-3 mol with respect to 1 mol of hydrolysable groups. There is no particular limitation on the catalyst added as needed, but an acid catalyst, a base catalyst, or the like can be used. The addition amount of the catalyst may be used in the range of 0.001 to 10 parts by weight, for example, 0.1 to 8 parts by weight based on 100 parts by weight of the total weight of the monomer.

 The photosensitive resin composition according to the embodiment includes the (B) quinonediazide compound. The photosensitive resin composition containing a tunon diazide compound forms the positive type by which an exposure part is removed with a developing solution. The quinonediazide compound that can be used is not particularly limited, but for example, a compound obtained by ester bonding of naphthoquinonediazidesulfonic 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 compounds in which the para position is each independently one of hydrogen or a substituent represented by the following general formula (2):

 (Formula 2)

In Chemical Formula 2 ¹² , R ¹³ , and R ¹⁴ each independently represent any one of ci to ciq alkyl, carboxyl, phenyl and substituted phenyl groups, and R ¹² , R ¹³ , and R ¹⁴ together form a ring. It may be.

In R ¹² , R ¹³ , and R ¹⁴ of the group represented by the above formula .2, the alkyl group may be any of unsubstituted or substituted. Specific examples of the alkyl group include methyl group, ethyl group, η-propyl group, isopropyl group, η-butyl group, isobutyl group, t-butyl group, n-nuxyl group, cyclonuclear group, η-heptyl group and η-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, a fluorene ring, and the like.

 In the case where the ortho position and the para position of the phenolic hydroxyl group are groups other than the above, for example, a methyl group, oxidative decomposition occurs by thermal curing, whereby a conjugated compound represented by a quinoid structure is formed, and the cured film is colored and colorless. Transparency is lowered. These quinonediazide compounds are compounds having a phenolic hydroxyl group and

It can synthesize | combine by well-known esterification reaction with naphthoquinone diazide sulfonic-acid chloride. As a specific example of the compound which has a phenolic hydroxyl group, the following compounds are mentioned (all are the products of Unshu Chemical Co., Ltd.).

_// : _/ O 6Π _09Ϊ0 2ΜΙ _>< ί _S SP _{0 /} J _0Z AV

 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. The 4-naphthoquinone diazide sulfonic acid ester compound or the 5-naphthoquinone diazide sulfonic acid ester compound can be selected according to the exposure wavelength. 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). When the amount of the quinonediazide compound added is less than 0.1 part by weight, the dissolution contrast between the exposed portion and the non-exposed portion is too low to have a realistic photosensitive property. In addition, in order to obtain a better dissolution contrast 1 The weight part or more is preferable. When the amount of the quinone diazide compound added 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. As it becomes, the colorless transparency of the 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.

 Moreover, the photosensitive resin composition which concerns on the said embodiment contains the (C) solvent. 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. With these solvents, a siloxane compound and a quinonediazide compound dissolve uniformly, After coating, film formation can achieve high transparency without causing cloudiness of the film.

 Although there is no restriction | limiting in particular in the compound which has an alcoholic hydroxyl group, Preferably, the compound whose boiling point is 1-10 degreeC-250 degreeC under atmospheric pressure can be 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 1 UTC, the film will dry too quickly and the film surface will be 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, 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-butane, 3-methyl-3-methoxy-1-butanol, and the like. have. Among these, especially compounds having a carbonyl group are preferable, and diacetone alcohol can be 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.

 Although there is no restriction | limiting in particular in the cyclic compound which has a carbonyl group, Preferably, the compound which has a boiling point of 150 degreeC-250 degreeC under atmospheric pressure can be used. Boiling point

If it is higher than 250 ° C., the amount of remaining solvent in the film increases, and the film shrinkage during curing increases, so that good elasticity cannot be obtained. If the boiling point is lower than 150 ° C, the film dries too quickly Coating surface worsens, such as a rough surface.

 As a specific example of the cyclic compound which has a carbonyl group, (gamma)-butylollactone, -valerlactone, (delta) -valerlactone, propylene carbonate, N-methyl pyridone, a cyclonuxanonone, cycloheptanone, etc. are mentioned. Among these, in particular, gamma -butyl olactone can 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, the weight ratio thereof is not particularly limited. Preferably, the ratio of the compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group is about 99 to 50: 1 to 50, or, for example, 97 to 60: 3. To 40. The compound having an alcoholic hydroxyl group in 99 weight ⁰ /. More when (a cyclic compound having a carbonyl group is less than 1, increased _^0/0), the compatibility of the siloxane compound and the quinonediazide compound of formula (1) poor, and cured film whitening And transparency may fall. In addition, when the compound having an alcoholic hydroxyl group is less than 50 parts by weight ⁰ / ο (a cyclic compound having a carbonyl group is more than 50 parts by weight _^0/0), the storage tends to occur a condensation banung US banung silanol groups of a siloxane compound of formula (1) Stability This can go bad.

The photosensitive resin composition according to the above embodiment may further include other solvents within a range that does not impair the effects of the present invention. As other solvents, ethyl acetate, η-propyl acetate, isopropyl acetate, η-butyl acetate, isobutyl acetate, propylene glycol mono methyl ether acetate, 3-methoxy-1-butyl acetate, 3-methyl-3-meth ethoxy-1-ester such as butyl acetate, methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone, ketones such as acetyl acetone, diethyl ether, diisopropyl ether, ^di-η-butyl ether, diphenyl ether Ethers, such as these, are mentioned.

Although there is no restriction | limiting in particular in the addition amount of a solvent, Preferably it can use in the range of 100-1,000 weight part with respect to 100 weight part of said siloxane compounds of the said General formula (1). Alternatively, the solvent may be included so that the solid content is 10 to 50 weight ⁰ /. 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.

The photosensitive resin composition according to the embodiment is a photosensitive resin, if necessary Further components commonly used in the composition may further include, for example, silane coupling agents, surfactants, and the like.

 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 reactive substituents include carboxyl groups, methacryloyl groups, isocyanate groups, epoxy groups and the like.

 Specific examples of the silane coupling agent include trimethicsilyl benzoic acid, γ-methacryloxypropyltrimethicsilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ. One or more types selected from -glycidoxypropyltrimethicsilane, γ-glycidoxypropyltriethyl silane and β- (3,4-epoxycyclonucleosilane) ethyltrimethoxysilane can be used, preferably In terms of residual film ratio 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. It doesn't work.

 The silane coupling agent is in the range of αοι to 10 parts by weight based on the loo parts by weight of the compound represented by the formula (1) (based on the solid content) in the photosensitive composition, for example,

It may be included in the range of 0.1 to 5 parts by weight. When the content of the silane coupling agent is 0.01 parts by weight or more, the adhesion to the substrate is improved, when 10 parts by weight or less, the thermal stability is improved at high temperatures, and the phenomenon that staining occurs after development can be prevented.

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 Co., Ltd.), ΒΜ-1000, ΒΜ-1100 (manufactured by BM CHEMIE), Megapack F142 D, Copper F172, Copper F173, Copper F183 (Dai Nippon Ink Chemical Industries, Ltd.) Kabushiki Kaisha), Florade FC-135, East FC-170 C, East FC-430, East FC-431 (manufactured by Sumitomo 3M Limited), Surflon S-112, East S-1 13, East S- 131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (Asahi Glass) Kabushiki Kaisha), Eprop EF301, 303, East 352 (new Kawasaki Kaisha), SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-57, Fluorine systems, such as DC-190 (Toray Silicone Co., Ltd. make), and Silicone surfactants; Polyoxyethylene lauryl ether,

Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, etc.

Polyoxyethylene alkyl ethers, polyoxyethylene octylphenyl ether,

Polyoxyethylene aryl ethers such as polyoxyethylene nonylphenyl ether,

Polyoxyethylene dilaurate, polyoxyethylene distearate

Nonionic surfactants such as polyoxyethylene dialkyl esters; Organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.) or (meth) acrylic acid copolymer polyflow Νο.57,95 (manufactured by Kyoeisha Chemical Co., Ltd.) 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, 0.1 to 5 parts by weight based on 100 parts by weight (based on the solid content) of the compound represented by Chemical Formula 1. 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.

 According to one embodiment, the photosensitive resin composition may further include, in addition to the above components, additional components conventionally used in the thermosetting resin composition and / or the photosensitive resin composition, if necessary. The photosensitive resin composition which concerns on an example may contain additives, such as a dissolution promoter, a dissolution inhibitor, a surfactant, a stabilizer, and an antifoamer, as needed.

 In particular, the dissolution promoter can improve the sensitivity. As a dissolution promoter, the compound which has a phenolic hydroxyl group, or a Ν-hydroxy dicarboxymid compound is used preferably. As a specific example, the compound which has the phenolic hydroxyl group used for the quinonediazide compound is mentioned.

 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, and the like, and prebaked with a heating apparatus such as a hot plate or an obon. Prebaking is carried out in the range of 50 ^° C to 150 ^° C for 30 seconds to 30 minutes, the film thickness after prebaking may be 0.1 to 15 / m. After prebaking, stepper, mirror projection mask aligner (ΜΡΑ), parallel Exposure can be performed at an exposure dose of lOmJ / cuf to 500 mJ / cuf in the wavelength band of 200 nm to 450 nm using an ultraviolet visible exposure machine such as a light mask aligner (PLA). After the exposure, the exposed portion is dissolved by development to obtain a positive pattern. 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, and quaternary compounds such as tetramethylammonium hydroxide and choline. The aqueous solution containing 2 or more types of ammonium salts 1 type black, etc. are mentioned.

 It is preferable to rinse with water after image development. In addition, if necessary, 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.

 Thereafter, it is preferable to carry out bleaching exposure. Bleaching exposure

By carrying out, the unbanung quinonediazide compound remaining in the film is photolyzed to further improve the light transparency of the film. As a bleaching exposure method, about 100 J / m <^2> -20,000 J / m <^2> (wavelength conversion of 365 nm exposure amount) is exposed to the whole surface using ultraviolet visible exposure machines, such as PLA.

 Bleaching exposed film, if necessary, soft-baking in the range of 50 ° C to 150 ° C with a heating device such as a hot plate, oven, and then 150 ° C to 450 ° C with a heating device such as a hot plate, oven In the range of, for example, from 10 minutes to 5 hours

The desired cured film can be manufactured by post-bake.

 As described above, the cured film has high heat resistance, transparency, crack resistance, dielectric constant, solvent resistance, and good pattern resolution. Therefore, the cured film can be effectively used for a display element, a semiconductor element, or an optical waveguide material.

 For example, the cured film according to the embodiment prepared as described above, the light transmittance of 90% or more, for example, 92% or more, for example, 95% or more in the 400 nm wavelength range in the case of a 2 의 thick cured film In addition, the residual film ratio is high, such as 70% or more, for example, 75% or more, for example, 80% or more.

 Conventional acrylic insulating film is above 250 ° C due to low heat resistance

There is a problem that yellowing decreases the transmittance, and the polymer decomposes and the chemical resistance decreases. Although the silsesquioxane containing an acrylic group or an epoxy group has improved heat resistance than an acrylic insulating film, the transmittance is still lowered at a high temperature and there is a problem of low residual film after development.

A photosensitive resin composition comprising a siloxane compound, a quinonediazide compound, and a solvent represented by Formula 1 according to one embodiment may be a structural unit represented by (0 _3/2 Si—Y—Si0 _3/2 ) in the siloxane compound, That is, through the role of a crosslinker of the carbosilane structural unit, it is possible to easily control the hardness of the cured film prepared therefrom to form a coating film of high hardness, thereby improving the high temperature attack resistance, and also through the cured film It can effectively prevent the penetration of solvents and the like. Accordingly, the cured film prepared by curing the composition solves the problem of the remaining film which is not formed as a flat film due to the reduced film thickness after development, and also has excellent chemical resistance after curing, thereby eliminating the phenomenon of pattern collapse. In addition, as compared with the conventional acrylic copolymer or silsesquioxane copolymerized with an organic compound, it has a high heat resistance, it shows a characteristic that does not discolor even at a curing temperature of 350 ^° C or more.

 The cured film is a thin film such as a liquid crystal display device or an organic EL display device.

Cores or cladding of optical waveguides, such as planarizing films for transistor (TFT) substrates, protective or insulating films such as touch panel sensor elements, interlayer insulating films of semiconductor devices, planarizing films for solid-state imaging devices, microlens array patterns, or optical semiconductor devices It can be used as a material.

 According to another embodiment, a device including the cured film is provided. The 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, but is not limited thereto.

 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.

 [Form for implementation of invention]

 (Example)

 Synthesis Example 1 Preparation of Polysiloxane

66.75 g (0.49 mol) of methyltrimethoxysilane in a 500 ml three-necked flask, 89.24 g (0.45 mol) of phenyltrimethicoxysilane, 21.28 g (0.06 mol) of 1,2-bistriethoxysilylethane, and 177.27 g of PGMEAl- were added, and 0.315 g (50) of nitric acid was added to 21.62 g of water with stirring at room temperature. Aqueous nitric acid solution with ppm) was added over 10 minutes. The flask is then immersed in an oil bath at 25 ^° C. and stirred for 60 minutes, then the oil bath is over 60 minutes

It heated up to 1 HC. From this, the mixture was heated and stirred for 2 hours (internal temperature was 100 to 10 ^° C.) to obtain a polysiloxane solution. A total of 67.3 g of byproduct methanol and water were released during the reaction. Solid content concentration of the obtained polysiloxane solution was 40 weight%. The molecular weight (polystyrene equivalent) of the obtained polysiloxane was weight average molecular weight (Mw) = l, 970.

The obtained resin solution was apply | coated to a silicon wafer so that the film thickness after prebaking might be set to 2, and the dissolution rate with respect to 2.38% TMAH aqueous solution was measured at room temperature, and it was 1750 A / sec.

 The composition, molecular weight, and dissolution rate of the prepared polysiloxane in aqueous TMAH solution after prebaking are shown in Table 1 below.

 Synthesis Example 2: Preparation of Polysiloxane

In a 500 ml three-necked flask, 66.75 g (() .46 mol) of methyltrimethoxysilane, 89.24 g (0.45 mol) of phenyltrimethoxysilane, and 31.91 g (0.09) of 1,2-bistriethoxysilylethane mol) and 187.9 g of PGMEAl-18 were added, and an aqueous nitric acid solution in which 0.315 g (50 ppm) of nitric acid was dissolved in 21.62 g of water was added over 10 minutes while stirring at room temperature. The flask is then immersed in an oil bath at 25 ^° C. and stirred for 60 minutes, then the oil bath is over 60 minutes

1 to 10 ^° C. From this, the mixture was heated and stirred for 4 hours (internal temperature was 100 to 110 ^° C.) to obtain a solution of polysiloxane. A total of 73.75 g of byproduct methanol and water were discharged to the reaction layer. Solid content concentration of the obtained polysiloxane solution was 40 weight%.

The molecular weight (polystyrene equivalent) of the obtained polysiloxane is weight average

Molecular weight (Mw) = 4,750. The obtained resin solution was apply | coated so that the film thickness after prebaking might be set to 2 on a silicon wafer, and the dissolution rate with respect to 2.38% TMAH aqueous solution was measured, and it was 820 A / sec.

 The composition, molecular weight, and dissolution rate of the prepared polysiloxane in aqueous TMAH solution after prebaking are shown in Table 1 below.

 Synthesis Example 3: Preparation of Polysiloxane

58.57 g (0.43 mol) methyltrimethicsilane in a 500 ml three-necked flask, 89.24 g (0.45 mol) of phenyltrimethoxysilane, 42.55 g (0.12 mol) of 1,2-bistriethoxysilylethane, 190.36 g of PGMEA were added, and 0.315 g (50) of nitric acid was added to 21.62 g of water with stirring at room temperature. The aqueous nitric acid solution dissolved in ppm) was added over 10 minutes. The flask is then immersed in an oil bath at 25 ^° C. and stirred for 60 minutes, and then the oil bath is placed over 60 minutes.

It heated up to 1 HC. From this, the mixture was heated and stirred for 5 hours (internal temperature was 100 to 10 ^° C.) to obtain a solution of polysiloxane. A total of 97.25 g of the byproduct methanol and water were spilled in the reaction. The obtained polysiloxane solution solid content concentration was 40 weight%. The molecular weight (polystyrene equivalent) of the obtained polysiloxane was weight average molecular weight (Mw) = 6,920.

The obtained resin solution was apply | coated to a silicon wafer so that the film thickness after prebaking might be set to 2, and the dissolution rate with respect to 5% TMAH aqueous solution was measured, and it was 350 A / sec. The composition, molecular weight, and dissolution rate of the prepared polysiloxane in aqueous TMAH solution after prebaking are shown in Table 1 below.

 Synthesis Example 4 Preparation of Polysiloxane

 In a 500 ml three-necked flask, 68.1 1 g (0.50 mol) of methyltrimethoxysilane,

89.24 g (0.45 mol) of phenyltrimethoxysilane, 17.73 g (0.05 mol) of 1,2-bistriethoxysilylethane, and 175.08 g of PGMEA were added, and 0.315 g (50) of nitric acid was added to 21.62 g of water with stirring at room temperature. Nitric acid aqueous solution which dissolved ppm) was added over 10 minutes. The flask is then immersed in an oil bath at 25 ^° C. and stirred for 60 minutes, after which the oil bath is poured over 60 minutes.

1 to 10 ^° C. From this, the mixture was heated and stirred for 1 hour (internal temperature was 100 to 10 ^° C.) to obtain a solution of polysiloxane D. In the reaction, the byproduct methane and water are added together.

59.36 g was spilled. Solid content concentration of the obtained polysiloxane solution was 40 weight%. The molecular weight (polystyrene equivalent) of the obtained polysiloxane is weight average

Molecular weight (Mw) = l, 765. The obtained resin solution was apply | coated to a silicon wafer so that the film thickness after prebaking might be set to 2 (micro) (eta), and the dissolution rate with respect to 2.38% TMAH aqueous solution was measured, and it was 6000A / sec.

 The composition, molecular weight, and dissolution rate of the prepared polysiloxane in aqueous TMAH solution after prebaking are shown in Table 1 below.

 Synthesis Example 5 Preparation of Polysiloxane

 74.92 g (0.55 mol) of methyltrimethoxysilane in a 500 ml three-necked flask,

89.24 g (0.45 mol) of phenyltrimethoxysilane and 164.16 g of PGMEA were added thereto, and the mixture was stirred at room temperature. A TMAH aqueous solution dissolved in 0.456 g (50 ppm) of TMAH in 21.62 g of water was added over 10 minutes while stirring. The flask was then immersed in an oil bath at 25 ^° C. and stirred for 60 minutes, after which the oil bath was heated to 110 ^° C. over 60 minutes. By heating and stirring for 3 hours (internal temperature is 100-110 ^° C), a solution of polysiloxane was obtained. A total of 59.36 g of the byproduct methanol and water were leaked in the reaction. Solid content concentration of the obtained polysiloxane solution was 40 weight%. The molecular weight (polystyrene equivalent) of the obtained polysiloxane was weight average molecular weight (Mw) = 3,130. The obtained resin solution was apply | coated to the silicon wafer so that the film thickness after prebaking might be set to 2, and the dissolution rate with respect to 2.38% TMAH aqueous solution was measured, and it was 160 A / sec.

 The composition, molecular weight, and dissolution rate of the prepared polysiloxane in aqueous TMAH solution after prebaking are shown in Table 1 below.

 Synthesis Example 6 Preparation of Polysiloxane

In a 500 ml three-necked flask, 68.11 g (0.50 mol) of methyltrimethoxysilane, 89.24 g (0.45 mol) of phenyltrimethoxysilane, and 17.73 g (0.05 mol) of 1,2-bistrisfexysilylethane , PGMEA-175.08 g was added, and TMAH aqueous solution which melt | dissolved 0.456 g (50 ppm) of TMAH in 21.62 g of water was added over 10 minutes, stirring at room temperature. The flask is then immersed in an oil bath at 25 ^° C. and stirred for 60 minutes, then the oil bath is over 60 minutes

1 to 10 ^° C. By heating and stirring for 3 hours (internal temperature is 100-110 ^° C), a solution of polysiloxane was obtained. A total of 59.36 g of the byproduct methanol and water were spilled in the reaction. Solid content concentration of the obtained polysiloxane solution was 40 weight%.

The molecular weight (polystyrene equivalent) of the obtained polysiloxane is weight average

Molecular weight (Mw) = l, 765. The obtained resin solution was apply | coated to a silicon wafer so that the film thickness after prebaking might be set to 2, and the dissolution rate with respect to 2.38% TMAH aqueous solution was measured, and it was 6000 A / sec.

 The composition, molecular weight, and dissolution rate of the prepared polysiloxane in aqueous TMAH solution after prebaking are shown in Table 1 below.

 TABLE 1

0 _3/2 Si-

MeSi0 _3/2 PheSi0 _3/2 Molecular Weight

CH ₂ CH ₂ -catalyst dissolution rate

(Mol _^0/0) (mol%) (g / mole)

Si0 _3/2 (mole _^0/0) 2.38%

 5% TMAH TMAH

 (A / sec)

(A / sec)

Synthesis Example 1 49 45 6 Acid 1970 1750-Synthesis Example 2 46 45 9 Acid 4750 820-Synthesis Example 3 43 45 12 Acid 6920-350 Synthesis Example 4 50 45 5 Acid 1765 6000-Synthesis Example 5 55 45 0 Alkali 3130 160- Synthesis Example 6 50 45 5 Alkali 4260-200 Examples and Evaluations: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

By mixing the polysiloxane and naphthoquinone diazide compound prepared in the synthesis example, and a solvent to prepare a photosensitive resin composition according to the following Examples and Comparative Examples, and coating the composition prepared in each Example and Comparative Example on a substrate After prebaking, exposure and development, and rinsing with pure water, the diameter of the contact hole is measured and the remaining film ratio is calculated. In addition, after carrying out plastic curing at 350 ^° C. after front exposure, the transmittance is measured and the shape of the film is observed. Each measurement was carried out by the following method, and the results are shown in Table 2 below:

 (1) Calculation of residual rate

 The remaining film ratio was calculated according to the following formula.

Residual film rate (%) = (film thickness after development ÷ film thickness after prebaking) ^χ 100

 (2) calculation of photosensitivity

 After image development, the exposure amount (henceforth this optimal exposure amount) which forms 5 hole patterns with the width of one to one is made into photosensitive sensitivity.

 (3) resolution

 The minimum pattern dimension after image development in the optimum exposure amount was the post-development resolution, and the minimum pattern dimension after curing was the post-curing resolution.

 (4) Measurement of light transmittance

Using a MultiSpec-1500 (trade name, manufactured by SHIMADZU Corporation), only the glass substrate was measured first, and the ultraviolet visible absorption spectrum was used as a reference. next, A cured film of the photosensitive resin composition was formed on the glass substrate (the pattern exposure was not performed), the sample was measured by a single beam, a light transmittance of 400 nm wavelength per urn was obtained, and the difference from the reference was determined as the light transmittance of the cured film. I did it.

 Example 1: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

Were combined wave the polysiloxane 50 parts by weight ^0/50% by weight and the polysiloxane obtained in Preparation Example 3 obtained in Synthesis Example 1, here naphthoquinonediazide compound on: the (MIPHOTO TPA517 Miwon Commercial Co., Ltd. ) a total of the polysiloxane Add 2 weights ⁰ /. Based on weight. After adding the solvent which mixed PGMEA and GBL to this, it mixed under yellow lamp, stirred, it was made into a homogeneous solution, and it filtered with a 0.2 kPa filter to prepare the photosensitive resin composition.

The composition was spin applied to a 10 x 10 class using a spin coater (Mikasa Corporation) and then prebaked at 110 ^° C. for 90 seconds using a hot plate (SCW-636 from Dainippon Screen Mfg. Co., Ltd.). , 3 was adjusted to have a film thickness. After prebaking, it exposed at 120 mJ / cuf using the i, g, h line exposure machine (UX-1200SM-AKS03 by the Ushio company), developed in 2.38% TMAH aqueous solution, and rinsed with pure water. As a result, it was confirmed that the contact hole (C / H) pattern of 5 mm 3 was removed without a residue or the like. Further, after exposing the surface at l, 000 mJ / crf and performing plastic curing at 350 ^° C., a good shape was maintained such that the corners were shrunk at a transmittance of 97%, and a pattern of 5 was maintained.

 Example 2: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

The polysiloxane obtained by the polysiloxane 50% by weight of Synthetic Example 3 obtained in Synthesis Example 2, 50 increase ⁰ /. Except that, to prepare a photosensitive resin composition in the same manner as in Example 1, and using this in the same way a cured film using the Prepared.

As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that the 3.5 contact hole (C / H) pattern was eliminated without residue. In addition, as a result of full exposure at l, 000 mJ / cii and plastic curing at 350 ^° C., a good shape was maintained at a degree of transparency with corners at 97% transmittance, and a pattern of 3.5 was maintained.

Example 3: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film Polysiloxane 30 parts by weight _^0/0 obtained in Synthesis Example 1, except for using heunhap polysiloxane 20% by weight obtained in the polysiloxane 50 parts by weight _^0/0, and Synthesis Example 3 obtained in Synthesis Example 2, and the embodiment the photosensitive in the same manner as in Example 1 The resin composition was manufactured, and the cured film was produced by the same method from that.

As a result of developing and washing on the cured film under the same conditions as in Example 1, it was confirmed that the five contact hole (C / H) patterns were eliminated without residue. In addition, as a result of full exposure at l, 000 mJ / cuf and plastic curing at 350 ^° C., a good shape was maintained such that the edges were shrunk at a transmittance of 98%, and a pattern of 5 was maintained.

 Example 4: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

Heunhap as polysiloxanes with 30% by weight obtained in Synthesis Example 1, Synthesis Example 2, a polysiloxane obtained in 40 parts by weight _^0/0, and the same method as in Example 1, except that used heunhap polysiloxane 30% by weight obtained in Synthesis Example 3, and the solution Was prepared, and the cured film was manufactured from the same method from the same.

As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that the four contact hole (C / H) patterns were eliminated without residues. In addition, as a result of performing full-surface exposure at l, 000 mJ / ciif and performing plastic curing at 350 ^° C., a good shape was maintained such that the edges were shrunk at a transmittance of 98%, and a pattern of 4 was maintained.

 Example 5: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

A mixed solution in the same manner as in Example 1, except that 40 weight ⁰ /. Of the polysiloxane obtained in Synthesis Example 1, 40 weight% of the polysiloxane obtained in Synthesis Example 2, and 20 weight% of the polysiloxane obtained in Synthesis Example 3 were mixed and used. Was prepared, and the cured film was manufactured from the same method from the same.

As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that the contact hole (C / H) pattern of 4 was eliminated without residue. In addition, as a result of full exposure at l, 000 mJ / ciif and plastic curing at 350 ^° C., a good shape was maintained such that the edges were shrunk at a transmittance of 98%, and a pattern of 4 was maintained.

Example 6: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film A mixed solution was prepared in the same manner as in Example 1, except that 35 wt% of the polysiloxane obtained in Synthesis Example 1, 45 wt% of the polysiloxane obtained in Synthesis Example 2, and 20 wt% of the polysiloxane obtained in Synthesis Example 3 were mixed and used. Furthermore, the cured film was manufactured from the same method from that.

As a result of developing and washing all the same conditions as in Example 1 with respect to the cured film, it was confirmed that the 5 μιη contact hole (C / H) pattern was removed without a residue or the like. In addition, after exposing the surface at l, 000 mJ / cuf and performing plastic curing at 350 ^° C., a good shape was maintained such that the edges were shrunk at a transmittance of 98%, and a pattern of 5 was maintained.

 Comparative Example 1: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

And polysiloxane 50 parts by weight _^0/0 obtained in Synthesis Example 4, to prepare a heunhap solution the polysiloxane 50 parts by weight ⁰ /. Obtained in Synthesis Example 6 in the same manner as in Example 1, except that, and used heunhap, as also the same manner therefrom A cured film was prepared. As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that 15 contact hole (C / H) patterns were eliminated without residue. Moreover, as a result of fully exposing to l, 000 mJ / ciif and performing plastic curing at 350 ^° C., a good shape was maintained at a degree of corner sharpness at 97% of transmittance, and a pattern of 15 μηι was maintained.

Comparative Example 2 _: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

Polysiloxanes with 50% by weight obtained in Synthesis Example 4, except that used heunhap polysiloxane 50 parts by weight _^0/0 obtained in Synthesis Example 5, to prepare a heunhap solution in the same manner as in Example 1, and also in the same manner from which a cured film Prepared. As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that 10 contact hole (C / H) patterns were eliminated without residues. In addition, after exposing the surface at l, 000 mJ / cirf and performing plastic curing at 350 ^° C., a good shape was maintained such that the corners were shrunk at a transmittance of 97%, and a pattern of 10 was maintained.

 Comparative Example 3: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

In the same manner as described except with 50 parts by weight polysiloxane and _^0/0 obtained in Synthesis Example 5, 50 parts by weight polysiloxane ⁰ /. Heunhap obtained in Synthesis Example 6, and Example 1 A mixed solution was prepared and a cured film was produced from the same method from the same. As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that 20 contact hole (C / H) patterns were eliminated without residues. In addition, after exposing the surface at l, 000 mJ / cirf and performing plastic curing at 350 ^° C., a good shape was maintained such that corners were shrunk at a transmittance of 97%, and a pattern of 20 was maintained.

 Comparative Example 4: Preparation and Evaluation of Photosensitive Resin Composition and Cured Film

A mixed solution in the same manner as in Example 1, except that 35% by weight of polysiloxane obtained in Synthesis Example 4, 45% by weight of polysiloxane obtained in Synthesis Example 5, ⁰ /. And 20% by weight of polysiloxane obtained in Synthesis Example 6 were mixed. Was prepared, and the cured film was manufactured from the same method from the same.

As a result of developing and washing on the cured film under the same conditions as those in Example 1, it was confirmed that the contact hole (C / H) pattern of 7 was eliminated without residue. In addition, as a result of performing full-surface exposure at l, 000 mJ / ciif, and performing plastic curing at 350 ^° C., a good shape was maintained such that corners were shrunk at a transmittance of 97%, and a pattern of 7 was maintained.

 TABLE 2

 Light transmission siloxane residual film rate after curing after photobaking

 Film thickness Film thickness Resolution ᄋ Copolymer (%)

(mJ / cuf) (IM) (%) Example 1 Synthesis Example 1 + 3 3.01 2.71 90.03 120 5 97 Example 2 Synthesis Example 2 + 3 3.10 2.72 89.45 100 3.5 97 Example 3 Synthesis Example 1 + 2 + 3 3.03 2.70 89.11 50 5 98 Example 4 Synthesis Example 1 + 2 + 3 3.12 2.70 86.54 100 4 98 Example 5 Synthesis Example 1 + 2 + 3 3.1 1 2.73 87.78 70 4 98 Example 6 Synthesis Example 1 + 2 + 3 2.98 2.73 91.61 50 5 97 Comparative Example 1 Synthesis Example 4 + 6 3.33 2.70 82 120 15 97 Comparative Example 2 Synthesis Example 4 + 5 3.34 2.70 82 100 10 97 Comparative Example 3 Synthesis Example 5 + 6 3.36 2.72 82 200 20 97 Comparative Example 4 Synthesis Example 4 + 5 + 6 3.23 2.71 84.37 120 7 _. 97 From Table 2 above, the siloxane compound represented by Formula 1 according to one embodiment has a polystyrene reduced weight average molecular weight of 3,000 g / mole or less as measured by (i) gel permeation chromatography. Compounds having a dissolution rate of at least 1.500 A / sec for 2.38 weight ⁰ / «aqueous solution of ΤΜΑΗ after baking, or (H)

Conversion of polystyrene standard sample measured by gel permeation chromatography

A siloxane compound having a weight average molecular weight of 3,000 g / mole or more and 6,000 g / mole or less and a dissolution rate of the pre-baked membrane in a 2.38 weight ⁰ / o TMAH aqueous solution of 200 A / sec or more and 1,500 A / sec or less; And (iii) a gel having a polystyrene measured by the permeation chromatography standard sample in terms of weight-average molecular weight of 6,000 g / mole or more and the pre-baking after a film is 5.0 wt _^0/0, the dissolution rate of the TMAH aqueous solution of 200 A / sec or more 3,000 A / It turns out that the cured film manufactured by hardening | curing the photosensitive resin composition contained as a mixture containing the siloxane compound which is the second or less has a residual film rate of 85% or more, the resolution after hardening is less than 7, and has a high light transmittance.

However, the siloxane compound according to Synthesis Example 4 having a weight average molecular weight of the siloxane compound of 1,765 g / mole and a dissolution rate of 6,000 A / sec in a 2.38 weight ⁰ / o TMAH aqueous solution of the membrane, having a weight average molecular weight of 3,130 g / mole Siloxane compound according to Synthesis Example 5, wherein the membrane has a solubility in aqueous solution of 2.38 weight ⁰ / «aqueous solution of ΤΜΑΗ, 160 A / sec, and / or

Photosensitive resin composition containing these mixtures when used in combination with a siloxane compound according to Synthesis Example 6 having a weight average molecular weight of 4,260 g / mole and having a dissolution rate of 5.0 A in a 5.0 weight ⁰ / o TMAH aqueous solution of 200 A / sec. and (Comparative example 1, Comparative example 2, and Comparative example ^4), after curing the resolution of not less than 7, the glass makreul can know the lowered to less than 85%.

In particular, the weight average molecular weight of the siloxane compound is 1,765 g / mole, does not include the siloxane compound according to Synthesis Example 4 having a dissolution rate of 6,000 A / sec in the 2.38 weight% TMAH aqueous solution of the membrane, the weight average molecular weight 3,130 g / mole a film 2.38 weight ⁰ /. the siloxane compound, and the weight average molecular weight of solubility of the 160 a / sec synthesis example 5 to the TMAH aqueous solution, and 4,260 g / mole, the film 5.0 weight _^0/0, the dissolution rate of the TMAH aqueous solution 200 Comparative example using the siloxane compound according to Synthesis Example 6 which is A / second in combination It can be seen that the resolution after curing of the photosensitive resin composition of 3 is 20, and the residual film ratio is further lowered to less than 82%.

 In conclusion, it can be seen that the photosensitive resin composition according to the embodiment can increase the resolution and the residual film ratio after curing of the cured film prepared therefrom and maintain high light transmittance.

 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 concepts of the present invention defined in the following claims are also provided. It belongs to the scope of the present invention.

Claims

Claims Claim 1 (A) A siloxane compound represented by the following formula (1); A photosensitive resin composition comprising (B) a quinonediazide compound and (C) a solvent, wherein the siloxane compound represented by the formula (1) is one or more of the siloxane compounds of the following (i) and (ii), and the following (Hi) Photosensitive resin composition containing the mixture of siloxane compounds of:

 [Formula 1]

^{(R 1 R 2 R 3 Si0} 1/2) M (R 4 R Si0 2/2) D (R 6 Si0 3/2) Ti (0 3/2 Si-Y-Si0 3/2) T 2 (Si0 _4/2 ) Q

 (In Formula 1,

R ¹ to R ⁶ are each independently 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, RO-, R (C = 0)-(where R is a substituted or unsubstituted C1 to C30 alkyl group) Substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, or substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof,

 Y 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,

 0 <M <0.5, 0 <D <0.5, 0.5 <TK1, 0 <T2 <0.2, 0 <Q <0.5,

 M + D + T1 + T2 + Q = 1,

The structural units represented by M, D, T1, T2, and Q may each include one or more different structural units.) (i) a polystyrene standard sample weight average molecular weight of 3,000 g / mole or less, as determined by gel permeation chromatography (GPC);

Siloxane compounds having a dissolution rate of 2.38 weight ⁰ / o TMAH aqueous solution of the film after prebaking in at least 1,500 A / sec;

(ii) The weight average molecular weight in terms of polystyrene standard sample measured by gel permeation chromatography was 3,000 g / mole or more and 6,000 g / mole or less and the rate of dissolution of the membrane after prebaking in a 2.38 weight ⁰ / o TMAH aqueous solution was 200 A / sec. Siloxane compounds which are 1,500 A / sec or more; And

(iii) The weight average molecular weight in terms of polystyrene standard sample measured by gel permeation chromatography is 6,000 g / mole or more, and the dissolution rate of the membrane after prebaking in a 5.0 weight ⁰ / o TMAH aqueous solution is 200 A / sec or more and 3,000 A / sec. The siloxane compound which is the following.

[Claim 2]

 The photosensitive resin composition of claim 1, wherein M, D, and Q of Formula 1 are all 0, and 0.8 <T1 <1, and 0 <Τ2 <0.2.

 [Claim 3]

 In Formula 1, in Formula 1, M, D, and Q are all 0, 0.85 ≦ T1 <1, and

The photosensitive resin composition whose 0 <Τ2 <0.15.

 [Claim 4]

In Formula 1, at least one of R ^{One To} R ⁶ Of Formula 1 comprises a substituted or unsubstituted C6 To C30 aryl group, At least one of R ^{One To} R ⁶ Is a substituted or unsubstituted C1 To C30 Alkyl group Photosensitive resin composition comprising a.

 [Claim 5]

 The photosensitive resin composition of claim 1, wherein VII of Formula 1 is a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, or a substituted or unsubstituted C6 to C30 arylene group.

 [Claim 6]

In claim 1, based on the total weight of the siloxane compound represented by the general formula (1), the siloxane compound of the above (i) is 20 parts by weight ⁰ /. To 80 A photosensitive resin composition which comprises by weight _^0/0.

[Claim 7] In the li, based on the total weight of the siloxane compound represented by Formula 1, the siloxane compound of (H) is 20% by weight ⁰ /.

 [Claim 8]

In claim 1, based on the total weight of the siloxane compound represented by the general formula (1), the siloxane compound of the above (iii) is 10 weight _^0/0 to 70 parts by weight ⁰ /. Containing photosensitive resin composition.

 [Claim 9]

 Cured film obtained by hardening the photosensitive resin composition of Claim 1.

 [Claim 10]

_. 10. The planarization film of claim 9, wherein the cured film comprises a planarization film for a thin film transistor (TFT) substrate of a liquid crystal display device or an organic EL display device, a protective film or insulating film for a touch panel sensor device, an interlayer insulation film for a semiconductor device, a planarization film for a solid-state imaging device, Cured film which is a core or clad material of a micro lens array pattern or the optical waveguide of an optical semiconductor element.

 [Claim 1 11]

The cured film of claim 19, wherein the cured film exhibits a hole property of less than 7 // m at 200 ^° C. or more, and has a light transmittance of 90% or more at a thickness of 2.5 β, 400 nm.

 [Claim 12]

 10. The cured film of claim 9, wherein the cured film has a residual film ratio of 85% or more defined as "(film thickness after unexposure after development ÷ film thickness after prebaking) <100".

 [Claim 13]

 An electronic device comprising the cured film of claim 9.