KR101921143B1 - Photo-sensitive Composition, Cured Film Prepared Therefrom, and Device Incoporating the Cured Film - Google Patents

Abstract

(A) a photosensitive resin composition comprising a compound represented by the following formula (1), (B) a quinone diazide compound, and (C) a solvent, a cured film obtained by curing the composition, and a cured film :
(Formula 1)
^{(R 1 R 2 R 3 SiO} 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 Si-Y-SiO 3/2) T2 (SiO _4/2 ) _Q
In Formula 1,
R ¹ to R ⁶ , Y, M, D, T 1, T 2, and Q are as defined in the description of the invention.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a photosensitive resin composition, a cured film formed therefrom, and a device having a cured film (Photo-sensitive Composition, Cured Film Prepared Therefrom, and Device Incorporating the Cured Film)

A photosensitive resin composition, a cured film formed therefrom, and a device having the cured film.

In order to realize more precise and high resolution in a liquid crystal display, an organic EL display, etc., the aperture ratio of the display device must be raised. This is because a transparent planarization film is provided as a protective film on the TFT substrate to overlap the data line and the pixel electrode, . As a material for forming such an organic insulating film for a TFT substrate, a material having high heat resistance, high transparency, crack resistance at high temperature, low dielectric constant, and chemical resistance is required.

Conventionally, a light-sensitive resin composition comprising a combination of a phenolic resin and a quinone diazide compound or a combination of an acrylic resin and a quinone diazide compound has been mainly used. However, these materials start to decompose slowly at 230 DEG C or higher, and there is a problem that the film thickness is lowered or cracks are generated, or the substrate is colored by high temperature treatment and the transmittance is lowered.

On the other hand, in recent years, touch panels have been employed in liquid crystal displays and the like. In order to improve transparency and functionality of touch panels, attempts have been made to heat treat or form films at higher temperatures for the purpose of high transparency and high conductivity of ITO, ought. Along with this, the protective film or insulating film of the transparent electrode member is required to have heat resistance to high temperature treatment. However, since the acrylic resin is insufficient in heat resistance and chemical resistance, the cured film is colored due to the high-temperature treatment of the substrate, the high-temperature film formation such as a transparent electrode, or various kinds of etching solution treatment, There is a problem in that the conductivity of the electrode is deteriorated. Therefore, it can not be used in a process of forming a film at a high temperature by using a device such as PECVD on the transparent film material.

Even in organic EL devices, cracks and decomposition products generated from the above materials adversely affect the luminous efficiency and life span of the organic EL device, and therefore can not be said to be an optimum material for use. An acrylic material imparted with heat resistance may also crack at 300 ° C or higher, otherwise the dielectric constant generally increases. Therefore, the parasitic capacitance due to the insulating film is increased due to the high dielectric constant, which causes a problem in the quality of the picture quality due to the increase of the power consumption or the delay of the liquid crystal element driving signal. Even in the case of an insulating material having a high dielectric constant, for example, it is possible to reduce the capacitance by increasing the film thickness, but it is generally not preferable to form a uniform thick film and the amount of material used is also increased.

On the other hand, silsesquioxane is known as a material having high heat resistance and high transparency. In particular, a photosensitive composition comprising a silsesquioxane compound having an acrylic group added to a specific silsesquioxane, an unsaturated compound containing an unsaturated carboxylic acid and an epoxy group, and an acrylic copolymer obtained by copolymerizing an olefinically unsaturated compound and a quinone diazide compound Have been proposed. However, since these compounds also have a high content of organic compounds, they have a problem of heat resistance which is colored and yellow after being cured after being cured at a high temperature of 250 ° C. or higher and have a low permeability. Since the residual film ratio after development is low, a flat film is not formed or NMP the chemical resistance to a solvent such as pyrrolidone, tetramethylammonium hydroxide (TMAH) solution and 10% NaOH is also reduced.

As a system in which a quinone diazide compound is combined with a siloxane polymer in order to impart positive photosensitivity to the siloxane polymer, a material obtained by combining a siloxane polymer having a phenolic hydroxyl group at the terminal thereof with a quinone diazide compound, A material obtained by combining a siloxane polymer having a carboxyl group added thereto and a quinone diazide compound is known. However, since these materials contain a large amount of quinone diazide compound, or phenolic hydroxyl groups are present in the siloxane polymer, coloring of the coating film tends to occur during whitening or thermal curing, and cracking occurs at a high temperature of 300 ° C or higher And can not be used as a material with high transparency due to a decrease in transmittance. In addition, since these materials have low transparency, there is also a problem that the sensitivity is low at the time of pattern formation.

When a photosensitive composition made solely of a polysiloxane and a quinone diazide compound is thermally cured, crosslinking and high molecular weight are caused by dehydration condensation of a silanol group in the polysiloxane. In this thermosetting process, the film is low-viscosity and melted at a high temperature before the thermal curing of the pattern sufficiently progresses, and patterns such as holes and lines obtained after development flow. As a result, cracks do not occur, but degradation of the pattern, which degrades the resolution, occurs and must be prevented.

On the other hand, when a system of a polysiloxane insoluble in developer and a polysiloxane soluble in solubility is combined with a quinone diazide compound, patterns of holes and lines obtained after development are collapsed upon heating and curing, resulting in "pattern sagging" And a photosensitive composition for preventing this is proposed. However, if a polysiloxane insoluble in a developing solution is used, it will dissolve after development, but re-adherence of residues or unstable water starting to melt may cause development pattern defects. In order to prevent pattern deterioration, it is necessary to sufficiently increase the molecular weight of the siloxane. As a result, as the photosensitive material, sensitivity is low and high reaction energy is required. Further, there is a drawback that the residual film ratio is not sufficient and the loss of the material is large.

One embodiment provides a photosensitive resin composition which has high heat resistance, high transparency, and low dielectric constant and is excellent in solubility in an alkali solution.

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

Another embodiment provides an element comprising the cured film.

One embodiment provides a photosensitive resin composition comprising (A) a compound represented by the following formula (1), (B) a quinone diazide compound, and (C) a solvent:

(Formula 1)

^{(R 1 R 2 R 3 SiO} 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 Si-Y-SiO 3/2) T2 (SiO _4/2 ) _Q

In Formula 1,

R ¹ to R ⁶ are each independently selected from the group consisting of hydrogen, hydroxy, halogen, 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, A substituted or 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, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, RO-, R (C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof. The total Si Atomic number Based on the R ¹ to R ⁶ is bonded to more than 60 mole% Si atoms are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl An aryl group, or a combination thereof,

Y represents a substituted or unsubstituted C4 to C30 alkylene group, a substituted or unsubstituted C4 to C30 alkenylene group, a substituted or unsubstituted C4 to C30 cycloalkylene group, a substituted or unsubstituted C3 to C30 heterocycloalkylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

0 < 0.4, 0 < D < 0.4, 0.6 &

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.

In the formula (1), M and Q are each 0, and 0? D? 0.2, 0.65? T1 <1, and 0 <T2 <0.2.

In the formula (1), M, D, and Q are all 0, 0.8? T1 <1, and 0 <T2 <0.2.

In the above formula (1), R ¹ to R ⁶ may each independently be a C ¹ to C 6 alkyl group or a C 6 to C 12 aryl group.

In Formula 1, Y may be a linear or branched C4 to C30 alkylene group, a linear or branched C4 to C30 alkenylene group, a C4 to C12 cycloalkylene group, a C6 to C18 arylene group, or a combination thereof.

In Formula 1, Y may be a linear or branched C4 to C20 alkylene group, a linear or branched C4 to C20 alkenylene group, a cyclohexylene group, a cyclooctanylene group, a phenylene group, or a combination thereof.

The functional group which bonds to at least 60 mol% of Si atoms based on the total moles of Si atoms of the compound represented by the formula (1) is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, A substituted or unsubstituted C1 to C30 heteroaryl group, or a combination thereof.

The photosensitive resin composition may have a solubility in a 2.38% aqueous TMAH solution of 500 Å / sec to 5,000 Å / sec in a prebaked film.

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

The cured film may be used as a flattening film for a thin film transistor (TFT) substrate of a liquid crystal display element or an organic EL display element, a protective film or insulating film of a touch panel sensor element, an interlayer insulating film of a semiconductor element, a flattening film for a solid- Or a core or a clad material of an optical waveguide of an optical semiconductor device .

According to another embodiment, there is provided an element comprising the cured film.

The light-sensitive resin composition according to one embodiment can increase the surface area in the polysiloxane resin and can control the spatial arrangement thereof, thereby facilitating the penetration of the basic developer. Thus, the composition has excellent solubility in an alkali developing solution, It is possible to provide a cured film having high heat resistance, high permeability, low dielectric constant, and high resolution. The cured film can be usefully used for manufacturing a planarizing film for a thin film transistor (TFT) substrate, an interlayer insulating film for a semiconductor device, and the like.

Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C 1 to C 30 arylalkyl group, a C 7 to C 30 arylalkyl group, a C 1 to C 30 alkoxy group, a C 1 to C 20 heteroalkyl group, a C 3 to C 20 heteroarylalkyl group, a C 3 to C 30 cycloalkyl group, a C 3 to C 15 cycloalkenyl group, C6 to C15 cycloalkynyl groups, C3 to C30 heterocycloalkyl groups, and combinations thereof.

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

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

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

The photosensitive resin composition according to one embodiment provides a photosensitive resin composition comprising (A) a compound represented by the following formula (1), (B) a quinone diazide compound, and (C)

(Formula 1)

^{(R 1 R 2 R 3 SiO} 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 Si-Y-SiO 3/2) T2 (SiO _4/2 ) _Q

In Formula 1,

R ¹ to R ⁶ are each independently selected from the group consisting of hydrogen, hydroxy, halogen, 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, A substituted or 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, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, RO-, R (C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof. The total Si Atomic number Based on the R ¹ to R ⁶ is bonded to more than 60 mole% Si atoms are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl An aryl group, or a combination thereof,

Y represents a substituted or unsubstituted C4 to C30 alkylene group, a substituted or unsubstituted C4 to C30 alkenylene group, a substituted or unsubstituted C4 to C30 cycloalkylene group, a substituted or unsubstituted C3 to C30 heterocycloalkylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

0 < 0.4, 0 < D < 0.4, 0.6 &

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.

The photosensitive resin composition according to this embodiment comprises a carbosilane-based organic spacer represented by _{"O 3/2 Si-Y} -SiO 3/2" in the compound represented by the formula (1), wherein the organic spacer Formula 1 Lt; RTI ID = 0.0 &gt; siloxane &lt; / RTI &gt; structural units. _{"O 3/2 Si-Y} -SiO 3/2" structural unit of the bridges is, Y is a substituted or unsubstituted C4 to C30 alkylene group, a substituted or unsubstituted C4 to C30 alkenylene group, a substituted or A substituted or unsubstituted C3 to C30 heterocycloalkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof To increase the porosity of the resin by introducing a flexible hydrocarbon-based chain between the structural units of the resin prepared from the compound of formula (I). Accordingly, the _{"O 3/2 Si-Y} -SiO 3/2" resins are prepared from compounds of the formula (1) containing the structural unit is increased, the surface area and porosity, from a compound of the formula (1) Permeability of an alkali developer or the like into the produced resin may be increased. Accordingly, the photosensitive resin composition containing the compound of Formula 1 has excellent solubility in an alkali developing solution of the exposed portion, and crack resistance of the cured film produced therefrom can be improved as the flexibility of the resin increases.

The solubility of the polysiloxane resin itself in the developer and the structure of the resin play an important role in the solubility of the photosensitive resin composition containing the polysiloxane in an alkali developer. Generally, the siloxane has a high rate of hydrolysis and condensation reaction under water and a catalyst, so that it is easy to form a compact cage or cyclic structure. This makes it difficult to increase the molecular weight of the siloxane polymer and may interfere with the contact of the silanol in the resin with the alkali developing solution. In order to solve such a problem, a linear polysiloxane was prepared by synthesizing a photosensitive siloxane composition containing a silane compound forming a structural unit represented by " D " in the above formula (1) However, such a polysiloxane has a disadvantage of low hardness and poor coatability upon spin coating.

On the other hand, the hydrolysis and condensation reaction of the siloxane polymer is mainly due to the silanol groups contained in the siloxane. By replacing a part of the silanol groups with an acyl group or the like, the solubility in the alkaline developer Of the total population. However, there is a problem that the cured product obtained from these siloxanes has no resistance to a chemical solution such as a photoresist stripping solution, and has limited usable applications.

Thus, although a polysiloxane using tetraethoxysilane as a bridge in resin has been developed for improving the chemical resistance, Residues may remain after development, resulting in bad results in terms of sensitivity.

As described above, the present inventors have found that by introducing a flexible hydrocarbon-based chain or ring structure between structural units of a siloxane resin using a carbosilane-based spacer, the surface area and porosity of the resin produced from the siloxane compound containing the same can be increased And by decreasing the packing density of the resin from this, the alkali developer easily penetrates into the resin to provide excellent solubility to the developer, and flexibility and crack resistance can be improved Thereby realizing a positive photosensitive resin composition.

The photosensitive resin compositions according to the present embodiment showed differences in the solubility and crack resistance of the developer depending on the length of the carbon chain of the linking group represented by Y in the carbosilane-based organic spacer structural units and the difference in the spatial three-dimensional structure Therefore, it will be understood by those skilled in the art that Y in the above-described carbosilane-based organic spacer structural unit can be suitably selected in the above-described range according to the intended use and desired physical properties of the photosensitive resin composition to be produced will be.

Meanwhile, the photosensitive resin composition according to this embodiment may contain at least 60 mol%, for example, at least 65 mol%, for example at least 70 mol% of the Si atoms based on the total moles of Si atoms of the compound represented by the formula Each of R ¹ to R ⁶ independently represents a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 hetero An aryl group, or a combination thereof.

When a functional group such as an aryl group, an arylalkyl group or a heteroaryl group is substituted for a Si atom in an amount of 60 mol% or more based on the total number of moles of Si atoms in the polysiloxane represented by the formula (1), the photosensitive resin composition containing the same, The strength is increased and the crack incidence can be reduced, and also the chemical resistance to alkaline developer such as TMAH is increased.

As shown by the above formula (1), the siloxane compound comprises at least 0.6 the structural unit represented by (R ⁶ SiO _3/2) in the compounds in a molar fraction, and _{(O 3/2 Si-Y} -SiO 3 / ₂ ), and the remaining structural units may each contain less than 0.4.

In one embodiment, T1 among the constituent units constituting the compound represented by Formula 1 is 0.6? T1 <1, for example, 0.65? T1 <1, for example, 0.7? T1 <1, Lt; T1 < 1, for example, 0.8? T1 <1.

When the structural unit represented by T1 in the above formula (1), that is, (R ⁶ SiO _3/2 ) is included in the above range, the photosensitive resin composition comprising the compound has high storage stability, High transmittance, high hardness, high retention rate, high resolution, and excellent sensitivity to light.

Further, the content of the structural unit represented by the T2 of the structural units constituting the compound represented by general formula (1), _{i.e., (O 3/2 Si-} Y-SiO 3/2) is, for 0 <T2 <0.2, for example, 0 <T2? 0.17, for example 0 <T2? 0.15, for example 0 <T2? 0.13, 0 <T2? 0.09, for example 0 <T2? 0.08, for example 0 <T2? 0.07, 0 < T2 < / = 0.03.

If they include structural units represented by _{(O 3/2 Si-Y} -SiO 3/2) to the above range, a photosensitive including while still increasing the flexibility and porosity of the compound represented by general formula (1), which as described above, The resin composition forms a dense film through sufficient cross-linking when curing the resin composition, and has high mechanical strength, chemical resistance, and high residual film ratio.

Moreover, crack resistance according to _{(O 3/2 Si-Y} -SiO 3/2) by including appropriately adjusted within the range of the structural unit represented by the high degree of crosslinking, and the resin main chain (Backbone) increase in carbon content And chemical resistance are improved, the film thickness after development is reduced to solve the problem of a residual film ratio that can not form a flat film, and an organic insulating film excellent in chemical resistance and crack resistance at high temperature after curing can be realized.

In one embodiment, M and Q in formula 1 may be 0, 0? D? 0.2, 0.65? T1 <1, and 0 <T2 <0.2. Specifically, M, D, and Q in the above formula (1) are all 0, 0.8? T1 <1, and 0 <T2 <0.2.

When the content of each structural unit in the compound represented by Formula 1 is within the above range, the compound represented by Formula 1 may have high heat resistance, transparency, chemical resistance, crack resistance, and low dielectric constant.

In the above formula (1), R ¹ to R ⁶ may each independently be a C ¹ to C 6 alkyl group or a C 6 to C 12 aryl group.

C1 to C6 alkyl group in the R ¹ to R ⁶ may be a methyl group, may be a C6 to C12 aryl group is a phenyl group.

In one embodiment, Y in formula (1) is a linear or branched C4 to C30 alkylene group, a linear or branched C4 to C30 alkenylene group, a C4 to C12 cycloalkylene group, a C6 to C18 arylene group, . Specifically, Y in formula (1) may be a linear or branched C4 to C20 alkylene group, a linear or branched C4 to C20 alkenylene group, a cyclohexylene group, a cyclooctanylene group, a phenylene group, or a combination thereof .

When Y in Formula 1 is an alkylene group having 4 or more carbon atoms, an alkenylene group having 4 or more carbon atoms, a cycloalkylene group having 4 or more carbon atoms, a heterocycloalkylene group, an arylene group, or a heteroarylene group, .

Accordingly, the photosensitive resin composition may have a solubility in a 2.38% aqueous TMAH solution of 500 Å / sec to 5,000 Å / sec, for example, 500 Å / sec to 4,500 Å / sec to 43,000 A / sec, for example, 500 A / sec to 4,000 A / sec But is not limited to these.

As described above, the composition according to this embodiment can be prepared by appropriately controlling the structural units of the respective structural units in the compound represented by the formula (1), for example, the structural unit of the carbosilane-based organic spacer within the above- The solubility in an alkali developing solution can be easily controlled.

The compound represented by the general formula (1) is, for example, R ¹ R ² R ³ 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 Z ¹¹ Z ¹² , And monomers represented by SiZ ¹³ Z ¹⁴ Z ¹⁵ Z ¹⁶ can be obtained by hydrolysis and condensation polymerization. Wherein Z ¹ to Z ¹⁶ are each independently a C ¹ to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof, wherein R ¹ to R ⁶ and Y have the same meanings as defined above for formula .

The hydrolysis and polycondensation reaction for preparing the compound represented by the formula (1) can be carried out by a general method well known to those skilled in the art. For example, adding a solvent, water and, if necessary, a catalyst to the above mixture of monomers and stirring at a temperature of 50 ° C to 150 ° C, for example, 90 ° C to 130 ° C for 0.5 hours to 100 hours do. During the stirring, the hydrolysis by-products (alcohol such as methanol) and condensation by-products can be distilled and removed by distillation, if necessary.

The reaction solvent is not particularly limited, but usually the same solvent as the solvent contained in the photosensitive resin composition according to the embodiment can be used.

The amount of the solvent to be added may be 10 to 1000 parts by weight based on 100 parts by weight of the total weight of the monomers. The amount of water to be used for the hydrolysis reaction may be in the range of 0.5 to 3 mol per 1 mol of the hydrolyzable group.

The catalyst to be added is not particularly limited, but an acid catalyst, a base catalyst and the like can be used. The amount of the catalyst to be added may be in the range of 0.01 to 10 parts by weight based on 100 parts by weight of the total weight of the monomers.

The compound represented by the formula (1) may be used alone or in combination of two or more.

The molecular weight of the compound of Formula 1 may be about 1,000 to 500,000, for example, about 1,000 to 100,000, for example, in terms of a polystyrene standard sample measured by Gel Permeation Chromatography (GPC) For example, from about 3,000 to about 20,000, such as from about 3,000 to about 15,000, such as from about 3,000 to about 10,000, such as from about 3,000 to about 8,000, such as from about 3,000 to about 10,000, To 6,000, for example, from 3,000 to 5,000.

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

The photosensitive resin composition according to this embodiment includes (B) a quinone diazide compound. A photosensitive resin composition comprising a quinone diazide compound forms a positive type in which an exposed portion is removed by a developer. No particular limitation is imposed on the quinone diazide compound that can be used. For example, a compound in which a naphthoquinone diazide sulfonic acid is ester-bonded to a compound having a phenolic hydroxyl group can be used. The ortho position of the phenolic hydroxyl group of the compound, And para position are each independently selected from the group consisting of hydrogen and a substituent represented by the following formula (2):

(2)

In Formula 2,

R ¹² , R ¹³ and R ¹⁴ each independently represents a C1 to C10 alkyl group, a carboxyl group, a phenyl group or a substituted phenyl group, 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 the general formula (2), the alkyl group may be unsubstituted or substituted. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a n-hexyl group, a cyclohexyl group, , A trifluoromethyl group, and a 2-carboxyethyl group. The substituted phenyl group includes a phenyl group substituted with a hydroxy group. R ¹² , R ¹³ and R ¹⁴ may form a ring together, and specific examples thereof include a cyclopentane ring, a cyclohexane ring, an adamantane ring, and a fluorene ring.

When the ortho position and the para position of the phenolic hydroxyl group are other than the above groups, for example, a methyl group, oxidative decomposition occurs due to thermal curing to form a conjugated system represented by a quinoid structure, The transparency deteriorates. These quinone diazide compounds can be synthesized by a known esterification reaction between a compound having a phenolic hydroxyl group and naphthoquinone diazidesulfonic acid chloride. Specific examples of the compound having a phenolic hydroxyl group include the following compounds (all available from Honshu Chemical Industry Co., Ltd.).

As naphthoquinonediazidesulfonic acid, 4-naphthoquinonediazidesulfonic acid or 5-naphthoquinonediazidesulfonic acid can be used. The 4-naphthoquinonediazide sulfonic acid ester compound is suitable for i-line exposure because it has absorption in the i-line (wavelength 365 nm) region. Further, the 5-naphthoquinone diazidesulfonic acid ester compound is suitable for exposure at a wide wavelength because absorption occurs in a wide wavelength range. Depending on the exposure wavelength, a 4-naphthoquinonediazide sulfonic acid ester compound or a 5-naphthoquinone diazide sulfonic acid ester compound can be selected. A 4-naphthoquinone diazidesulfonic acid ester compound and a 5-naphthoquinone diazidesulfonic acid ester compound may be mixed and used.

The amount of the quinone diazide compound to be added is not particularly limited. For example, 0.1 to 15 parts by weight, for example, 1 to 10 parts by weight, based on 100 parts by weight of the siloxane compound of Formula 1 may be used. When the addition amount of the quinone diazide compound 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 practically no photosensitivity. Further, 1 part by weight or more is preferable in order to obtain better dissolution contrast. When the addition amount of the quinone diazide compound is more than 15 parts by weight, the compatibility of the siloxane compound and the quinone diazide compound is deteriorated, resulting in whitening of the coating film, or coloration due to decomposition of the quinone diazide compound The colorless transparency of the cured film deteriorates. In order to obtain a film having a higher transparency, it is preferable that the quinone diazide compound is used in an amount of 10 parts by weight or less.

Further, the photosensitive resin composition according to this embodiment contains (C) a solvent.

The usable solvent is not particularly limited, but preferably a compound having an alcoholic hydroxyl group and / or a cyclic compound having a carbonyl group is used. When these solvents are used, the siloxane compound and the quinone diazide compound dissolve uniformly, so that the film is not whitened at the time of coating after application, and high transparency can be achieved.

The compound having an alcoholic hydroxyl group is not particularly limited, but preferably a compound having a boiling point of 110 to 250 DEG C at atmospheric pressure can be used. If the boiling point is higher than 250 ° C, the amount of the residual solvent in the film becomes large, and the film shrinkage ratio upon curing becomes large, and good flatness can not be obtained. If the boiling point is lower than 110 ° C, the film becomes too dry during coating, resulting in roughness of the film surface.

Specific examples of the compound having an alcoholic hydroxyl group include acetol, 3-hydroxy-3-methyl-2-butanone, 4-hydroxy- Propylene glycol monomethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono n-butyl ether, propylene glycol monomethyl ether, Butyl ether, propylene glycol mono t-butyl ether, 3-methoxy-1-butanol and 3-methyl-3-methoxy-1-butanol. Of these, compounds having a carbonyl group are particularly preferable, and diacetone alcohol is particularly preferably used. These compounds having an alcoholic hydroxyl group may be used alone or in combination of two or more.

The cyclic compound having a carbonyl group is not particularly limited, but preferably a compound having a boiling point of 150 ° C to 250 ° C at atmospheric pressure can be used. If the boiling point is higher than 250 占 폚, the amount of the residual solvent in the film becomes large, so that the film shrinks during curing and the good elasticity can not be obtained. If the boiling point is lower than 150 ° C, the film becomes too dry during the coating, resulting in a rough film surface and poor coatability.

Specific examples of the cyclic compound having a carbonyl group include? -Butylolactone,? -Valerolactone,? -Valerolactone, propylene carbonate, N-methylpyrrolidone, cyclohexanone and cycloheptanone . Of these, especially? -Butyrolactone can be preferably used. These cyclic compounds having a carbonyl group may be used singly or in combination of two or more kinds.

The compound having an alcoholic hydroxyl group and the cyclic compound having a carbonyl group may be used alone or in combination. The weight ratio of the compound having an alcoholic hydroxyl group to the cyclic compound having a carbonyl group is preferably about 99 to 50: 1 to 50, or, for example, 97 to 60: 3 / RTI &gt; When the amount of 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 siloxane compound and the quinone diazide compound of the formula (1) becomes poor and the cured film becomes white can do. When the amount of the compound having an alcoholic hydroxyl group is less than 50% by weight (more than 50% by weight of the cyclic compound having a carbonyl group), the condensation reaction of unreacted silanol groups in the siloxane compound of the formula (1) tends to occur and storage stability may deteriorate .

The photosensitive resin composition according to the above embodiments may further contain other solvents insofar as the effect of the present invention is not impaired. Other examples of the solvent include ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, propylene glycol monomethyl ether acetate, 3-methoxy- Butyl acetate, and the like; ketones such as methyl isobutyl ketone, diisopropyl ketone, diisobutyl ketone and acetyl acetone; ketones such as diethyl ether, diisopropyl ether, di-n-butyl ether, diphenyl ether And the like.

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

The photosensitive resin composition according to the above embodiments may further contain additional components commonly used in the photosensitive resin composition, for example, a silane coupling agent, a surfactant, and the like, if necessary.

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

Specific examples of the silane-based coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane,? -Glycidoxypropyltriethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and preferably at least one selected from the group consisting of Gamma -glycidoxypropyltriethoxysilane and / or gamma -glycidoxypropyltrimethoxysilane having an epoxy group can be used in view of adhesion between the residual film ratio and the substrate, but the present invention is not limited thereto Do not.

The silane coupling agent may be contained in the photosensitive composition in the range of 0.01 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 the formula (1). 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 amount is 10 parts by weight or less, the thermal stability is improved at a high temperature, and the occurrence of unevenness after development can be prevented.

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

Examples of the surfactant include FZ2122 (Dow Corning Toray Corporation), BM-1000, BM-1100 (manufactured by BM CHEMIE), Megafac F142D, Copper F172, Copper F173, Copper F183 S-113, S-131 (manufactured by Sumitomo 3M Limited), Florad FC-135, FC-170C, FC-430 and FC-431 , S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105 and SC-106 (Asahi Garasu Co., SH-193, SZ-6032, SF-8428, DC-57, DC (available from Shin-Aichi Kasei Kogyo Co., Ltd.) -190 (manufactured by Toray Silicone Co., Ltd.); Polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether, polyoxyethylene aryl ethers such as polyoxyethylene octylphenyl ether and polyoxyethylene nonylphenyl ether , Polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, and other nonionic surfactants; (Manufactured by Shin-Etsu Chemical Co., Ltd.) or (meth) acrylic acid-based copolymer polyflow No. 57,95 (manufactured by Kyoeisha Chemical Co., Ltd.) And can be used in parallel.

The surfactant may be used in an amount 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 Formula 1. When the content of the surfactant is 0.05 parts by weight or more, the coatability is improved and cracks are not generated on the coated surface, and when the content is 10 parts by weight or less, it is advantageous in terms of cost.

In addition to the above components, the photosensitive resin composition according to one embodiment may further include additional components that are conventionally used in the thermosetting resin composition and / or the photosensitive resin composition, if necessary. For example, the photosensitive resin composition according to the above embodiment may contain additives such as a dissolution accelerator, a dissolution inhibitor, a surface active agent, a stabilizer, and an antifoaming agent, if necessary.

In particular, the dissolution enhancer can improve the sensitivity. As the solubility promoting agent, a compound having a phenolic hydroxyl group or an N-hydroxydicarboximide compound is preferably used. As a specific example, a compound having a phenolic hydroxyl group used in a quinone diazide compound can be mentioned.

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

The photosensitive resin composition according to this embodiment is coated on a base substrate by a known method such as spinner, dipping, or slit, and is prebaked by a heating device such as a hot plate or oven. The prebaking may be performed at a temperature in the range of 50 ° C to 150 ° C for 30 seconds to 30 minutes, and the film thickness after prebaking may be 0.1 to 15 μm.

After pre-baking, an ultraviolet visible light exposure apparatus such as a stepper, a mirror projection mask aligner (MPA), and a parallel light mask aligner (PLA) was used to measure the exposure amount at a wavelength band of 200 nm to 450 nm at 10 mJ / cm 2 to 500 mJ / As shown in FIG.

After exposure, the exposed portion is dissolved by development to obtain a positive pattern. As the developing method, it is preferable to immerse the developing solution for 5 seconds to 10 minutes by a method such as shower, dipping, paddle, or the like. As the developer, a known alkali developer can be used. Specific examples thereof include inorganic alkalis such as hydroxides, carbonates, phosphates, silicates and borates of alkali metals, amines such as 2-diethylaminoethanol, monoethanolamine and diethanolamine, quaternary ammonium salts such as tetramethylammonium hydroxide and choline Or an aqueous solution containing one or more of these.

After development, it is preferable to rinse with water. If necessary, drying baking may be performed in a range of 50 ° C to 150 ° C by a heating apparatus such as a hot plate or an oven.

Then, it is preferable to perform the bleaching exposure. By carrying out the bleaching exposure, the unreacted quinonediazide compound remaining in the film is photodegraded, so that the optical transparency of the film can be further improved. As a bleaching exposure method, an entire surface is exposed to an exposure dose of about 100 J / m ² to about 20,000 J / m ² (equivalent to a wavelength of 365 nm in terms of exposure dose) using an ultraviolet exposure apparatus such as PLA.

If necessary, the film subjected to the bleaching exposure may be subjected to a soft bake in a range of 50 ° C to 150 ° C by a heating apparatus such as a hot plate or an oven, and then heated at 150 ° C to 450 ° C by a heating apparatus such as a hot plate, For example, post-bake for 10 minutes to 5 hours to prepare a desired cured film.

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

According to another embodiment, there is provided an element comprising the cured film.

The element may be a liquid crystal display element, an organic EL element, a semiconductor device, a solid-state image pickup element, or the like that includes the cured film as a flattening film of a TFT substrate, but is not limited thereto.

Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.

( Example )

compare Synthetic example  One: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Then, a solution of phenyltrimethoxysilane, methyltrimethoxysilane, and 1,2-bis (trimethoxysilyl) ethane in a molar ratio of 0.70: 0.225: 0.075 Was added dropwise over 1 hour. After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGEMA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by GPC, and the weight average molecular weight was 2,350. Further, the solution of polysiloxane obtained was applied to a silicon wafer by a spin coater so that the film thickness after pre-baking was 2 占 퐉, and the dissolution rate in a 2.38% TMAH aqueous solution after prebaking was measured and found to be 400 占 sec.

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

compare Synthetic example  2: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Subsequently, 30 g of a mixture containing phenyltrimethoxysilane and 1,2-bis (trimethoxysilyl) ethane in a molar ratio of 0.925: 0.075 was added over 1 hour . After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGMEA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The polystyrene reduced weight average molecular weight of the prepared polysiloxane was 2,350. Further, the obtained resin solution was applied to a silicon wafer by a spin coater so that the film thickness after prebaking was 2 占 퐉, and the dissolution rate in a 2.38% TMAH aqueous solution after prebaking was measured and found to be 400 占 / sec.

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

Synthetic example  One: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Subsequently, 30 g of a mixture containing phenyltrimethoxysilane, methyltrimethoxysilane, and a compound represented by the following formula (3) in a molar ratio of 0.70: 0.225: 0.075 was added dropwise over 1 hour. After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGEMA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by GPC, and the weight average molecular weight was 2,350. The solution of the polysiloxane thus obtained was applied to a silicon wafer by a spin coater so as to have a thickness of 2 탆 after pre-baking, and the dissolution rate in a 2.38% TMAH aqueous solution after prebaking was measured to be 800 Å / second.

(Formula 3)

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

Synthetic example  2: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Subsequently, 30 g of a mixture containing phenyltrimethoxysilane, methyltrimethoxysilane, and a compound represented by the following formula (4) in a molar ratio of 0.70: 0.225: 0.075 was added dropwise over 1 hour. After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGEMA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by GPC and found to be 2,870. The solution of the polysiloxane thus obtained was applied to a silicon wafer by a spin coater so that the film thickness after pre-baking was 2 占 퐉, and the dissolution rate in a 2.38% TMAH aqueous solution after prebaking was measured to be 1,800 占 sec .

(Formula 4)

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

Synthetic example  3: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Subsequently, 30 g of a mixture containing phenyltrimethoxysilane, methyltrimethoxysilane, and a compound represented by the following formula (5) in a molar ratio of 0.70: 0.225: 0.075 was added dropwise over 1 hour. After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGEMA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by gel permeation chromatography (GPC: HLC-8220GPC manufactured by Toso Co., Ltd.) and found to have a weight average molecular weight of 2,930. The solution of polysiloxane thus obtained was applied to a silicon wafer by a spin coater (MS-A100; manufactured by Mikasa) so that the film thickness after prebaking was 2 占 퐉, and the dissolution rate in a 2.38% TMAH aqueous solution after prebaking was measured In other words, it was 2,200 A / sec.

(Formula 5)

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

Synthetic example  4: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Subsequently, 30 g of a mixture containing phenyltrimethoxysilane, methyltrimethoxysilane and a compound represented by the following formula (6) in a molar ratio of 0.70: 0.225: 0.075 was added dropwise over 1 hour. After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGEMA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by GPC and found to be 3,580. Further, the solution of the polysiloxane obtained above was applied to a silicon wafer by a spin coater so that the film thickness after pre-baking was 2 탆, and the dissolution rate in a 2.38% TMAH aqueous solution after pre-baking was measured to be 3,800 Å / sec .

(Formula 6)

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

compare Synthetic example  3: Polysiloxane  Synthetic and alkaline Dissolution rate for developer  Measure

1 kg of a mixed solvent obtained by mixing water and propylene glycol monomethyl ether acetate (PGMEA) at a weight ratio of 1: 5 was introduced into a three-necked flask, and then 10 g of a 10% HNO ₃ aqueous solution was added while maintaining the temperature at 23 ° C. Subsequently, 30 g of a mixture containing phenyltrimethoxysilane, methyltrimethoxysilane, and TEOS (tetraethyl orthosilicate) in a molar ratio of 0.70: 0.225: 0.075 was added dropwise over 1 hour. After completion of the dropwise addition, condensation polymerization was carried out while heating to reflux at 50 ° C for 3 hours. Subsequently, after cooling to room temperature, the water layer was removed to prepare a polymer solution dissolved in PGEMA. The resulting polymer solution was washed with water to remove reaction by-products. The obtained organic layer was reduced in pressure and concentrated to remove the solvent. To the concentrate was added propylene glycol monomethyl ether acetate (PGMEA) so as to have a solid concentration of 30% by weight. The molecular weight (in terms of polystyrene) of the obtained polysiloxane was measured by GPC, and the weight average molecular weight was 2,190. The polysiloxane solution thus obtained was applied on a silicon wafer by a spin coater so as to have a thickness of 2 탆 after pre-baking, and was immersed in a 2.38% TMAH aqueous solution after pre-baking, but was not dissolved. The dissolution rate of the polysiloxane-coated silicon wafer in a 5% TMAH aqueous solution was measured, and the dissolution rate was 1,400 Å / sec.

The weight average molecular weights measured and the dissolution rate in 2.38% TMAH aqueous solution are shown in Table 1 below.

Example  1 to 1 and Comparative Example  1 to 3: Cured film  Manufacturing and Evaluation

To each of the siloxane copolymer solutions obtained in Synthesis Examples 1 to 4 and Comparative Synthesis Examples 1 to 3, a naphthoquinone diazide compound represented by the following formula (7) was added in an amount of 3% by weight based on the total composition weight, PGMEA and GBL Were added to a mixture of 25 wt% and 8 wt% of the total composition, respectively, and mixed under a yellow lamp or the like. The mixed solution was spin-coated on an organic substrate to a thickness of 3 탆, pre-baked at 120 캜 for 90 seconds, and then exposed with an i, g, and h line exposer. Thereafter, the resist film was developed with a 2.38 wt% TMAH aqueous solution or a 5.0 wt% TMAH aqueous solution, rinsed with pure water, and then subjected to a full exposure at 1,000 mJ / cm 2 and then baked at 350 캜. 1 to 3 were prepared. After curing the cured film at room temperature, cracking of the coated sample on each substrate was confirmed by an optical microscope, and the results are shown in Table 1 below.

(Formula 7)

로 치환되고 나머지 하나는 수소 원자이거나, 또는 세 개 모두

로 치환되어 있다.In Formula 7, at least ^{two of} Q ¹ , Q ² , and Q ³ are

And the other is a hydrogen atom, or all three

.

Polysiloxane The weight average molecular weight of the polysiloxane
(Mw) Crack occurrence ADR (Å / sec)
TMAH 2.38% 5% Comparative Example 1 Comparative Synthesis Example 1 2350 △ 400 Comparative Example 2 Comparative Synthesis Example 2 2350 X 400 Example 1 Synthesis Example 1 2350 X 800 Example 2 Synthesis Example 2 2870 X 1800 Example 3 Synthesis Example 3 2930 X 2200 Example 4 Synthesis Example 4 3580 X 3800 Comparative Example 3 Comparative Synthesis Example 3 2190 ○ - 1400

In Table 1, X indicates that cracks did not occur, O indicates that cracks occurred, and DELTA indicates that the number of cracks occurred when the reproducibility was evaluated was similar to the case where cracks did not occur.

As can be seen from the above Table 1, in the case of the cured films according to Examples 1 to 4 prepared from the polysiloxane having a carbosilane-based spacer having a hydrocarbon connecting group having 4 or more carbon atoms, cracks were not generated at all in the thermal shock test. In addition, the solubility of these polysiloxanes in aqueous 2.38% TMAH solution after prebaking exceeded 500 Å / sec.

On the other hand, in the case of the cured film prepared from the polysiloxane prepared in Comparative Synthesis Example 1, cracks occurred in some samples in the thermal shock test and the solubility in the 2.38% TMAH aqueous solution after prebaking was also less than 500 Å / sec Respectively.

In the case of Comparative Example 2, the cracking resistance of the cured film was maintained to some extent by using the polysiloxane according to Comparative Synthesis Example 2 in which the aryl group content was 90% or more, but the one having less than 4 carbon atoms contained in the polysiloxane- , The solubility in a 2.38% TMAH aqueous solution after pre-baking was as low as less than 500 Å / sec, as in Comparative Example 1.

In the case of Comparative Example 3 using the polysiloxane prepared in Comparative Synthesis Example 3 in which TEOS was used as a spacer instead of the carbosilane-based spacer, it was not dissolved in the aqueous solution of 2.38% TMAH but dissolved only in the aqueous solution of 5% TMAH. In addition, most of the cured films obtained by curing the polysiloxane were cracked in the thermal shock test.

Thus, according to embodiments of the present invention, a carbosilane spacer having a hydrocarbon linkage group having 4 or more carbon atoms in the polysiloxane, and wherein the functional group bonded to the Si atom in an amount of 70 mol% or more based on the moles of all Si atoms in the polysiloxane is an aryl group The photosensitive resin composition containing the polysiloxane has excellent solubility in an alkali developing solution and crack resistance of the cured film produced therefrom is improved.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof,

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (10)

(A) a positive photosensitive resin composition comprising a compound represented by the following formula (1), (B) a quinone diazide compound, and (C) a solvent:
(Formula 1)
^{(R 1 R 2 R 3 SiO} 1/2) M (R 4 R 5 SiO 2/2) D (R 6 SiO 3/2) T1 (O 3/2 Si-Y-SiO 3/2) T2 (SiO _4/2 ) _Q
In Formula 1,
R ¹ to R ⁶ are each independently selected from the group consisting of hydrogen, hydroxy, halogen, 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, A substituted or 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, A substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, RO-, R (C = O) -, wherein R is a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 A substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or a combination thereof. The total Si Atomic number Based on the R ¹ to R ⁶ is bonded to more than 60 mole% Si atoms are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl An aryl group, or a combination thereof,
Y represents a substituted or unsubstituted C4 to C30 alkylene group, a substituted or unsubstituted C4 to C30 alkenylene group, a substituted or unsubstituted C4 to C30 cycloalkylene group, a substituted or unsubstituted C3 to C30 heterocycloalkylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,
0 < 0.4, 0 < D < 0.4, 0.6 &
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. The positive photosensitive resin composition according to claim 1, wherein M and Q in the formula (1) are 0, 0? D? 0.2, 0.65? T1 <1, and 0 <T2 <0.2. The positive photosensitive resin composition according to claim 1, wherein M, D and Q in the formula (1) are all 0, and 0.8 < T1 < 1 and 0 < The positive photosensitive resin composition according to claim 1, wherein R ¹ to R ⁶ in Formula 1 are each independently a C ¹ to C 6 alkyl group or a C 6 to C 12 aryl group. The method according to claim 1, wherein Y in the formula (1) is a linear or branched C4 to C30 alkylene group, a linear or branched C4 to C30 alkenylene group, a C4 to C12 cycloalkylene group, a C6 to C18 arylene group, A positive photosensitive resin composition. The method according to claim 1, wherein Y in the formula (1) is a linear or branched C4 to C20 alkylene group, a linear or branched C4 to C20 alkenylene group, a cyclohexylene group, a cyclooctanylene group, a phenylene group, A positive photosensitive resin composition. The positive photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a solubility in a 2.38% aqueous TMAH solution of 500 Å / sec to 5,000 Å / sec in a prebaked film. A cured film obtained by curing the positive photosensitive resin composition according to any one of claims 1 to 7. An element comprising a cured film according to claim 8. The functional group which is bonded to at least 60 mol% of Si atoms based on the total moles of Si atoms of the compound represented by the formula (1) is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 To C30 arylalkyl group, a substituted or unsubstituted C1 to C30 heteroaryl group, or a combination thereof.