KR101906281B1 - Photo-sensitive Composition, Cured Film Prepared Therefrom, and Device Incoporating the Cured Film - Google Patents

Abstract

(A) a photosensitive resin composition containing a siloxane compound represented by the following formula (1), (B) a quinone diazide compound and (C) a solvent and having an acid value of 200 mgKOH / g or less, a cured film obtained by curing the composition, and Providing a device comprising the cured film:
[Chemical Formula 1]
(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _1/2 -Y ¹ -SiO _1/2 R ⁶ R ⁷ ) _M2 (R ⁸ R ⁹ SiO _2/2 ) _D1 (R ^{10 _{SiO 2/2 -Y 2 -SiO 2/2 R 11}} ) D2 (R 12 R 13 Si-Y 3) D3 (R 14 SiO 3/2) T1 (SiO 3/2 -Y 4 -SiO 3/2) _T2 (SiO _{4/2) Q1}
In Formula 1,
The definition of R ¹ to R ¹⁴ , Y ¹ to Y ⁴ , M ¹ , M 2, D ¹ , D 2, D 3, T 1, T 2 and Q 1 is as described 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 the 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. In order to secure the conduction between the TFT substrate electrode and the ITO electrode It is necessary to form hole patterns of about 50 mu m to several mu m.

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 a high temperature of 200 占 폚 or more, and cause a problem of low film thickness or cracking, or the transparent film is colored by high temperature treatment of the substrate, and the transmittance is lowered.

In recent years, in order to improve the transparency and the functionality of the touch panel, a transparent electrode member made of ITO having high transparency and high conductivity has been used for a liquid crystal display or the like. However, . 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 that the conductivity of the electrode is lowered. Therefore, it can not be used in a process of forming a film at a high temperature by using a device such as PE-CVD on the transparent film material.

Also in the organic EL device, cracks and decomposition products generated from the above materials have no adverse effect on the luminous efficiency and lifetime of the organic EL device, and therefore, they are not suitable for use. In addition, the acrylic material imparted with heat resistance may also crack at 300 DEG C or higher, otherwise the dielectric constant generally increases. As a result, the parasitic capacitance due to the insulating film becomes large due to the high dielectric constant, which causes power consumption to increase and a problem of image quality due to 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.

A combination of a quinone diazide compound and a quinone diazide compound having a phenolic hydroxyl group at the terminal thereof, or a combination of a quinone diazide compound with a quinone diazide compound in order to impart positive photosensitivity to the siloxane polymer, a phenolic hydroxyl group or a carboxyl group And a combination of a siloxane polymer and a quinone diazide compound are known. However, these materials contain a large amount of quinone diazide compounds, or phenolic hydroxyl groups are present in the siloxane polymer, which tends to cause discoloration upon whitening or thermal curing of the coating film, and cracking may occur under severe high temperature conditions of 300 ° C or higher , And thus can not be used as a material with high transparency due to a decrease in transmittance. Further, since these materials have low transparency, there is also a problem that the sensitivity is low during 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, before the thermal curing of the pattern sufficiently progresses, it is melted by the low viscosity of the film due to the high temperature, and patterns such as holes and lines obtained after the development flow. As a result, cracks do not occur, but degradation of the pattern, which degrades the resolution, occurs and must be prevented.

In addition, when a quinone diazide compound is combined with a polysiloxane-insoluble polysiloxane and a polysiloxane compound which is insoluble in a developer, patterns of holes and lines obtained after development are collapsed upon heating and curing, resulting in "pattern sagging" A photosensitive composition 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, the photosensitive material has low sensitivity 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 capable of maintaining the molecular weight of the siloxane polymer and the content and shape of the alkali-soluble group during storage while having high solubility in an alkali developing 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 siloxane compound represented by the following formula (1), (B) a quinone diazide compound, and (C) a solvent and having an acid value of 200 mgKOH / g or less:

[Chemical Formula 1]

(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _1/2 -Y ¹ -SiO _1/2 R ⁶ R ⁷ ) _M2 (R ⁸ R ⁹ SiO _2/2 ) _D1 (R ^{10 _{SiO 2/2 -Y 2 -SiO 2/2 R 11}} ) D2 (R 12 R 13 Si-Y 3) D3 (R 14 SiO 3/2) T1 (SiO 3/2 -Y 4 -SiO 3/2) _T2 (SiO _{4/2) Q1}

In Formula 1,

R ¹ to R ¹⁴ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, 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 alkynyl 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 C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or combinations thereof,

Y ¹ to Y ⁴ each independently represent a single bond, oxygen, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heteroalkylene group , A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

1, 0? T1 <1, 0? T2 <1, and 0? Q1 <1, 0? M1 <1, 0? M2 <1, 0? D1 <

M1 + M2 + D1 + D2 + D3 + T1 + T2 + Q1 = 1,

The structural units represented by M1, M2, D1, D2, D3, T1, T2, and Q1 may each include one or more different structural units.

The acid value of the photosensitive resin composition may be 4 to 160 mgKOH / g or less.

The acid value of the photosensitive resin composition may be 6 or more and 140 mgKOH / g or less.

The acid value of the photosensitive resin composition may be 10 to 120 mgKOH / g or less.

The photosensitive resin composition may have a dissolution rate of 3.000 Å / second or less in a 2.38% by weight aqueous solution of TMAH in the prebaked film.

The weight average molecular weight of the siloxane compound represented by the formula (1) in the photosensitive resin composition may be 1,000 to 50,000 g / mole, which is converted to a polystyrene standard sample as measured by Gel Permeation Chromatography (GPC).

In the general formula (1), M1 and M2 are all 0, and 0? D1 <0.5, 0? D2 <0.2, 0? D3 <0.2, 0.5? T1 <1, 0? T2 <0.2, have.

In the formula (1), M1 and M2 are all 0 and 0? D1 <0.3, 0? D2 <0.2, 0? D3 <0.2, 0.7? T1 <1, 0 <T2 <0.2, .

In Formula 1, at least one of R ¹ to R ¹⁴ includes a substituted or unsubstituted C6 to C30 aryl group, and at least one of R ¹ to R ¹⁴ may include a substituted or unsubstituted C1 to C30 alkyl group .

In the general formula (1), Y ¹ to Y ⁴ are each, independently, A substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C30 cycloalkylene group.

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 photosensitive resin composition according to one embodiment can maintain the molecular weight of the polysiloxane and the content and form of the substituted alkali-soluble groups thereof at a certain level during storage, and can have high solubility in an alkaline developer after curing. Therefore, the composition is advantageous for the production of a cured film having high transparency, high heat resistance, low dielectric constant property, and high mechanical strength, yet having high resolution and patternability.

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 comprises (A) a photosensitive resin composition containing a siloxane compound represented by the following formula (1), (B) a quinone diazide compound, and (C) a solvent and having an acid value of 200 mgKOH / g or less do:

[Chemical Formula 1]

(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _1/2 -Y ¹ -SiO _1/2 R ⁶ R ⁷ ) _M2 (R ⁸ R ⁹ SiO _2/2 ) _D1 (R ^{10 _{SiO 2/2 -Y 2 -SiO 2/2 R 11}} ) D2 (R 12 R 13 Si-Y 3) D3 (R 14 SiO 3/2) T1 (SiO 3/2 -Y 4 -SiO 3/2) _T2 (SiO _{4/2) Q1}

In Formula 1,

R ¹ to R ¹⁴ are each independently hydrogen, a hydroxyl group, a 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,

Y ¹ to Y ⁴ each independently represent a single bond, oxygen, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heteroalkylene group , A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,

1, 0? T1 <1, 0 <T2 <1, and 0? Q1 <1, 0? D1 <1, 0? D1 <

M1 + M2 + D1 + D2 + D3 + T1 + T2 + Q1 = 1,

The structural units represented by M1, M2, D1, D2, D3, T1, T2, and Q1 may each include one or more different structural units.

In a liquid crystal display, an organic EL display, and the like, a method of increasing the aperture ratio of a display device as a method of realizing still higher precision and higher resolution is known. This is a method of improving the resolution and the sensitivity of the touch panel as compared with the related art by making the transparent flattening film as a heat shielding film on the TFT substrate to overlap the data line and the pixel electrode. Such a monocarbon film material for a TFT substrate requires a material having both high heat resistance, high transparency, and low dielectric constant. Conventionally, a material obtained by combining a phenolic resin and a quinone diazide compound, or an acrylic resin and a quinone diazide compound There is a combination of materials. However, as described above, these materials have a problem that the heat resistance is insufficient and the transparency is lowered due to coloration of the substrate during the high temperature processing.

It has been considered to use a siloxane polymer as a material having high heat resistance, high transparency and low dielectric constant characteristics. In order to impart positive photosensitivity to the siloxane polymer, a quinone diazide compound may be used in combination with other conventional positive compositions. For this purpose, the siloxane polymer may have a phenolic hydroxyl group at the terminal thereof, A hydroxyl group or an alkoxy group-containing siloxane polymer which is easily condensed can be used.

When a polymer having a silanol group or an alkoxy group is applied for imparting solubility to a developing solution of a siloxane polymer, the functional group has a high reactivity at a low temperature as well as at a normal temperature. Especially, when the water is present, &Lt; / RTI &gt; Therefore, in order to maintain the solubility of the siloxane polymer, it is preferable to remove moisture or to substitute a silanol group with a more stable functional group such as an ether group, an ester group or a phenol group, or other functional groups capable of imparting solubility in place of the silanol group The substitution reaction has been further advanced to improve the stability of the siloxane polymer. However, these substituted functional groups are less soluble than the silanol itself, and the functions themselves are also different, ultimately making it difficult to maintain the desired photosensitivity.

The inventors of the present invention have found that when the siloxane polymer is excellent in solubility in a developing solution after curing, it is possible to maintain the molecular weight of the siloxane polymer without changing the type and content of alkali-soluble groups such as silanol groups or alkoxy groups contained in the siloxane polymer during storage, As a result, the above-mentioned effect can be achieved by maintaining the acid value of the photosensitive resin composition containing the siloxane polymer, the quinone diazide compound, and the solvent at a certain level The present invention has been completed.

As described above, the silanol groups and alkoxy groups, which are alkali-soluble groups, have high reactivity even at room temperature and low temperature. Therefore, even when the siloxane polymer having the alkali-soluble group is stored in a refrigerator at about 5 ° C, the continuous condensation reaction between silanol groups or alkoxy groups The molecular weight of the siloxane polymer tends to increase continuously. As a result, the film obtained by curing the above-mentioned siloxane polymer having an increased molecular weight can no longer maintain its solubility in an alkali developing solution.

In the case where the acid value of the photosensitive resin composition containing the siloxane polymer and the quinone diazide compound and the solvent is maintained at 200 mgKOH / g or less as in the above embodiment, as shown in the following examples, the siloxane polymer , The weight average molecular weight of the siloxane polymer does not substantially change within about one week after the composition is stored at 5 DEG C in a refrigerator and the solubility of the membrane prepared in the 2.38% aqueous solution of TMAH The same was maintained. In addition, even after the composition was stored at 5 占 폚 for about one month in a refrigerator, the change in the weight average molecular weight of the siloxane polymer in each composition was insignificant. . In addition, the solubility of the membrane prepared from the composition in aqueous 2.38% TMAH solution was also slightly decreased, but the difference was not large.

On the other hand, there is a difference in the degree of change in the weight average molecular weight and availability of the siloxane polymer with time depending on the acid value of the composition. For example, as can be seen from the examples described below, in the case of adding about 10 ppm of para-toluenesulfonic acid to the composition, that is, Example 1 in which the acid value of the composition is about 20 mgKOH / g, The weight average molecular weight of the siloxane copolymers having different weight average molecular weights according to Synthesis Examples 1 to 4 was the smallest in the change of the weight average molecular weight with time and the change in solubility of the membrane prepared therefrom to the 2.37% TMAH aqueous solution was the smallest. On the other hand, in Example 3 in which the content of acid added to the composition was more than 100 mgKOH / g, the weight average molecular weight of the siloxane copolymer gradually increased with time. Also, the decrease in solubility of the membrane prepared from the membrane to the aqueous solution of 2.37% TMAH was also larger. However, as in Examples 1 to 3, when the acid value of the composition was 200 mgKOH / g or less, the change in the weight average molecular weight of the siloxane copolymer and the change in solubility to the alkali developer Much less. However, as in Comparative Example 1, when the acid value of the composition exceeds 200 mgKOH / g, the change in the weight average molecular weight of the siloxane copolymer and the decrease in the solubility to the alkaline developer, rather than Comparative Example 2, It appears large.

Therefore, the photosensitive resin composition according to the embodiment can easily improve the stability during storage of the photosensitive resin composition by controlling the acid value of the composition, and can easily maintain the availability of the film formed therefrom with the alkali developer .

For example, the acid value of the photosensitive resin composition is 0 to 200 mgKOH / g, for example, 4 to 160 mgKOH / g, for example, 6 to 140 mgKOH / g, / g or less, for example, 15 or more and 100 mgKOH / g or less, for example, 20 or more and 80 mgKOH / g or less.

The acid value can be measured by an indicator titration method using an alkaline titrant solution. Specifically, about 3 g of the silicone polymer sample is quantitatively (S) and diluted to about 11 g of PGMEA. 14 g of the sample solution is placed in an Erlenmeyer flask and mixed with 80 g of a measurement solution mixed with 100 g of toluene, 95 g of isopropyl alcohol and 5 g of distilled water. The solution prepared above is titrated with a 0.1 mol / L potassium hydroxide titrant solution. While reading the pH of the solution mixed with the sample, the necessary amount (A1) of the titrant solution necessary for the pH of the solution to be 10 is read while the titrant solution is put into the titration apparatus (KEM kyoto Electronics, AT-610-ST) To be quantified. To obtain the precise acid value of the silicone polymer, the amount (A2) of the appropriate solution (A2) required to titrate the pH of the blank solution to 10 by using a blank solution (80 g of measurement solution + 14 g of PGMEA) , And the acid value of the silicon polymer is calculated by substituting into the following formula (1).

(1)

Acid value  ( mgKOH / g) = (A1-A2) x f / S

In the above formula (1), A1 and A2 represent the amount (mL) of the 0.1 mol / L potassium hydroxide titrant solution used for neutralization of the blank solution containing the sample solution and the silicon polymer respectively, f is 0.1 mol / L hydroxide S represents the amount of the sample (g) (provided that when the sample contains a solvent, the amount (g) excluding the solvent).

On the other hand, in the case of using the siloxane polymer according to Synthesis Example 2 and Synthesis Example 3 containing the D1 structural unit in the siloxane polymer represented by the above formula (1) in the photosensitive resin composition, A polymer having a larger weight average molecular weight than that of the siloxane polymer can be prepared, and thus the solubility in an alkali developer is reduced. Particularly, when the siloxane polymer of Synthesis Example 3, in which the content of the D1 structural unit is twice that of Synthesis Example 2, is used, the weight average molecular weight of the siloxane polymer is further increased and the solubility in an alkali developer is further reduced.

Accordingly, the photosensitive resin composition according to the present embodiment can easily control the weight average molecular weight of the siloxane polymer and the solubility of the membrane prepared from the siloxane polymer in the alkaline developer by controlling the content of each structural unit in the siloxane polymer represented by the formula (1) It can be seen that it can be controlled.

For example, in the above formula (1), M1 and M2 are all 0 and 0? D1 <0.5, 0? D2 <0.2, 0? D3 <0.2, 0.5? T1 <1, Q1 < 0.2.

That is, the siloxane compound is (R ¹⁴ SiO _3/2) contains at least 0.5 mole fraction of T1 structural unit as represented by, and _{(O 3/2 Si-Y} 4 -SiO 3/2) of the formula (1) Lt; RTI ID = 0.0 &gt; T2 &lt; / RTI &gt;

If they include structural units represented by _{(O 3/2 Si-Y} 4 -SiO 3/2) to the above range, the photosensitive resin composition comprising a compound of the formula (1) is dense with a sufficient cross-linking upon curing Structure, it has high mechanical strength, chemical resistance, and high residual film ratio.

In _{addition, (O 3/2 Si-} Y 4 -SiO 3/2) structural unit represented by the cross-linking agent is contained, and the function within the compound represented by general formula (1), therefore, appropriately adjusted within the range of the structural unit The hardness of the coating film can be easily controlled and the hardness of the coated film can be improved. The resulting coating film of high hardness has a high crack resistance at a high temperature and at the same time effectively prevents penetration of the organic solvent, It is possible to solve the problem of a residual film ratio which can not form a flat film and to realize an organic insulating film excellent in chemical resistance after curing, crack resistance at high temperature, etch resistance and the like.

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, For example, 0.75? T1 <1, for example, 0.8? T1 <1, for example, 0.85? T1 <1, for example 0.9? T1 <1, for example, 0.95? T1 <

In addition, in one embodiment, the structural unit represented by the T2 of the structural units constituting the compound of the formula (1), _{i.e., (O 3/2 Si-} Y 4 -SiO 3/2) is 0 <T2 <0.2 For example 0 <T2? 0.17, for example 0 <T2? 0.15, for example 0 <T2? 0.13, for example 0 <T2? 0.12, for example 0 < For example 0 < T0 < / RTI &gt; 0.09, for example 0 & , For example, 0 < T2 < = 0.03.

In one embodiment, M1 and M2 in the formula 1 are all 0 and 0? D? 1? 0.3, 0? D? 2 0.2, 0? D3 <0.2, 0.7? T1 <1, 0 < Q1 < 0.2.

On the other hand, in the case of the siloxane polymer prepared in Synthesis Example 4, unlike the siloxane polymer represented by the above formula (1), it does not contain a T2 structural unit. Accordingly, the weight average molecular weight of the siloxane polymer to be produced is relatively low relative to the weight average molecular weight of the polymer according to Synthesis Examples 1 to 3 which is the siloxane polymer represented by the above formula (1). Nevertheless, the solubility of a film prepared from a photosensitive resin composition containing the polymer is also lowest.

As described above, the photosensitive resin composition according to the present invention comprises the siloxane polymer represented by the above formula (1), the quinone diazide compound, and a solvent, wherein the acid value of the composition is adjusted to 100 mgKOH / g or less, It is also known that the stability of the photosensitive resin composition during storage can be improved by appropriately changing the content of each structural unit of the siloxane polymer represented by the formula (1), and the availability of the film produced therefrom to the alkali developer can be maintained .

For example, the photosensitive resin composition may have a dissolution rate in a 2.38% by weight aqueous solution of TMAH of 3,000 Å / second or less, for example, 2,5000 Å / second or less, for example, 2,000 Å / And not more than 1,500 ANGSTROM / sec, for example, 100 ANGSTROM to 3,000 ANGSTROM or less, for example, 150 ANGSTROM or more and 3,000 ANGSTROM or less, for example, 200 ANGSTROM or more and 2,500 ANGSTROM or less For example, not less than 200 Å / s and not more than 2,000 Å / s, such as not less than 200 Å / s and not more than 1,500 Å / s, such as not less than 250 Å / , But are not limited to these.

The weight average molecular weight of the siloxane compound represented by the formula (1) in terms of polystyrene standard sample measured by gel permeation chromatography (GPC) in the photosensitive resin composition is 1,000 to 10,000 g / mole, for example, And may be, for example, 1,500 to 5,000 g / mole, for example 1,500 to 3,500 g / mole, for example, 2,000 to 3,000 g / mole.

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

In Formula 1, at least one of R ¹ to R ¹⁴ includes a substituted or unsubstituted C6 to C30 aryl group, and at least one of R ¹ to R ¹⁴ may include a substituted or unsubstituted C1 to C30 alkyl group have.

In the above formula (1), Y ¹ to Y ⁴ are each, independently, A substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C30 cycloalkylene group.

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 -Y ¹ -SiZ ³ R ⁶ R ⁷ , a monomer represented by R ⁸ R ⁹ SiZ ⁴ Z ⁵ and a monomer represented by R ¹⁰ SiZ ⁶ Z ⁷ -Y ² -SiZ ⁸ Z ⁹ R ¹¹ , a monomer represented by R ¹² R ¹³ Si-Y ³ , a monomer represented by R ¹⁴ SiZ ¹⁰ Z ¹¹ Z ¹² , and a monomer represented by Z ¹³ Z ¹⁴ Z ¹⁵ Si- Y is ^4- SiZ ¹⁶ Z ¹⁷ Z ¹⁸ , And monomers represented by SiZ ¹⁹ Z ²⁰ Z ²¹ Z ²² can be obtained by hydrolysis and condensation polymerization of at least one monomer selected from the group consisting of R ¹⁴ SiZ ¹⁰ Z ¹¹ Z ¹² and Z ¹³ Z ¹⁴ Z ¹⁵ Si-Y ⁴ -SiZ ¹⁶ Z ¹⁷ Z ¹⁸ And the like. Here, the definitions of R ¹ to R ¹⁴ are as defined above, and Z ¹ to Z ²² are each independently a C ¹ to C 6 alkoxy group, a hydroxy group, a halogen, a carboxyl group, or a combination thereof.

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 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 monomers.

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 ¹⁵ , R ¹⁶ and R ¹⁷ each independently represents any one of a C 1 to C 10 alkyl group, a carboxyl group, a phenyl group and a substituted phenyl group, and R ¹⁵ , R ¹⁶ and R ¹⁷ together form a ring You may.

In the groups represented by the general formula (2), R ¹⁵ , R ¹⁶ , and R ¹⁷ , 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 deg. C, the amount of the residual solvent in the film increases, and the film shrinkage ratio during 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. When the boiling point is higher than 250 占 폚, the amount of the residual solvent in the film becomes large, and the film shrinkage increases during curing and 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 )

Synthetic example  1 to 4: Siloxane  Preparation of Copolymer

Synthetic example  One

42.45 g (0.214 mol) of phenyltrimethoxysilane, 36.99 g (0.272 mol) of methyltrimethoxysilane and 14.05 g (0.039 mol) of 1,2-bistriethoxysilylethane were added to a 500 ml three-necked flask, and 177.34 g And an aqueous solution of 3.22 g of paratoluenesulfonic acid dissolved in 30.85 g of water was added over 10 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 30 DEG C and stirred for 240 minutes, and then the water layer was removed to prepare a polymer solution dissolved in toluene. The resultant polymer solution was washed with water to remove the residual catalyst, and further a neutral polymer solution was distilled under reduced pressure to finally obtain a carbosilane-siloxane copolymer solution (A) in which propylene glycol monomethyl ether acetate (PGMEA) ). The solid content concentration of the obtained carbosilane-siloxane copolymer solution (A) was 30% by weight. The molecular weight of the obtained carbosilane-siloxane copolymer (A) was measured by GPC and found to be 2,012 g / mol in terms of weight average molecular weight converted to a polystyrene standard sample.

The equipment used for the molecular weight measurement was HLC-8220 GPC, and the sequence of the column flow was as follows:

Shodex KF-80 (main column) → Shodex KF-804 → Shodex KF-803 → Shodex KF-80 → Shodex KF-80 (main column)

The molecular weight measurement temperature is 40 占 폚, the pressure is 700 psi, and the flow rate is 1 cc / min.

Synthetic example  2

In a 500 ml three-necked flask, 42.45 g (0.214 mol) of phenyltrimethoxysilane, 29.24 g (0.215 mol) of methyltrimethoxysilane, 14.05 g (0.039 mol) of 1,2-bistriethoxysilylethane, (0.050 mol) of toluene, 177.34 g of toluene was added, and an aqueous solution obtained by dissolving 3.22 g of para-toluene sulfonic acid in 30.85 g of water was added over 10 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 30 DEG C and stirred for 240 minutes, and then the water layer was removed to prepare a polymer solution dissolved in toluene. The resulting polymer solution was washed with water to remove the residual catalyst, and further a neutral polymer solution was distilled off under reduced pressure to finally obtain a carbosilane-siloxane copolymer solution (A) in which propylene glycol monomethyl ether acetate (PGMA) ). The concentrate concentration of the obtained carbosilane-siloxane copolymer solution (A) was 30% by weight. The molecular weight of the obtained carbosilane-siloxane copolymer (A) was measured by GPC and found to be 2,431 g / mol in terms of weight average molecular weight converted to a polystyrene standard sample.

The equipment for measuring the molecular weight and the measurement conditions are the same as in Synthesis Example 1. [

Synthetic example  3

In a 500 ml three-necked flask, 42.45 g (0.214 mol) of phenyltrimethoxysilane, 22.17 g (0.163 mol) of methyltrimethoxysilane, 14.05 g (0.039 mol) of 1,2-bistriethoxysilylethane, (0.10 mol) of toluene, 177.34 g of toluene was added, and an aqueous solution obtained by dissolving 3.22 g of para-toluene sulfonic acid in 30.85 g of water was added over 10 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 30 DEG C and stirred for 240 minutes, and then the water layer was removed to prepare a polymer solution dissolved in toluene. The resultant polymer solution was washed with water to remove the residual catalyst, and further a neutral polymer solution was distilled under reduced pressure to finally obtain a carbosilane-siloxane copolymer solution (A) in which propylene glycol monomethyl ether acetate (PGMEA) ). The concentrate concentration of the obtained carbosilane-siloxane copolymer solution (A) was 30% by weight. The molecular weight of the obtained carbosilane-siloxane copolymer (A) was measured by GPC and found to be 2,891 g / mol in terms of weight average molecular weight converted to a polystyrene standard sample.

The equipment for measuring the molecular weight and the measurement conditions are the same as in Synthesis Example 1. [

Synthetic example  4

42.45 g (0.214 mol) of phenyltrimethoxysilane, 22.17 g (0.163 mol) of methyltrimethoxysilane, 4.76 g (0.039 mol) of tetraethoxysilane and 12.21 g (0.10 mol) of dimethyldimethoxysilane were placed in a 500 ml three- Was added 177.34 g of toluene and an aqueous solution of 3.22 g of paratoluenesulfonic acid dissolved in 30.85 g of water was added over 10 minutes while stirring at room temperature. Thereafter, the flask was immersed in an oil bath at 30 DEG C and stirred for 240 minutes, and then the water layer was removed to prepare a polymer solution dissolved in toluene. The resulting polymer solution was washed with water to remove the residual catalyst, and a further neutral polymer solution was finally distilled under reduced pressure to obtain a carbosilane-siloxane copolymer solution (A) in which propylene glycol monomethyl ether acetate (PGMEA) . The concentrate concentration of the obtained carbosilane-siloxane copolymer solution (A) was 30% by weight. The molecular weight of the obtained carbosilane-siloxane copolymer (A) was measured by GPC and found to be 1,548 g / mol in terms of weight average molecular weight converted to a polystyrene standard sample.

The equipment for measuring the molecular weight and the measurement conditions are the same as in Synthesis Example 1. [

Example  1 to 3 and Comparative Example  One: Cured film  Manufacturing and Prebake  Evaluation of solubility of alkaline developer for backfilm

Example  One

10 ppm of p-toluenesulfonic acid was added to each of the neutral liquid mixtures obtained in Synthesis Examples 1 to 4 and stirred well to prepare a solution having an acid value of 20 mgKOH / g. These solutions were each stored at 5 ° C in a refrigerator, Periodically, the weight average molecular weight of the siloxane copolymer and the change in solubility (Dissolve rate) in the TMAH 2.38% solution from the composition were measured on the dates described.

The equipment for measuring the molecular weight and the measurement conditions are the same as in Synthesis Example 1. [

The solubility measurement method for the alkali developer is as follows:

The liquid mixture stored in a refrigerator at 5 DEG C is spin coated on a silicon wafer to a thickness of about 2 mu m and then heated on a hot plate at 100 DEG C for 60 seconds to remove the remaining solvent. Thereafter, the film thickness of the coated film was measured with a Tencor, and then the silicon wafer having this film was immersed in a 2.38% TMAH aqueous solution contained in a 23 ° C water bath while maintaining a constant temperature. The time from the time of immersion to the time when the film disappears is measured. At this time, the dissolution rate is obtained by dividing the initial film thickness by the time until the film completely disappears. When the dissolution rate is remarkably low, the dissolution rate can be calculated in the same manner by measuring the thickness of the film after immersing for a predetermined time.

Weight average molecular weight Availability (Å / sec) Early 1 day 2 days 4 days 8 days 16th 32nd Early 1 day 2 days 4 days 8 days 16th 32nd Synthesis Example 1 2012 2012 2012 2012 2052 2072 2113 2110 2110 2110 2110 2068 2047 2005 Synthesis Example 2 2431 2431 2431 2431 2480 2504 2553 1080 1080 1080 1080 1058 1048 1026 Synthesis Example 3 2891 2891 2891 2891 2949 2978 3036 612 612 612 612 600 594 581 Synthesis Example 4 1548 1548 1548 1548 1579 1594 1625 52 52 52 52 51 50 49

Example  2

To each of the neutral liquid mixtures obtained in Synthesis Examples 1 to 4, 50 ppm of p-toluenesulfonic acid was added and stirred well to prepare a solution having an acid value of 80 mgKOH / g. Periodically, the weight average molecular weight of the siloxane copolymer and the change in solubility (Dissolve rate) in the TMAH 2.38% solution from the composition were measured on the dates described.

The equipment and measurement conditions for the molecular weight measurement are the same as in Synthesis Example 1, and the method for measuring the solubility in the alkali developer is the same as that described in Example 1 above.

Weight average molecular weight Availability (Å / sec) Early 1 day 2 days 4 days 8 days 16th 32nd Early 1 day 2 days 4 days 8 days 16th 32nd Synthesis Example 1 2012 2012 2012 2092 2133 2173 2193 2110 2110 2110 2026 1983 1941 1920 Synthesis Example 2 2431 2431 2431 2528 2577 2625 2650 1080 1080 1080 1037 1015 994 983 Synthesis Example 3 2891 2891 2891 3007 3064 3122 3151 612 612 612 588 575 563 557 Synthesis Example 4 1548 1548 1548 1610 1641 1672 1687 52 52 52 50 49 48 47

Example  3

100 ppm of p-toluenesulfonic acid was added to each of the neutral liquid mixtures obtained in Synthesis Examples 1 to 4 and stirred well to prepare a solution having an acid value of 160 mgKOH / g. Periodically, the weight average molecular weight of the siloxane copolymer and the change in solubility (Dissolve rate) in the TMAH 2.38% solution from the composition were measured on the dates described.

The equipment and measurement conditions for the molecular weight measurement are the same as in Synthesis Example 1, and the method for measuring the solubility in the alkali developer is the same as that described in Example 1 above.

Weight average molecular weight Availability (Å / sec) Early 1 day 2 days 4 days 8 days 16th 32nd Early 1 day 2 days 4 days 8 days 16th 32nd Synthesis Example 1 2012 2113 2213 2314 2414 2515 2616 2110 2005 1899 1794 1688 1583 1477 Synthesis Example 2 2431 2553 2674 2796 2917 3039 3160 1080 1026 972 918 864 810 756 Synthesis Example 3 2891 3036 3180 3325 3469 3614 3758 612 581 551 520 490 459 428 Synthesis Example 4 1548 1625 1703 1780 1858 1935 2012 52 49 47 44 42 39 36

Comparative Example  One

200 ppm of p-toluenesulfonic acid was added to each of the neutral liquid mixtures obtained in Synthesis Examples 1 to 4 and stirred well to prepare a solution having an acid value of 320 mgKOH / g. Periodically, the weight average molecular weight of the siloxane copolymer and the change in solubility (Dissolve rate) in the TMAH 2.38% solution from the composition were measured on the dates described.

The equipment and measurement conditions for the molecular weight measurement are the same as in Synthesis Example 1, and the method for measuring the solubility in the alkali developer is the same as that described in Example 1 above.

Weight average molecular weight Availability (Å / sec) Early 1 day 2 days 4 days 8 days 16th 32nd Early 1 day 2 days 4 days 8 days 16th 32nd Synthesis Example 1 2012 2253 2414 2616 2716 2817 3018 2110 1857 1688 1477 1372 1266 1055 Synthesis Example 2 2431 2674 2917 3039 3160 3282 3403 1080 950 864 756 702 648 540 Synthesis Example 3 2891 3180 3469 3614 3758 3903 4047 612 539 490 428 398 367 306 Synthesis Example 4 1548 1703 1858 1935 2012 2090 2167 52 46 42 36 34 31 26

Comparative Example  2

The neutral liquid mixtures obtained in Synthesis Examples 1 to 4 were each stored at 5 ° C in a refrigerator, and the weight average molecular weight of the siloxane copolymer was measured periodically on the dates shown in Table 5 below, Dissolve rate changes were measured.

The equipment and measurement conditions for the molecular weight measurement are the same as in Synthesis Example 1, and the method for measuring the solubility in the alkali developer is the same as that described in Example 1 above.

Weight average molecular weight Availability (Å / sec) Early 1 day 2 days 4 days 8 days 16th 32nd Early 1 day 2 days 4 days 8 days 16th 32nd Synthesis Example 1 2012 2213 2414 2515 2616 2716 2817 2110 1899 1688 1583 1477 1372 1266 Synthesis Example 2 2431 2530 2548 2755 2823 3087 3317 1080 972 864 810 756 702 648 Synthesis Example 3 2891 2891 3051 3091 3297 3500 3906 612 551 490 459 428 398 367 Synthesis Example 4 1548 1638 1683 1788 1805 1916 2164 52 47 42 39 36 34 31

evaluation

As can be seen from Tables 1 to 3, the photosensitive resin compositions according to Examples 1 to 3 having an acid value of 200 mgKOH / g or less of the photosensitive resin composition containing the siloxane copolymer according to formula (1) The weight average molecular weight of the siloxane copolymer does not change or the degree of change is extremely small up to about one week, and the change in the weight average molecular weight is less than 10% even when it exceeds one month. In particular, in the case of Example 1 in which the acid value of the photosensitive resin composition is 20 mgKOH / g, the rate of increase of the weight average molecular weight of the siloxane copolymer is 5% or less even when it is more than one month after storage at 5 占 폚. In addition, the solubility of these photosensitive resin compositions in a 2.38% TMAH aqueous solution was not large. Similar to the change in the weight average molecular weight, the solubility was not changed until 1 week after storage at 5 ° C, and the solubility did not decrease significantly even when it exceeded one month. Particularly, in the case of the compositions of Example 1 and Example 2, in which the acid value of the photosensitive resin composition was 100 mgKOH / g or less, the change in solubility in the aqueous solution of 2.38% TMAH was not large even after one month of storage at 5 ° C.

On the other hand, in Example 3 in which the amount of acid added to the composition exceeded 100 mgKOH / g, the weight average molecular weight of the siloxane copolymer gradually increased with time. Also, the decrease in solubility of the membrane prepared from the membrane to the aqueous solution of 2.37% TMAH was also larger. However, as in Examples 1 to 3, when the acid value of the composition was 200 mgKOH / g or less, the change in the weight average molecular weight of the siloxane copolymer and the change in solubility to the alkali developer Much less. However, as in Comparative Example 1, when the acid value of the composition exceeds 200 mgKOH / g, the change in the weight average molecular weight of the siloxane copolymer and the decrease in the solubility to the alkaline developer, rather than Comparative Example 2, It appears large.

From the above results, it can be seen that the storage stability of the composition can be improved by adjusting the acid value of the composition of the photosensitive resin composition according to one embodiment, and the solubility of the film produced therefrom to the alkali developer can be also maintained.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, And falls within the scope of the present invention.

Claims (13)

(A) a siloxane compound represented by the following formula (1)
(B) a quinone diazide compound, and
(C) Solvent
, And an acid value of not more than 200 mgKOH / g:
[Chemical Formula 1]
(R ¹ R ² R ³ SiO _1/2 ) _M1 (R ⁴ R ⁵ SiO _1/2 -Y ¹ -SiO _1/2 R ⁶ R ⁷ ) _M2 (R ⁸ R ⁹ SiO _2/2 ) _D1 (R ^{10 _{SiO 2/2 -Y 2 -SiO 2/2 R 11}} ) D2 (R 12 R 13 Si-Y 3) D3 (R 14 SiO 3/2) T1 (SiO 3/2 -Y 4 -SiO 3/2) _T2 (SiO _{4/2) Q1}
In Formula 1,
R ¹ to R ¹⁴ each independently represent a hydrogen atom, a hydroxy group, a halogen atom, 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 alkynyl 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 C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group), or combinations thereof,
Y ¹ to Y ⁴ each independently represent a single bond, oxygen, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 heteroalkylene group , A substituted or unsubstituted C2 to C30 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, or a combination thereof,
1, 0? T1 <1, 0 <T2 <1, and 0? Q1 <1, 0? D1 <1, 0? D1 <
M1 + M2 + D1 + D2 + D3 + T1 + T2 + Q1 = 1,
The structural units represented by M1, M2, D1, D2, D3, T1, T2, and Q1 may each include one or more different structural units. The photosensitive resin composition according to claim 1, wherein the acid value of the photosensitive resin composition is 4 mgKOH / g or more and 160 mgKOH / g or less. The photosensitive resin composition according to claim 1, wherein the acid value of the photosensitive resin composition is 6 mgKOH / g or more and 140 mgKOH / g or less. The photosensitive resin composition according to claim 1, wherein the acid value of the photosensitive resin composition is 10 mgKOH / g or more and 120 mgKOH / g or less. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition has a dissolution rate of 3,000 A / sec or less in a 2.38% by weight aqueous solution of TMAH in a prebaked film. The photosensitive resin composition according to claim 1, wherein the weight average molecular weight of the siloxane compound represented by the formula (1) in the photosensitive resin composition, converted to a polystyrene standard sample, measured by Gel Permeation Chromatography (GPC) is 1,000 g / mole to 50,000 g / mole. 1, 0 < T < 0.2, and 0 < = 0.2, Q1 < 0.2. 1, 0 < T < 0.2, and 0 < = 0.2, Q1 < 0.2. Wherein at least one of R ¹ to R ¹⁴ in Formula 1 includes a substituted or unsubstituted C6 to C30 aryl group and at least one of R ¹ to R ¹⁴ is a substituted or unsubstituted C1 to C30 alkyl group . The compound according to claim 1, wherein Y ¹ to Y ⁴ in the formula (1) A substituted or unsubstituted C1 to C20 alkylene group, or a substituted or unsubstituted C3 to C30 cycloalkylene group. A cured film obtained by curing the photosensitive resin composition according to any one of claims 1 to 10. The method according to claim 11, wherein the cured film is a planarizing 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 micro lens array pattern, or a cured film which is a core or clad material of an optical waveguide of an optical semiconductor element . An element comprising a cured film according to claim 12.